JP2024023177A - Light absorption anisotropic film, laminate, method of manufacturing laminate, and image display device - Google Patents

Abstract

To provide a light absorption anisotropic film which maintains superior alignability of a dichroic material and provide good light resistance when used in a laminate, and to provide a laminate, a manufacturing method therefor, and an image display device using the same.SOLUTION: A light absorption anisotropic film is provided, containing dichroic materials having an azo group, and at least one type of antioxidant, where content of the antioxidant is 1-25 mol% with respect to the total molar mass of the dichroic materials, and at least one of the dichroic materials has a structure represented by a formula (1) below.SELECTED DRAWING: None

Description

The present invention relates to a light-absorbing anisotropic film, a laminate, a method for manufacturing the laminate, and an image display device.

Conventionally, when attenuation, polarization, scattering, light blocking functions, etc. of irradiated light, including laser light and natural light, were required, devices were used that operated on different principles for each function. Therefore, products corresponding to the above functions were manufactured using different manufacturing processes for each function.
For example, in liquid crystal displays (LCDs), linear polarizing plates and circular polarizing plates are used to control optical rotation and birefringence in display. Furthermore, circularly polarizing plates are also used in organic light emitting diodes (OLEDs) to prevent reflection of external light.

Iodine has been widely used as a dichroic substance in these polarizing plates (polarizing elements), but polarizing elements using organic dyes as dichroic substances instead of iodine are also being considered.
For example, Patent Document 1 describes a polarizing film formed from a composition containing a predetermined azo dye and a polymerizable liquid crystal compound ([Claim 1]).

Japanese Patent Application Publication No. 2016-006502

The present inventors investigated the polarizing film described in Patent Document 1 and found that it has excellent initial orientation of azo dyes (hereinafter simply referred to as "orientation"). It has been revealed that the light resistance is inferior depending on the layer structure of the laminate containing the material.

Therefore, the present invention provides a light-absorbing anisotropic film that can maintain excellent orientation of dichroic substances and improve light resistance when provided in a laminate, a laminate, and a method for producing the same. The object of the present invention is to provide an image display device using the same.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that by providing a light-absorbing anisotropic film containing a dichroic substance having an azo group and an antioxidant, the present inventors have realized the superior properties of dichroic substances. The present inventors have discovered that a laminate with good light resistance can be obtained while maintaining good orientation, and have completed the present invention.
That is, it has been found that the above object can be achieved with the following configuration.

[1] A light-absorbing anisotropic film containing a dichroic substance having an azo group and at least one type of antioxidant.
[2] The light absorption anisotropic film according to [1], wherein the antioxidant contains at least one of hindered phenol, hindered amine, thioether, and phosphite compound.
[3] The light-absorbing anisotropic film according to [1] or [2], wherein the antioxidant is contained in an amount of 0.1 to 20% by mass based on the dichroic substance.
[4] The light absorption anisotropic film according to any one of [1] to [3], wherein the dichroic substance having an azo group is a dichroic substance represented by the following formula (1).

In formula (1), A ¹ , A ² and A ³ each independently represent a divalent aromatic group which may have a substituent.
In formula (1), L ¹ and L ² each independently represent a substituent.
In formula (1), m represents an integer of 1 to 4, and when m is an integer of 2 to 4, a plurality of A ² 's may be the same or different from each other.
[5] The light absorption anisotropic film according to any one of [1] to [4], wherein the dichroic substance has a structure represented by the following formula (2).

In formula (2), A ⁴ represents a divalent aromatic group which may have a substituent.
In formula (2), L ³ and L ⁴ each independently represent a substituent.
In formula (2), E represents any one of a nitrogen atom, an oxygen atom, and a sulfur atom.
In formula (2), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or an alkoxy group that may have a substituent.
In formula (2), R ² represents a hydrogen atom or an alkyl group which may have a substituent.
In formula (2), R ³ represents a hydrogen atom or a substituent.
In formula (2), n represents 0 or 1. However, when E is a nitrogen atom, n is 1, and when E is an oxygen atom or a sulfur atom, n is 0.
[6] The light-absorbing anisotropic film according to [5], wherein in formula (2), A ⁴ is a phenylene group.
[7] The light-absorbing anisotropic film according to [5] or [6], wherein in formula (2), at least one of L ³ and L ⁴ contains a crosslinkable group.
[8] The light-absorbing anisotropic film according to any one of [5] to [7], wherein in formula (2), both L ³ and L ⁴ contain a crosslinkable group.
[9] The light absorption anisotropic film according to [7] or [8], wherein the crosslinkable group is an acryloyl group or a methacryloyl group.
[10] The light-absorbing anisotropic film according to any one of [1] to [9], wherein the light-absorbing anisotropic film further contains a liquid crystal compound.
[11] A laminate comprising the light-absorbing anisotropic film according to any one of [1] to [10] and a transparent resin layer, where the light-absorbing anisotropic film and the transparent resin layer are adjacent to each other. .
[12] The transparent resin layer according to [11], wherein the transparent resin layer is a layer obtained using a curable composition containing at least one of a polymerizable compound and a polymer obtained by polymerizing the polymerizable compound. laminate.
[13] The laminate according to [11] or [12], wherein the transparent resin layer further contains particles.
[14] having a transparent support on the side opposite to the transparent resin layer provided adjacent to the light-absorbing anisotropic film, and having an alignment film between the transparent support and the light-absorbing anisotropic film; The laminate according to any one of [11] to [13].
[15] The alignment film is a photoalignment film formed using a composition containing a photoalignment compound,
The photoalignment compound is a photosensitive compound having a photoreactive group that causes at least one of dimerization and isomerization by the action of light,
The photoreactive group has a skeleton of at least one derivative or compound selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, azobenzene compounds, polyimide compounds, stilbene compounds, and spiropyran compounds, [ 14].
[16] The laminate according to any one of [11] to [15], further comprising an adhesive layer on the side of the transparent resin layer opposite to the light-absorbing anisotropic film side.
[17] The laminate according to [16], further comprising a λ/4 plate on the side of the adhesive layer opposite to the transparent resin layer side.
[18] A method for producing a laminate having a light-absorbing anisotropic film and a transparent resin layer, comprising:
A light-absorbing anisotropic film forming step of forming a light-absorbing anisotropic film using a composition containing a dichroic substance represented by the following formula (1) and at least one type of antioxidant;
A transparent resin layer forming step of forming a transparent resin layer on the light-absorbing anisotropic film using a curable composition containing at least one of a polymerizable compound and a polymer obtained by polymerizing the polymerizable compound. A method for manufacturing a laminate, comprising:

In formula (1), A ¹ , A ² and A ³ each independently represent a divalent aromatic group which may have a substituent.
In formula (1), L ¹ and L ² each independently represent a substituent.
In formula (1), m represents an integer of 1 to 4, and when m is an integer of 2 to 4, a plurality of A ² 's may be the same or different from each other.
[19] An image comprising the laminate according to any one of [11] to [17], and a display element installed on the side of the laminate opposite to the light-absorbing anisotropic film side of the transparent resin layer. Display device.

According to the present invention, a light-absorbing anisotropic film that can maintain excellent orientation of a dichroic substance and improve light resistance when provided in a laminate, a laminate, and a method for manufacturing the same; An image display device using the same can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of the laminate of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the laminate of the present invention.

The present invention will be explained in detail below.
Although the description of the constituent elements described below may be made based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as the lower limit and upper limit.
Further, in this specification, "(meth)acrylic" means a generic term for "acrylic" and "methacrylic", and "(meth)acrylate" means a generic term for acrylate and methacrylate.

[Laminated body]
The laminate of the present invention is a laminate having a light-absorbing anisotropic film and a transparent resin layer.
Further, the light absorption anisotropic film included in the laminate of the present invention is a film obtained using a composition containing a dichroic substance represented by formula (1) described below.
Further, the transparent resin layer of the laminate of the present invention is obtained using a curable composition containing particles and at least one of a polymerizable compound and a polymer obtained by polymerizing the polymerizable compound. It is a layer.
Here, "transparent" as used in the present invention indicates that the transmittance of visible light is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

In the present invention, as described above, by providing a light-absorbing anisotropic film containing a dichroic substance having an azo group and an antioxidant, excellent orientation of the dichroic substance can be maintained and light resistance can be maintained. This results in a laminate with good properties.
Although the details of this reason have not yet been clarified, the present inventors assume that it is due to the following reason.
First, the present inventors investigated the cause of poor light resistance in conventionally known polarizing elements (polarizing films) that use organic dyes as dichroic substances, and found that dichroic substances were generated during the photooxidation process. It was determined that the cause was decomposition by radicals. Therefore, in the present invention, it is considered that the light resistance was improved as a result of adding an antioxidant, which is known to sometimes quench radicals.
Furthermore, it has been found that when an antioxidant is added to a conventionally known polarizing element (polarizing film), the orientation of the dichroic substance is reduced. Surprisingly, it has been found that by using the dichroic substance discovered in the present invention and an antioxidant, it is possible to improve the light resistance while maintaining the excellent orientation of the dichroic substance. It is thought that as a result of the antioxidant promoting crystallization of the dichroic substance, the anisotropy of the dichroic dye increased and it exhibited excellent orientation.
Further, surprisingly, the present inventors have found that by providing a transparent resin layer on the light-absorbing anisotropic film, the orientation and light resistance of the dichroic substance can be further improved. This is thought to be because the provision of the transparent resin layer suppressed scattering and decomposition of the antioxidant.

FIGS. 1 and 2 are schematic cross-sectional views showing an example of the laminate of the present invention.
Here, the laminate 10 shown in FIG. 1 has a layer structure (hereinafter also abbreviated as "Structure 1") having a transparent support 12, an alignment film 14, a light absorption anisotropic film 16, and a transparent resin layer 18 in this order. It is a laminate of.
Further, the laminate 20 shown in FIG. 2 has a layer structure (hereinafter also referred to as "Structure 2") having a transparent support 12, an alignment film 14, a light absorption anisotropic film 16, a transparent resin layer 18, and an adhesive layer 19 in this order. ) is a laminate.
In addition, although the example of FIG. 1 and FIG. 2 showed the aspect in which the laminated body of this invention has a transparent support and an alignment film, it is not limited to this, and the laminated body of this invention has a transparent support and an alignment film. It is not necessary to have at least one of them.

[Light absorption anisotropic film]
The light absorption anisotropic film included in the laminate of the present invention is a film obtained using a composition containing a dichroic substance. As the dichroic substance, a dichroic substance represented by the following formula (1) (hereinafter also abbreviated as "specific dichroic substance") is preferable.
The light absorption anisotropic film may contain the following dichroic substance itself, may contain a polymer of the following dichroic substance, or may contain both of these. good.

Here, in formula (1), A ¹ , A ² and A ³ each independently represent a divalent aromatic group which may have a substituent.
Moreover, in formula (1), L ¹ and L ² each independently represent a substituent.
Further, in formula (1), m represents an integer of 1 to 4, and when m is an integer of 2 to 4, the plurality of A ² 's may be the same or different from each other. Note that m is preferably 1 or 2.

