Laminate and Image Display Device

Abstract

The present invention addresses the problems of providing a layered body that enables the production of an image display device having excellent display performance and discoloration resistance, and of providing an image display device that uses the layered body. The layered body according to the present invention has two substrates and a polarizer layer disposed between the two substrates, wherein: the polarizer layer contains one or more types of azo dyes having at least two intramolecular azo bonds; the moisture permeability of each of the two substrates is 10-3g / m2∙day or less; and the amount of water present between the two substrates is 0.9 g / m2 or less.

Description

Technical Field

[0001] The present invention relates to a laminate and an image display device.

Background Art

[0002] Conventionally, when an attenuation function, a polarization function, a scattering function, a light shielding function, or the like of irradiation light including laser light or natural light is required, devices operating on different principles for each function have been used. Therefore, products corresponding to the above functions have also been manufactured by different manufacturing processes for each function. For example, in an image display device (e.g., a liquid crystal display device), a linear polarizer or a circular polarizer is used to control the optical rotation or birefringence in display. Also, in an Organic Light Emitting Diode (OLED), a circular polarizer is used to prevent reflection of external light.

[0003] Conventionally, iodine has been widely used as a dichroic substance in these polarizers, but polarizers using an organic dye as a dichroic substance instead of iodine have also been studied. For example, Patent Document 1 describes a light absorption anisotropic film (polarizer layer) formed using a composition containing a dichroic substance having a predetermined structure ([Claim 1][Claim 14]).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The inventors prepared a polarizer layer described in Patent Document 1, and in accordance with practical aspects (for example, a circular polarizing plate for the purpose of anti-reflection of an organic electroluminescence smartphone), this polarizer layer was sandwiched from both sides by substrates with low moisture permeability (for example, glass substrates). When the obtained laminate was exposed to high-temperature conditions for a long time, it was found that a yellowish discolored region occurred in the central part of the in-plane of the laminate. In addition, as a result of repeated studies by the inventors, it was found that the degree of discoloration occurring in the central part of the laminate varies depending on the composition of the adhesive used in the production of the laminate and the conditions during the production of the laminate.

[0006] Therefore, an object of the present invention is to provide a laminate capable of producing an image display device excellent in display performance and discoloration resistance, and an image display device using the same.

Means for Solving the Problems

[0007] As a result of intensive studies on the above problems, the inventors have found that the above problems can be solved by the following configuration.

[0008] [1] A laminate having two substrates and a polarizer layer disposed between the two substrates, wherein the polarizer layer contains one or more azo dyes having two or more azo bonds in the molecule, the moisture permeability of both of the two substrates is 10 -3 g / m 2 ·day or less, and the amount of moisture present between the two substrates is 0.9 g / m 2 or less. The laminate. [2] The laminate according to [1], wherein the amount of moisture present between the two substrates is 0.7 g / m 2 or less. [3] The laminate according to [1], wherein the amount of moisture present between the two substrates is 0.4 g / m 2 or less. [4] The laminate according to any one of [1] to [3], further having at least one adhesive layer disposed between the two substrates. [5] The total content of the reducing agent in at least one adhesive layer is 0.04 g / m 2 or less, the laminate according to [4]. [6] The thickness of each of at least one adhesive layer is 100 μm or more, the laminate according to [4] or [5]. [7] A laminate having two substrates, a polarizer layer disposed between the two substrates, and at least one adhesive layer disposed between the two substrates, wherein the polarizer layer contains at least one azo dye having two or more azo bonds in the molecule, the moisture permeabilities of the two substrates are both 10 -3 g / m 2 ·day or less, and the total thickness of at least one adhesive layer is 70 μm or less, the laminate. [8] The total content of the reducing agent in at least one adhesive layer is 0.04 g / m 2 or less, the laminate according to [7]. [9] The total thickness of at least one adhesive layer is 50 μm or more, the laminate according to [7] or [8].

[10] A laminate having two substrates, a polarizer layer disposed between the two substrates, at least one low moisture permeability layer disposed between the two substrates, and at least one adhesive layer disposed between the two substrates, wherein the polarizer layer contains at least one azo dye having two or more azo bonds in the molecule, the moisture permeabilities of the two substrates are both 10 -3 g / m 2 ·day or less, at least one low moisture permeability layer is disposed between the polarizer layer and at least one adhesive layer, and the moisture permeabilities of at least one low moisture permeability layer are both 20 g / m 2 ·day or less, the laminate.

[11] At least one low moisture permeability layer has a cyclic polyolefin resin, the laminate according to

[10] .

[12] The total content of the reducing agent in at least one adhesive layer is 0.04 g / m 2The laminate according to

[10] or

[11] below.

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

[12] , wherein both of the two substrates are glass substrates.

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

[13] , wherein the thicknesses of the two substrates are both 100 to 1100 μm.

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

[14] , wherein the azo dye is a compound represented by the following formula (1).

[16] An image display device having the laminate according to any one of [1] to

[15] .

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a laminate capable of producing an image display device excellent in display performance and discoloration resistance, and an image display device using the same.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made 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 including the numerical values described before and after "~" as the lower limit value and the upper limit value. Also, 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 substances used in combination, unless otherwise specified. Also, in this specification, the regulations regarding the substrate (for example, thickness, type, etc.) refer to the common regulations regarding the two substrates, unless otherwise specified. Also, in this specification, when there are a plurality of adhesive layers, the regulations regarding the adhesive layer (for example, thickness, reducing agent content, etc.) refer to the common regulations regarding the plurality of adhesive layers, unless otherwise specified. In addition, in this specification, when there are a plurality of low moisture permeability layers, the regulations regarding the low moisture permeability layers (for example, thickness, moisture permeability, etc.) refer to the common regulations regarding the plurality of low moisture permeability layers 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”.

[0011] <Laminate> The laminate of the present invention is the laminate according to the following first aspect to third aspect.

[0012] The laminate according to the first aspect of the present invention is a laminate having two substrates and a polarizer layer disposed between the two substrates, wherein the polarizer layer contains one or more azo dyes having two or more azo bonds in the molecule, and the moisture permeability of both of the two substrates is 10 -3 g / m 2 ·day or less, and the amount of moisture present between the two substrates is 0.9 g / m 2 or less, which is a laminate.

[0013] The laminate according to the second aspect of the present invention is a laminate having two substrates, a polarizer layer disposed between the two substrates, and at least one adhesive layer disposed between the two substrates, wherein the polarizer layer contains one or more azo dyes having two or more azo bonds in the molecule, and the moisture permeability of both of the two substrates is 10 -3 g / m 2 ·day or less, and the total thickness of the at least one adhesive layer is 70 μm or less, which is a laminate.

[0014] The laminate according to the third aspect of the present invention is a laminate having two substrates, a polarizer layer disposed between the two substrates, at least one low moisture permeability layer disposed between the two substrates, and at least one adhesive layer disposed between the two substrates, wherein the polarizer layer contains one or more azo dyes having two or more azo bonds in the molecule, and the moisture permeability of both of the two substrates is 10-3 g / m 2 ·day or less, and at least one low moisture permeability layer is disposed between the polarizer layer and at least one adhesive layer, and the moisture permeability of each of the at least one low moisture permeability layer is 20 g / m 2 ·day or less, and it is a laminate.

[0015] Hereinafter, the members constituting the laminate according to the first to third aspects of the present invention (hereinafter, also abbreviated as "the laminate of the present invention" when no particular distinction is required) will be described in detail.

[0016] [Substrate] The laminate of the present invention has two substrates. The moisture permeability of the substrate is 10 -3 g / m 2 ·day or less, and from the viewpoint of durability of an organic electroluminescent device, a liquid crystal display device, etc. to which the laminate of the present invention is applied, 10 -4 g / m 2 ·day or less is preferable, and 10 -5 g / m 2 ·day or less is more preferable. The lower limit is not particularly limited, but it is often 10 -10 g / m 2 ·day or more. The method for measuring the moisture permeability of the substrate is as follows. It is measured using a water vapor transmission rate measuring device (AQUATRAN2 (registered trademark) manufactured by MOCON, INC.) under the conditions of a measurement temperature of 40°C and a relative humidity of 90%.

[0017] The material constituting the substrate is not particularly limited and may be an inorganic substance or an organic substance. As the substrate, if the moisture permeability is lower than the specified value, it is not particularly limited, and examples thereof include a glass substrate and a gas barrier film. More specifically, a glass substrate such as a sealing glass used in an organic electroluminescent device, a glass in a liquid crystal cell, and a surface cover glass, and a gas barrier film such as a high barrier film and a barrier film used in an organic electroluminescent device are included. The substrate may have a single-layer structure or a multilayer structure. On the surface side of each substrate, one or more functional layers such as a surface hardening layer (hard coat layer) and a low reflection layer that suppresses surface reflection occurring at the air interface may be provided.

[0018] The substrate is preferably transparent, and is preferably a so-called transparent substrate. In this specification, "transparent" means that the transmittance of visible light is 60% or more, preferably 80% or more, and more preferably 90% or more. The upper limit is not particularly limited, but is often less than 100%.

[0019] In the present invention, for the reason that the effects of the present invention are manifested, it is preferable that both of the two substrates are glass substrates.

[0020] The thickness of the substrate is not particularly limited, but from the viewpoint of thinning, 1100 μm or less is preferable, 700 μm or less is more preferable, and 500 μm or less is still more preferable. The lower limit is not particularly limited, but 10 μm or more is preferable, 50 μm or more is more preferable, 100 μm or more is still more preferable, and 200 μm or more is particularly preferable. In the present invention, for the reason that the effects of the present invention are manifested, it is preferable that the thicknesses of both of the two substrates are 100 to 1100 μm, more preferably 100 to 700 μm, and still more preferably 200 to 500 μm.

[0021] [Polarizer layer] The laminate of the present invention has a polarizer layer. The polarizer layer included in the laminate of the present invention contains one or more azo dyes having two or more azo bonds in the molecule (hereinafter, formally also abbreviated as "azo dye of the present invention"). The azo dye of the present invention is preferably a dichroic substance having dichroism. In the present invention, the dichroic substance means a dye having different absorbances depending on the direction.

[0022] [Azo dye] The azo dye of the present invention may or may not exhibit liquid crystallinity. When the azo dye exhibits liquid crystallinity, it may exhibit either nematicity or smecticity. The temperature range showing the liquid crystal phase is preferably from room temperature (about 20°C to 28°C) to 300°C, and more preferably from 50°C to 200°C from the viewpoints of handleability and manufacturing suitability. The azo dye of the present invention is preferably a compound having a chromophore which is a nucleus and has two or more azo bonds, and a side chain bonded to the terminal of the chromophore. The chromophore preferably has a structure having an aromatic ring group (for example, an aromatic hydrocarbon group, an aromatic heterocyclic group) in addition to the azo bond, more preferably a bisazo or trisazo structure having an aromatic ring group and two or three azo bonds, and still more preferably a bisazo structure having an aromatic heterocyclic group (particularly preferably a thienothiazole group) and two azo bonds. The side chain is not particularly limited, and examples thereof include groups represented by R1, R2 or R3 in the following formula (1).

[0023] The azo dye of the present invention is preferably a compound represented by the formula (1) from the viewpoints that the alignment degree of the polarizer layer is further improved and an image display device having more excellent display performance and discoloration resistance can be produced (hereinafter abbreviated as "points where the effects of the present invention are more excellent").

[0024]

Chemical formula

[0025] In the formula (1), Ar1 and Ar2 each independently represent a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and a phenylene group is preferable from the viewpoints of more excellent effects of the present invention.

[0026] In formula (1), R1 represents a hydrogen atom, or an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, an acyloxy group, an alkyl carbonate 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 alkylphosphoric amide group, an alkylimino group, or an alkylsilyl group, which may have a substituent. Examples of the alkyl group having a substituent in R1 include a group in which a carbon atom of the alkyl group is substituted by -O-, -CO-, -C(O)-O-, -O-C(O)-, -Si(CH3)2-O-Si(CH3)2-, -N(R1’)-, -N(R1’)-CO-, -CO-N(R1’)-, -N(R1’)-C(O)-O-, -O-C(O)-N(R1’)-, -N(R1’)-C(O)-N(R1’)-, -CH=CH-, -C≡C-, -N=N-, -C(R1’)=CH-C(O)- or -O-C(O)-O-. One or more carbon atoms of the alkyl group may be substituted by the above groups, or two or more carbon atoms of the alkyl group may be substituted by the above groups. The number of carbon atoms of the alkyl group in R1 is preferably 1 to 20, more preferably 2 to 18, still more preferably 4 to 14, and particularly preferably 8 to 12. The alkyl group in R1 may have any of linear, branched and cyclic structures, but from the viewpoint of more excellent effects of the present invention, a linear or branched structure is preferred, and a linear structure is more preferred. When R1 is a group other than a hydrogen atom, a hydrogen atom of each group may be substituted by 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. One or more hydrogen atoms of each group may be substituted by the above groups, or two or more hydrogen atoms of each group may be substituted by the above groups. R1’ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. In each group, when there are a plurality of R1’, they may be the same as or different from each other.

[0027] In formula (1), R2 and R3 each independently represent a hydrogen atom or an alkyl group, alkenyl group, alkoxy group, acyl group, alkyloxycarbonyl group, alkylamide group, alkylsulfonyl group, aryl group, arylcarbonyl group, arylsulfonyl group, aryloxycarbonyl group, or arylamide group, which may have a substituent. Examples of the alkyl group having a substituent in R2 and R3 include a group in which a carbon atom of the alkyl group is substituted by -O-, -S-, -C(O)-, -C(O)-O-, -O-C(O)-, -C(O)-S-, -S-C(O)-, -Si(CH3)2-O-Si(CH3)2-, -NR2’-, -NR2’-CO-, -CO-NR2’-, -NR2’-C(O)-O-, -O-C(O)-NR2’-, -NR2’-C(O)-NR2’-, -CH=CH-, -C≡C-, -N=N-, -C(R2’)=CH-C(O)-, or -O-C(O)-O-. One or more carbon atoms of the alkyl group may be substituted by the above groups, or two or more carbon atoms of the alkyl group may be substituted by the above groups. The number of carbon atoms of the alkyl group in R2 and R3 is preferably 1 to 20, more preferably 1 to 16, still more preferably 1 to 8, and particularly preferably 1 to 4. The alkyl group in R2 and R3 may have any of linear, branched, and cyclic structures, but from the viewpoint of more excellent effects of the present invention, a linear or branched structure is preferred, and a linear structure is more preferred. When R2 and R3 are groups other than a hydrogen atom, the hydrogen atoms of each group may be substituted by a halogen atom, nitro group, cyano group, -OH group, -N(R2’)2, amino group, -C(R2’)=C(R2’)-NO2, -C(R2’)=C(R2’)-CN, or -C(R2’)=C(CN)2. One or more hydrogen atoms of each group may be substituted by the above groups, or two or more hydrogen atoms of each group may be substituted by the above groups. R2’ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. In each group, when there are a plurality of R2’s, they may be the same as or different from each other. R2 and R3 may be bonded to each other to form a ring, or R2 or R3 may be bonded to Ar2 to form a ring.

