JP7022151B2 - Laminated body, manufacturing method of laminated body and image display device - Google Patents

Description

The present invention relates to a laminate, a method for manufacturing the laminate, and an image display device.

Conventionally, when an attenuation function, a polarization function, a scattering function, a light shielding function, etc. of irradiation light including laser light or natural light are required, a device that operates by a different principle for each function has been used. Therefore, products corresponding to the above functions are also manufactured by different manufacturing processes for each function.
For example, in a liquid crystal display (LCD), a linear polarizing plate or a circular polarizing plate is used to control the turning property and the double refractive index in the display. Further, in an organic light emitting diode (OLED), a circular polarizing plate is also used to prevent reflection of external light.

Iodine has been widely used as a dichroic substance in these polarizing plates (polarizing elements), but a polarizing element using an organic dye as a dichroic substance instead of iodine has also been studied.
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 Unexamined Patent Publication No. 2016-006502

The present inventors have examined the polarizing film described in Patent Document 1, and found that the polarizing film is excellent in the initial orientation of the azo dye (hereinafter, simply referred to as “orientation”). It was clarified that the high temperature durability and the wet heat durability are inferior depending on the layer structure of the containing laminate.

Therefore, it is an object of the present invention to provide a laminate which maintains excellent orientation of a dichroic substance and has good high temperature durability and wet heat durability, a method for producing the same, and an image display device using the same. And.

As a result of diligent studies to achieve the above problems, the present inventors have polymerized with particles together with a light absorption anisotropic film obtained by using a composition containing a dichroic substance having a predetermined structural formula. By providing a transparent resin layer obtained by using a curable composition containing at least one of a sex compound and a polymer obtained by polymerizing the above-mentioned polymerizable compound, excellent orientation of a dichroic substance can be obtained. The present invention has been completed by finding that the laminate has good high-temperature durability and high-wet-heat durability while maintaining the same.
That is, it was found that the above problem can be achieved by the following configuration.

[1]
A laminate having a light absorption anisotropic film and a transparent resin layer.
The light absorption anisotropic film is a film obtained by using a composition containing a dichroic substance represented by the formula (1) described later.
A laminate in which the transparent resin layer is a layer obtained by using a curable composition containing particles and at least one of a polymerizable compound and a polymer obtained by polymerizing the polymerizable compound.
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 the formula (1), m represents an integer of 1 to 4, and when m is an integer of 2 to 4, a plurality of A ^2s may be the same or different from each other.
[2]
The laminate according to [1], wherein the particles are inorganic particles.
[3]
The laminate according to [1] or [2], wherein the average particle diameter of the particles is 5 to 300 nm.
[4]
The laminate according to any one of [1] to [3], wherein the transparent resin layer has a refractive index of 1.5 to 2.0 at a wavelength of 550 nm.
[5]
The laminate according to any one of [1] to [4], wherein the particles are alumina hydrate particles.
[6]
The laminate according to any one of [1] to [5], wherein the average aspect ratio of the particles is 2 or more.
[7]
The laminate according to any one of [1] to [6], wherein the composition further contains a liquid crystal compound.
[8]
It has a transparent support on the side opposite to the transparent resin layer of the light absorption anisotropic film.
The laminate according to any one of [1] to [7], which has an alignment film between the transparent support and the light absorption anisotropic film.
[9]
The alignment film is a photoalignment film formed by using a composition containing a photoalignment compound.
The photo-alignment compound is a photosensitive compound having a photoreactive group in which at least one of dimerization and isomerization is generated by the action of light.
The photoreactive group has a skeleton of at least one derivative or compound selected from the group consisting of a cinnamon acid derivative, a coumarin derivative, a chalcone derivative, a maleimide derivative, an azobenzene compound, a polyimide compound, a stilbene compound and a spiropyran compound. The laminate according to [8].
[10]
The laminate according to any one of [1] to [9], wherein the dichroic substance has a structure represented by the formula (2) described later.
In formula ( ² ), A4 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 atom of nitrogen atom, oxygen atom and sulfur atom.
In the formula (2), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.
In formula (2), R ² represents an alkyl group which may have a hydrogen atom or a substituent.
In formula (2), R ³ represents a hydrogen atom or a substituent.
In equation (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.
[11]
The laminate according to [10], wherein A4 is a phenylene group in the formula ( ² ).
[12]
The laminate according to [10] or [11], wherein at least one of L ³ and L ⁴ contains a crosslinkable group in the formula (2).
[13]
The laminate according to any one of [10] to [12], wherein both L ³ and L ⁴ contain a crosslinkable group in the formula (2).
[14]
The laminate according to [12] or [13], wherein the crosslinkable group is an acryloyl group or a methacryloyl group.
[15]
The laminate according to any one of [1] to [14], further comprising an adhesive layer on the side of the transparent resin layer opposite to the light absorption anisotropic film side.
[16]
The laminate according to [15], wherein the adhesive layer contains an antistatic agent.
[17]
Further, the laminate according to [15] or [16], which has a λ / 4 plate on the side of the adhesive layer opposite to the transparent resin layer side.
[18]
A method for manufacturing a laminate having a light absorption anisotropic film and a transparent resin layer.
A light absorption anisotropic film forming step of forming a light absorption anisotropic film using a composition containing a dichroic substance represented by the formula (1) described later.
A transparent resin layer is formed on the light absorption anisotropic film by using a curable composition containing particles and at least one of a polymerizable compound and a polymer obtained by polymerizing the polymerizable compound. A method for producing a laminate, which comprises a transparent resin layer forming step.
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 the formula (1), m represents an integer of 1 to 4, and when m is an integer of 2 to 4, a plurality of A ^2s may be the same or different from each other.
[19]
An image display device comprising the laminate according to any one of [1] to [17] and a display element installed on the side opposite to the light absorption anisotropic film side of the transparent resin layer in the laminate. ..