In the above formula (1), the "divalent aromatic group which may have a substituent" represented by A ¹ , A ² and A ³ will be explained.
Examples of the above-mentioned substituents include substituent group G described in paragraphs [0237] to [0240] of JP-A No. 2011-237513, and among them, halogen atoms, alkyl groups, alkoxy groups, and alkoxycarbonyl groups. (for example, methoxycarbonyl, ethoxycarbonyl, etc.), or aryloxycarbonyl group (for example, phenoxycarbonyl, 4-methylphenoxycarbonyl, 4-methoxyphenylcarbonyl, etc.), etc., and an alkyl group is more preferable, with 1 to 1 carbon atoms. The alkyl group of 5 is particularly preferred.
On the other hand, examples of the divalent aromatic group include a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group.
Examples of the divalent aromatic hydrocarbon group include arylene groups having 6 to 12 carbon atoms, and specific examples include phenylene groups, cumenylene groups, mesitylene groups, tolylene groups, and xylylene groups. It will be done. Among them, a phenylene group is preferred.
Moreover, as the divalent aromatic heterocyclic group, a group derived from a monocyclic or bicyclic heterocycle is preferable. Atoms other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom. When the aromatic heterocyclic group has a plurality of ring-constituting atoms other than carbon, these may be the same or different. Specifically, the aromatic heterocyclic group includes a pyridylene group (pyridine-diyl group), a quinolylene group (quinoline-diyl group), an isoquinolylene group (isoquinoline-diyl group), a benzothiadiazole-diyl group, and a phthalimido-diyl group. , and thienothiazole-diyl group (hereinafter abbreviated as "thienothiazole group").
Among the above divalent aromatic groups, divalent aromatic hydrocarbon groups are preferred.

Here, it is preferable that any one of A ¹ , A ² and A ³ is a divalent thienothiazole group which may have a substituent. In addition, specific examples of the substituents of the divalent thienothiazole group are the same as the substituents in the above-mentioned "divalent aromatic group which may have a substituent", and preferred embodiments are also the same.
Furthermore, among A ¹ , A ² and A ³ , A ² is more preferably a divalent thienothiazole group. In this case, A ¹ and A ² represent a divalent aromatic group which may have a substituent.
When A ² is a divalent thienothiazole group, it is preferable that at least one of A ¹ and A ² is a divalent aromatic hydrocarbon group which may have ^a substituent; It is more preferable that both of A ² are divalent aromatic hydrocarbon groups which may have a substituent.

In the above formula (1), the "substituent" represented by L ¹ and L ² will be explained.
The above-mentioned substituents include a group introduced to improve solubility or nematic liquid crystallinity, a group having electron-donating or electron-withdrawing properties introduced to adjust the color tone as a dye, or a group that fixes the orientation. A group having a cross-linkable group (polymerizable group) introduced for the purpose of achieving this is preferable.
For example, as a substituent, an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group) group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably 2 to 20 carbon atoms, More preferably an alkenyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl group and 3-pentynyl group), aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl group, 2,6-diethylphenyl group, 3,5- ditrifluoromethylphenyl group, styryl group, naphthyl group, biphenyl group, etc.), substituted or unsubstituted amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably An amino group having 0 to 6 carbon atoms, such as an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, an anilino group, etc.), an alkoxy group (preferably a carbon number of 1 to 20, More preferably a carbon number of 1 to 15, examples include methoxy group, ethoxy group, butoxy group, etc.), an oxycarbonyl group (preferably a carbon number of 2 to 20, more preferably a carbon number of 2 to 15, Particularly preferably 2 to 10 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, etc.), acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, Particularly preferably 2 to 6 carbon atoms, examples include acetoxy group, benzoyloxy group, acryloyl group, methacryloyl group, etc.), acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms) , particularly preferably a carbon number of 2 to 6, such as an acetylamino group and a benzoylamino group), an alkoxycarbonylamino group (preferably a carbon number of 2 to 20, more preferably a carbon number of 2 to 10) , particularly preferably a carbon number of 2 to 6, such as a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably a carbon number of 7 to 20, more preferably a carbon number of 7 to 16, particularly preferably (7 to 12 carbon atoms, such as phenyloxycarbonylamino group), sulfonylamino group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms) (for example, methanesulfonylamino group, benzenesulfonylamino group, etc.), sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms) Examples include sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, and phenylsulfamoyl group), carbamoyl group (preferably 1 to 20 carbon atoms, more preferably 1 carbon number) to 10, particularly preferably 1 to 6 carbon atoms, such as unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group, etc.), alkylthio group (preferably 1 to 6 carbon atoms), 20, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, such as methylthio group and ethylthio group), arylthio group (preferably 6 to 20 carbon atoms, more preferably has 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group), a sulfonyl group (preferably has 1 to 20 carbon atoms, more preferably has 1 to 10 carbon atoms, particularly preferably has 1 to 6 carbon atoms, such as mesyl group and tosyl group), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 carbon number) -6, such as methanesulfinyl group and benzenesulfinyl group), ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms) (For example, unsubstituted ureido group, methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably has 1 to 6 carbon atoms and includes, for example, diethyl phosphoamide group, phenyl phosphoamide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, , iodine atom, etc. ), cyano group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, azo group, heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms) , for example, a heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom, and a sulfur atom, such as an epoxy group, an oxetanyl group, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, and a morpholino group. , benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms) Examples of the silyl group include trimethylsilyl group and triphenylsilyl group.
These substituents may be further substituted with other substituents. Furthermore, when two or more substituents are present, they may be the same or different. Further, if possible, they may be bonded to each other to form a ring.

The substituents represented by L ¹ and L ² are preferably an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, or a substituent. Aryl group that may have a substituent, alkoxy group that may have a substituent, oxycarbonyl group that may have a substituent, acyloxy group that may have a substituent, substituent An acylamino group which may have a substituent, an amino group which may have a substituent, an alkoxycarbonylamino group which may have a substituent, a sulfonylamino group which may have a substituent, a substituent A sulfamoyl group that may have a substituent, a carbamoyl group that may have a substituent, an alkylthio group that may have a substituent, a sulfonyl group that may have a substituent, and a sulfamoyl group that may have a substituent. A ureido group, a nitro group, a hydroxy group, a cyano group, an imino group, an azo group, a halogen atom, and a heterocyclic group, which may have a substituent, and more preferably an alkyl group that may have a substituent. , an alkenyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, an oxycarbonyl group that may have a substituent, These include an acyloxy group which may have a substituent, an amino group which may have a substituent, a nitro group, an imino group, and an azo group.

It is preferable that at least one of L ¹ and L ² contains a crosslinkable group (polymerizable group), and it is more preferable that both L ¹ and L ² contain a crosslinkable group.
Specific examples of the crosslinkable group include the polymerizable groups described in paragraphs [0040] to [0050] of JP-A No. 2010-244038, and from the viewpoint of reactivity and synthesis suitability, acryloyl groups, A methacryloyl group, an epoxy group, an oxetanyl group, or a styryl group is preferred, and an acryloyl group or a methacryloyl group is preferred.

Preferred embodiments of L ¹ and L ² include an alkyl group substituted with the above crosslinkable group, a dialkylamino group substituted with the above crosslinkable group, and an alkoxy group substituted with the above crosslinkable group. .

In the present invention, since the degree of orientation of the specific dichroic substance contained in the light absorption anisotropic film is further improved, the specific dichroic substance has a structure represented by the following formula (2). Preferably.

Here, in formula (2), A ⁴ represents a divalent aromatic group which may have a substituent.
Moreover, in formula (2), L ³ and L ⁴ each independently represent a substituent.
Further, in formula (2), E represents any one of a nitrogen atom, an oxygen atom, and a sulfur atom.
Furthermore, in formula (2), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or an alkoxy group that may have a substituent.
Moreover, in formula (2), R ² represents a hydrogen atom or an alkyl group which may have a substituent.
Moreover, in formula (2), R ³ represents a hydrogen atom or a substituent.
Further, in formula (2), n represents 0 or 1. However, when E is a nitrogen atom, n is 1, and when E is an oxygen atom or a sulfur atom, n is 0.

In the above formula (2), specific examples and preferred embodiments of the "optionally substituted divalent aromatic group" represented by A ⁴ are as follows: A ¹ to A ³ in the above formula (1) are It is the same as the "divalent aromatic group which may have a substituent".
A particularly preferred embodiment of ^A4 is a phenylene group.

In the above formula (2), specific examples and preferred embodiments of the "substituent" represented by L ³ and L ⁴ are the same as the "substituent" represented by L ¹ and L ² in the above formula (1).
A preferred embodiment of L ³ and L ⁴ is that at least one of L ³ and L ⁴ contains a crosslinkable group, and a more preferred embodiment is that both L ³ and L ⁴ contain a crosslinkable group. That's true. As a result, the degree of orientation of the specific dichroic substance contained in the light-absorbing anisotropic film is further improved, and the high temperature durability and moist heat durability of the laminate are further improved.
Further, a preferable embodiment of the crosslinkable group for L ³ and L ⁴ is an acryloyl group or a methacryloyl group.

In the above formula (2), E represents any one of a nitrogen atom, an oxygen atom, and a sulfur atom, and is preferably a nitrogen atom from the viewpoint of synthesis suitability.
In addition, from the viewpoint of making the specific dichroic substance one that has absorption on the short wavelength side (for example, one that has a maximum absorption wavelength near 500 to 530 nm), E in the above formula (1) is is preferably an oxygen atom.
On the other hand, from the viewpoint of making it easier to make the specific dichroic substance have absorption on the longer wavelength side (for example, one with a maximum absorption wavelength near 600 nm), E in the above formula (1) is A nitrogen atom is preferred.

In the above formula (2), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or an alkoxy group that may have a substituent; An alkyl group which may be substituted is preferred.
Next, the "alkyl group which may have a substituent" and "alkoxy group which may have a substituent" represented by R ¹ will be explained.
Examples of the substituent include a halogen atom and the like.
Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms. Among these, a linear alkyl group having 1 to 6 carbon atoms is preferred, a linear alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group or an ethyl group is even more preferred.
Examples of the alkoxy group include alkoxy groups having 1 to 8 carbon atoms. Among these, an alkoxy group having 1 to 6 carbon atoms is preferred, an alkoxy group having 1 to 3 carbon atoms is more preferred, and a methoxy group or an ethoxy group is particularly preferred.

In the above formula (2), R ² represents a hydrogen atom or an alkyl group that may have a substituent, and is preferably an alkyl group that may have a substituent.
Specific examples and preferred embodiments of the "alkyl group that may have a substituent" represented by ^R2 are the same as the "alkyl group that may have a substituent" in R1 of formula ( ² ) above. Therefore, its explanation will be omitted.
Note that R ² is a group that exists in formula (2) when E is a nitrogen atom (that is, it means the case where n=1). On the other hand, when E is an oxygen atom or a sulfur atom, R ² becomes a group that does not exist in formula (2) (that is, it means the case where n=0).

In the above formula (2), R ³ represents a hydrogen atom or a substituent.
The specific examples and preferred embodiments of the "substituent" represented by ^R3 are the same as the substituent in the "divalent aromatic group which may have a substituent" described above, and the preferred embodiments are also the same. , the explanation thereof will be omitted.