[0028] From the viewpoint of more excellent effects of the present invention, R1 is preferably an electron-withdrawing group, and R2 and R3 are preferably groups with low electron-donating properties. Specific examples of the group in which R1 is an electron-withdrawing group include, as R1, an alkylsulfonyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, an acyloxy group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylsulfinyl group, an alkylureido group, and an alkyl group in which a carbon atom is substituted with -C(O)-O- and -O-. As the alkyl group in which a carbon atom is substituted with -C(O)-O- and -O-, a group represented by R11-C(O)-O-R12-O- is preferable. R11 represents a linear or branched alkyl group having 1 to 6 (preferably 1 to 3) carbon atoms, and R12 represents a linear or branched alkylene group having 1 to 20 (preferably 2 to 18) carbon atoms. Specific examples of the case where R2 and R3 are groups with low electron-donating properties include groups having the following structures. The groups having the following structures are shown in a form including the nitrogen atom to which R2 and R3 are bonded in the above formula (1).

[0029]

Chemical formula

[0030] Specific examples of the azo dye are shown below, but are not limited thereto.

[0031]

Chemical formula

[0032] From the perspective of adjusting the color tone of the polarizer, the azo dye of the present invention preferably has a maximum absorption wavelength in the range of 560 nm or more and 700 nm or less (more preferably 560 to 650 nm, particularly preferably 560 to 640 nm). The maximum absorption wavelength (nm) of the azo dye in this specification is determined from the ultraviolet-visible light spectrum in the wavelength range of 380 to 800 nm measured by a spectrophotometer using a solution in which the azo dye is dissolved in a good solvent.

[0033] The polarizer layer may contain a plurality of azo dyes or may contain dichroic substances other than azo dyes. The azo dye and the dichroic substance other than the azo dye may or may not be polymerized in the polarizer layer. The polarizer layer may contain a low-molecular liquid crystal compound or a high-molecular liquid crystal compound. Each of the low-molecular liquid crystal compound and the high-molecular liquid crystal compound may or may not be polymerized in the polarizer layer.

[0034] The thickness of the polarizer layer is not particularly limited, but from the perspective of flexibility when the laminate of the present invention described later is used as a polarizing element, it is preferably 100 to 8000 nm, and more preferably 300 to 5000 nm.

[0035] Examples of the method for producing the polarizer layer include a method of forming by applying a polarizer-forming composition containing a liquid crystal compound, an azo dye, etc. Hereinafter, each component contained in the polarizer-forming composition will be described in detail.

[0036] <Liquid crystal compound> As the liquid crystal compound contained in the polarizer-forming composition, both a high-molecular liquid crystal compound and a low-molecular liquid crystal compound can be used, and from the reason that the degree of alignment can be increased, it is preferable to use a high-molecular liquid crystal compound. Here, the "high-molecular liquid crystal compound" refers to a liquid crystal compound having a repeating unit in its chemical structure. Also, the "low-molecular liquid crystal compound" refers to a liquid crystal compound having no repeating unit in its chemical structure. Examples of the polymeric liquid crystalline compound include, for example, the thermotropic liquid crystalline polymer described in JP-A-2011-237513, and the polymeric liquid crystalline compound described in paragraphs

[0012] to

[0042] of WO 2018 / 199096. Examples of the low-molecular liquid crystalline compound include, for example, the liquid crystalline compounds described in paragraphs

[0072] to

[0088] of JP-A-2013-228706. Among them, a liquid crystalline compound exhibiting smectic properties is preferable. Further, as the liquid crystalline compound, a polymeric liquid crystalline compound and a low-molecular liquid crystalline compound may be used in combination.

[0037] The liquid crystalline compound is preferably a polymeric liquid crystalline compound containing a repeating unit represented by the following formula (1) (hereinafter also abbreviated as "repeating unit (1)") because the degree of alignment of the obtained polarizer layer becomes higher.

[0038]

Chemical formula

[0039] In the above formula (1), P1 represents the main chain of the repeating unit, L1 represents a single bond or a divalent linking group, SP1 represents a spacer group, M1 represents a mesogen group, and T1 represents a terminal group.

[0040] Specific examples of the main chain of the repeating unit represented by P1 include, for example, groups represented by the following formulas (P1-A) to (P1-D). Among them, from the viewpoints of the diversity of the monomer as a raw material and ease of handling, the group represented by the following formula (P1-A) is preferable.

[0041]

Chemical formula

[0042] In the above formulas (P1-A) to (P1-D), "*" represents the bonding position with L1 in the above formula (1). In the above formulas (P1-A) to (P1-D), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The above alkyl group may be a linear or branched alkyl group, or an alkyl group having a cyclic structure (cycloalkyl group). Further, the number of carbon atoms of the above alkyl group is preferably 1 to 5. The group represented by the above formula (P1-A) is preferably a unit of a partial structure of a poly(meth)acrylate obtained by polymerization of a (meth)acrylate. The group represented by the above formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of an epoxy group of a compound having an epoxy group. The group represented by the above formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of an oxetane group of a compound having an oxetane group. The group represented by the above formula (P1-D) is preferably a siloxane unit of polysiloxane obtained by polycondensation of a compound having at least one of an alkoxysilyl group and a silanol group. Here, examples of the compound having at least one of an alkoxysilyl group and a silanol group include a compound having a group represented by the formula SiR 14 (OR 15 )2-. In the formula, R 14 is synonymous with R 14 in (P1-D), and a plurality of R 15 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0043] In the above formula (1), L1 is a single bond or a divalent linking group. Examples of the divalent linking group represented by L1 include -C(O)O-, -OC(O)-, -O-, -S-, -C(O)NR 3 -, -NR 3 C(O)-, -SO2-, and -NR 3 R 4- etc. In the formula, R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. When P1 is a group represented by the formula (P1-A), since the degree of alignment of the obtained polarizer layer becomes higher, L1 is preferably a group represented by -C(O)O-. When P1 is a group represented by the formulas (P1-B) to (P1-D), since the degree of alignment of the obtained polarizer layer becomes higher, L1 is preferably a single bond.

[0044] In the above formula (1), the spacer group represented by SP1 preferably contains at least one structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure, and a fluoroalkylene structure because it is likely to exhibit liquid crystallinity and for reasons such as the availability of raw materials. Here, the oxyethylene structure represented by SP1 is preferably a group represented by *-(CH2-CH2O) n1 -*. In the formula, n1 represents an integer of 1 to 20, and * represents the bonding position with L1 or M1 in the above formula (1). For reasons that the degree of alignment of the obtained polarizer layer becomes higher, n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and most preferably 3. Also, the oxypropylene structure represented by SP1 is preferably a group represented by *-(CH(CH3)-CH2O) n2 -*. In the formula, n2 represents an integer of 1 to 3, and * represents the bonding position with L1 or M1. Also, the polysiloxane structure represented by SP1 is preferably a group represented by *-(Si(CH3)2-O) n3 -*. In the formula, n3 represents an integer of 6 to 10, and * represents the bonding position with L1 or M1. Also, the fluoroalkylene structure represented by SP1 is preferably a group represented by *-(CF2-CF2) n4The group represented by - * is preferred. In the formula, n4 represents an integer of 6 to 10, and * represents the bonding position with L1 or M1.

[0045] In the above formula (1), the mesogenic group represented by M1 is a group showing the main skeleton of liquid crystal molecules contributing to liquid crystal formation. Liquid crystal molecules exhibit liquid crystallinity which is an intermediate state (mesophase) between the crystalline state and the isotropic liquid state. There is no particular limitation on the mesogenic group. For example, it is possible to refer to "Flussige Kristalle in Tabellen II" (published by VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, in 1984), particularly the descriptions on pages 7 to 16, and "Liquid Crystal Handbook" edited by the Liquid Crystal Handbook Editorial Committee (published by Maruzen, in 2000), particularly the descriptions in Chapter 3. As the mesogenic group, a group having at least one cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group is preferred. The mesogenic group preferably has an aromatic hydrocarbon group, more preferably has 2 to 4 aromatic hydrocarbon groups, and even more preferably has 3 aromatic hydrocarbon groups, because the degree of orientation of the obtained polarizer layer becomes higher.

[0046] As the mesogenic group, from the viewpoints of the expression of liquid crystallinity, the adjustment of the liquid crystal phase transition temperature, the availability of raw materials and the synthetic suitability, and because the degree of orientation of the obtained polarizer layer becomes higher, a group represented by the following formula (M1-A) or the following formula (M1-B) is preferred, and a group represented by the formula (M1-B) is more preferred.

[0047]

Chemical formula

[0048] In the formula (M1-A), A1 is a divalent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group. These groups may be substituted with an alkyl group, a fluorinated alkyl group, an alkoxy group or a substituent. The divalent group represented by A1 is preferably a 4- to 6-membered ring. Further, the divalent group represented by A1 may be a monocyclic ring or a condensed ring. * represents the bonding position with SP1 or T1.

[0049] Examples of the divalent aromatic hydrocarbon group represented by A1 include a phenylene group, a naphthylene group, a fluorene-diyl group, an anthracene-diyl group, and a tetracene-diyl group. From the viewpoints of the diversity of the design of the mesogen skeleton and the availability of raw materials, a phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable.

[0050] The divalent heterocyclic group represented by A1 may be either aromatic or non-aromatic, but from the viewpoint of further improving the degree of orientation, it is preferably a divalent aromatic heterocyclic group. Examples of the atoms other than carbon that constitute the divalent aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom. When the aromatic heterocyclic group has a plurality of atoms other than carbon that constitute the ring, these may be the same or different. Specific examples of the divalent aromatic heterocyclic group include, for example, a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, a thienylene (thiophene-diyl group), a quinolyrene group (quinoline-diyl group), an isoquinolyrene group (isoquinoline-diyl group), an oxazole-diyl group, a thiazole-diyl group, an oxadiazole-diyl group, a benzothiazole-diyl group, a benzothiadiazole-diyl group, a phthalimide-diyl group, a thienothiazole-diyl group, a thiazolothiazole-diyl group, a thienothiophene-diyl group, and a thienooxazole-diyl group.

[0051] Specific examples of the divalent alicyclic group represented by A1 include a cyclopentylene group and a cyclohexylene group.

[0052] In the formula (M1-A), a1 represents an integer of 1 to 10. When a1 is 2 or more, the plurality of A1s may be the same or different.

[0053] In formula (M1-B), A2 and A3 are each independently a divalent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group. Specific examples and preferred embodiments of A2 and A3 are the same as those of A1 in formula (M1-A), and thus the description thereof is omitted. In formula (M1-B), a2 represents an integer of 1 to 10. When a2 is 2 or more, the plurality of A2s may be the same or different, the plurality of A3s may be the same or different, and the plurality of LA1s may be the same or different. a2 is preferably an integer of 2 or more, and more preferably 2, because the degree of orientation of the obtained polarizer layer becomes higher. In formula (M1-B), when a2 is 1, LA1 is a divalent linking group. When a2 is 2 or more, the plurality of LA1s are each independently a single bond or a divalent linking group, and at least one of the plurality of LA1s is a divalent linking group. When a2 is 2, for the reason that the degree of orientation of the obtained polarizer layer becomes higher, it is preferable that one of the two LA1s is a divalent linking group and the other is a single bond.

[0054] In formula (M1-B), examples of the divalent linking group represented by LA1 include -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-, -O-C(O)O-, -N(Z)C(O)-, -C(O)N(Z)-, -C(Z)=C(Z’)-C(O)O-, -O-C(O)-C(Z)=C(Z’)-, -C(Z)=N-, -N=C(Z)-, -C(Z)=C(Z’)-C(O)N(Z”)-, -N(Z”)-C(O)-C(Z)=C(Z’)-, -C(Z)=C(Z’)-C(O)-S-, -S-C(O)-C(Z)=C(Z’)-, -C(Z)=N-N=C(Z’)-(Z, Z’, Z” independently represent hydrogen, 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-, etc. Among them, -C(O)O- is preferred because the degree of orientation of the obtained polarizer layer becomes higher. LA1 may be a group combining two or more of these groups.

[0055] Specific examples of M1 include, for example, the following structures. In the following specific examples, "Ac" represents an acetyl group.

[0056]

Chemical formula

[0057]

Chemical formula

[0058]

Chemical formula

[0059]

Chemical formula

[0060] [Chemistry]

[0061] [Chemistry]

[0062] [Chemistry]

[0063] In the above formula (1), as the terminal group represented by T1, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkoxycarbonyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms (ROC(O)-: R is an alkyl group), an acyloxy group having 1 to 10 carbon atoms, an acylamino group having 1 to 10 carbon atoms, an alkoxycarbonylamino group having 1 to 10 carbon atoms, a sulfonylamino group having 1 to 10 carbon atoms, a sulfamoyl group having 1 to 10 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, and a ureido group having 1 to 10 carbon atoms, a (meth)acryloyloxy group-containing group, etc. may be mentioned. As the above (meth)acryloyloxy group-containing group, for example, a group represented by -L-A (L represents a single bond or a linking group. Specific examples of the linking group are the same as those of L1 and SP1 described above. A represents a (meth)acryloyloxy group) may be mentioned.

[0064] 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 the degree of orientation of the obtained polarizer layer becomes higher. These terminal groups may be further substituted by these groups or by the polymerizable groups described in JP-A-2010-244038.

[0065] T1 is preferably a polymerizable group because it has better adhesion to the adjacent layer and can improve the cohesive force as a film. The polymerizable group 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 preferred examples include an acryloyl group or a methacryloyl group. In this case, it is known that the polymerization rate is generally faster for the acryloyl group, 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, and 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 particularly preferred.

[0066] The weight average molecular weight (Mw) of the polymer liquid crystalline compound containing the repeating unit represented by the above formula (1) is preferably 1000 to 500000, more preferably 2000 to 300000, because the degree of orientation of the obtained polarizer layer becomes higher. If the Mw of the polymer liquid crystalline compound is within the above range, the handling of the polymer liquid crystalline compound becomes easy. In particular, from the viewpoint of suppressing cracks during coating, the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably 10000 or more, more preferably 10000 to 300000. Also, from the viewpoint of the temperature latitude of the degree of orientation, the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably less than 10000, more preferably 2000 or more and less than 10000. Here, the weight average molecular weight and the number average molecular weight in the present invention are values measured by the gel permeation chromatography (GPC) method. · Solvent (eluent): N-methylpyrrolidone · Apparatus name: TOSOH HLC-8220GPC · Column: Three TOSOH TSKgel Super AWM-H (6 mm × 15 cm) columns connected in series were used. · Column temperature: 25 °C · Sample concentration: 0.1 mass% · Flow rate: 0.35 mL / min · Calibration curve: A calibration curve based on seven samples of TOSOH TSK standard polystyrene with Mw = 2,800,000 to 1050 (Mw / Mn = 1.03 to 1.06) was used.

[0067] In the present invention, for the reason that it becomes easier to adjust the compatibility with the above-described azo dyes and the dichroic substances described later, the logP value of the liquid crystalline compound is preferably from 0.0 to 10, more preferably from 1.0 to 7.0, and still more preferably from 2.0 to 5.0. Here, the logP value is an index expressing the hydrophilic and hydrophobic properties of the chemical structure, and is sometimes called the hydrophilic-lipophilic parameter. The logP value can be calculated using software such as ChemBioDraw Ultra or HSPiP (Ver. 4.1.07). Also, it can be determined experimentally by the method of OECD Guidelines for the Testing of Chemicals, Sections 1, Test No. 117, etc. In the present invention, unless otherwise specified, the value calculated by inputting the structural formula of the compound into HSPiP (Ver. 4.1.07) is adopted as the logP value.