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a laminated body which maintains excellent orientation of a dichroic substance and has good high temperature durability and wet heat durability, a method for producing the same, and an image display device using the same.

FIG. 1 is a schematic cross-sectional view showing an example of the laminated body of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the laminated body of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of a laminated body of a comparative example. FIG. 4 is a schematic cross-sectional view showing an example of a laminated body of a comparative example.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, "(meth) acrylic" means a general term for "acrylic" and "methacrylic", and "(meth) acrylate" means a general term for acrylate and methacrylate.

[Laminate]
The laminate of the present invention is a laminate having a light absorption anisotropic film and a transparent resin layer.
Further, the light absorption anisotropic film possessed by the laminate of the present invention is a film obtained by using a composition containing a dichroic substance represented by the formula (1) described later.
Further, the transparent resin layer contained in the laminate of the present invention was obtained by using a curable composition containing particles and at least one of a polymerizable compound and a polymer obtained by polymerizing the above-mentioned polymerizable compound. It is a layer.
Here, "transparent" in the present invention means 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, a polymer obtained by polymerizing a polymerizable compound and the above-mentioned polymerizable compound together with a light absorption anisotropic film containing a dichroic substance represented by the formula (1) described later. By providing the transparent resin layer obtained by using the curable composition containing at least one of them, the excellent orientation of the dichroic substance is maintained, and both high temperature durability and wet heat durability are good. It becomes a laminated body.
The details of this reason have not been clarified yet, but the present inventors speculate that it is due to the following reasons.
First, the present inventors investigated the causes of inferior high-temperature durability and wet-heat durability of a conventionally known polarizing element (polarizing film) using an organic dye as a dichroic substance, and found that the polarizing element has other functions. It has been found that when an adhesive layer is formed on a polarizing element when a layer (for example, a retardation film or the like) is bonded, a problem of inferior high temperature durability and wet heat durability is remarkably generated.
Therefore, in the present invention, by providing a transparent resin layer obtained by using a curable composition containing at least one of a polymerizable compound and a polymer obtained by polymerizing the above-mentioned polymerizable compound, another It is considered that the transfer of the dichroic substance to the functional layer and the adhesive layer was suppressed, and as a result, the excellent orientation of the bicolor substance was maintained, and the high temperature durability and the wet heat durability were improved. In particular, the particles contained in the transparent resin layer are transferred to the other layer of the dichroic substance contained in the light absorption anisotropic film, and the components contained in the other layer are transferred to the light absorption anisotropic film. It is thought to effectively suppress the transition.
Furthermore, surprisingly, the present inventors have found that the use of a transparent resin layer containing particles can further suppress the reflection of light by the light absorption anisotropic film. That is, a part of the light incident on the display element from the light absorption anisotropic film side (visual recognition side) may be reflected at the interface between the light absorption anisotropic film and the adhesive layer. In response to this problem, when the transparent resin layer contains particles, the transparent resin layer functions as a refractive index adjusting layer between the light absorption anisotropic film and the adhesive layer, and the light in the light absorption anisotropic film functions. Reflection can be further suppressed.