In the above formula (2), n represents 0 or 1. However, when E is a nitrogen atom, n is 1, and when E is an oxygen atom or a sulfur atom, n is 0.

Specific dichroic substances represented by the above formula (1) include compounds described in paragraphs [0051] to [0081] of JP-A No. 2010-152351, the content of which is Incorporated herein.
Among these, the specific dichroic substance having the structure represented by the above formula (2) is the compound (D-1) described in paragraphs [0074] to [0081] of JP-A No. 2010-152351. In addition to (D-53), the following compounds (D-54) to (D-58) are also suitable.

Specific examples of dichroic substances are shown below, but the invention is not limited thereto.

The content of the dichroic substance is preferably 1 to 25% by mass, particularly preferably 5 to 20% by mass, based on the total mass of all solids in the composition.
In the present invention, since the dichroic substance can be oriented with a higher degree of orientation while suppressing precipitation of the dichroic substance, the light-absorbing anisotropic film is used together with the above-mentioned dichroic substance to form a liquid crystal. The film is preferably formed using a composition (hereinafter also referred to as "liquid crystal composition") containing a liquid crystal compound.

<Liquid crystal compound>
As the liquid crystal compound contained in the liquid crystal composition, both low molecular liquid crystal compounds and high molecular liquid crystal compounds can be used.
Here, the term "low-molecular liquid crystal compound" refers to a liquid crystal compound that does not have repeating units in its chemical structure.
Furthermore, the term "polymer liquid crystal compound" refers to a liquid crystal compound having repeating units in its chemical structure.
Examples of the low-molecular liquid crystal compound include those described in JP-A No. 2013-228706.
Examples of the polymeric liquid crystalline compound include thermotropic liquid crystalline polymers described in JP-A No. 2011-237513. Further, the polymeric liquid crystal compound may have a crosslinkable group (eg, an acryloyl group and a methacryloyl group) at the terminal.

<Interface improver>
It is preferable that the liquid crystal composition contains an interface improver. By including an interface improver, it is expected that the smoothness of the coated surface will be improved, the degree of orientation will be improved, repellency and unevenness will be suppressed, and the in-plane uniformity will be improved.
As the interface improver, one that makes the liquid crystalline compound horizontal on the coating surface side is preferable, and the compounds (horizontal alignment agents) described in paragraphs [0253] to [0293] of JP 2011-237513 A can be used. can.
When the liquid crystal composition contains an interface improver, the content of the interface improver is from 0.001 to 100 parts by mass of the dichroic substance and the liquid crystal compound in the liquid crystal composition. The amount is preferably 5 parts by weight, and preferably 0.01 to 3 parts by weight.

<Polymerization initiator>
The liquid crystal composition may contain a polymerization initiator.
The polymerization initiator is not particularly limited, but it is preferably a photosensitive compound, that is, a photopolymerization initiator.
As the photopolymerization initiator, various compounds can be used without particular limitation. Examples of photopolymerization initiators include α-carbonyl compounds (US Pat. Nos. 2,367,661 and 2,367,670), asiloin ether (US Pat. No. 2,448,828), and α-hydrocarbon-substituted aromatic acyloins. compound (US Pat. No. 2,722,512), polynuclear quinone compound (US Pat. No. 3,046,127 and US Pat. No. 2,951,758), combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) ), acridine and phenazine compounds (JP 60-105667 and US Pat. No. 4,239,850), oxadiazole compounds (US Pat. No. 4,212,970), and acylphosphine oxide compounds (JP 4,212,970) 63-40799, Japanese Patent Publication No. 5-29234, Japanese Patent Application Laid-open No. 10-95788, and Japanese Patent Application Publication No. 10-29997).
As such a photopolymerization initiator, commercially available products can be used, and examples include Irgacure 184, Irgacure 907, Irgacure 369, Irgacure 651, Irgacure 819, and Irgacure OXE-01 manufactured by BASF.
When the liquid crystal composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is 0 to 100 parts by mass of the dichroic substance and the liquid crystal compound in the liquid crystal composition. 0.01 to 30 parts by weight are preferred, and 0.1 to 15 parts by weight are preferred. When the content of the polymerization initiator is 0.01 parts by mass or more, the curability of the light-absorbing anisotropic film is good, and when the content is 30 parts by mass or less, the orientation of the light-absorbing anisotropic film is good. becomes.

<Antioxidant>
As the antioxidant, any known antioxidant can be used without particular limitation. An example of this is described in "Comprehensive Technology of Polymer Stabilization - Mechanism and Application Development" supervised by Yasukazu Ohkatsu, published by CMC. Types of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Furthermore, it is preferable to use a phenolic antioxidant or an amine antioxidant in combination with a phosphorus antioxidant or a sulfur antioxidant.

Examples of phenolic antioxidants include ADEKA STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 (manufactured by ADEKA), IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 245, 259, 3114, 565 (manufactured by BFA), and the like.

As amine antioxidants, Sanol LS-770, Sanol LS-765, Sanol LS-2626 (manufactured by Sankyo Co., Ltd.), Adekastab LA-77, LA-57, LA-52, LA-62, LA-63, LA -67, LA-68, LA-72 (manufactured by ADEKA), TINUVIN123, TINUVIN144, TINUVIN622, TINUVIN765, TINUVIN944 (manufactured by Ciba Specialty Chemicals).
Further, in the present invention, an amine compound capable of quenching radicals can also be used. Examples include polyethylene glycol bisTEMPO (manufactured by Aldrich), bissebacate bisTEMPO, and the like.

Examples of the phosphorus antioxidant include ADEKA STAB PEP-8, PEP-36, HP-10, 2112 (manufactured by ADEKA), IRGAFOS168 (manufactured by BASF), and the like.

Examples of sulfur-based antioxidants include ADEKA STAB AO-412S and AO-503S (manufactured by ADEKA).

From the viewpoint of the orientation of the dichroic substance, the antioxidant preferably has an orientational molecule with L/D (L: length, D: width) of 1.2 or more.

The content of the antioxidant is preferably 1 to 25 mol%, particularly preferably 5 to 20 mol%, based on the total molar mass of the dichroic substance. The higher the content, the more the decomposition of the dichroic substance due to photooxidation can be suppressed, but the above content is preferable because it is easier to achieve both the orientation of the dichroic substance.

<Solvent>
The liquid crystal composition preferably contains a solvent from the viewpoint of workability and the like.
Examples of solvents include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, 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, etc.), alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, 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, 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, it is preferable to use organic solvents, and it is more preferable to use halogenated carbons or ketones.
When the liquid crystal composition contains a solvent, the content of the solvent is preferably 80 to 99% by mass, more preferably 83 to 97% by mass, based on the total mass of the liquid crystal composition. It is preferably 85 to 95% by mass, and more preferably 85 to 95% by mass.

<Other ingredients>
The liquid crystal composition may further contain a dichroic substance other than the above specific dichroic substance, or may contain a plurality of the above specific dichroic substances. When containing a plurality of dichroic substances, from the viewpoint of further curing the liquid crystal composition, it is preferable to contain a dichroic substance having a crosslinking group that crosslinks with the specific dichroic substance; It is more preferable to contain a plurality of dichroic substances.

<Formation method>
The method for forming a light-absorbing anisotropic film using the above-mentioned liquid crystal composition is not particularly limited, and includes the step of coating the above-mentioned liquid crystal composition on a transparent support to form a coating film (hereinafter referred to as " An example of a method includes, in this order, a step of orienting the liquid crystal component contained in the coating film (hereinafter also referred to as an "orientation step").
Note that the liquid crystal component is a component that includes not only the above-mentioned liquid crystal compound but also a dichroic substance having liquid crystallinity when the above-mentioned dichroic substance has liquid crystallinity.

(Coating film formation process)
The coating film forming step is a step of coating a liquid crystal composition on a transparent support to form a coating film.
A liquid crystal composition is applied onto a transparent support by using a liquid crystal composition containing the above-mentioned solvent or by heating the liquid crystal composition to form a liquid such as a melt. It becomes easier.
Specific examples of methods for applying the liquid crystalline composition include roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, and die coating. Known methods include a method, a spray method, and an inkjet method.
Note that in this embodiment, an example is shown in which the liquid crystal composition is coated on a transparent support, but the present invention is not limited to this, and for example, the liquid crystal composition is coated on an alignment film provided on a transparent support. may be applied. Details of the alignment film will be described later.

(Orientation process)
The alignment process is a process of aligning the liquid crystal component contained in the coating film. As a result, a light-absorbing anisotropic film is obtained.
The orientation process may include a drying process. Components such as the solvent can be removed from the coating film by the drying treatment. The drying treatment may be performed by leaving the coating film at room temperature for a predetermined period of time (for example, natural drying), or by heating and/or blowing air.
Here, the liquid crystal component contained in the liquid crystal composition may be oriented by the coating film forming step or drying treatment described above. For example, in an embodiment in which the liquid crystal composition is prepared as a coating solution containing a solvent, the coating film having light absorption anisotropy (i.e., the coating film having light absorption anisotropy (i.e., (absorption anisotropic film) is obtained.
When the drying treatment 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 below may not be performed.

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 manufacturing suitability. When the transition temperature is 10° C. or higher, there is no need for cooling treatment or the like to lower the temperature to a temperature range in which a liquid crystal phase is exhibited, which is preferable. Furthermore, if the above transition temperature is 250°C or lower, high temperatures are not required even when the temperature range is higher than the temperature range in which the liquid crystal phase is exhibited, and the temperature is higher than that of the isotropic liquid state, which results in wasted thermal energy and damage to the substrate. This is preferable because deformation, alteration, etc. can be reduced.

Preferably, the orientation step includes heat treatment. Thereby, the liquid crystal component contained in the coating film can be oriented, so that the coating film after the heat treatment can be suitably used as a light-absorbing anisotropic film.
The heat treatment is preferably performed at 10 to 250°C, more preferably from 25 to 190°C, from the viewpoint of manufacturing suitability. Further, the heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.

The orientation step may include a cooling treatment performed after the heat treatment. The cooling treatment is a treatment in which the coated film after heating is cooled to about room temperature (20 to 25° C.). Thereby, the orientation of the liquid crystal component contained in the coating film can be fixed. The cooling means is not particularly limited, and any known method can be used.
Through the above steps, a light absorption anisotropic film can be obtained.
In this embodiment, drying treatment, heat treatment, and the like are mentioned as methods for aligning the liquid crystal component contained in the coating film, but the method is not limited thereto, and any known alignment treatment can be used.

(Other processes)
The method for producing a laminate may include a step of curing the light-absorbing anisotropic film (hereinafter also referred to as a "curing step") after the orientation step.
For example, when the light-absorbing anisotropic film has a crosslinkable group (polymerizable group), the curing step is performed by heating and/or light irradiation (exposure). Among these, it is preferable that the curing step is carried out by light irradiation.
Various light sources can be used for curing, including infrared rays, visible light, and ultraviolet rays, but ultraviolet rays are preferred. Moreover, 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 the exposure is performed while heating, the heating temperature during the exposure is preferably 25 to 140° C., depending on the transition temperature of the liquid crystalline component contained in the light-absorbing anisotropic film to the liquid crystal phase.
Further, the exposure may be performed under a nitrogen atmosphere. When curing of the light-absorbing anisotropic film progresses by radical polymerization, it is preferable to perform exposure under a nitrogen atmosphere because inhibition of polymerization by oxygen is reduced.