[0068] In the present invention, the content of the liquid crystalline compound is preferably an amount that is 8 to 99 mass% in the solid content of the composition for forming a polarizer, and more preferably an amount that is 8 to 96 mass%. Here, the "solid content in the composition for forming a polarizer" refers to the components excluding the solvent. Specific examples of the solid content include the above-described liquid crystalline compound and azo dye, as well as the dichroic substances, polymerization initiator, surfactant, etc. described later.

[0069] <Azo dye> The azo dye contained in the composition for forming a polarizer is the same dye as the azo dye of the present invention described above.

[0070] The composition for forming a polarizer may contain a plurality of the above-described azo dyes. When the composition for forming a polarizer contains a plurality of azo dyes, from the viewpoint of making the obtained polarizer layer approach black, at least one azo dye having a maximum absorption wavelength in the range of 560 nm or more and less than 700 nm and at least one azo dye having a maximum absorption wavelength in the range of 370 nm or more and less than 560 nm are preferably used in combination.

[0071] The azo dye may have a crosslinkable group. Specific examples of the crosslinkable group include, for example, (meth)acryloyl group, epoxy group, oxetanyl group, styryl group, etc. Among them, the (meth)acryloyl group is preferable.

[0072] <Dichroic substance> The composition for forming a polarizer may contain a dichroic substance other than the azo dye. The dichroic substance other than the azo dye may also have a crosslinkable group. Specific examples of the crosslinkable group include, for example, (meth)acryloyl group, epoxy group, oxetanyl group, styryl group, etc. Among them, the (meth)acryloyl group is preferable. The dichroic substance contained in the composition for forming a polarizer is not particularly limited, and examples include visible light absorbing substances (dichroic dyes), luminescent substances (fluorescent substances, phosphorescent substances), ultraviolet absorbing substances, infrared absorbing substances, nonlinear optical substances, carbon nanotubes, inorganic substances (for example, quantum rods), etc. Conventionally known dichroic substances (dichroic dyes) can be used. Specifically, for example, paragraphs

[0067] to

[0071] of Japanese Patent Application Laid-Open No. 2013-228706, paragraphs

[0008] to

[0026] of Japanese Patent Application Laid-Open No. 2013-227532, paragraphs

[0008] to

[0015] of Japanese Patent Application Laid-Open No. 2013-209367, paragraphs

[0045] to

[0058] of Japanese Patent Application Laid-Open No. 2013-14883, paragraphs

[0012] to

[0029] of Japanese Patent Application Laid-Open No. 2013-109090, paragraphs

[0009] to

[0017] of Japanese Patent Application Laid-Open No. 2013-101328, paragraphs

[0051] to

[0065] of Japanese Patent Application Laid-Open No. 2013-37353, paragraphs

[0049] to

[0073] paragraphs

[0016] to

[0018] of Japanese Patent Application Laid-Open No. Hei 11-305036, paragraphs

[0009] to

[0011] of Japanese Patent Application Laid-Open No. 2001-133630,

[0030] to

[0169] of Japanese Patent Application Laid-Open No. 2011-215337, paragraphs

[0021] to

[0075] of Japanese Patent Application Laid-Open No. 2010-106242, paragraphs

[0011] to

[0025] of Japanese Patent Application Laid-Open No. 2010-215846, paragraphs

[0017] to

[0069] of Japanese Patent Application Laid-Open No. 2011-048311, paragraphs

[0013] to

[0133] of Japanese Patent Application Laid-Open No. 2011-213610, paragraphs of Japanese Patent Application Laid-Open No. 2011-237513

[0074] to

[0246] , paragraphs

[0005] to

[0051] of Japanese Patent Application Laid-Open No. 2016-006502, paragraphs

[0005] to

[0041] of WO2016 / 060173, paragraphs

[0008] to

[0062] of WO2016 / 136561, paragraphs

[0014] to

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

[0014] to

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

[0013] to

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

[0014] to

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

[0021] to

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

[0043] to

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

[0043] to

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

[0050] to

[0074] of International Publication No. 2020 / 004106, etc. are included.

[0073] In the composition for forming a polarizer, two or more dichroic substances other than the azo dyes described above may be used in combination.

[0074] In the present invention, for the reason that the display performance and durability of the image display device become better, the difference between the logP value of the above azo dye and the logP value of the above liquid crystalline compound is preferably 5.0 or more, more preferably 7.0 or more, and still more preferably 7.0 or more and less than 10.0. Here, regarding the difference (absolute value) between the logP value of the azo dye and the logP value of the liquid crystalline compound, when a plurality of azo dyes or liquid crystalline compounds are used, it means the maximum difference among the differences calculated from the logP values of each compound.

[0075] The content of the azo dye and the dichroic substance other than the azo dye is preferably 1 to 400 parts by mass, more preferably 2 to 100 parts by mass, and still more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the above liquid crystalline compound from the viewpoint that the effects of the present invention are more excellent. Also, the content of the azo dye and the dichroic substance other than the azo dye is preferably an amount that becomes 1 to 50% by mass in the solid content in the composition for forming a polarizer layer, and more preferably an amount that becomes 2 to 40% by mass.

[0076] <Polymerization initiator> The composition for forming a polarizer layer preferably contains a polymerization initiator. The polymerization initiator is not particularly limited, but is preferably a compound having photosensitivity, that is, a photopolymerization initiator. As the photoinitiator, various compounds can be used without particular limitation. Examples of photoinitiators include α-carbonyl compounds (specifications of U.S. Patent Nos. 2,367,661 and 2,367,670), acyloin ethers (specification of U.S. Patent No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (specification of U.S. Patent No. 2,722,512), polynuclear quinone compounds (specifications of U.S. Patent Nos. 3,046,127 and 2,951,758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (specification of U.S. Patent No. 3,549,367), acridine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667 and specification of U.S. Patent No. 4,239,850), oxadiazole compounds (specification of U.S. Patent No. 4,212,970), o-acyl oxime compounds (Japanese Patent Laid-Open No. 2016-27384

[0065] ), and acylphosphine oxide compounds (Japanese Patent Publication No. 63-40799, Japanese Patent Publication No. 5-29234, Japanese Patent Laid-Open No. 10-95788, and Japanese Patent Laid-Open No. 10-29997), etc. As such photoinitiators, commercially available products can also be used, and examples include Irgacure-184, Irgacure-907, Irgacure-369, Irgacure-651, Irgacure-819, Irgacure-OXE-01, and Irgacure-OXE-02 manufactured by BASF.

[0077] When the composition for forming a polarizer layer contains a photoinitiator, the content of the photoinitiator is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, based on 100 parts by mass in total of the above azo dye, dichroic substances other than the azo dye, and the above liquid crystalline compound in the composition for forming a polarizer layer. When the content of the photoinitiator is 0.01 part by mass or more, the durability of the polarizer layer becomes good, and when it is 30 parts by mass or less, the degree of orientation of the polarizer layer becomes better. The photoinitiator may be used alone or in combination of two or more. When two or more photoinitiators are included, the total amount thereof is preferably within the above range.

[0078] <Surfactant> The composition for forming a polarizer layer preferably contains a surfactant. By including a surfactant, it is expected to improve the smoothness of the coating surface, further improve the degree of orientation, suppress repellency and unevenness, and improve the in-plane uniformity. As the surfactant, those that make the dichroic substance and the liquid crystalline compound horizontal on the coating surface side are preferable. For example, the compounds described in paragraphs

[0155] to

[0170] of International Publication No. 2016 / 009648, the compounds described in paragraphs

[0253] to

[0293] of Japanese Patent Application Laid-Open No. 2011-237513 (horizontal alignment agent), etc. can be used.

[0079] The surfactant contained in the composition for forming a polarizer layer of the present invention may be a fluorine-containing polymer having a repeating structure B1 represented by the following formula (B-1) and a repeating structure B2 having a fluorine atom.

[0080] (Repeating structure B1) The repeating structure B1 of the fluorine-containing polymer is a repeating structure represented by the following formula (B-1).

[0081]

Chemical formula

[0082] In the above formula (B-1), R 1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. Also, L 1 represents a single bond or -CO-. Also, Sp represents a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms. However, among the -CH2- constituting a part of the hydrocarbon group, one or two or more non-adjacent -CH2- may each independently be substituted with -O-, -S-, -NH-, or -N(Q)-, and Q represents a substituent. L 2 and L 3 each independently represent a single bond or a divalent linking group.

[0083] R in the above formula (B-1)1 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group.

[0084] L in the above formula (B-1) 1 is preferably -CO-.

[0085] Examples of the linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms represented by Sp in the above formula (B-1) include a linear or branched divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a divalent aromatic heterocyclic group having 6 to 20 carbon atoms. Among them, a linear or branched divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferred. Here, as the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkylene group having 1 to 15 carbon atoms is preferred, and an alkylene group having 1 to 8 carbon atoms is more preferred. Specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, a heptylene group, etc. are preferably exemplified. In addition, as described above, Sp is such that one or two or more non-adjacent -CH2- among the -CH2- constituting a part of the linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms may be independently substituted with -O-, -S-, -NH-, or -N(Q)-. Examples of the substituent represented by Q include the above-described substituent W, and among them, an alkyl group, an alkoxy group, or a halogen atom is preferred.

[0086] L in the above formula (B-1) 2 and L 3 Examples of the divalent linking group represented by one embodiment include, for example, -C(O)O-, -OC(O)-, -O-, -S-, -C(O)NR L1 -, -NR L1 C(O)-, -SO2-, and -NR L1 R L2 - and the like. In the formula, R L1 and R L2Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of the substituent which the alkyl group having 1 to 6 carbon atoms may have include the above-described substituent W, and among them, an alkyl group, an alkoxy group, or a halogen atom is preferable.

[0087] In the above formula (B-1), A represents a divalent linking group represented by any one of the following formulas (A-1) to (A-15). However, * in the following formulas (A-1) to (A-15) represents the bonding position with L 2 or L 3 and the carbon atoms constituting the ring structure in the following formulas (A-1) to (A-15) may be substituted with heteroatoms and may have substituents. Examples of the substituent which the carbon atoms constituting the ring structure may have include the above-described substituent W, and among them, an alkyl group, an alkoxy group, or a halogen atom is preferable.

[0088]

Chemical formula

[0089] Specific examples of the divalent linking group represented by any of the above formulas (A-1) to (A-15) include, for example, a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran-2,5-diyl group, a 1,4-piperazine group, a 1,4-piperidine group, a 1,3-dioxane-2,5-diyl group, a tetrahydrothiopyran-2,5-diyl group, a 1,4-bicyclo(2,2,2)octylene group, a decahydronaphthalene-2,6-diyl group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a pyrazine-2,5-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, a 2,6-naphthylene group, a phenanthrene-2,7-diyl group, a 9,10-dihydrophenanthrene-2,7-diyl group, a 1,2,3,4,4a,9,10a-octahydrophenanthrene 2,7-diyl group, a 9-fluorenone-2,7-diyl, a fluorene 2,7-diyl group, a thienothiophene-3,6-diyl group, a carbazole-3,6-diyl group, and a carbazole-2,7-diyl group, etc.

[0090] In formula (B-1) above, A is preferably a divalent linking group represented by any of the above formulas (A-1), (A-4), (A-7), (A-10), and (A-13) because the degree of orientation of the formed polarizer layer becomes higher, and more preferably a divalent linking group represented by either of (A-7) and (A-13).

[0091] In formula (B-1) above, D represents a hydrogen-bonding group composed of a hydrogen atom and a non-metal atom of Groups 14 to 16. However, the non-metal atom may have a substituent. Here, examples of the non-metal atoms of Groups 14 to 16 include, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and a carbon atom, etc. Examples of substituents that non-metal atoms (particularly nitrogen atoms and carbon atoms) may have include, for example, a halogen atom, an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (e.g., a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, and a hydroxyl group, etc.

[0092] Examples of such hydrogen-bonding groups include, for example, a hydrogen-bond donating group and a hydrogen-bond accepting group, etc. Specific examples of the hydrogen-bond donating group include, for example, an amino group, an amide group, a urea group, a urethane group, a sulfonylamino group, a sulfo group, a phospho group, a hydroxy group, a mercapto group, a carboxyl group, a methylene group substituted with an electron-withdrawing group, a methine group substituted with an electron-withdrawing group, etc. Among them, a carboxyl group and an amide group are preferable. Specific examples of the hydrogen-bond accepting group include, for example, a heteroatom having a lone pair of electrons on a heteroatom-containing ring, a hydroxy group, an aldehyde, a ketone, a carboxyl group, a carboxylic acid ester, a carboxylic acid amide, a lactone, a lactam, a sulfonic acid amide, a sulfo group, a phospho group, a phosphoric acid amide, a urethane, a urea, an ether structure (particularly a polymer structure having an oxygen atom contained in a polyether structure), an aliphatic amine, an aromatic amine, etc. Among them, a carboxyl group and an amide group are preferable.

[0093] (Repeating structure B2) The repeating structure B2 contained in the above fluorine-containing polymer is a repeating structure having a fluorine atom.

[0094] In the present invention, the content of the repeating structure B2 is preferably 15 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass with respect to the total mass of the surfactant because the degree of orientation of the formed polarizer layer becomes higher. In addition, the repeating structure B2 may be contained alone or in combination of two or more in the surfactant. When two or more repeating structures B2 are contained, the content of the repeating structure B2 means the total content of the repeating structure B2.

[0095] (Repeating structure B3) In the present invention, from the reason that the upper layer coatability with respect to the formed polarizer layer is good, it is preferable that the fluorine-containing polymer further contains a repeating structure B3 derived from a monomer having a molecular weight of 300 or less in addition to the repeating structures B1 and B2 described above.

[0096] As the repeating structure B3, from the reason that the upper layer coatability with respect to the formed polarizer layer becomes better, it is preferably a repeating structure represented by the following formula (N-1). The repeating structure B3 has a structure different from the repeating structure B2 described above and preferably does not contain a fluorine atom.

[0097] [Chemical formula]

[0098] In formula (N-1), R B11 and R B12 each independently represent a hydrogen atom or a substituent. However, when R B11 and R B12 are substituents, R B11 and R B12 may be linked to form a ring.

[0099] R B11 The total of the molecular weight of and R B12 is preferably 200 or less, more preferably 100 or less, and still more preferably 70 or less. If the total of the above molecular weights is 100 or less, the interaction between the repeating structures B3 is further improved, and the compatibility between the surfactant and the liquid crystal molecules can be further reduced. As a result, there are few alignment defects, and a polarizer layer with excellent alignment degree can be obtained. RB11 The molecular weight of and R B12 The lower limit of the total of the molecular weights of is preferably 2 or more.

[0100] R B11 and R B12 As the substituent represented by, from the viewpoint of more excellent effects of the present invention, it is preferably an organic group, more preferably an organic group having 1 to 15 carbon atoms, still more preferably an organic group having 1 to 12 carbon atoms, and particularly preferably an organic group having 1 to 8 carbon atoms. Examples of the above organic group include linear, branched or cyclic alkyl groups, aromatic hydrocarbon groups, and heterocyclic groups.