1 and 2 show schematic cross-sectional views showing an example of the laminated body of the present invention.
Here, the laminated body 10 shown in FIG. 1 has a layer structure having a transparent support 12, an alignment film 14, a light absorption anisotropic film 16 and a transparent resin layer 18 in this order (hereinafter, also abbreviated as “Structure 1”). It is a laminated body of.
Further, the laminated body 20 shown in FIG. 2 has a layer structure 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 (hereinafter, also referred to as “configuration 2”). It is a laminated body of (abbreviated).
In the examples of FIGS. 1 and 2, the laminate of the present invention shows an embodiment having a transparent support and an alignment film, but the laminate of the present invention is not limited to this, and the laminate of the present invention is a transparent support and an alignment film. You do not have to have at least one.
Further, the transparent resin layer may be formed directly on the light absorption anisotropic film, or another layer may be sandwiched between the transparent resin layer and the light absorption anisotropic film.
On the other hand, FIGS. 3 and 4 are schematic cross-sectional views showing an example of the laminated body of the comparative example.
Here, the laminate 30 shown in FIG. 3 is a laminate having a layer structure (hereinafter, also abbreviated as “Structure 3”) having a transparent support 12, an alignment film 14, and a light absorption anisotropic film 16 in this order. ..
Further, the laminated body 40 shown in FIG. 4 is a laminated layer having a transparent support 12, an alignment film 14, a light absorption anisotropic film 16 and an adhesive layer 19 in this order (hereinafter, also abbreviated as “configuration 4”). The body.

[Light absorption anisotropic film]
The light absorption anisotropic film of the laminate of the present invention uses a composition containing a dichroic substance represented by the following formula (1) (hereinafter, also abbreviated as “specific dichroic substance”). The resulting membrane.
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 them. good.

Here, in the formula (1), A ¹ , A ² and A ³ each independently represent a divalent aromatic group which may have a substituent.
Further, in the formula (1), L ¹ and L ² each independently represent a substituent.
Further, in the equation (1), m represents an integer of 1 to 4, and when m is an integer of 2 to 4, a plurality of A ^2s may be the same or different from each other. In addition, 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 described.
Examples of the substituent include the substituent group G described in paragraphs [0237] to [0240] of JP-A-2011-237513, and among them, a halogen atom, an alkyl group, an alkoxy group, and an alkoxycarbonyl group. (For example, methoxycarbonyl, ethoxycarbonyl, etc.) or aryloxycarbonyl group (for example, phenoxycarbonyl, 4-methylphenoxycarbonyl, 4-methoxyphenylcarbonyl, etc.) are preferable, an alkyl group is more preferable, and the number of carbon atoms is 1 to 1. 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 an arylene group having 6 to 12 carbon atoms, and specific examples thereof include a phenylene group, a cumenylene group, a mesitylene group, a trilene group, and a xylylene group. Be done. Of these, a phenylene group is preferable.
Further, as the divalent aromatic heterocyclic group, a group derived from a monocyclic or bicyclic heterocyclic ring is preferable. Examples of the atom 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 atoms constituting a ring other than carbon, they may be the same or different. Specific examples of the aromatic heterocyclic group include pyridylene group (pyridine-diyl group), quinolylene group (quinoline-diyl group), isoquinolilen group (isoquinoline-diyl group), benzothiazyl-diyl group, and phthalimide-diyl group. , And a thienothiazole-diyl group (hereinafter, abbreviated as "thienotiazole group") and the like.
Among the above divalent aromatic groups, a divalent aromatic hydrocarbon group is preferable.