In the present invention, the thickness of the light absorption anisotropic film is not particularly limited, and is preferably 0.1 to 5.0 μm, more preferably 0.3 to 1.5 μm.

The average refractive index of the light absorption anisotropic film at a wavelength of 550 nm is preferably 1.45 to 2.50, more preferably 1.50 to 1.90.
In this specification, the average refractive index (n _ave ) of the light absorption anisotropic film is represented by the following formula (R1).
Formula (R1) n _ave = (n _x + _ny + n _z )/3
In formula (R1), the direction in which the refractive index is maximum in the plane is the x-axis, the direction perpendicular to it is the y-axis, and the direction normal to the plane is the z-axis, and the refractive indices are n _x , n _y , _nz . Each refractive index is measured using a spectroscopic ellipsometry M-2000U manufactured by Woollam.

[Transparent resin layer]
The transparent resin layer included in the laminate of the present invention is a layer obtained using a curable composition containing at least one of a polymerizable compound and a polymer obtained by polymerizing the polymerizable compound. Furthermore, it is preferable that the transparent resin layer contains inorganic particles.
The transparent resin layer contains the polymerizable compound itself, contains a polymer obtained by polymerizing the polymerizable compound (hereinafter also simply referred to as "polymer"), or contains both the polymerizable compound and the polymer. .

<Particle>
Examples of the particles include organic particles, inorganic particles, and organic-inorganic composite particles containing an organic component and an inorganic component.
Examples of organic particles include styrene resin particles, styrene-divinylbenzene copolymer particles, acrylic resin particles, methacrylic resin particles, styrene-acrylic copolymer particles, styrene-methacrylic copolymer particles, melamine resin particles, and two types of these. Examples include resin particles containing the above.
Specific examples of inorganic particles include alumina particles, alumina hydrate particles, silica particles, zirconia particles, and inorganic oxide particles such as clay minerals (eg, smectite).
Examples of organic-inorganic composite particles include core-shell particles of a resin constituting the organic particles as an organic component and an inorganic oxide constituting the inorganic particles as an inorganic component.
Among the above, the particles are preferably inorganic particles, more preferably inorganic oxide particles, and even more preferably silica particles, alumina particles, or alumina hydrate particles, from the viewpoint of superior high-temperature durability and moist heat durability of the laminate. Particularly preferred are silica particles.
The particles may be used alone or in combination of two or more.

The average particle diameter of the particles is preferably 1 to 300 nm, more preferably 10 to 200 nm, particularly preferably 5 to 100 nm. Within the above range, a cured product (transparent resin layer) with excellent particle dispersibility, high temperature durability, moist heat durability, and transparency can be obtained.
Here, the average particle diameter of the particles can be determined from a photograph obtained by observation using a TEM (transmission electron microscope) or SEM (scanning electron microscope). Specifically, the projected area of the particles is determined, and the corresponding circle equivalent diameter (diameter of a circle) is determined as the average particle diameter of the particles. Note that the average particle diameter in the present invention is an arithmetic mean value of circle equivalent diameters obtained for 100 particles.
Note that for the TEM, an apparatus similar to the transmission electron microscope "JEM-2010HC" (trade name, manufactured by JEOL Ltd.) can be used. Further, for the SEM, an apparatus similar to the ultra-high resolution field emission scanning electron microscope "SU8010" (trade name, manufactured by Hitachi High-Technologies, Ltd.) can be used.
Furthermore, when using commercially available particles as the particles, catalog values are preferentially adopted as the average particle diameter of the particles. In this case, the average particle diameter of the particles is preferably a number average particle diameter measured based on a dynamic light scattering method. Specifically, a mixed solution or a dispersion containing particles is diluted with an arbitrary solvent, and the resulting diluted solution is measured using a dynamic light scattering method. For this measurement, it is preferable to use Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd.

The particles may have any shape such as spherical, acicular, fibrous, columnar, or plate-like, but spherical particles are preferable because they can be packed densely in the film because of the superior light resistance of the laminate. .

The particles may be added to the curable composition in the form of a colloidal liquid dispersed in a solvent (at least one of water and an organic solvent).
As the colloidal liquid, commercially available products can be used, such as AS-200 and AS-520-A (all manufactured by Nissan Chemical Industries, Ltd.), 10A, 10D, 10C, F-3000, CSA-110AD, Alumina sol such as A2, F-1000, A2K5-10 (all manufactured by Kawaken Fine Chemicals), MEK-ST-40, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP, MIBK-ST , MIBK-ST-L, CHO-ST-M, EAC-ST, PMA-ST, TOL-ST, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM Examples include silica sols such as -AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L, and MEK-EC-2130Y (all manufactured by Nissan Chemical Industries, Ltd.).

The content of particles is preferably 0 to 90% by mass, more preferably 30 to 85% by mass, based on the total mass of all solids in the curable composition.

<Polymerizable compounds and polymers>
A polymerizable compound means a compound that has a polymerizable group and can form a polymer through polymerization.
Examples of the polymerizable compound include monofunctional polymerizable compounds containing one polymerizable group in one molecule, and polyfunctional polymerizable compounds containing two or more of the same or different polymerizable groups in one molecule. The polymerizable compound may be a monomer or a multimer such as an oligomer or a prepolymer.
Examples of the polymerizable group include radically polymerizable groups and cationic polymerizable groups, with radically polymerizable groups being preferred. Examples of the radically polymerizable group include ethylenically unsaturated bond groups. Examples of cationic polymerizable groups include epoxy groups and oxetane groups.
Examples of the ethylenically unsaturated bond group include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, an allyl group, and the like, with an acryloyl group and a methacryloyl group being preferred.

Specific examples of the polymerizable compound include, for example, the compounds described in paragraphs 0051 to 0059 of JP 2016-150537, and the compounds described in paragraphs 0046 to 0072 of JP 2016-056341.
Further, specific examples include compounds represented by the following formulas, among which 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate represented by CEL2021P below is preferred.

Examples of the polymerizable compound having a hydrophilic group include KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd. and polyfunctional acrylamide FAM-401 (manufactured by Fuji Film Corporation).

The total content of the polymerizable compound and polymer is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50 to 98% by mass based on the total mass of the total solid content of the polymerizable composition.

<Polymerization initiator>
The composition for forming a transparent resin may contain a polymerization initiator.
The polymerization initiator is not particularly limited, but it is preferably a photosensitive compound, ie, a radical photopolymerization initiator or a cationic photopolymerization initiator (photoacid generator).
As the photoradical polymerization initiator, the same ones as those explained in connection with the above-mentioned liquid crystal composition can be mentioned.

<<<Cationic polymerization initiator>>>
The cationic polymerization initiator is preferably a cationic photopolymerization initiator.
The cationic photopolymerization initiator may be anything that can generate cations as active species upon irradiation with light, and any known cationic photopolymerization initiator can be used without any limitations. Specific examples include known sulfonium salts, ammonium salts, iodonium salts (eg, diaryliodonium salts), triarylsulfonium salts, diazonium salts, iminium salts, and the like. More specifically, for example, cationic photopolymerization initiators represented by formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, JP-A-8-283320 Examples of cationic polymerization catalysts may be mentioned in Paragraph 0020 of , the contents of which are incorporated herein. Further, the cationic photopolymerization initiator can be synthesized by a known method and is also available as a commercially available product. Commercially available products include, for example, CI-1370, CI-2064, CI-2397, CI-2624, CI-2639, CI-2734, CI-2758, CI-2823, CI-2855, and CI-5102 manufactured by Nippon Soda. Examples include PHOTOINITIATOR 2047 manufactured by Rhodia, UVI-6974 and UVI-6990 manufactured by Union Carbide, and CPI-10P manufactured by Sun-Apro.

As the cationic photopolymerization initiator, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of the sensitivity of the photopolymerization initiator to light, the stability of the compound, and the like. Furthermore, from the viewpoint of weather resistance, iodonium salts are most preferred.

Specific commercial products of iodonium salt-based cationic photopolymerization initiators include, for example, B2380 manufactured by Tokyo Kasei Co., Ltd., BBI-102 manufactured by Midori Kagaku Co., Ltd., WPI-113 manufactured by Wako Pure Chemical Industries, Ltd., and manufactured by Wako Pure Chemical Industries, Ltd. Examples include WPI-124, WPI-169 manufactured by Wako Pure Chemical Industries, Ltd., WPI-170 manufactured by Wako Pure Chemical Industries, Ltd., and DTBPI-PFBS manufactured by Toyo Gosei.

Further, as specific examples of iodonium salt compounds that can be used as cationic photopolymerization initiators, the following compounds PAG-1 and PAG-2 can be mentioned.

<Solvent>
In addition to the hydrophilic monomer, the curable composition preferably contains a solvent from the viewpoint of workability and the like.
Examples of the solvent include the same solvents as those explained for the liquid crystal composition described above.

<Formation method>
Examples of the method for forming the transparent resin layer include a method in which the curable composition is applied onto the light-absorbing anisotropic film described above, dried, and then fixed by polymerization.
Here, the coating method is not particularly limited, and examples thereof include dip coating, air knife coating, curtain coating, roller coating, die coating, wire bar coating, and gravure coating.
Here, polymerization conditions are not particularly limited, but in polymerization by light irradiation, it is preferable to use ultraviolet rays. The irradiation amount is preferably 10 mJ/cm ² to 50 J/cm ² , more preferably 20 mJ/cm ² to 5 J/cm ² , even more preferably 30 mJ/cm ² to 3 J/cm ² . , 50 to 1000 mJ/cm ² is particularly preferred. Moreover, in order to promote the polymerization reaction, it may be carried out under heating conditions.

The thickness of the transparent resin layer is not particularly limited, and is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

[Transparent support]
The laminate of the present invention may have a transparent support on the opposite side of the light-absorbing anisotropic film from the transparent resin layer.
Examples of materials forming the transparent support include polycarbonate polymers; polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate; acrylic polymers such as polymethyl methacrylate; polystyrene, acrylonitrile-styrene copolymers (AS Styrenic polymers such as resins; polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; vinyl chloride polymers; amide polymers such as nylon and aromatic polyamides; imide polymers; sulfone polymers; polyethers Sulfone-based polymers; polyetheretherketone-based polymers; polyphenylene sulfide-based polymers; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers; arylate-based polymers; polyoxymethylene-based polymers; and epoxy-based polymers.

Further, as a material for forming the transparent support, thermoplastic norbornene resin can be preferably used. Examples of such thermoplastic norbornene resins include Zeonex and Zeonor manufactured by Nippon Zeon Co., Ltd., and Arton manufactured by JSR Corporation.
Furthermore, as a material for forming the transparent support, a cellulose polymer represented by triacetyl cellulose (TAC) can also be preferably used.

In the present invention, the thickness of the transparent support is not particularly limited, and is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 10 to 80 μm.