[0101] The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 12, and still more preferably 1 to 8. The carbon atom of the alkyl group is -O-, -Si(CH3)2-, -(Si(CH3)2O) g -, -(OSi(CH3)2) g -(g represents an integer of 1 to 10), -N(Z)-, -C(Z)=C(Z’)-, -C(Z)=N-, -N=C(Z)-, -C(O)-, -OC(O)-, -C(O)O-, -O-C(O)O-, -N(Z)C(O)-, -C(O)N(Z)-, -C(Z)=C(Z’)-C(O)O-, -O-C(O)-C(Z)=C(Z’)-, -C(Z)=N-, -N=C(Z)-, -C(Z)=C(Z’)-C(O)N(Z”)-, -N(Z”)-C(O)-C(Z)=C(Z’)-, -C(Z)=C(Z’)-C(O)-S-, -S-C(O)-C(Z)=C(Z’)-, -C(Z)=N-N=C(Z’)-(Z, Z’ and Z” each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, a cyano group, or a halogen atom.), -C≡C-, -N=N-, -S-, -C(S)-, -S(O)-, -SO2-, -(O)S(O)O-, -O(O)S(O)O-, -SC(O)-, and -C(O)S-, and may be substituted with a group formed by combining two or more of these groups. Among the groups in which the carbon atom of the alkyl group may be substituted, from the viewpoint of more excellent effects of the present invention, -O-, -C(O)-, -N(Z)-, -OC(O)-, or -C(O)O- is preferable. The hydrogen atom of the alkyl group is a halogen atom, a cyano group, an aryl group, a nitro group, -OZ H , -C(O)Z H , -C(O)OZ H , -OC(O)Z H , -OC(O)OZ H , -NZ H Z H ’, -NZ H C(O)Z H , -NZ H C(O)OZ H ’, -C(O)NZ H Z H ’, -OC(O)NZ H Z H , -NZ H C(O)NZ H ’OZ H ’’, -SZ H , -C(S)Z H , -C(O)SZ H , or, -SC(O)Z H , and may be substituted therewith. Z H , Z H ’ and Z H ’’ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cyano group, or a nitro group. Among the groups in which the hydrogen atom of the alkyl group may be substituted, -OH, -COOH, or an aryl group (preferably a phenyl group) is preferable in terms of more excellent effects of the present invention.

[0102] The hydrogen atom of the aromatic hydrocarbon group and the hydrogen atom of the heterocyclic group are a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, -OZ H , -C(O)Z H , -C(O)OZ H , -OC(O)Z H , -OC(O)OZ H , -NZ H Z H , -NZ H C(O)Z H , -NZ H C(O)OZ H ’, -C(O)NZ H Z H ’, -OC(O)NZH Z H ’, -NZ H C(O)NZ H ’OZ H ’’, -SZ H , -C(S)Z H , -C(O)SZ H , -SC(O)Z H , -B(OH)2 may be substituted. Z H , Z H ’ and Z H ’’ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cyano group, or a nitro group. Among the groups in which the hydrogen atoms of the aromatic hydrocarbon group and the hydrogen atoms of the heterocyclic group may be substituted, -OH and -B(OH)2 are preferred in terms of more excellent effects of the present invention.

[0103] R B11 and R B12 each independently is preferably a hydrogen atom or an organic group having 1 to 15 carbon atoms in terms of more excellent effects of the present invention. The preferred embodiments of the organic group are as described above. In terms of more excellent effects of the present invention, R B11 and R B12 Among them, at least one is preferably a substituent, and more preferably at least one is an organic group having 1 to 15 carbon atoms.

[0104] R B11 and R B12 The ring formed by the linkage of R and R is a heterocyclic ring containing a nitrogen atom in formula (N-1), and may further contain heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom in the ring. R B11 and R B12 The ring formed by the linkage of R and R is preferably a 4- to 8-membered ring, more preferably a 5- to 7-membered ring, and still more preferably a 5- to 6-membered ring in terms of more excellent effects of the present invention. R B11 and R B12 The number of carbon atoms constituting the ring formed by the linkage of R and R is preferably 3 to 7, and more preferably 3 to 6 in terms of more excellent effects of the present invention. RB11 and R B12 The ring formed by the connection of and R may or may not have aromaticity, but from the viewpoint of more excellent effects of the present invention, it is preferably non-aromatic. R B11 and R B12 Specific examples of the ring formed by the connection of and R include the following groups.

[0105]

Chemical formula

[0106] R B13 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a cyano group. Among them, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom is more preferable. The number of carbon atoms of the above alkyl group is 1 to 5, preferably 1 to 3, and more preferably 1. The alkyl group may have any of linear, branched and cyclic structures.

[0107] Specific examples of the repeating structure B3 are shown below, but the repeating structure B3 is not limited to the following structures.

[0108]

Chemical formula

[0109] The content of the repeating structure B3 is preferably 3 to 75% by mass, more preferably 15 to 70% by mass, and still more preferably 20 to 65% by mass based on the total mass of all the repeating structures of the fluorine-containing polymer. If the content of the repeating structure B3 is within the above range, the effects of the present invention are more excellent. The repeating structure B3 may be contained alone or in combination of two or more in the surfactant. When two or more repeating structures B3 are contained, the content of the repeating structure B3 means the total content of the repeating structure B3.

[0110] (Another repeating structure (Part 1)) The above fluorine-containing polymer may further have a repeating structure represented by the following general formula (M-3).

[0111] [Chemical formula]

[0112] In the above formula (M-3), R3 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms, L3 represents a single bond or a divalent linking group, and T3 represents an aromatic ring. Examples of the linking group of L3 include the same groups as SP21 in the above formula (F-2). Examples of the aromatic ring group of T3 include aromatic hydrocarbon ring groups such as a benzene ring group, a naphthalene ring group, an anthracene ring group, and a phenanthroline ring group; aromatic heterocyclic groups such as a furan ring group, a pyrrole ring group, a thiophene ring group, a pyridine ring group, a thiazole ring group, and a benzothiazole ring group. Among them, a benzene ring group (for example, a 1,4-phenyl group, etc.) is preferable. By including these groups in the polymer, the compatibility can be improved.

[0113] Specific examples of the monomer that forms the repeating structure represented by the above formula (M-3) include structures represented by the following formulas (M3-1) to (M3-5), but the present invention is not limited thereto.

[0114] [Chemical formula]

[0115] (Another repeating structure (Part 2)) The above fluorine-containing polymer may further have a repeating structure represented by the following general formula (M-4).

[0116] [Chemical formula]

[0117] In the above formula (M-4), R4 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms, L4 represents a single bond or a divalent linking group, and Q4 represents a crosslinkable group represented by the above formulas (P1) to (P30). Examples of the linking group of L4 include the same groups as SPW in the above formula (W1), and include an aromatic hydrocarbon group having 4 to 20 carbon atoms, a cyclic alkylene group having 4 to 20 carbon atoms, and a heterocyclic group having 1 to 20 carbon atoms. A linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 4 to 20 carbon atoms are preferred, and it is preferred to have -O-, -CO-O-, -CO-NH-, -O-CO-.

[0118] When Q4 represents a group containing a cationic polymerizable group, the cationic polymerizable group is not particularly limited, and examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group. As the cationic polymerizable group, an alicyclic ether group or a vinyloxy group is preferred, an epoxy group, an oxetanyl group or a vinyloxy group is more preferred, an epoxy group or an oxetanyl group is still more preferred, and an epoxy group is particularly preferred. The epoxy group is particularly preferably an alicyclic epoxy group. In addition, each of the above groups may have a substituent. When Q4 represents a group containing a radical polymerizable group, the radical polymerizable group is not particularly limited, and examples thereof include a group containing a polymerizable carbon-carbon double bond. Specifically, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acrylamide group, a vinyl group, a styryl group, an allyl group, etc. are mentioned, and a (meth)acryloyloxy group is preferred. In addition, each of the above groups may have a substituent. By including these groups, the adhesion between layers can be improved when a plurality of polarizer layers are laminated.

[0119] Specific examples of the monomer that forms the repeating structure represented by the above formula (M-4) include monomers represented by the following formulas (M4-1) to (M4-17), but the present invention is not limited thereto.

[0120]

Chem.

[0121] The above fluorine-containing polymer may be a polymer having a block structure, a graft structure, a branch structure or a star structure. By having such a block structure, a graft structure, a branch structure or a star structure, the fluorine atom groups exist as clusters, which is preferable in terms of improving the migration property to the surface of the polymer coating film and the like. In addition, in a copolymer having a random structure with a fluorine-substituted alkyl chain length of 1 to 4, although the clusters of fluorine atom groups are small and the solubility in general-purpose solvents is excellent, the migration property to the surface of the coating film is low. On the other hand, the above polymer has a high migration property to the surface of the coating film even when the fluorine-substituted alkyl chain length is 1 to 4 due to the existence of the fluorine atom groups as clusters. By adding such a copolymer to the composition, the surface tension of the coating film can be reduced, and the wettability (uniform coating property) of the composition to the substrate during coating and the flatness of the coating film surface can be made good, which is preferable.

[0122] In the present invention, when the composition for forming a polarizer contains a surfactant, since the display performance and durability of the image display device become better, the difference between the logP value of the surfactant and the logP value of the above liquid crystalline compound is preferably less than 3.1, more preferably less than 1.4, and still more preferably from 0 to less than 1.4. Here, regarding the difference (absolute value) between the logP value of the surfactant and the logP value of the liquid crystalline compound, when a plurality of surfactants or liquid crystalline compounds are used, it refers to the minimum difference among the differences calculated from the logP values of each compound.

[0123] When the composition for forming a polarizer layer contains a surfactant, the content of the surfactant is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, based on 100 parts by mass in total of the above azo dye, the dichroic substance other than the azo dye and the above liquid crystalline compound in the composition for forming a polarizer layer. The surfactant may be used alone or in combination of two or more. When two or more surfactants are included, it is preferable that the total amount is within the above range.

[0124] <Adhesion improver> From the viewpoint of adhesion to the barrier layer described later, the composition for forming a polarizer layer may contain an adhesion improver. Examples of the adhesion improver include compounds containing a hydroxyl group, a carboxyl group, and a boronic acid group, and compounds containing a boronic acid group are preferable. Examples of the compound containing a boronic acid group preferably include compounds represented by the following formula.

[0125]

Chemical formula

[0126] In the formula, R 1 and R 2 each independently represents a hydrogen atom, or a substituted or unsubstituted aliphatic hydrocarbon group, aryl group or heterocyclic group. R 3 represents a substituent containing a functional group capable of bonding to a (meth)acrylic group.

[0127] <Solvent> From the viewpoint of workability and the like, the composition for forming a polarizer layer preferably contains a solvent. Examples of the solvent include organic solvents such as ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether, tetrahydropyran, dioxolane, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, trichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, etc.), alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, isopentyl alcohol, neopentyl alcohol, diacetone alcohol, benzyl alcohol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, 1,2-dimethoxyethane, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, etc.), and heterocyclic compounds (e.g., pyridine, etc.), as well as water. These solvents may be used alone or in combination of two or more. Among these solvents, from the viewpoint of taking advantage of the effect of excellent solubility of the composition for forming a polarizer layer, ketones (especially cyclopentanone, cyclohexanone), ethers (especially tetrahydrofuran, cyclopentyl methyl ether, tetrahydropyran, dioxolane), and amides (especially dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone) are preferred.

[0128] When the composition for forming a polarizer layer contains a solvent, the content of the solvent is preferably 80 to 99% by mass, more preferably 83 to 97% by mass, and particularly preferably 85 to 95% by mass based on the total mass of the composition for forming a polarizer layer. The solvent(s) may be used alone or in combination of two or more. When two or more solvents are included, the total amount thereof is preferably within the above range.

[0129] <Method for manufacturing a polarizer layer> The method for manufacturing the polarizer layer is not particularly limited. However, from the reason that the degree of orientation of the obtained polarizer layer becomes higher, a step of applying the above-described composition on the alignment film to form a coating film (hereinafter, also referred to as "coating film forming step"), and a step of aligning the azo dye and the dichroic substance other than the azo dye contained in the coating film (hereinafter, also referred to as "alignment step") are preferably provided in this order (hereinafter, also referred to as "this manufacturing method"). Hereinafter, each step will be described.

[0130] (Coating film forming step) The coating film forming step is a step of applying the above-described composition for forming a polarizer layer on the alignment film to form a coating film. The liquid crystalline compound in the coating film is horizontally aligned by the interaction between the alignment film and (when the composition contains an interface modifier) the interface modifier. By using the above-described composition containing the solvent, or using the composition made into a liquid material such as a melt by heating or the like, it becomes easy to apply the composition on the alignment film. Examples of the coating method of the composition include known methods such as roll coating method, gravure printing method, spin coating method, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, spray method, and inkjet method.

[0131] (Alignment film) The alignment film used in the coating film use step will be described. Any alignment film may be used as long as it can horizontally align the liquid crystalline compound contained in the composition. It can be provided by means such as rubbing treatment on the film surface of an organic compound (preferably a polymer), oblique evaporation of an inorganic compound, formation of a layer having microgrooves, or accumulation of an organic compound (e.g., ω-tricosanoic acid, dioctadecyldimethylammonium chloride, methyl stearate) by the Langmuir-Blodgett method (LB film). Furthermore, an alignment film that generates an alignment function by applying an electric field, applying a magnetic field, or irradiating light is also known. Among them, in the present invention, from the viewpoint of ease of controlling the pretilt angle of the alignment film, an alignment film formed by rubbing treatment is preferable, and from the viewpoint of alignment uniformity, a photoalignment film formed by light irradiation is also preferable.

[0132] (1) Rubbing-treated alignment film As the polymer material used for the alignment film formed by rubbing treatment, there are descriptions in many documents, and a number of commercially available products can be obtained. In the present invention, polyvinyl alcohol or polyimide, and their derivatives are preferably used. For the alignment film, reference can be made to the description on pages 43, line 24 to page 49, line 8 of International Publication No. 2001 / 88574A1. The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.01 to 2 μm.

[0133] (2) Photoalignment film As a photo-alignment material used for an alignment film formed by light irradiation, there are descriptions in a number of documents and the like. In the present invention, for example, azo compounds described in JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007-121721, JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, Patent No. 3883848, Patent No. 4151746; aromatic ester compounds described in JP-A-2002-229039; maleimide and / or alkenyl-substituted nadimide compounds having a photo-alignment unit described in JP-A-2002-265541, JP-A-2002-317013; photo-crosslinkable silane derivatives described in Patent No. 4205195, Patent No. 4205198; JP-T-2003-520878, JP-T-2004-529220; or photo-crosslinkable polyimide, polyamide, or ester described in Patent No. 4162850 are mentioned as preferred examples. More preferably, they are azo compounds, photo-crosslinkable polyimide, polyamide, or ester.