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. The specific example of the substituent of the divalent thienothiazole group is the same as the substituent in the above-mentioned "divalent aromatic group which may have a substituent", and the preferred embodiment is also the same.
Further, among A ¹ , A ² and A ³ , it is more preferable that A ² is 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, at least one of A ¹ and A ² is preferably a divalent aromatic hydrocarbon group which may have a substituent, preferably A ¹ and It is more preferable that both 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 described.
As the substituent, a group introduced to enhance solubility or nematic liquid crystal property, a group having electron donating or electron attracting property introduced to adjust the color tone as a dye, or an orientation-immobilized group is used. A group having a crosslinkable group (polymerizable group) to be introduced is preferable.
For example, the substituent is 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, and for example, a methyl group, an ethyl group, or an isopropyl group. Group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like), alkenyl group (preferably 2 to 20 carbon atoms, etc.) It is more preferably an alkenyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, a 3-pentenyl group and the like), and 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, and examples thereof include a propargyl group and a 3-pentynyl group), aryl. A 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, for example, a phenyl group, a 2,6-diethylphenyl group, 3,5- Ditrifluoromethylphenyl group, styryl group, naphthyl group, biphenyl group and the like, substituted or unsubstituted amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 10 carbon atoms). It is an amino group having 0 to 6 carbon atoms, and examples thereof include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, an anirino group and the like), an alkoxy group (preferably 1 to 20 carbon atoms, etc.). It is more preferably 1 to 15 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a butoxy group and the like, an oxycarbonyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, etc.). Particularly preferably, it is 2 to 10, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, etc.), an acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, etc.). Particularly preferably 2 to 6, for example, an acetoxy group, a benzoyloxy group, an acryloyl group, a methacryloyl group and the like), an acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms). Particularly preferably, it has 2 to 6 carbon atoms, and examples thereof include an acetylamino group and a benzoylamino group) and an alkoxycarbonylamino group (preferably 2 carbon atoms). ~ 20, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, for example, a methoxycarbonylamino group and the like), and an aryloxycarbonylamino group (preferably 7 to 20 carbon atoms). It preferably has 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include a phenyloxycarbonylamino group and the like, and a sulfonylamino group (preferably 1 to 20 carbon atoms, more preferably 1 carbon atom). ~ 10, particularly preferably 1 to 6 carbon atoms, for example, a methanesulfonylamino group, a benzenesulfonylamino group, etc.), a sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 carbon atoms). It is -10, particularly preferably 0 to 6 carbon atoms, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, a phenylsulfamoyl group, etc.), a carbamoyl group (preferably carbon). The number is 1 to 20, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include an unsubstituted carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, and a phenylcarbamoyl group. ), Alkylthio group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include a methylthio group and an ethylthio group), an arylthio group. (Preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, a phenylthio group and the like), a sulfonyl group (preferably 1 to 20 carbon atoms, etc.) It is more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include a mesyl group and a tosyl group), a sulfinyl group (preferably 1 to 20 carbon atoms, and more preferably carbon atoms. The number is 1 to 10, particularly preferably 1 to 6, and examples thereof include a methanesulfinyl group and a benzenesulfinyl group), a ureido group (preferably 1 to 20, more preferably 1 carbon number). ~ 10, particularly preferably 1 to 6 carbon atoms, and examples thereof include an unsubstituted ureido group, a methyl ureido group, a phenyl ureido group, etc.), a phosphate amide group (preferably 1 to 20 carbon atoms, etc.). It is more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include a diethyl phosphate amide group and a phenyl phosphate amide group). , Hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom and the like. ), Cyano group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, azo group, heterocyclic group (preferably 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms heterocyclic group. , For example, a heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom, and a sulfur atom, for example, an epoxy group, an oxetanyl group, an imidazolyl group, a pyridyl group, a quinolyl group, a frill group, a piperidyl group, a morpholino group. , Benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like), silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms. It is a silyl group and includes, for example, a trimethylsilyl group, a triphenylsilyl group and the like).
These substituents may be further substituted with these substituents. Moreover, when it has two or more substituents, it may be the same or different. Further, if possible, they may be combined with each other to form a ring.