[Alignment film]
The laminate of the present invention may have an alignment film between the transparent support and the light-absorbing anisotropic film.
Examples of methods for forming an alignment film include rubbing an organic compound (preferably a polymer) on the film surface, oblique vapor deposition of an inorganic compound, forming a layer having microgrooves, and the Langmuir-Blodgett method (LB film). ) of organic compounds (eg, ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearate, etc.). Further, alignment films are also known that exhibit an alignment function by applying an electric field, a magnetic field, or irradiation with light.
Among these, in the present invention, an alignment film formed by rubbing treatment is preferred from the viewpoint of ease of controlling the pretilt angle of the alignment film, and a photo-alignment film formed by light irradiation is also preferred from the viewpoint of alignment uniformity.

<Rubbing alignment film>
Polymer materials used for the alignment film formed by rubbing are described in many documents, and many commercially available products are available. In the present invention, polyvinyl alcohol, polyimide, and derivatives thereof are preferably used. Regarding the alignment film, reference can be made to the descriptions from page 43, line 24 to page 49, line 8 of International Publication No. WO 01/88574A1. The thickness of the alignment film is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm.

<Photo alignment film>
Photoalignment compounds used in alignment films formed by light irradiation are described in numerous documents. In the present invention, for example, JP-A No. 2006-285197, JP-A No. 2007-76839, JP-A No. 2007-138138, JP-A No. 2007-94071, JP-A No. 2007-121721, JP-A No. 2007 Azo compounds described in -140465, JP 2007-156439, JP 2007-133184, JP 2009-109831, Patent No. 3883848, and Patent No. 4151746, JP 2002-229039 Aromatic ester compounds described in JP-A No. 2002-265541, maleimide and/or alkenyl-substituted nadimide compounds having photo-alignable units described in JP-A No. 2002-317013, Patent No. 4205195, Patent No. 4205198 Preferable examples include photocrosslinkable silane derivatives described in Japanese Patent Publication No. 2003-520878, Japanese Patent No. 2004-529220, and photocrosslinkable polyimides, polyamides, or esters described in Japanese Patent No. 4162850. More preferred are azo compounds, photocrosslinkable polyimides, polyamides, or esters.

Among these, it is preferable to use a photosensitive compound having a photoreactive group that undergoes at least one of dimerization and isomerization due to the action of light as the photoalignment compound.
Further, the photoreactive group has a skeleton of at least one derivative or compound selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, azobenzene compounds, polyimide compounds, stilbene compounds, and spiropyran compounds. It is preferable.

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

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

As a means of obtaining linearly polarized light, there are methods using polarizing plates (e.g., iodine polarizing plate, dichroic dye polarizing plate, and wire grid polarizing plate), prism-based elements (e.g., Glan-Thompson prism), or using Brewster's angle. A method using a reflective polarizer, or a method using light emitted from a laser light source having polarized light can be adopted. Alternatively, only light of a required wavelength may be selectively irradiated using a filter, a wavelength conversion element, or the like.

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

If patterning is necessary, a method of applying light irradiation using a photomask as many times as required for pattern production, or a method of writing a pattern by laser beam scanning can be adopted.

[Adhesive layer]
The laminate of the present invention is advantageous in that the above-mentioned transparent resin layer is laminated with another functional layer (for example, a λ/4 plate described later) on the side opposite to the light-absorbing anisotropic film side. An adhesive layer may be provided on the opposite side of the resin layer to the light absorption anisotropic film side.
In addition, in this specification, the "adhesive layer" is a concept that includes the "adhesive layer." Here, "adhesion" is a type of adhesion, and means that even after a certain period of time has passed after it is pasted on an adherend, there is little change in the sticking force (adhesive force), and it can be peeled off if necessary. do. Moreover, "adhesion" is a concept that includes the above-mentioned "adhesion" and simply means that objects to be pasted are stuck together in a unified state.

The adhesive layer preferably contains an adhesive. Examples of adhesives include rubber adhesives, (meth)acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinylpyrrolidone adhesives, and polyvinyl pyrrolidone adhesives. Examples include acrylamide adhesives and cellulose adhesives.
Among these, acrylic adhesives (pressure-sensitive adhesives) are preferred from the viewpoints of transparency, weather resistance, heat resistance, and the like.

The adhesive layer may contain an antistatic agent. The antistatic agent diffuses into the light-absorbing anisotropic film and tends to cause a decrease in the degree of orientation of the dichroic substance when exposed to high temperatures or when subjected to moist heat. In order to solve such problems, if the laminate of the present invention having a transparent resin layer is used, the excellent orientation of the dichroic substance can be maintained even when exposed to high temperatures and after being subjected to moist heat. That is, when the laminate of the present invention has an adhesive layer containing an antistatic agent, the effects of the present invention are more effectively exhibited.
Examples of the antistatic agent include compounds having organic cations and compounds having inorganic cations. As the compound having an organic cation, for example, ionic compounds described in paragraphs [0067] to [0077] of PCT Publication No. 2011-504537 are preferably used. As the compound having an inorganic cation, for example, the metal salts described in paragraphs [0045] to [0046] of Japanese Patent Publication No. 2008-517137 are preferably used.
The content of the antistatic agent is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the total solid content of the adhesive layer.

The adhesive layer can be formed, for example, by applying an adhesive solution (adhesive composition) onto a release sheet, drying it, and then transferring it to the surface of the transparent resin layer; applying an adhesive solution to the surface of the transparent resin layer. It can be formed by direct coating and drying.
The adhesive solution (adhesive composition) is prepared, for example, as a solution of about 10 to 40% by mass by dissolving or dispersing the adhesive 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 methods, screen coating methods, fountain coating methods, dipping methods, spray methods, etc. can be adopted.
The adhesive composition may contain the above-mentioned antistatic agent, and may also contain other components (for example, a curing agent, a coupling agent, etc.).

In addition, as the constituent material of the release sheet, for example, a suitable thin film such as a synthetic resin film such as polyethylene, polypropylene, or polyethylene terephthalate; a rubber sheet; a paper; a cloth; a nonwoven fabric; a net; a foam sheet; a metal foil; Can be mentioned.

In the present invention, the thickness of any adhesive layer is not particularly limited, but is preferably 3 to 50 μm, more preferably 4 to 40 μm, and particularly preferably 5 to 30 μm.

[λ/4 plate]
The laminate of the present invention may have a λ/4 plate on the side opposite to the transparent resin layer side of the adhesive layer described above.
Here, the "λ/4 plate" is a plate that has a λ/4 function, specifically, the function of converting linearly polarized light of a certain wavelength into circularly polarized light (or from circularly polarized light to linearly polarized light). It is a board with
Specific examples of the λ/4 plate include, for example, US Patent Application Publication No. 2015/0277006.
For example, examples of embodiments in which the λ/4 plate has a single layer structure include a stretched polymer film, a retardation film in which an optically anisotropic layer having a λ/4 function is provided on a support, etc. Further, as an embodiment in which the λ/4 plate has a multilayer structure, a specific example is a broadband λ/4 plate formed by laminating a λ/4 plate and a λ/2 plate.

[Application]
The laminate of the present invention can be used as a polarizing element (polarizing plate), and specifically, can be used as, for example, a linearly polarizing plate or a circularly polarizing plate.
When the laminate of the present invention does not have an optically anisotropic layer such as the above-mentioned λ/4 plate, the laminate can be used as a linear polarizing plate. On the other hand, when the laminate of the present invention has the above-mentioned λ/4 plate, the laminate can be used as a circularly polarizing plate.

[Method for manufacturing laminate]
The method for manufacturing a laminate of the present invention is a method for manufacturing a laminate for producing the laminate of the present invention described above.
The method for producing a laminate of the present invention uses a composition containing a dichroic substance (specific dichroic substance) represented by the above-mentioned formula (1) on the above-mentioned transparent support. a light-absorbing anisotropic film forming step for forming a tropic film;
A transparent resin layer is formed on the light-absorbing anisotropic film using a curable composition containing the above-mentioned particles, the above-mentioned polymerizable compound, and at least one of the polymer obtained by polymerizing the above-mentioned polymerizable compound. and a transparent resin layer forming step.

[Light absorption anisotropic film formation process]
In the light absorption anisotropic film forming step, a light absorption anisotropic film is formed using a composition containing a dichroic substance (specific dichroic substance) represented by the above formula (1) on the above-mentioned transparent support. This is a process of forming a tropic film.
Here, the composition is preferably a liquid crystal composition as described in the light absorption anisotropic film included in the laminate of the present invention.
In addition, the method for forming the light-absorbing anisotropic film using the composition is the same method as described for the light-absorbing anisotropic film included in the laminate of the present invention, that is, the coating film forming step described above. and a forming method including an orientation step.

[Transparent resin layer formation process]
The transparent resin layer forming step is a step of forming a transparent resin layer included in the laminate of the present invention on the above-described light-absorbing anisotropic film using the above-mentioned curable composition.
Further, as a method for forming the transparent resin layer using the curable composition, the same method as that described for the transparent resin layer included in the laminate of the present invention can be mentioned.

[Image display device]
The image display device of the present invention includes the above-described laminate of the present invention, and a display element installed on the side of the transparent resin layer opposite to the light-absorbing anisotropic film side of the above-described laminate.
The display element used in the image display device of the present invention is not particularly limited, and includes, for example, a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as "EL") display panel, a plasma display panel, and the like.
Among these, a liquid crystal cell or an organic EL display panel is preferable, and a liquid crystal cell is more preferable. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, an organic EL display device using an organic EL display panel as a display element, and a liquid crystal display device is preferable. More preferred.

[Liquid crystal display device]
A liquid crystal display device that is an example of the image display device of the present invention is a liquid crystal display device that includes the above-described laminate of the present invention (however, it does not include a λ/4 plate) and a liquid crystal cell.
In addition, in the present invention, it is preferable to use the laminate of the present invention as a polarizing element on the front side among the laminates provided on both sides of the liquid crystal cell, and the laminate of the present invention is preferably used as the polarizing element on the front side and the rear side. It is more preferable to use
The liquid crystal cell constituting the liquid crystal display device will be described in detail below.

<Liquid crystal cell>
The liquid crystal cell used in the liquid crystal display device is preferably in VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, or TN (Twisted Nematic) mode. It is not limited to these.
In a TN mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are further twisted at an angle of 60 to 120 degrees. TN mode liquid crystal cells are most commonly used as color TFT (Thin Film Transistor) liquid crystal display devices, and are described in numerous documents.
In a VA mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied. VA mode liquid crystal cells include (1) narrowly defined VA mode liquid crystal cells in which rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when voltage is applied (Japanese Patent Application Laid-Open No. 2002-2002); In addition to (2) a multi-domain (MVA mode) liquid crystal cell (SID97, described in Digest of tech. Papers (Proceedings) 28 (1997) 845) in which the VA mode is multi-domained to expand the viewing angle. ), (3) Liquid crystal cell in a mode (n-ASM mode) in which rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied, and twisted and multi-domain aligned when a voltage is applied (Proceedings of the Japan Liquid Crystal Conference 58-59) (1998)) and (4) SURVIVAL mode liquid crystal cell (presented at LCD International 98). Further, it may be any of PVA (Patterned Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Sustained Alignment). Details of these modes are described in Japanese Patent Application Laid-open No. 2006-215326 and Japanese Patent Application Publication No. 2008-538819.
In an IPS mode liquid crystal cell, rod-shaped liquid crystal molecules are aligned substantially parallel to the substrate, and when an electric field parallel to the substrate surface is applied, the liquid crystal molecules respond in a planar manner. In the IPS mode, a black display occurs when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are perpendicular to each other. A method of using an optical compensatory sheet to reduce leakage light during black display in an oblique direction and improve the viewing angle is disclosed in JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522. JP-A-11-133408, JP-A-11-305217, JP-A-10-307291, and the like.