[0134] Among these, as the photo-alignment compound, it is preferable to use a photosensitive compound having a photoreactive group in which at least one of dimerization and isomerization occurs by the action of light. Examples of the photoreactive group include a group having a cinnamic acid (cinnamoyl) structure (skeleton), a group having a coumarin structure (skeleton), a group having a chalcone structure (skeleton), a group having a benzophenone structure (skeleton), and a group having an anthracene structure (skeleton). Among these groups, a group having a cinnamoyl structure and a group having a coumarin structure are preferable, and a group having a cinnamoyl structure is more preferable.

[0135] In addition, the photosensitive compound having the above photo-alignment group may further have a crosslinkable group. As the crosslinkable group, a thermally crosslinkable group that causes a curing reaction by the action of heat or a photo-crosslinkable group that causes a curing reaction by the action of light is preferable, and a crosslinkable group having both a thermally crosslinkable group and a photo-crosslinkable group may also be used. Examples of the crosslinkable group include at least one selected from the group consisting of an epoxy group, an oxetanyl group, a group represented by -NH-CH2-O-R (where R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a group having an ethylenically unsaturated double bond, and a blocked isocyanate group. Among them, an epoxy group, an oxetanyl group, and a group having an ethylenically unsaturated double bond are preferable. Note that a 3-membered cyclic ether group is also called an epoxy group, and a 4-membered cyclic ether group is also called an oxetanyl group. Specific examples of the group having an ethylenically unsaturated double bond include, for example, a vinyl group, an allyl group, a styryl group, an acryloyl group, and a methacryloyl group, and an acryloyl group or a methacryloyl group is preferable.

[0136] A photo-aligned film is manufactured by irradiating the photo-aligned film formed from the above material with linearly polarized light or non-polarized light. In this specification, "linearly polarized light irradiation" and "non-polarized light irradiation" are operations for causing a photoreaction in a photo-alignment material. The wavelength of the light used varies depending on the photo-alignment material used and is not particularly limited as long as it is the wavelength required for the photoreaction. The peak wavelength of the light used for light irradiation is preferably 200 nm to 700 nm, and ultraviolet light with a peak wavelength of 400 nm or less is more preferable.

[0137] Light sources used for light irradiation include commonly used light sources, such as lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps, various lasers [e.g., semiconductor lasers, helium-neon lasers, argon ion lasers, helium cadmium lasers, and YAG (yttrium aluminum garnet) lasers], light-emitting diodes, and cathode ray tubes, etc.

[0138] As a means for obtaining linearly polarized light, a method using a polarizing plate (for example, an iodine polarizing plate, a dichroic substance polarizing plate, and a wire grid polarizing plate), a method using a prism element (for example, a Glan-Taylor prism) or a reflective polarizer using a Brewster angle, or a method using light emitted from a laser light source having polarization can be adopted. Further, only light of a required wavelength may be selectively irradiated using a filter or a wavelength conversion element or the like.

[0139] In the case of linearly polarized light, a method of irradiating the alignment film with light perpendicularly or obliquely from the upper surface or the back surface with respect to the alignment film surface is adopted. The incident angle of the light varies depending on the photo-alignment material, but is preferably 0 to 90° (perpendicular), and more preferably 40 to 90°. In the case of non-polarized light, the alignment film is irradiated with non-polarized light obliquely. The incident angle is preferably 10 to 80°, more preferably 20 to 60°, and particularly preferably 30 to 50°. The irradiation time is preferably 1 minute to 60 minutes, and more preferably 1 minute to 10 minutes.

[0140] When patterning is required, a method of performing light irradiation using a photomask the number of times required for pattern formation, or a method of writing a pattern by laser light scanning can be adopted.

[0141] The alignment film may be formed on any substrate, or the substrate itself may also serve as the alignment film. The substrate for the alignment film can be appropriately selected, and examples thereof include glass and polymer films. The light transmittance of the substrate is preferably 80% or more. When a polymer film is used as the substrate, it is preferable to use an optically isotropic polymer film. Specific examples and preferred embodiments of the polymer can be applied to the description in paragraph

[0013] of JP-A-2002-22942. Further, even a polymer such as conventionally known polycarbonate or polysulfone, which is likely to exhibit birefringence, can be used after modifying the molecules described in WO 2000 / 26705 to reduce the expressibility.

[0142] The alignment film and the substrate of the alignment film may or may not be removed from the laminate and left. As a method of not leaving the alignment film and the substrate of the alignment film in the laminate, after forming a polarizer layer on the alignment film, the surface of the polarizer layer is bonded to a material constituting the laminate, for example, a substrate, and then the substrate of the alignment film is peeled off. There are also methods such as this. At this time, only the substrate of the alignment film may be removed and only the alignment film may be left in the laminate.

[0143] (Alignment step) The alignment step is a step of aligning the liquid crystal component contained in the coating film. Thereby, the polarizer layer of the present invention is obtained. The alignment step may have a drying process. By the drying process, components such as a solvent can be removed from the coating film. The drying process may be performed by a method of leaving the coating film at room temperature for a predetermined time (for example, natural drying), or may be performed by a method of heating and / or blowing air. Here, the liquid crystal component contained in the composition for forming a polarizer layer may be aligned by the above-described coating film forming step or drying process. For example, in an embodiment where the composition for forming a polarizer is prepared as a coating solution containing a solvent, the coating film is dried to remove the solvent from the coating film, whereby a polarizer layer is obtained. When the drying process is performed at a temperature equal to or higher than the transition temperature of the liquid crystal component contained in the coating film to the liquid crystal phase, the heat treatment described later may not be performed.

[0144] The transition temperature of the liquid crystal component contained in the coating film to the liquid crystal phase is preferably 10 to 250°C, more preferably 25 to 190°C from the viewpoint of production suitability and the like. When the transition temperature is 10°C or higher, a cooling process or the like for lowering the temperature to the temperature range exhibiting the liquid crystal phase is not required, which is preferable. Further, when the transition temperature is 250°C or lower, a high temperature is not required even when changing to an isotropic liquid state at a temperature higher than the temperature range exhibiting the liquid crystal phase once, and waste of thermal energy, as well as deformation and alteration of the substrate can be reduced, which is preferable.

[0145] The alignment process preferably includes a heat treatment. By doing so, the liquid crystal components contained in the coating film can be aligned, so that the coating film after the heat treatment can be suitably used as the optical polarizer layer. From the perspective of manufacturing suitability and the like, the heat treatment is preferably at 10 to 250 °C, more preferably at 25 to 190 °C. Also, the heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.

[0146] The alignment process may have a cooling treatment performed after the heat treatment. The cooling treatment is a process of cooling the coating film after heating to about room temperature (20 to 25 °C). By doing so, the alignment of the liquid crystal components contained in the coating film can be fixed. The cooling means is not particularly limited and can be carried out by known methods. Through the above processes, a polarizer layer can be obtained. In this embodiment, examples of the method for aligning the liquid crystal components contained in the coating film include a drying treatment and a heat treatment, etc., but it is not limited thereto and can be carried out by known alignment treatments.

[0147] (Other processes) The method for manufacturing the polarizer layer may have a process of curing the polarizer layer (hereinafter, also referred to as the "curing process") after the above alignment process. The curing process is carried out, for example, by heating and / or light irradiation (exposure) when the polarizer layer has a crosslinkable group (polymerizable group). Among these, the curing process is preferably carried out by light irradiation. Various light sources such as infrared rays, visible light, or ultraviolet rays can be used as the light source for curing, but ultraviolet rays are preferred. Also, ultraviolet rays may be irradiated while heating during curing, or ultraviolet rays may be irradiated through a filter that transmits only a specific wavelength. When exposure is carried out while heating, the heating temperature during exposure is preferably 25 to 140 °C, although it also depends on the transition temperature of the liquid crystal components contained in the polarizer layer to the liquid crystal phase. Also, the exposure may be performed in a nitrogen atmosphere. When the curing of the polarizer layer proceeds by radical polymerization, it is preferable to perform the exposure in a nitrogen atmosphere because the inhibition of polymerization by oxygen is reduced.

[0148] [Optical anisotropic film] The laminate of the present invention preferably has an optical anisotropic film. Here, the optical anisotropic film refers to all films that cause a phase difference, and examples thereof include a stretched polymer film and a retardation film provided with an optical anisotropic layer having a liquid crystalline compound oriented on a support. Here, there are no particular restrictions on the orientation direction of the liquid crystalline compound contained in the optical anisotropic layer, and examples include horizontal, vertical, and twisted orientations with respect to the film surface. Also, specific functions of the optical anisotropic film include, for example, a λ / 4 plate, a λ / 2 plate, and the like. Also, the optical anisotropic layer may be composed of a plurality of layers. For an optical anisotropic layer composed of a plurality of optical anisotropic layers, for example, reference can be made to the descriptions in paragraphs

[0008] to

[0053] of JP-A-2014-209219. Also, such an optical anisotropic film and the above-described polarizer layer may be provided in contact with each other, or another layer may be provided therebetween. Examples of such a layer include an adhesive layer or an adhesive layer for ensuring adhesion.

[0149] In the laminate of the present invention, it is preferable to use a λ / 4 plate as the above-described optical anisotropic film, and it is more preferable to have a λ / 4 plate on the polarizer layer. Here, the "λ / 4 plate" is a plate having a λ / 4 function, and specifically, it is a plate having a function of converting linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). For example, as an embodiment in which the λ / 4 plate has a single-layer structure, specifically, a stretched polymer film, a retardation film provided with an optical anisotropic layer having a λ / 4 function on a support, and the like can be mentioned. As an embodiment in which the λ / 4 plate has a multilayer structure, specifically, a broadband λ / 4 plate formed by laminating a λ / 4 plate and a λ / 2 plate can be mentioned.

[0150] [Barrier layer] The laminate of the present invention may have a barrier layer on the polarizer layer. Here, the barrier layer is also called a gas barrier layer (oxygen barrier layer), and has a function of protecting the polarizing element of the present invention from gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers. Regarding the barrier layer, for example, refer to the descriptions in paragraphs

[0014] to

[0054] of Japanese Patent Application Laid-Open No. 2014-159124, paragraphs

[0042] to

[0075] of Japanese Patent Application Laid-Open No. 2017-121721, paragraphs

[0045] to

[0054] of Japanese Patent Application Laid-Open No. 2017-115076, paragraphs

[0010] to

[0061] of Japanese Patent Application Laid-Open No. 2012-213938, and paragraphs

[0021] to

[0031] of Japanese Patent Application Laid-Open No. 2005-169994.

[0151] [Adhesive layer] The laminate according to the first aspect of the present invention preferably has at least one adhesive layer between the two substrates described above. In addition, the laminates according to the second and third aspects of the present invention have at least one adhesive layer between the two substrates described above. Such an adhesive layer is not particularly limited, but can be preferably used, for example, between the base material and the polarizer layer, between the polarizer layer and the optically anisotropic layer, or between the base material and the optically anisotropic layer.

[0152] Examples of the adhesive contained in the adhesive layer include rubber-based adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, cellulose adhesives, etc. From the viewpoints of transparency, weather resistance, heat resistance, etc., acrylic adhesives are preferred. In addition, the materials described in paragraphs

[0034] to

[0057] of Japanese Patent Application Laid-Open No. 2014-152198 can also be preferably used.

[0153] The adhesive layer can be formed, for example, by applying a solution of an adhesive onto a release sheet, drying it, and then transferring it onto the surface of the transparent resin layer; by directly applying a solution of the adhesive onto the surface of the transparent resin layer and drying it; and so on. The solution of the adhesive is prepared, for example, as a solution of about 10 to 40% by mass in which the adhesive is dissolved or dispersed in a solvent such as toluene or ethyl acetate. As the coating method, roll coating methods such as reverse coating and gravure coating, spin coating method, screen coating method, fountain coating method, dipping method, spray method, etc. can be adopted.

[0154] Examples of the constituent material of the release sheet include synthetic resin films such as polyethylene, polypropylene, and polyethylene terephthalate; rubber sheets; paper; cloth; non-woven fabrics; nets; foamed sheets; metal foils; and other appropriate thin sheets.

[0155] The laminate of the present invention may have a plurality of adhesive layers. The plurality of adhesive layers may have the same or different contained components and thicknesses.

[0156] In the present invention, it is desirable that the adhesive contains as little as possible a compound that can promote the decomposition reaction of the azo dye in order to enhance the discoloration resistance of the laminate. Here, examples of the compound that can promote the decomposition reaction of the azo dye include water, reducing agents, nucleophilic compounds, acids, bases, etc. In particular, it is preferable to suppress the presence of water and reducing agents with respect to the discoloration of the azo dye.

[0157] In particular, for the reason that the discoloration resistance is better, the content of the reducing agent in each of at least one adhesive layer is preferably 0.04 g / m 2 or less, and more preferably 0.03 g / m 2 or less. Also, for the same reason, when there are a plurality of adhesive layers, the total content of the reducing agent in all the adhesive layers is preferably 0.04 g / m 2 or less, and more preferably 0.03 g / m2 It is more preferable that it is as follows.

[0158] Since water itself has nucleophilicity and promotes azo bond decomposition, and also has the effect of promoting reactions with reducing agents, acids, and bases, it is desirable to suppress its abundance. In the laminate of the present invention, the amount of moisture present between two substrates is 0.8 g / m 2 It is preferably below, and 0.7 g / m 2 It is more preferably below, and 0.6 g / m 2 It is even more preferably below, and 0.4 g / m 2 It is particularly preferably below, and 0.3 g / m 2 It is most preferably below. Note that in the laminate according to the first aspect of the present invention, the amount of moisture present between two substrates is 0.9 g / m 2 It is below.

[0159] Here, the method for measuring the moisture content is to measure the change amount (initial mass - dry mass) between the initial mass of the laminate to be measured and the dry mass after decomposition and drying at 120°C for 2 hours, and convert the result per unit area. Moreover, the initial mass is the mass measured immediately after leaving the laminate to be measured in an environment of a temperature of 25°C and a relative humidity of 60% for 3 days. Moreover, the dry mass after decomposition is the mass measured immediately after peeling off one of the two substrates within 30 minutes after measuring the initial mass and drying at 120°C for 2 hours.

[0160] In addition, since it becomes easy to reduce the amount of moisture brought into the space between the two substrates of the laminate and adjust it to the above-described range, the water content of the adhesive layer is preferably 0.4% or less, and more preferably 0.3% or less. Here, the water content refers to the value measured using a Karl Fischer moisture meter after leaving the adhesive layer to be measured in an environment of a temperature of 25°C and a relative humidity of 60% for 3 days. When using a commercially available adhesive layer for the laminate of the present invention, it can be measured in a state where the liner of the commercially available adhesive layer is peeled off. In addition, the moisture content of the adhesive layer can be adjusted by a method such as drying the adhesive layer in an environment with a lower relative humidity than the environment in which the laminate is produced before producing the laminate.

[0161] Since the reducing agent can easily decompose the azo bond, it is desirable to suppress its abundance. Examples of the reducing agent include phenolic compounds such as p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol; quinone compounds such as hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone; amine compounds such as p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine; thioether compounds such as phenothiazine, distearylthiodipropionate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitroso benzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N,N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrodimethylamine, p-nitro-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitroso benzene, 2,4,6-tri-tert-butylnitroso benzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, etc. nitroso compounds; Examples thereof include. Also, hydrazines such as hydrazine, methylhydrazine, 1,1-dimethylhydrazine and phenylhydrazine, and pyrrolidones such as N-methylpyrrolidone, N-ethylpyrrolidone and N-vinylpyrrolidone also act as reducing agents for azo bonds.