[Organic EL display device]
As an organic EL display device which is an example of an image display device of the present invention, for example, from the viewing side, the above-described laminate of the present invention (including a transparent support, an alignment film, an adhesive layer, and a λ/4 plate) and an organic EL display panel in this order. In this case, the laminate includes a transparent support, an alignment film, an anisotropic light absorption film, a transparent resin layer, an adhesive layer, and a λ/4 plate arranged in this order from the viewing side.
Furthermore, an organic EL display panel is a display panel constructed 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 structure of the organic EL display panel is not particularly limited, and a known structure may be employed.

The present invention will be explained in more detail below based on Examples. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the Examples shown below.

[Example 1]
<Preparation of transparent support 1>
An alignment film coating solution having the following composition was continuously applied onto a TAC substrate (TG40, manufactured by Fuji Film Corporation) having a thickness of 40 μm using a #8 wire bar. Thereafter, by drying with hot air at 100° C. for 2 minutes, a transparent support 1 in which a polyvinyl alcohol (PVA) alignment film with a thickness of 0.8 μm was formed on the TAC base material was obtained.
Note that the modified polyvinyl alcohol was added to the alignment film coating solution so that the solid content concentration was 4 wt%.
――――――――――――――――――――――――――――――
Composition of alignment film coating liquid――――――――――――――――――――――――――――
70 parts by mass of modified polyvinyl alcohol water as shown below 30 parts by mass of methanol ――――――――――――――――――――――――――――

Modified polyvinyl alcohol

<Formation of alignment film 1>
41.6 parts by mass of butoxyethanol, 41.6 parts by mass of dipropylene glycol monomethyl, and 15.8 parts by mass of pure water were added to 1 part by mass of photoalignment material E-1 having the following structure, and the resulting solution was Composition 1 for forming an alignment film was prepared by pressure filtration using a 0.45 μm membrane filter.
Next, the obtained alignment film forming composition 1 was applied onto the transparent support 1 and dried at 60° C. for 1 minute. Thereafter, the obtained coating film was irradiated with linearly polarized ultraviolet rays (illuminance 4.5 mW, irradiation amount 500 mJ/cm ² ) using a polarized ultraviolet exposure device, and alignment film 1 (Azo (E-1) ) was produced.

<Formation of light-absorbing anisotropic film 1>
On the obtained alignment film 1, the following liquid crystal composition 1 (abbreviated as "composition 1" in Table 1 below) was continuously applied with a #4 wire bar to form a coating film 1. .
Next, the coating film 1 was heated at 140° C. for 90 seconds, and the coating film 1 was cooled to room temperature (23° C.).
Then, it was heated at 80° C. for 60 seconds and cooled to room temperature again.
Thereafter, the light-absorbing anisotropic film 1 was produced on the alignment film 1 by irradiating the film with a high-pressure mercury lamp for 60 seconds at an illuminance of 28 mW/cm ² .
――――――――――――――――――――――――――――――――
Composition of liquid crystal composition 1――――――――――――――――――――――――――――――――
The following yellow azo dye Y-1 0.23 parts by mass The following magenta azo dye M-1 0.21 parts by mass The following cyan azo dye C-1 0.46 parts by mass The following polymer liquid crystal compound P-1 4.03 parts by mass Antioxidation Agent Irganox 1076 (manufactured by BASF) 0.034 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF) 0.043 parts by mass Surface modifier F-1 below 0.039 parts by mass Cyclopentanone 66.50 parts by mass Tetrahydrofuran 28.50 Mass part――――――――――――――――――――――――――――――――

Yellow azo dye Y-1

Magenta azo dye Y-1

Cyanazo dye C-1

Polymer liquid crystal compound P-1

Antioxidant Irganox1076

Interface modifier F-1

[Example 2, 3]
In forming the light-absorbing anisotropic film, the laminates of Examples 2 and 3 were prepared in the same manner as in Example 1, except that Liquid Crystal Composition 1 was changed to Liquid Crystal Compositions 2 and 3 shown below. Obtained.
――――――――――――――――――――――――――――――――
Composition of liquid crystal composition 2――――――――――――――――――――――――――――――――
The following yellow azo dye Y-1 0.13 parts by mass The following magenta azo dye M-2 0.21 parts by mass The following cyan azo dye C-2 0.56 parts by mass The following polymeric liquid crystal compound P-2 4.03 parts by mass Antioxidation Agent Irganox 1076 (manufactured by BASF) 0.034 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF) 0.043 parts by mass Surface modifier F-1 below 0.039 parts by mass Cyclopentanone 66.50 parts by mass Tetrahydrofuran 28.50 Mass part――――――――――――――――――――――――――――――――

Yellow azo dye Y-1

Magenta azo dye M-2

Cyanazo dye C-2

Polymer liquid crystal compound P-2

――――――――――――――――――――――――――――――――
Composition of liquid crystal composition 3――――――――――――――――――――――――――――――――
The following yellow azo dye Y-2 0.23 parts by mass The following magenta azo dye M-3 0.21 parts by mass The following cyan azo dye C-3 0.46 parts by mass The following polymeric liquid crystal compound P-2 4.03 parts by mass Antioxidation Agent Irganox 1076 (manufactured by BASF) 0.034 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF) 0.043 parts by mass Surface modifier F-1 below 0.039 parts by mass Cyclopentanone 66.50 parts by mass Tetrahydrofuran 28.50 Mass part――――――――――――――――――――――――――――――――

Yellow azo dye Y-2

Magenta azo dye M-3

Cyanazo dye C-3

[Examples 4 to 10]
In forming the light-absorbing anisotropic film, a liquid crystal composition was prepared in the same manner as in Example 2, except that the antioxidant Irganox 1076 was changed to various antioxidants and amounts shown in Table 1 below. Laminated bodies of Examples 4 to 10 were obtained in the same manner as in Example 2 except that the following methods were used.
The structures of various antioxidants used in forming the light-absorbing anisotropic films in Examples 4 to 10 are shown below.

ADEKA STAB LA-77 (manufactured by ADEKA)

Irgafos168 (manufactured by BASF)

SumilizerGM (manufactured by Sumitomo Chemical)

Compound A

[Synthesis of compound A]

Dibutylhydroxytoluene (BHT) (200 mg) was added to a solution of methanesulfonyl chloride (MsCl) (73.4 mmol, 5.7 mL) in tetrahydrofuran (THF) (70 mL), and the internal temperature was cooled to -5°C. A THF solution of 1,8-octanedicarboxylic acid (33.3 mmol, 6.75 g) and diisopropylethylamine (DIPEA) (75.6 mmol, 13.0 mL) was added dropwise thereto, taking care not to raise the internal temperature above 0°C. did. After stirring at -5°C for 30 minutes, N,N-dimethyl-4-aminopyridine (DMAP) (200 mg) was added, and diisopropylethylamine (75.6 mmol, 13.0 mL) and 4-hydroxy-2,2, A solution of 6,6-tetramethylpiperidine 1-oxyl free radical (60.6 mmol, 10.4 g) in tetrahydrofuran (THF) and dimethylacetamide (DMAc) was added dropwise so that the internal temperature did not rise above 0°C. Thereafter, the mixture was stirred at room temperature for 4 hours. After methanol (5 mL) was added to stop the reaction, water and ethyl acetate were added. The solvent was removed from the organic layer extracted with ethyl acetate using a rotary evaporator, and the organic layer was purified by column chromatography using ethyl acetate and hexane to obtain 10.2 g of compound A (yield: 60%) as a white solid. .

[Example 11]
<Synthesis of liquid crystalline compounds>
Lub et al. Recl. Trav. Chim. A liquid crystal compound (1-6) represented by the following formula (1-6) was synthesized by the method described in Pays-Bas, 115, 321-328 (1996).

Next, a liquid crystal compound (1-7) represented by the following formula (1-7) was synthesized with reference to the synthesis method of the compound (1-6) above.

<Preparation of liquid crystal composition 11>
Liquid crystal composition 11 (abbreviated as "composition 11" in Table 1 below) was prepared by mixing the following components and stirring at 80° C. for 1 hour.

――――――――――――――――――――――――――――――
Composition of liquid crystal composition 11――――――――――――――――――――――――――――――
Liquid crystal compound (1-6) 50 parts by mass Liquid crystal compound (1-7) 50 parts by mass Azo dye (G-205; manufactured by Hayashibara Biochemical Research Institute) 2.5 parts by mass Compound A 0.2 parts by mass Polymerization initiator Irgacure 369 (manufactured by BASF) 6 parts by mass Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.2 parts by mass Cyclopentanone 250 parts by mass ―――――――――――― ――――――――――――――――――――

A laminate of Example 10 was obtained in the same manner as in Example 1, except that Liquid Crystal Composition 1 was changed to Liquid Crystal Composition 11 and a light-absorbing anisotropic film was formed according to the following formation method. .

<Formation method>
Liquid crystal composition 2 was applied onto alignment film 1 by spin coating to a thickness of 0.7 μm. Thereafter, after heating and drying on a hot plate at 120°C for 3 minutes, it was quickly cooled to 70°C or lower, and then, using an ultraviolet irradiation device, it was irradiated with an exposure amount of 2400 mJ/cm ² (365 nm standard) to harden. Ta.

[Example 12]
On the light absorption anisotropic film of Example 7, the following transparent resin layer forming composition 1 was continuously applied using a #2 wire bar and dried at 40° C. for 90 seconds.
Thereafter, the resin composition was cured by irradiation using a high-pressure mercury lamp for 10 seconds at an illuminance of 30 mW/cm ² to produce a laminate in which the transparent resin layer A was formed on the light-absorbing anisotropic film.

――――――――――――――――――――――――――――――――
Composition A for forming transparent resin layer
――――――――――――――――――――――――――――――――
DPHA: 29 parts by mass of dipentaerythritol hexaacrylate Polymerization initiator IRGACURE819 (manufactured by BASF) 1 part by mass Ethanol 70 parts by mass ――――――――――

dipentaerythritol hexaacrylate

[Examples 13-14]
In forming the transparent resin layer, Examples 13 and 14 were prepared in the same manner as in Example 12, except that the transparent resin layer forming composition A was changed to the transparent resin layer forming compositions B and C shown below. A laminate was obtained.

――――――――――――――――――――――――――――――――
Composition B for forming transparent resin layer
――――――――――――――――――――――――――――――――
・The following CEL2021P (manufactured by Daicel) 144 parts by mass ・The following IRGACURE127 (manufactured by BASF) 3 parts by mass ・The following CPI-100P (propylene carbonate solution) 6 parts by mass ・Megafac RS-90 (manufactured by DIC) 0.3 parts by mass・Methyl ethyl ketone (MEK) 347 parts by mass――――――――――――――――――――――――――――――

CEL2021P

IRGACURE127

Photocationic polymerization initiator (CPI-100P)

――――――――――――――――――――――――――――――――
Composition C for forming transparent resin layer
――――――――――――――――――――――――――――――――
- 54 parts by mass of the above CEL2021P (manufactured by Daicel) - 3 parts by mass of IRGACURE127 (manufactured by BASF) - 3 parts by mass of the above CPI-100P (propylene carbonate solution) - Organosilica sol MEK-EC-2130Y (manufactured by Nissan Chemical)
300 parts by mass・Megafac RS-90 (manufactured by DIC) 7.5 parts by mass・Methyl ethyl ketone (MEK) 133 parts by mass―――――――――――――――――――――― ――――――――――

[Example 15]
<Formation of alignment film 2>
(Synthesis of polymer E-2)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 100.0 parts by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 500 parts by mass of methyl isobutyl ketone, and 10 parts by mass of triethylamine were added. 0 parts by mass was added, and the mixture was stirred at room temperature. Next, 100 parts by mass of deionized water was dropped into the resulting mixture from a dropping funnel over 30 minutes, and the mixture was reacted at 80° C. for 6 hours while being mixed under reflux. After the reaction was completed, the organic phase was taken out and washed with a 0.2% by mass ammonium nitrate aqueous solution until the water after washing became neutral. Thereafter, the solvent and water were distilled off from the obtained organic phase under reduced pressure to obtain a polyorganosiloxane having an epoxy group as a viscous transparent liquid.
When ¹ H-NMR (Nuclear Magnetic Resonance) analysis was performed on this polyorganosiloxane having an epoxy group, a peak based on the oxiranyl group was obtained at around chemical shift (δ) = 3.2 ppm with the theoretical intensity, indicating that the reaction It was confirmed that no side reactions of epoxy groups occurred in the epoxy resin. This polyorganosiloxane having epoxy groups had a weight average molecular weight Mw of 2,200 and an epoxy equivalent of 186 g/mol.
Next, in a 100 mL three-neck flask, 10.1 parts by mass of the polyorganosiloxane having an epoxy group obtained above and an acrylic group-containing carboxylic acid (Toagosei Co., Ltd., trade name "Aronix M-5300", acrylic acid ω- 0.5 parts by mass of carboxypolycaprolactone (degree of polymerization n≈2), 20 parts by mass of butyl acetate, 1.5 parts by mass of the cinnamic acid derivative obtained by the method of Synthesis Example 1 of JP 2015-26050A, and , and 0.3 parts by mass of tetrabutylammonium bromide were added, and the resulting mixture was stirred at 90° C. for 12 hours. After stirring, the mixture was diluted with butyl acetate in an amount equivalent (mass) to the obtained mixture, and the diluted mixture was further washed with water three times. The resulting mixture was concentrated and diluted with butyl acetate, which was repeated twice to finally obtain a solution containing a polyorganosiloxane having a photo-alignable group (polymer E-2 below). The weight average molecular weight Mw of this polymer E-2 was 9,000. Furthermore, as a result of ¹ H-NMR analysis, the component having a cinnamate group in Polymer E-2 was 23.7% by mass.

(Preparation of alignment film forming composition 2)
Composition 2 for forming an alignment film was prepared by mixing the following components.
――――――――――――――――――――――――――――――――
Composition of alignment film forming composition 2――――――――――――――――――――――――――――――
The above polymer E-2 10.67 parts by mass The following low molecular compound R-1 5.17 parts by mass The following additive (B-1) 0.53 parts by mass Butyl acetate 8287.37 parts by mass Propylene glycol monomethyl ether acetate
2071.85 parts by mass――――――――――――――――――――――――――――

Additive (B-1): TA-60B manufactured by Sun-Apro (see structural formula below)

Composition 2 for forming an alignment film was applied onto the TAC support by spin coating, and the support coated with Composition 2 for forming an alignment film was dried on a hot plate at 80° C. for 5 minutes to remove the solvent. A coating film was formed.
The obtained coating film was irradiated with polarized ultraviolet rays (25 mJ/cm ² , ultra-high pressure mercury lamp) to produce alignment film 2 (indicated as cinnamoyl (E-2) in Table 1 below).

A laminate of Example 15 was obtained in the same manner as in Example 1 except that alignment film 2 was used instead of alignment film 1.

[Example 16]
<Formation of alignment film 3>
Composition 3 for forming an alignment film was applied onto the dried PET support using a #4 bar, and the applied composition 3 for forming an alignment film was dried at 80°C for 15 minutes, and then heated at 250°C for 1 hour. A coating film was formed on the PET support.
The resulting coating film was irradiated with polarized ultraviolet light (1 J/cm ² , ultra-high pressure mercury lamp) once to produce an alignment film 3 (indicated as polyimide in Table 1 below) on the PET support.

――――――――――――――――――――――――――――――――
Composition of alignment film forming composition 3――――――――――――――――――――――――――――
Polyimide alignment film material (SE-130, manufactured by Nissan Chemical Co., Ltd.) 2.0 parts by mass N-methylpyrrolidone 98.0 parts by mass―――――――――――――――――――― ――――――――――――

A laminate of Example 16 was obtained in the same manner as in Example 1 except that alignment film 3 was used instead of alignment film 1.

[Comparative Examples 1 and 2]
The laminates of Comparative Examples 1 and 2 were produced in the same manner as in Example 1, except that Liquid Crystal Composition 1 was changed to Liquid Crystal Compositions 12 and 13 below, respectively.
――――――――――――――――――――――――――――――――
Composition of liquid crystal composition 12――――――――――――――――――――――――――――――
The above yellow azo dye Y-1 0.13 parts by mass The above magenta azo dye M-1 0.21 parts by mass The above cyan azo dye C-1 0.56 parts by mass The above polymeric liquid crystal compound P-1 4.03 parts by mass Start of polymerization Agent IRGACURE 819 (manufactured by BASF) 0.043 parts by mass Surface modifier F-1 below 0.039 parts by mass Cyclopentanone 66.50 parts by mass Tetrahydrofuran 28.50 parts by mass ―――――――――――― ――――――――――――――――――――

――――――――――――――――――――――――――――――――
Composition of liquid crystal composition 13――――――――――――――――――――――――――――――
Liquid crystal compound (1-6) 50 parts by mass Liquid crystal compound (1-7) 50 parts by mass Azo dye (G-205; manufactured by Hayashibara Biochemical Research Institute) 2.5 parts by mass Polymerization initiator Irgacure 369 (BASF ) 6 parts by mass Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.2 parts by mass Cyclopentanone 250 parts by mass ―――――――――――――――――― ――――――――――――――

<Orientation degree>
With a linear polarizer inserted into the light source side of an optical microscope (manufactured by Nikon Corporation, product name "ECLIPSE E600 POL"), the laminates of Examples and Comparative Examples were set on the sample stage, and a multichannel spectrometer (Ocean The absorbance of the laminate in the wavelength range of 400 to 700 nm was measured using a product manufactured by Optics (product name: "QE65000"), and the degree of orientation was calculated using the following formula. The results are shown in Table 1 below.
Orientation degree: S = [(Az0/Ay0)-1]/[(Az0/Ay0)+2]
Az0: Absorbance for polarized light in the absorption axis direction of the laminate Ay0: Absorbance for polarized light in the polarization axis direction of the laminate

<Light resistance>
With the adhesive layer and glass bonded to the surface of the transparent resin layer in the produced laminate, set it in a light resistance tester (manufactured by Suga Test Instruments Co., Ltd., trade name "Xenon Weather Meter X25"), and test the glass substrate. The light absorption anisotropic film side of the material was irradiated with light from a xenon lamp light source at 200,000 lux for 100 hours (equivalent to an integrated light amount of 20 million lux·h). The transmittance before and after this test was measured and evaluated according to the following criteria. The results are shown in Table 1 below.
7: Transmittance change is less than 0.2% 6: Transmittance change is 0.2% or more and less than 0.5% 5: Transmittance change is 0.5% or more and less than 1.0% 4: Transmittance change is 1 .0% or more and less than 1.5% 3: Transmittance change is 1.5% or more and less than 3.0% 2: Transmittance change is 3.0% or more and less than 5.0% 1: Transmittance change is 5.0% %that's all

In Table 1, "ratio to dye" means the molar ratio of antioxidant to the content (mol) of liquid crystal compound P-1 in the liquid crystal composition.

From the evaluation results in Table 1, it can be seen that the light-absorbing anisotropic film containing a dichroic substance and an antioxidant, and the laminate in which a transparent resin layer is adjacent to the light-absorbing anisotropic film contain a dichroic substance and an antioxidant. It was found that excellent orientation was maintained and light resistance was good in all cases.

[Example 28]
[Preparation of λ/4 retardation film 1]
<Preparation of composition for photo-alignment film>
A composition similar to the alignment film forming composition 2 used in forming the alignment film 2 used in Example 20 was prepared.

<Preparation of coating liquid for optically anisotropic layer>
An optically anisotropic layer coating liquid having the following composition was prepared.
――――――――――――――――――――――――――――――――
Coating liquid for optically anisotropic layer――――――――――――――――――――――――――――――――
The following liquid crystal compound L-3 42.00 parts by mass The following liquid crystal compound L-4 42.00 parts by mass The following polymerizable compound A-1 16.00 parts by mass The following low molecular compound B-2 6.00 parts by mass The following polymerization Initiator S-1 (oxime type) 0.50 parts by mass Leveling agent G-1 below 0.20 parts by mass Hysolve MTEM (manufactured by Toho Chemical Industries, Ltd.) 2.00 parts by mass NK Ester A-200 (Shin Nakamura Chemical Industries, Ltd.) ) 1.00 parts by mass Methyl ethyl ketone 424.8 parts by mass ――――――――――――――――――――――――――――――――
The group adjacent to the acryloyloxy group in the following liquid crystal compounds L-3 and L-4 represents a propylene group (a group in which a methyl group is substituted with an ethylene group), and in the following liquid crystal compounds L-3 and L-4, represents a mixture of positional isomers differing in the position of the methyl group.