[0162] The amount of the reducing agent present between the two substrates of the laminate is preferably 0.04 g / m 2 or less, and more preferably 0.03 g / m 2 or less.

[0163] In the laminate according to the first and third aspects of the present invention, the thickness of the adhesive layer is not particularly limited, but is preferably 3 μm to 220 μm. In the laminate according to the first and third aspects of the present invention, for the reason that the effects of the present invention are manifested, it is preferable that the thickness of each of at least one adhesive layer is 100 μm or more, more preferably 100 to 300 μm, and still more preferably 100 to 220 μm.

[0164] In the laminate according to the first and third aspects of the present invention, when there are a plurality of adhesive layers, the total thickness of the adhesive layers is preferably 15 μm to 250 μm, more preferably 20 μm to 70 μm, and still more preferably 25 μm to 50 μm.

[0165] In the laminate according to the second aspect of the present invention, the thickness of the adhesive layer (the total thickness when there are a plurality of adhesive layers) is 70 μm or less, but for the reason that the effects of the present invention are manifested, it is preferably 50 μm or more.

[0166] <Low moisture permeability layer> The laminate according to the first and second aspects of the present invention preferably has at least one low moisture permeability layer between the above-mentioned two substrates in order to prevent the movement of moisture to the polarizer layer, and more preferably has at least one low moisture permeability layer between the polarizer layer and the adhesive layer. Further, the laminate according to the third aspect of the present invention has at least one low moisture permeability layer between the above-mentioned two substrates. Such a low moisture permeability layer may be a single layer or a plurality of layers may exist. When adhesive layers are located on both sides of the polarizer layer, low moisture permeability layers may exist on both sides of the polarizer layer, respectively.

[0167] Examples of the material of the low moisture permeability layer include olefin resins, acrylic resins, and polyethylene terephthalate resins. The olefin resin referred to here includes chain polyolefin resins and cyclic polyolefin resins. These resin films can be films formed by melt-extruding a raw material resin, uniaxially stretched films obtained by transverse stretching after film formation, biaxially stretched films obtained by longitudinal stretching after film formation and then transverse stretching, and the like.

[0168] Among these, from the viewpoint of more excellent effects of the present invention, it is preferable that at least one low moisture permeability layer contains a cyclic polyolefin resin.

[0169] The cyclic polyolefin resin is obtained, for example, by polymerizing a cyclic olefin monomer such as norbornene and other cyclopentadiene derivatives in the presence of a catalyst.

[0170] Examples of the cyclic polyolefin resin include resins obtained by subjecting norbornene or its derivative obtained by a Diels-Alder reaction from cyclopentadiene and olefins or (meth)acrylic acid or its esters to ring-opening metathesis polymerization using it as a monomer and then hydrogenating it; resins obtained by subjecting tetracyclododecene or its derivative obtained by a Diels-Alder reaction from dicyclopentadiene and olefins or (meth)acrylic acid or its esters to ring-opening metathesis polymerization using it as a monomer and then hydrogenating it; resins obtained by similarly subjecting at least two monomers selected from norbornene, tetracyclododecene, their derivatives, and other cyclic olefin monomers to ring-opening metathesis copolymerization and then hydrogenating it; resins obtained by addition copolymerizing a cyclic olefin such as norbornene, tetracyclododecene, or their derivatives with a chain olefin and / or an aromatic compound having a vinyl group, and the like.

[0171] Cyclic polyolefin resins can be easily obtained as commercial products. Examples of commercial products include, by their respective trade names, "TOPAS", which is produced by TOPAS ADVANCED POLYMERS GmbH and sold in Japan by Polyplastics Co., Ltd.; "Arton (registered trademark)", which is sold by JSR Corporation; "Zeonor (registered trademark)" and "Zeonex (registered trademark)", which are sold by Zeon Corporation; "Apel (registered trademark)", which is sold by Mitsui Chemicals, Inc., etc.

[0172] Typical examples of chain polyolefin resins are polyethylene resins and polypropylene resins. Among them, a homopolymer of propylene or a copolymer in which propylene is the main component and a comonomer copolymerizable therewith, such as ethylene, is copolymerized at a ratio of 1 to 20% by mass, preferably 3 to 10% by mass, is preferably used.

[0173] The polypropylene resin may contain an alicyclic saturated hydrocarbon resin. By containing the alicyclic saturated hydrocarbon resin, the retardation value is easily controllable. The content of the alicyclic saturated hydrocarbon resin is advantageously 0.1 to 30% by mass based on the polypropylene resin, and a more preferable content is 3 to 20% by mass.

[0174] Acrylic resins are typically polymers containing 50% by mass or more of methyl methacrylate units. The content of methyl methacrylate units is preferably 70% by mass or more, and may be 100% by mass.

[0175] Acrylic resins mainly composed of methyl methacrylate can be easily obtained as commercial products. For example, by their respective trade names, there are "Sumipex (registered trademark)", which is sold by Sumitomo Chemical Co., Ltd.; "Acrypet (registered trademark)", which is sold by Mitsubishi Rayon Co., Ltd.; "Delpet (registered trademark)", which is sold by Asahi Kasei Corporation; "Parapet (registered trademark)", which is sold by Kuraray Co., Ltd.; "Acrivue (registered trademark)", which is sold by Nippon Shokubai Co., Ltd., etc.

[0176] The polyethylene terephthalate-based resin means a resin in which 80 mol% or more of the repeating units are composed of ethylene terephthalate, and other dicarboxylic acid components and diol components may be copolymerized. Examples of other dicarboxylic acid components include isophthalic acid, 4,4'-dicarboxydiphenyl, 4,4'-dicarboxybenzophenone, bis(4-carboxyphenyl)ethane, adipic acid, sebacic acid, 1,4-dicarboxycyclohexane, and the like. Examples of other diol components include propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

[0177] These other dicarboxylic acid components and diol components can also be used in combination of two or more kinds if necessary. Also, oxycarboxylic acids such as p-hydroxybenzoic acid and p-β-hydroxyethoxybenzoic acid can be used in combination. Furthermore, as other copolymerization components, dicarboxylic acid components or diol components containing a small amount of amide bond, urethane bond, ether bond, carbonate bond, etc. may be used.

[0178] Polyethylene terephthalate-based resin films can be easily obtained as commercially available products. For example, under their respective trade names, there are "Diafoil (registered trademark)", "Hostafan (registered trademark)", and "Fusion (registered trademark)" sold by Mitsubishi Rayon Co., Ltd., "Teijin Tetoron Film (registered trademark)", "Melinex (registered trademark)", "Mylar (registered trademark)", and "Teflex (registered trademark)" sold by Teijin DuPont Films Ltd., "Toyobo Ester Film (registered trademark)", "Toyobo Espert Film (registered trademark)", "Cosmo Shine (registered trademark)", and "Crisper (registered trademark)" sold by Toyobo Co., Ltd., "Lumirror (registered trademark)" sold by Toray Film Processing Co., Ltd., "Embron (registered trademark)" and "Embret (registered trademark)" sold by Unitika Ltd., "Sky Roll (registered trademark)" sold by S.K.C. Co., Ltd., "Cofil (registered trademark)" sold by Takumi Co., Ltd., "Zuitong Polyester Film (registered trademark)" sold by Zuitong Co., Ltd., "Taiko Polyester Film (registered trademark)" sold by Futamura Chemical Co., Ltd., and so on. Among polyethylene terephthalate-based resin films, biaxially stretched products are particularly preferably used.

[0179] The thickness of the low moisture permeability layer is preferably 3 to 110 μm, more preferably 5 to 80 μm, and particularly preferably 10 to 55 μm.

[0180] The moisture permeability of the low moisture permeability layer is preferably 20 g / m 2 ·24 h or less, more preferably 10 g / m 2 ·24 h or less, and particularly preferably 5 g / m 2 ·24 h or less.

[0181] <Use> The laminate of the present invention can be used as a polarizing element (polarizing plate). Specifically, for example, it can be used as a linear polarizing plate or a circular polarizing plate. When the laminate of the present invention does not have an optically anisotropic layer such as the above λ / 4 plate, the laminate can be used as a linear polarizing plate. On the one hand, when the laminate of the present invention has the above λ / 4 plate, the laminate can be used as a circular polarizing plate.

[0182] <Image display device> The image display device of the present invention has the laminate of the present invention described above. The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as "EL") display panel, and a plasma display panel. Among these, a liquid crystal cell or an organic EL display panel is preferable. That is, as the image display device of the present invention, a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element are preferable.

[0183] [Viewing angle control layer] The image display device of the present invention may have a viewing angle control layer. Here, the viewing angle control layer is a layer that controls the transmittance when viewed from the front direction and the diagonal direction of the image display device used for preventing peeping and switching the viewing angle of the display device, and examples thereof include a light control film manufactured by 3M and a laminate using a polarizer layer having an absorption axis in the thickness direction. For the laminate using a polarizer layer having an absorption axis in the thickness direction, for example, reference can be made to the description in paragraphs

[0006] to

[0043] of International Publication No. 2018 / 079854. In addition, as an example of the organic EL display device which is an example of the image display device of the present invention, for example, a mode in which the above viewing angle control layer, the above-mentioned polarizer layer, the above-mentioned arbitrary polarizer layer, and the organic EL display panel are provided in this order from the viewing side is preferably cited.

[0184] [Liquid crystal display device] As an example of the liquid crystal display device which is an example of the image display device of the present invention, it is a liquid crystal display device having the laminate of the present invention described above (however, not including the λ / 4 plate) and a liquid crystal cell. In the present invention, among the laminates provided on both sides of the liquid crystal cell, it is preferable to use the laminate of the present invention as the front-side polarizing element, and it is more preferable to use the laminate of the present invention as the front-side and rear-side polarizing elements. The liquid crystal cell constituting the liquid crystal display device will be described in detail below.

[0185] 〔Liquid Crystal Cell〕 The liquid crystal cell used in the liquid crystal display device is preferably in a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode, but is not limited thereto. In the TN-mode liquid crystal cell, rod-shaped liquid crystalline molecules (rod-shaped liquid crystalline compounds) are substantially horizontally aligned and further twisted and aligned at 60 to 120°. The TN-mode liquid crystal cell is most widely used as a color TFT liquid crystal display device and is described in many documents. In a liquid crystal cell of the VA mode, rod-shaped liquid crystalline molecules are substantially vertically aligned when no voltage is applied. The liquid crystal cells of the VA mode include, in addition to (1) a liquid crystal cell of the narrow sense VA mode (described in Japanese Patent Application Laid-Open No. 2-176625) in which rod-shaped liquid crystalline molecules are substantially vertically aligned when no voltage is applied and substantially horizontally aligned when a voltage is applied, (2) a liquid crystal cell of the MVA mode (Multi-domain Vertical Alignment) in which the VA mode is multi-domainized for widening the viewing angle (described in SID97, Digest of tech.Papers (preliminary collection) 28 (1997) 845), (3) a liquid crystal cell of the n-ASM (Axially symmetric aligned microcell) mode in which rod-shaped liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain aligned when a voltage is applied (described in the preliminary collection of the Japanese Liquid Crystal Symposium 58-59 (1998)), and (4) a liquid crystal cell of the SURVIVAL mode (presented at LCD (liquid crystal display) International 98). Further, it may be any of the PVA (Patterned Vertical Alignment) type, the optical alignment type, and the PSA (Polymer-Sustained Alignment). Details of these modes are described in detail in Japanese Patent Application Laid-Open No. 2006-215326 and Japanese Patent Application Laid-Open No. 2008-538819. In a liquid crystal cell of the IPS mode, rod-shaped liquid crystalline molecules are substantially parallel to the substrate, and the liquid crystal molecules respond planarly when an electric field parallel to the substrate surface is applied. The IPS mode is black display when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal. Methods for reducing the leakage light during black display in the diagonal direction and improving the viewing angle by using an optical compensation sheet are disclosed in Japanese Patent Application Laid-Open No. 10-54982, Japanese Patent Application Laid-Open No. 11-202323, Japanese Patent Application Laid-Open No. 9-292522, Japanese Patent Application Laid-Open No. 11-133408, Japanese Patent Application Laid-Open No. 11-305217, Japanese Patent Application Laid-Open No. 10-307291, and the like.

[0186] [Organic EL display device] As an example of the image display device of the present invention, an organic EL display device (hereinafter abbreviated as "the organic EL display device of the present invention" in this paragraph) preferably has, for example, the above-described laminate of the present invention (including the adhesive layer and the λ / 4 plate) and the organic EL display panel in this order from the viewing side. In this case, the laminate is arranged in the order of a substrate (viewing side), an alignment film provided as necessary, a polarizer layer, a transparent resin layer, an adhesive layer, a λ / 4 plate, and a substrate (non-viewing side) from the viewing side. Note that the substrate on the non-viewing side of the laminate may also serve as the substrate of the organic EL display device. The organic EL display device of the present invention has excellent abrasion resistance and impact resistance by having a substrate on the viewing side. Further, due to the above-described characteristics, the organic EL display device of the present invention is preferably used, for example, in in-vehicle display devices and the like. Further, the organic EL display panel is a display panel configured using an organic EL element in which an organic light-emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.

Examples

[0187] Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0188] [Example 1] [Production of transparent support] [Production of core layer cellulose acylate dopant] The following composition was put into a mixing tank and stirred to dissolve each component, thereby preparing a cellulose acetate solution to be used as a core layer cellulose acylate dopant. ――――――――――――――――――――――――――――――――― Core layer cellulose acylate dopant ――――――――――――――――――――――――――――――――― · 100 parts by mass of cellulose acetate with an acetyl substitution degree of 2.88 · 12 parts by mass of polyester compound B described in the examples of JP-A-2015-227955 · 2 parts by mass of the following compound F · 430 parts by mass of methylene chloride (first solvent) · 64 parts by mass of methanol (second solvent) ―――――――――――――――――――――――――――――――――

[0189] Compound F

Chemical formula

[0190] <Preparation of outer layer cellulose acyl ate dope> 10 parts by mass of the following matting agent solution was added to 90 parts by mass of the above core layer cellulose acyl ate dope to prepare a cellulose acetate solution used as the outer layer cellulose acyl ate dope.

[0191] ――――――――――――――――――――――――――――――――― Matting agent solution ――――――――――――――――――――――――――――――――― · Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass · 76 parts by mass of methylene chloride (first solvent) · 11 parts by mass of methanol (second solvent) · 1 part by mass of the above core layer cellulose acyl ate dope ―――――――――――――――――――――――――――――――――

[0192] <Preparation of cellulose acyl ate film 1> ​After filtering the above core layer cellulose acetate dope and the above outer layer cellulose acetate dope with filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm, the above core layer cellulose acetate dope and the outer layer cellulose acetate dope on both sides thereof were simultaneously cast from a casting die onto a drum at 20 °C in three layers (band casting machine). Next, it was peeled off in a state where the solvent content was approximately 20% by mass, both ends in the width direction of the film were fixed with tenter clips, and it was dried while being stretched in the transverse direction at a stretching ratio of 1.1 times. Thereafter, it was further dried by being conveyed between the rolls of a heat treatment apparatus, and an optical film (transparent support) having a thickness of 40 μm was produced, and this was designated as cellulose acetate film 1. The in-plane retardation of the obtained cellulose acetate film 1 was 0 nm.

[0193] 〔Formation of Photoalignment Film PA1〕 A coating solution PA1 for forming a photoalignment film, which will be described later, was continuously coated on the above cellulose acetate film 1 with a wire bar. The support on which the coating film was formed was dried with warm air at 140 °C for 120 seconds, and then, the coating film was irradiated with polarized ultraviolet rays (10 mJ / cm 2 , using an ultra-high pressure mercury lamp) to form a photoalignment film PA1, and a TAC (triacetyl cellulose) film with a photoalignment film was obtained. The film thickness of the photoalignment film PA1 was 0.5 μm. ――――――――――――――――――――――――――――――――― Coating Solution PA1 for Photoalignment Film Formation ――――――――――――――――――――――――――――――――― · 100.00 parts by mass of the following polymer PA-1 · 8.25 parts by mass of the following acid generator PAG-1 · 0.6 part by mass of the following stabilizer DIPEA · 1126.60 parts by mass of xylene · 125.18 parts by mass of methyl isobutyl ketone ―――――――――――――――――――――――――――――――――

[0194] Polymer PA-1 [Chemistry]

[0195] Acid generator PAG-1 [Chemistry]

[0196] Stabilizer DIPEA [Chemistry]

[0197] [Fabrication of polarizer layer P1] On the obtained photo-alignment film PA1, a composition P1 for forming a polarizer layer with the following composition was continuously coated with a wire bar to form a coated layer P1. Next, the coated layer P1 was heated at 140 °C for 15 seconds and cooled until it reached room temperature (23 °C). Next, it was heated at the heating temperature described in Table 1 below for 60 seconds and cooled again until it reached room temperature. Thereafter, using an LED lamp (center wavelength 365 nm), it was irradiated for 2 seconds under irradiation conditions of an illuminance of 200 mW / cm 2 to fabricate a polarizer layer P1 on the photo-alignment film PA1. The film thickness of the polarizer layer P1 was 0.5 μm.

[0198] ――――――――――――――――――――――――――――――――― Composition of the composition P1 for forming a polarizer layer ――――――――――――――――――――――――――――――――― · The following first dichroic substance C-1: 0.59 parts by mass · The following second dichroic substance M-1: 0.36 parts by mass · The following third dichroic substance Y-1: 0.24 parts by mass · The following liquid crystalline compound L-1: 5.55 parts by mass · Polymerization initiator IRGACURE OXE-02 (manufactured by BASF) 0.21 parts by mass · The following surfactant F-1 0.055 parts by mass · Cyclopentanone 45.34 parts by mass · Tetrahydrofuran 45.34 parts by mass · Benzyl alcohol 2.33 parts by mass ―――――――――――――――――――――――――――――――――

[0199] Dichroic substance C-1 (maximum absorption wavelength: 570 nm)

Chemical formula

[0200] Dichroic substance M-1 (maximum absorption wavelength: 466 nm)

Chemical formula

[0201] Dichroic substance Y-1 (maximum absorption wavelength: 417 nm)

Chemical formula

[0202] Liquid crystalline compound L-1

Chemical formula

[0203] Surfactant F-1

Chemical formula

[0204] 〔Formation of oxygen barrier layer B1〕 On the polarizer layer P1, the coating liquid B1 having the following composition was continuously applied with a wire bar. Thereafter, by drying with warm air at 80°C for 5 minutes, a laminate A in which an oxygen barrier layer B1 made of polyvinyl alcohol (PVA) with a thickness of 1.0 μm was formed, that is, a laminate A including a cellulose acetate film 1 (transparent support), an optical alignment film PA1, a polarizer layer P1, and an oxygen barrier layer B1 adjacent to each other in this order was obtained. ――――――――――――――――――――――――――――――――― Composition of the coating liquid B1 for forming an oxygen barrier layer ――――――――――――――――――――――――――――――――― · 3.80 parts by mass of the following modified polyvinyl alcohol · 0.20 part by mass of the initiator Irg2959 · 70 parts by mass of water · 30 parts by mass of methanol ―――――――――――――――――――――――――――――――――

[0205] Modified polyvinyl alcohol

Chemical formula

[0206] 〔Preparation of the adhesive N1〕 An acrylate polymer was prepared according to the following procedure. In a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 95 parts by mass of butyl acrylate and 5 parts by mass of acrylic acid were polymerized by solution polymerization to obtain an acrylate polymer (A1) having an average molecular weight of 2 million and a molecular weight distribution (Mw / Mn) of 3.0.

[0207] Next, an acrylate-based pressure-sensitive adhesive was prepared with the following composition using the obtained acrylate-based polymer (A1). These compositions were applied using a die coater onto a separate film surface-treated with a silicone-based release agent and dried for 1 minute in an environment at 90°C, and then irradiated with ultraviolet rays (UV) under the following conditions to obtain an acrylate-based pressure-sensitive adhesive N1 with a film thickness of 15 μm. The composition of the acrylate-based pressure-sensitive adhesive N1 is shown below. The prepared acrylate-based pressure-sensitive adhesive N1 showed a moisture content of 0.60% after being left in an environment at a temperature of 25°C and a relative humidity of 60% for 3 days. Also, the content of the reducing agent in the prepared acrylate-based pressure-sensitive adhesive N1 was 0.01 g / m 2 less than. <UV Irradiation Conditions> · Fusion Company Electrodeless Lamp H Bulb · Illuminance 600 mW / cm 2 and light quantity 150 mJ / cm 2 · The UV illuminance and light quantity were measured using "UVPF-36" manufactured by Eye Graphics.

[0208] ――――――――――――――――――――――――――――――――― Acrylate-based Pressure-sensitive Adhesive N1 ――――――――――――――――――――――――――――――――― · Acrylate-based polymer (A1) 100 parts by mass · The following (A) polyfunctional acrylate-based monomer 11.1 parts by mass · The following (B) photoinitiator 1.1 parts by mass · The following (C) isocyanate-based crosslinking agent 1.0 parts by mass · The following (D) silane coupling agent 0.2 parts by mass ―――――――――――――――――――――――――――――――――

[0209] (A) Polyfunctional acrylate-based monomer: Tris(acryloyloxyethyl) isocyanurate, molecular weight = 423, trifunctional type (manufactured by Toagosei Co., Ltd., trade name "Allnex M-315") (B) Photoinitiator: A mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone in a mass ratio of 1:1, "Irgacure 500" manufactured by Ciba Specialty Chemicals (C) Isocyanate crosslinking agent: Trimethylolpropane-modified tolylene diisocyanate ("Coronate L" manufactured by Nippon Polyurethane Industry Co., Ltd.) (D) Silane coupling agent: 3-Glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.)

[0210] [Preparation of Adhesive N2] With the following composition, an acrylate-based adhesive was applied to a separate film surface-treated with a silicone-based release agent using a die coater and dried in an environment at 90 °C for 10 minutes to obtain an acrylate-based adhesive N2 with a film thickness of 200 μm. The composition of the acrylate-based adhesive is shown below. Note that p-methoxyphenol is added to improve the long-term storage stability of the adhesive, but on the other hand, it can act as a reducing agent for azo dyes. The prepared acrylate-based adhesive N2 contained 0.05 g / m 2 of p-methoxyphenol as a reducing agent. The prepared acrylate-based adhesive N2 showed a moisture content of 0.25% after being left in an environment at a temperature of 25 °C and a relative humidity of 60% for 3 days.

[0211] ――――――――――――――――――――――――――――――――― Acrylate-based adhesive N2 ――――――――――――――――――――――――――――――――― · SK Dyn 2147 (manufactured by Soken Chemical & Engineering Co., Ltd.) 100 parts by mass · p-Methoxyphenol 0.33 parts by mass ―――――――――――――――――――――――――――――――――

[0212] [Preparation of Evaluation Laminate A-1] An oxygen barrier layer B1 side of the above-mentioned laminate A cut into a 10 cm square was bonded to a 10 cm square of non-alkali glass Eagle XG with a thickness of 1.1 mm (manufactured by Corning Incorporated) using the above-mentioned adhesive N1 cut into a 10 cm square. Next, only the cellulose acetate film 1 contained in the laminate A was removed, and the removed surface and the non-alkali glass Eagle XG with a thickness of 1.1 mm were bonded using the above-mentioned adhesive N2 cut into a 10 cm square to produce a laminate A-1. The layer structure of the laminate A-1 is non-alkali glass Eagle XG, adhesive layer N1, oxygen barrier layer B1, polarizer layer P1, photo-alignment film PA1, adhesive layer N2, and non-alkali glass Eagle XG. When the amount of moisture present between the two non-alkali glasses of the produced laminate was measured, it was 0.67 g / m 2 It was. Also, the total content of the reducing agent contained in the adhesive layer of the produced laminate was 0.05 g / m 2 or more and less than 0.06 g / m 2 It was. On the other hand, the moisture permeability of the non-alkali glass used in the production was less than 1.0×10 -3 g / m 2 ·day.

[0213] [Example 2] A laminate A-2 was produced in the same manner as in Example 1 except that the acrylate-based adhesive N2 was changed to a commercially available sheet-like adhesive SA368 (manufactured by Shin Tack Kasei Co., Ltd.). The sheet-like adhesive SA368 showed a moisture content of 0.19% after being left for 3 days in an environment of a temperature of 25°C and a relative humidity of 60%. Also, the reducing agent content of the sheet-like adhesive SA368 was less than 0.01 g / m 2 It was. When the amount of moisture present between the two non-alkali glasses of the produced laminate was measured, it was 0.55 g / m 2 It was. Also, the total content of the reducing agent contained in the adhesive layer of the produced laminate was less than 0.01 g / m 2 It was.

[0214] [Example 3] [Production of Adhesive N3] For acrylate adhesive N2, acrylate adhesive N3 was obtained in the same manner as acrylate adhesive N2, except that the film thickness was changed to 50 μm. After acrylate adhesive N3 was left standing in an environment of 25°C and 60% relative humidity for 3 days, it showed a water content of 0.25%. Also, the prepared acrylate adhesive N3 contained 0.01 g / m 2 of p-methoxyphenol as a reducing agent.

[0215] Laminate A-3 was produced in the same manner as in Example 1, except that acrylate adhesive N2 was changed to acrylate adhesive N3. When the amount of moisture present between the two sheets of non-alkali glass of the produced laminate was measured, it was 0.30 g / m 2 . Also, the total content of the reducing agent contained in the adhesive layer of the produced laminate was 0.01 g / m 2 or more and less than 0.02 g / m 2 .

[0216] [Example 4] [Preparation of Adhesive N4] A commercially available acrylate adhesive solution SK Dain 2147() was applied using a die coater to a separate film surface-treated with a silicone-based release agent, and dried in an environment of 90°C for 10 minutes to obtain an acrylate adhesive N4 with a film thickness of 200 μm. After the prepared acrylate adhesive N4 was left standing in an environment of 25°C and 60% relative humidity for 3 days, it showed a water content of 0.25%. Also, the reducing agent content of the prepared acrylate adhesive N4 was less than 0.01 g / m 2 .

[0217] Laminate A-4 was produced in the same manner as in Example 1, except that acrylate adhesive N2 was changed to acrylate adhesive N4. When the amount of moisture present between the two sheets of non-alkali glass of the produced laminate was measured, it was 0.67 g / m 2 . In addition, the total content of the reducing agent contained in the pressure-sensitive adhesive layer of the produced laminate was less than 0.01 g / m 2 .

[0218] [Example 5] A laminate A-5 was produced in the same manner as in Example 1, except that the acrylate-based pressure-sensitive adhesive N2 was changed to a commercially available sheet-like pressure-sensitive adhesive CS9898 (manufactured by Nitto Denko Corporation). At that time, the above sheet-like pressure-sensitive adhesive CS9898 was left in a low-humidity environment (25°C, relative humidity 10%) for 24 hours, dehydrated, and then laminated. In addition, the content of the reducing agent in the sheet-like pressure-sensitive adhesive CS9898 was less than 0.01 g / m 2 . When the amount of moisture present between the two sheets of non-alkali glass of the produced laminate was measured, it was 0.77 g / m 2 . In addition, the total content of the reducing agent contained in the pressure-sensitive adhesive layer of the produced laminate was less than 0.01 g / m 2 .

[0219] [Example 6] To a 1.1-mm-thick non-alkali glass Eagle XG (manufactured by Corning), the oxygen barrier layer B1 side of the above laminate A was laminated using the above pressure-sensitive adhesive N1. Next, only the cellulose acylate film 1 contained in the above laminate A was removed, and a commercially available cycloolefin polymer film (Zeonex ZB12, film thickness 50 μm, manufactured by Nippon Zeon Co., Ltd.) was laminated on the removed surface. Further, the cycloolefin polymer film side of the above laminate and the 1.1-mm-thick alkali-free glass Eagle XG were laminated using a commercially available sheet-like pressure-sensitive adhesive CS9898 (manufactured by Nitto Denko Corporation) to produce a laminate A-6. The layer structure of the laminate A-6 is non-alkali glass Eagle XG, pressure-sensitive adhesive layer N1, oxygen barrier layer B1, polarizer layer P1, photo-alignment film PA1, pressure-sensitive adhesive layer N1, cycloolefin polymer film ZB12, sheet-like pressure-sensitive adhesive CS9898, non-alkali glass Eagle XG. The sheet-like pressure-sensitive adhesive CS9898 showed a moisture content of 0.69% after being left in an environment of 25°C and 60% relative humidity for 3 days. The amount of moisture present between the two sheets of alkali-free glass in the produced laminate was measured and found to be 1.64 g / m 2 at that time. Also, the total content of reducing agent contained in the pressure-sensitive adhesive layer of the produced laminate was less than 0.01 g / m 2 at that time. Also, the moisture permeability of the cycloolefin polymer film ZB12 was 1.8 g / m 2 ·day at that time.

[0220] [Example 7] [Formation of Photoalignment Film PA2] A coating solution PA2 for forming a photoalignment layer was prepared with the following composition, dissolved for 1 hour while stirring, and filtered through a 0.45 μm filter. The prepared coating solution PA2 for forming a photoalignment layer was continuously coated onto the above cellulose acylate film 1 with a wire bar. The support with the coating film formed was dried with warm air at 60°C for 120 seconds, and then, the coating film was irradiated with polarized ultraviolet rays (100 mJ / cm 2 , using an ultra-high pressure mercury lamp) to form a photoalignment film PA2, and a TAC (triacetyl cellulose) film with a photoalignment film was obtained.