[Preparation of cellulose acylate film 1]
(Preparation of core layer cellulose acylate dope)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution to be used as a core layer cellulose acylate dope.
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Core layer cellulose acylate dope──────────────────────────────────
Cellulose acetate with a degree of acetyl substitution of 2.88 100 parts by mass Polyester compound B described in the examples of JP-A-2015-227955 12 parts by mass The following compound F 2 parts by mass Methylene chloride (first solvent) 430 parts by mass Methanol ( Second solvent) 64 parts by mass ────────────────────────────────

Compound F

(Preparation of outer layer cellulose acylate dope)
10 parts by mass of the following matting agent solution was added to 90 parts by mass of the core layer cellulose acylate dope to prepare a cellulose acetate solution to be used as the outer layer cellulose acylate dope.
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Matting agent solution────────────────────────────────
Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass Methylene chloride (first solvent) 76 parts by mass Methanol (second solvent) 11 parts by mass The above core layer cellulose acylate dope 1 mass Department──────────────────────────────────

(Preparation of cellulose acylate film 1)
After filtering the core layer cellulose acylate dope and the outer layer cellulose acylate dope through a filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm, the core layer cellulose acylate dope and the outer layer cellulose acylate dope are placed on both sides. Three layers of the above were simultaneously cast from a casting port onto a drum at 20°C (band casting machine).
Next, the film was peeled off with a solvent content of approximately 20% by mass, and both ends of the film in the width direction were fixed with tenter clips, and the film was dried while being stretched in the transverse direction at a stretching ratio of 1.1 times.
Thereafter, the film was further dried by being conveyed between rolls of a heat treatment apparatus, thereby producing a cellulose acylate film 1 having a thickness of 40 μm. The in-plane retardation of the obtained cellulose acylate film 1 was 0 nm.

[Preparation of λ/4 retardation film 1]
Each of the photo-alignment film compositions prepared previously was applied to one side of the produced cellulose acylate film 1 using a bar coater.
After coating, the solvent was removed by drying on a hot plate at 120° C. for 1 minute to form a photoisomerizable composition layer with a thickness of 0.3 μm.
A photoalignment film was formed by irradiating the obtained photoisomerizable composition layer with polarized ultraviolet light (10 mJ/cm ² , using an ultra-high pressure mercury lamp).
Next, the optically anisotropic layer coating liquid prepared previously was applied onto the photo-alignment film using a bar coater to form a composition layer.
The formed composition layer was heated to 110°C on a hot plate, and then cooled to 60°C to stabilize the orientation.
Thereafter, the orientation was fixed at 60° C. by ultraviolet irradiation (500 mJ/cm ² , using an ultra-high pressure mercury lamp) under a nitrogen atmosphere (oxygen concentration 100 ppm) to form an optically anisotropic layer with a thickness of 2.3 μm. , λ/4 retardation film 1 was produced. The in-plane retardation of the obtained optical laminate was 140 nm.

[Preparation of positive C plate membrane 2]
As a temporary support, a commercially available triacetyl cellulose film "Z-TAC" (manufactured by Fuji Film Corporation) was used (this will be referred to as cellulose acylate film 2). After the cellulose acylate film 2 is passed through a dielectric heating roll at a temperature of 60°C and the film surface temperature is raised to 40°C, an alkaline solution having the composition shown below is coated on one side of the film using a bar coater. It was coated at 14 ml/m ² , heated to 110° C., and conveyed for 10 seconds under a steam-type far-infrared heater manufactured by Noritake Company Limited.
Next, 3 ml/m ² of pure water was applied using the same bar coater.
Next, after repeating water washing with a fountain coater and draining with an air knife three times, the film was transported to a drying zone at 70° C. for 10 seconds to dry, thereby producing a cellulose acylate film 2 subjected to alkali saponification treatment.
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Composition of alkaline solution (parts by mass)
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Potassium hydroxide 4.7 parts by mass Water 15.8 parts by mass Isopropanol 63.7 parts by mass Fluorine-containing surfactant SF-1
(C ₁₄ H ₂₉ O(CH ₂ CH _{2 O} ) ₂₀ H) 1.0 parts by mass Propylene glycol 14.8 parts by mass ────────────────────── ──────────

Using the cellulose acylate film 2 subjected to the alkali saponification treatment, a coating solution for forming an alignment film having the following composition was continuously applied using a #8 wire bar. It was dried with warm air at 60°C for 60 seconds and then with warm air at 100°C for 120 seconds to form an alignment film.
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Composition of coating liquid for forming alignment film────────────────────────────────
PVA (manufactured by Kuraray Co., Ltd., product name "Kuraray Poval PVA-103")
2.4 parts by mass Isopropyl alcohol 1.6 parts by mass Methanol 36 parts by mass Water 60 parts by mass ───

The following coating solution N was applied onto the cellulose acylate film 2 having the alignment film prepared above, and after aging at 60°C for 60 seconds, the air-cooled metal halide lamp (I-Graphics) of 70 mW/cm ² was placed in the air. The polymerizable rod-like liquid crystal compound was vertically aligned by irradiating it with 1000 mJ/cm ² of ultraviolet rays to fix the alignment state using a C-plate (manufactured by Co., Ltd.), thereby producing a positive C-plate film 1. Rth was −60 nm at a wavelength of 550 nm.

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Composition of coating liquid N for optically anisotropic layer────────────────────────────────
The following liquid crystal compound L-1 80 parts by mass The following liquid crystal compound L-2 20 parts by mass The following vertical liquid crystal compound additive (S01) 1 part by mass Ethylene oxide modified trimethylolpropane triacrylate (V#360, Osaka Organic Chemical Co., Ltd.) (manufactured by Nippon Kayaku 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 The following compound B03 0.4 parts by mass Methyl ethyl ketone 170 parts by mass Cyclohexanone 30 parts by mass ──────────────────────────────

<Preparation of circularly polarizing plate>
The positive C plate film 2 prepared above was transferred to the optically anisotropic layer side of the λ/4 retardation film 1 via an adhesive, and the cellulose acylate film 2 was removed. Further, the laminate produced in Example 1 was bonded to the cellulose acylate film 1 side of the λ/4 retardation film via an adhesive to obtain a circularly polarizing plate.

Disassemble the SAMSUNG GALAXY S5 equipped with an organic EL panel (organic EL display element), peel off the touch panel with circularly polarizing plate from the organic EL display device, peel off the circularly polarizing plate from the touch panel, and remove the organic EL display element and touch panel. and a circularly polarizing plate were isolated. Next, the isolated touch panel was bonded to the organic EL display element again, and the circularly polarizing plate produced above was bonded onto the touch panel with the positive C plate side facing the panel, to produce an organic EL display device.

The produced organic EL display device was evaluated in the same manner as when Pure Ace WR (manufactured by Teijin Ltd.) was used as the λ/4 plate. As a λ/4 plate, λ/4 retardation film 1 and It has been confirmed that similar effects can be obtained even when a laminate of positive C-plate films 2 is used.

10, 20 Optical laminate 12 Transparent support 14 Transparent resin layer 16 Photo alignment layer 18 Light absorption anisotropic layer

Claims (15)

A light-absorbing anisotropic film containing a dichroic substance having an azo group and at least one type of antioxidant,
The content of the antioxidant is 1 to 25 mol% with respect to the total molar mass of the dichroic substance,
The antioxidant has at least one of a hindered phenol, a hindered amine (excluding compounds having an N-oxyl structure), a thioether, and a phosphite compound,
At least one of the dichroic substances has a structure represented by the following formula (2),
A light-absorbing anisotropic film, wherein the content of the dichroic substance having the structure represented by the formula (2) is 5 to 25% by mass based on the total mass of the light-absorbing anisotropic film.

In the formula (2), A ⁴ represents a divalent aromatic group which may have a substituent.
In the formula (2), L ³ and L ⁴ each independently represent a substituent.
In the formula (2), E represents any one of a nitrogen atom, an oxygen atom, and a sulfur atom.
In the formula (2), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or an alkoxy group that may have a substituent.
In the formula (2), R ² represents a hydrogen atom or an alkyl group which may have a substituent.
In the formula (2), R ³ represents a hydrogen atom or a substituent.
In the formula (2), n represents 0 or 1. However, when E is a nitrogen atom, n is 1, and when E is an oxygen atom or a sulfur atom, n is 0. The light-absorbing anisotropic film according to claim 1, wherein in the formula (2), ^A4 is a phenylene group. The light absorption anisotropic film according to claim 1 or 2, wherein in the formula (2), at least one of ^L3 and ^L4 contains a crosslinkable group. The light-absorbing anisotropic film according to any one of claims 1 to 3, wherein in the formula (2), both L ³ and L ⁴ contain a crosslinkable group. The light absorption anisotropic film according to claim 3 or 4, wherein the crosslinkable group is an acryloyl group or a methacryloyl group. The light-absorbing anisotropic film according to any one of claims 1 to 5, wherein the light-absorbing anisotropic film further contains a liquid crystal compound. comprising the light absorption anisotropic film according to any one of claims 1 to 6 and a transparent resin layer,
A laminate in which the light-absorbing anisotropic film and the transparent resin layer are adjacent to each other. The laminate according to claim 7, wherein the transparent resin layer is a layer obtained using a curable composition containing at least one of a polymerizable compound and a polymer obtained by polymerizing the polymerizable compound. body. The laminate according to claim 7 or 8, wherein the transparent resin layer further contains particles. having a transparent support on the side opposite to the transparent resin layer provided adjacent to the light-absorbing anisotropic film, and having an alignment film between the transparent support and the light-absorbing anisotropic film; The laminate according to any one of claims 7 to 9. The alignment film is a photoalignment film formed using a composition containing a photoalignment compound,
The photoalignment compound is a photosensitive compound having a photoreactive group that undergoes at least one of dimerization and isomerization due to the action of light,
The photoreactive group has a skeleton of at least one derivative or compound selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, azobenzene compounds, polyimide compounds, stilbene compounds, and spiropyran compounds. The laminate according to claim 10. The laminate according to any one of claims 7 to 11, further comprising an adhesive layer on a side of the transparent resin layer opposite to the light-absorbing anisotropic film. The laminate according to claim 12, further comprising a λ/4 plate on a side of the adhesive layer opposite to the transparent resin layer side. A method for producing a laminate having a light-absorbing anisotropic film and a transparent resin layer, the method comprising:
A light-absorbing anisotropic film forming step of forming a light-absorbing anisotropic film using a dichroic substance having an azo group and a composition containing at least one type of antioxidant;
A transparent resin layer is formed on the light-absorbing anisotropic film using a curable composition containing at least one of a polymerizable compound and a polymer obtained by polymerizing the polymerizable compound. a forming step;
The content of the antioxidant is 1 to 25 mol% with respect to the total molar mass of the dichroic substance,
The antioxidant has at least one of a hindered phenol, a hindered amine (excluding compounds having an N-oxyl structure), a thioether, and a phosphite compound,
At least one of the dichroic substances has a structure represented by the following formula (2),
A method for producing a laminate, wherein the content of the dichroic substance having the structure represented by the formula (2) is 5 to 25% by mass based on the total mass of the light-absorbing anisotropic film.

In the formula (2), A ⁴ represents a divalent aromatic group which may have a substituent.
In the formula (2), L ³ and L ⁴ each independently represent a substituent.
In the formula (2), E represents any one of a nitrogen atom, an oxygen atom, and a sulfur atom.
In the formula (2), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or an alkoxy group that may have a substituent.
In the formula (2), R ² represents a hydrogen atom or an alkyl group which may have a substituent.
In the formula (2), R ³ represents a hydrogen atom or a substituent.
In the formula (2), n represents 0 or 1. However, when E is a nitrogen atom, n is 1, and when E is an oxygen atom or a sulfur atom, n is 0. An image display device comprising the laminate according to any one of claims 7 to 13, and a display element installed on the side of the transparent resin layer opposite to the light-absorbing anisotropic film side of the laminate. .