[0221] ――――――――――――――――――――――――――――――――― Coating Solution PA2 for Forming Photoalignment Film ――――――――――――――――――――――――――――――――― · 5.0 parts by mass of the following photoactive compound E-4 · 95.0 parts by mass of cyclopentanone ―――――――――――――――――――――――――――――――――

[0222] Photoactive Compound E-4 (weight average molecular weight; 51000)

Chemical formula

[0223] [Production of Polarizer Layer P2] The polarizer layer-forming composition P2 was prepared with the following composition, heated and dissolved at 80 °C for 2 hours while stirring, and filtered through a 0.45 μm filter. The prepared polarizer layer-forming composition P2 was applied onto the above-mentioned photo-aligned film PA2 using a wire bar. Next, the obtained coating film was heated at 120 °C for 60 seconds and cooled until it reached room temperature. Thereafter, ultraviolet rays with an exposure amount of 2000 mJ / cm 2 were irradiated using a high-pressure mercury lamp to form a polarizer layer P2 with a thickness of 1.7 μm. It was confirmed that the liquid crystal of the polarizer layer was in the smectic B phase.

[0224] ――――――――――――――――――――――――――――――――― Polarizer layer-forming composition P2 ――――――――――――――――――――――――――――――――― · 0.8 part by mass of the following dichroic dye D1 · 2.6 parts by mass of the following dichroic dye D2 · 2.2 parts by mass of the following dichroic dye D3 · 1.8 parts by mass of the following dichroic dye D4 · 100.0 parts by mass of the following liquid crystal compound M1 · 5.0 parts by mass of polymerization initiator IRGACURE369 (manufactured by BASF) · 0.9 part by mass of BYK361N (manufactured by BYK-Chemie Japan) · 925.0 parts by mass of cyclopentanone ―――――――――――――――――――――――――――――――――

[0225] Dichroic dye D1

Chemical formula

[0226] Dichroic dye D2

Chemical formula

[0227] Dichroic dye D3 [Chemistry]

[0228] Dichroic pigment D4 [Chemistry]

[0229] Liquid crystal compound M1 (mixed with compound A / compound B = 75 / 25)

[0230] (Compound A) [Chemistry]

[0231] (Compound B) [Chemistry]

[0232] [Formation of oxygen barrier layer B1] On the polarizer layer P2, the aforementioned coating liquid B1 was continuously applied with a wire bar. Then, by drying with warm air at 80°C for 5 minutes, a laminate AA in which an oxygen barrier layer B1 made of polyvinyl alcohol (PVA) with a thickness of 1.0 μm was formed, that is, a laminate AA including a cellulose acetate film 1 (transparent support), an optical alignment film PA2, a polarizer layer P2, and an oxygen barrier layer B1 adjacent to each other in this order was obtained. A laminate A-7 was produced in the same manner as in Example 2 except that laminate A was changed to laminate AA. When the amount of moisture present between two sheets of non-alkali glass of the produced laminate was measured, it was 0.55 g / m 2 . Also, the total content of the reducing agent contained in the adhesive layer of the produced laminate was less than 0.01 g / m 2 .

[0233] [Comparative Example 1] A laminate B-1 was produced in the same manner as in Example 1, except that the acrylate-based adhesive N2 was changed to a commercially available sheet-like adhesive CS9898 (manufactured by Nitto Denko Corporation). After being left standing in an environment of 25°C and 60% relative humidity for 3 days, the sheet-like adhesive CS9898 showed a moisture content of 0.69%. When the amount of moisture present between two sheets of non-alkali glass in the produced laminate was measured, it was 1.55 g / m 2 It was. Also, the total content of reducing agents contained in the adhesive layer of the produced laminate was less than 0.01 g / m 2 It was less than.

[0234] [Evaluation: Discoloration Resistance Test] For the laminates obtained in the examples and comparative examples, a test of leaving them standing in an environment of 105°C for 500 hours (a test assuming in-vehicle use) was conducted, and the discoloration at the center of the sample after the test was evaluated. For the evaluation, a spectrophotometer was used, and the color difference (difference in b) between the center and the periphery (the average of four points at the four corners of the sample and 1 cm inside each side) of the sample placed on white paper was used to evaluate with the following criteria. If it is evaluated as "C" or higher, it can be judged that the durability is acceptable. A: The color difference Δb between the center and the periphery is less than 1.0 B: The color difference Δb between the center and the periphery is 1.0 or more and less than 1.5 C: The color difference Δb between the center and the periphery is 1.5 or more and less than 2.5 D: The color difference Δb between the center and the periphery is 2.5 or more

[0235] The results of the above evaluation tests are shown in Table 1 below.

[0236]

Table 1

[0237] As shown in Table 1, it was confirmed that all of the laminates produced in Examples 1 to 7 were laminates with excellent discoloration resistance.

[0238] [Production of Organic EL Display Device] [Preparation of TAC Film A1 Having Positive A Plate A1] The coating solution PA3 for forming an optical alignment film having the following composition was continuously applied onto the above-mentioned cellulose acylate film 1 with a wire bar. The support on which the coating film was formed was dried with warm air at 140 °C for 120 seconds, and then, polarized ultraviolet rays were irradiated onto the coating film (10 mJ / cm 2 , using an ultra-high pressure mercury lamp) to form an optical alignment film PA3 with a thickness of 0.2 μm, and a TAC film with an optical alignment film was obtained.

[0239] ------------------------------------------------------------------------------------------------ Coating Solution PA3 for Forming Optical Alignment Film ------------------------------------------------------------------------------------------------ · 100.00 parts by mass of the following polymer PA-2 · 5.00 parts by mass of the above acid generator PAG-1 · 0.005 parts by mass of the above acid generator CPI-110TF · 16.50 parts by mass of isopropyl alcohol · 1072.00 parts by mass of butyl acetate · 268.00 parts by mass of methyl ethyl ketone ------------------------------------------------------------------------------------------------

[0240] Polymer PA-2 [Chemical formula]

[0241] The composition A-1 having the following composition was applied onto the above optical alignment film PA3 using a bar coater. The coating film formed on the optical alignment film PA3 was heated to 120 °C with warm air, and then cooled to 60 °C. After that, under a nitrogen atmosphere, ultraviolet rays with a wavelength of 365 nm were irradiated onto the coating film at 100 mJ / cm 2 using a high-pressure mercury lamp, and then heated to 120 °C while irradiating with 500 mJ / cm 2By irradiating the coating film with ultraviolet rays, the alignment of the liquid crystalline compound was fixed, and a TAC film A1 having a positive A plate A1 was produced. The thickness of the positive A plate A1 was 2.5 μm, and Re(550) was 144 nm. Also, the positive A plate A1 satisfied the relationship Re(450) ≦ Re(550) ≦ Re(650). Re(450) / Re(550) was 0.82.

[0242] ――――――――――――――――――――――――――――――――― Composition A-1 ――――――――――――――――――――――――――――――――― · 43.50 parts by mass of the following polymerizable liquid crystalline compound LA-1 · 43.50 parts by mass of the following polymerizable liquid crystalline compound LA-2 · 8.00 parts by mass of the following polymerizable liquid crystalline compound LA-3 · 5.00 parts by mass of the following polymerizable liquid crystalline compound LA-4 · 0.55 parts by mass of the following polymerization initiator PI-1 · 0.20 parts by mass of the following leveling agent T-1 · 235.00 parts by mass of cyclopentanone ―――――――――――――――――――――――――――――――――

[0243] Polymerizable liquid crystalline compound LA-1 (tBu represents a tertiary butyl group)

Chemical formula

[0244] Polymerizable liquid crystalline compound LA-2

Chemical formula

[0245] Polymerizable liquid crystalline compound LA-3

Chemical formula

[0246] Coincident liquid crystal compound LA-4 (Me represents a methyl group) [Chemical formula]

[0247] Polymerization initiator PI-1 [Chemical formula]

[0248] Leveling agent T-1 [Chemical formula]

[0249] [Preparation of TAC film C1 having a positive C plate C1] As a temporary support, the above-mentioned cellulose acylate film 1 was used. The cellulose acylate film 1 was passed through a dielectric heating roll at a temperature of 60 °C, and after the surface temperature of the film was raised to 40 °C, an alkaline solution having the following composition was applied to one side of the film using a bar coater at a coating amount of 14 ml / m 2 and heated to 110 °C, and conveyed under a steam type far-infrared heater manufactured by Noritake Company Limited for 10 seconds. Next, pure water was applied onto the film at 3 ml / m 2 using the bar coater as well. Next, after repeating the water washing by a fountain coater and the water draining by an air knife three times, the film was conveyed to a drying zone at 70 °C for 10 seconds to be dried, and the cellulose acylate film 1 subjected to alkali saponification treatment was produced.

[0250] ――――――――――――――――――――――――――――――――― (Alkaline solution) ――――――――――――――――――――――――――――――――― · 4.7 parts by mass of potassium hydroxide · 15.8 parts by mass of water · 63.7 parts by mass of isopropanol · Fluorine-containing surfactant SF-1 (C 14 H 29 O(CH2CH2O) 20 H) 1.0 part by mass · 14.8 parts by mass of propylene glycol ―――――――――――――――――――――――――――――――――

[0251] The coating solution PA4 for forming an alignment film having the following composition was continuously coated onto the above alkali-saponified cellulose acylate film 1 using a #8 wire bar. The obtained film was dried with warm air at 60°C for 60 seconds and further with warm air at 100°C for 120 seconds to form an alignment film PA4.

[0252] ――――――――――――――――――――――――――――――――― Coating solution PA4 for forming an alignment film ――――――――――――――――――――――――――――――――― · 2.4 parts by mass of polyvinyl alcohol (manufactured by Kuraray, PVA103) · 1.6 parts by mass of isopropyl alcohol · 36 parts by mass of methanol · 60 parts by mass of water ―――――――――――――――――――――――――――――――――

[0253] The coating solution C1 for forming a positive C plate having the following composition was coated onto the alignment film PA4. After the obtained coating film was aged at 60°C for 60 seconds, it was irradiated with ultraviolet rays of 1000 mJ / cm 2 using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 70 mW / cm 2 to fix its alignment state, thereby vertically aligning the liquid crystal compound and producing a TAC film C1 having a positive C plate C1 with a thickness of 0.5 μm. The Rth(550) of the obtained positive C plate was -60 nm.

[0254] ――――――――――――――――――――――――――――――――― Coating liquid C1 for forming a positive C plate ――――――――――――――――――――――――――――――――― · 80 parts by mass of the following liquid crystalline compound LC-1 · 20 parts by mass of the following liquid crystalline compound LC-2 · 1 part by mass of the following vertical alignment liquid crystalline compound aligning agent S01 · Ethylene oxide-modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Co., Ltd.) 8 parts by mass · Irgacure 907 (manufactured by BASF) 3 parts by mass · Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass · 0.4 part by mass of the following compound B03 · Methyl ethyl ketone 170 parts by mass · Cyclohexanone 30 parts by mass ―――――――――――――――――――――――――――――――――

[0255] Liquid crystalline compound LC-1

Chemical formula

[0256] Liquid crystalline compound LC-2

Chemical formula

[0257] Vertical alignment liquid crystalline compound aligning agent S01

Chemical formula

[0258] Compound B03

Chemical

[0259] 〔Preparation of Evaluation Laminate C-1〕 The retardation side of the TAC film A1 having the positive A plate A1 and the retardation side of the TAC film C1 having the positive C plate C1 were bonded together by UV irradiation of 600 mJ / cm 2 using the above UV adhesive composition. The thickness of the UV adhesive layer was 3 μm. Corona treatment was performed on the surfaces to be bonded with the UV adhesive. Next, the photo-alignment film PA3 and the cellulose acylate film 1 on the positive A plate A1 side were removed to obtain a retardation plate 1. The layer structure of the retardation plate 1 is the positive A plate A1, the UV adhesive layer, the positive C plate C1, the photo-alignment film PA4, and the cellulose acylate film 1. The oxygen barrier layer B1 side of the above laminate A was bonded to a non-alkali glass Eagle XG with a thickness of 1.1 mm (manufactured by Corning Incorporated) using the above adhesive N1. Next, only the cellulose acylate film 1 contained in the above laminate A was removed, and the removed surface was bonded to the positive A plate A1 side of the above retardation plate 1 using the above adhesive N1. Next, the photo-alignment film PA4 and the cellulose acylate film 1 on the positive C plate C1 side contained in the above retardation plate 1 were removed to prepare a laminate C-1. At this time, it was bonded so that the angle formed by the absorption axis of the polarizer layer P1 contained in the above laminate A and the slow axis of the positive A plate A1 was 45°. The layer structure of the laminate C-1 is non-alkali glass Eagle XG, adhesive layer N1, oxygen barrier layer B1, polarizer layer P1, photo-alignment film PA1, adhesive layer N1, positive A plate A1, UV adhesive layer, and positive C plate C1.

[0260] The GALAXY S5 manufactured by Samsung and equipped with an organic EL panel (organic EL display element) was disassembled. From the organic EL display device, the touch panel with a circular polarizing plate was peeled off, and further the circular polarizing plate was peeled off from the touch panel. The organic EL display element including the glass substrate, the touch panel, and the circular polarizing plate were isolated respectively. Subsequently, the isolated touch panel was bonded again to the organic EL display element, and further the positive C plate C1 side of the laminate C-1 prepared above was bonded onto the touch panel using the adhesive N2 so that no air entered, and an organic EL display device was fabricated.

[0261] Regarding the fabricated organic EL display device, the display performance under bright light was evaluated. Specifically, when the display screen of the display device was set to black display and the reflected light was observed when a fluorescent lamp was projected from the front and at a polar angle of 45 degrees, no color tint was visually recognized in black, indicating excellent display performance.

Claims

1. A laminate having two substrates and a polarizer layer disposed between the two substrates, further having one or two adhesive layers disposed between the two substrates and between the substrate and the polarizer layer, the polarizer layer containing one or more azo dyes having two or more azo bonds in the molecule, the moisture permeability of the two substrates both being 10 －３ g / m ２ ·day or less, the amount of moisture present between the two substrates being 0.9 g / m ２ or less, and the thickness of the adhesive layer being 100 μm or more in at least one of the adhesive layers.

2. The laminate according to claim 1, wherein the amount of moisture present between the two substrates is 0.7 g / m ２ or less.

3. The laminate according to claim 1, wherein the amount of moisture present between the two substrates is 0.4 g / m ２ or less.

4. The laminate according to any one of claims 1 to 3, wherein the content of the reducing agent in the adhesive layer is 0.04 g / m ２ or less. Here, when the laminate has two adhesive layers, the content of the reducing agent in the adhesive layer refers to the total content of the reducing agent in the two adhesive layers.

5. The laminate according to any one of claims 1 to 4, wherein both of the two substrates are glass substrates.

6. The laminate according to any one of claims 1 to 5, wherein the thickness of both of the two substrates is 100 to 1100 μm.

7. The laminate according to any one of claims 1 to 6, wherein the azo dye is a compound represented by the following formula (1). 【Chemical 1】 In the formula (1), Ar1 and Ar2 each independently represent a phenylene group which may have a substituent or a naphthylene group which may have a substituent. In the formula (1), R1 represents a hydrogen atom or an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, an acyloxy group, an alkyl carbonate 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 alkyl phosphate amide group, an alkylimino group, or an alkylsilyl group which may have a substituent. In the formula (1), R2 and R3 each independently represent a hydrogen atom or an alkyl group, an alkenyl group, 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 which may have a substituent. R2 and R3 may be bonded to each other to form a ring, or R2 or R3 may be bonded to Ar2 to form a ring. Claim 8 An image display device having the laminate according to any one of claims 1 to 7.

Images