The substituents represented by L ¹ and L ² are preferably an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. An aryl group which may have a group, an alkoxy group which may have a substituent, an oxycarbonyl group which may have a substituent, an acyloxy group which may have a substituent, and a substituent. Acrylic amino 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, and a substituent. Sulfamoyl group which may have a group, carbamoyl group which may have a substituent, an alkylthio group which may have a substituent, a sulfonyl group which may have a substituent, and a substituent. It is 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, and more preferably, an alkyl group which may have a substituent. , An alkenyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an oxycarbonyl group which may have a substituent, It is 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.

At least one of L ¹ and L ² preferably contains a cross-linking group (polymerizable group), and it is more preferable that both L ¹ and L ² contain a cross-linking group.
Specific examples of the crosslinkable group include the polymerizable group described in paragraphs [0040] to [0050] of JP-A-2010-244038, and an acryloyl group from the viewpoint of reactivity and synthetic suitability. A methacryloyl group, an epoxy group, an oxetanyl group, or a styryl group is preferable, and an acryloyl group or a methacryloyl group is preferable.

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

In the present invention, the specific dichroic substance has a structure represented by the following formula (2) for the reason that the degree of orientation of the specific dichroic substance contained in the light absorption anisotropic film is further improved. It is preferable to have.

Here, in the formula ( ² ), A4 represents a divalent aromatic group which may have a substituent.
Further, in the formula (2), L ³ and L ⁴ each independently represent a substituent.
Further, in the formula (2), E represents any atom of a nitrogen atom, an oxygen atom and a sulfur atom.
Further, in the formula (2), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent.
Further, in the formula (2), R ² represents an alkyl group which may have a hydrogen atom or a substituent.
Further, in the formula (2), R ³ represents a hydrogen atom or a substituent.
Further, 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.

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

Specific examples and preferred embodiments of the "substituent" represented by L ³ and L ⁴ in the above formula (2) are the same as those of 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 cross-linking group, and in a more preferred embodiment both L ³ and L ⁴ contain a cross-linking group. That is. As a result, the degree of orientation of the specific dichroic substance contained in the light absorption anisotropic film is further improved, and the high temperature durability and the wet heat durability of the laminate are further improved.
Further, a preferred embodiment of the crosslinkable group of L ³ and L ⁴ is an acryloyl group or a methacryloyl group.

In the above formula (2), E represents any of a nitrogen atom, an oxygen atom and a sulfur atom, and is preferably a nitrogen atom from the viewpoint of synthetic aptitude.
Further, from the viewpoint that it becomes easy to make the specific dichroic substance having absorption on the short wavelength side (for example, one having a maximum absorption wavelength in the vicinity of 500 to 530 nm), E in the above formula (1). Is preferably an oxygen atom.
On the other hand, from the viewpoint that it becomes easy to make a specific dichroic substance having absorption on the long wavelength side (for example, a substance having a maximum absorption wavelength near 600 nm), E in the above formula (1) is It is preferably a nitrogen atom.

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

In the above formula (2), R ² represents an alkyl group which may have a hydrogen atom or a substituent, and is preferably an alkyl group which may have a substituent.
Specific examples and preferred embodiments of the "alkyl group which may have a substituent" represented by R ² are the same as those of the "alkyl group which may have a substituent" in R ¹ of the above-mentioned formula (2). Therefore, the description thereof will be omitted.
In addition, R ² becomes a group existing in the formula (2) when E is a nitrogen atom (that is, it means the case of n = 1). On the other hand, when E is an oxygen atom or a sulfur atom, R ² becomes a group which does not exist in the 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 R ³ are the same as the substituents in the above-mentioned "divalent aromatic group which may have a substituent", and the preferred embodiments are also the same. , The explanation is omitted.

In the above equation (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 examples of the specific dichroic substance represented by the above formula (1) include the compounds described in paragraphs [0051] to [0081] of JP-A-2010-152351, and the contents thereof include. 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-2010-152351. In addition to (D-53), the following compounds (D-54) to (D-58) are also preferably mentioned.

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 the total solid content of the composition.
In the present invention, the light absorption anisotropic film is liquid crystal together with the above-mentioned dichroic substance because the dichroic substance can be oriented with a higher degree of orientation while suppressing the precipitation of the dichroic substance. It is preferable that the film is formed by using a composition containing a sex compound (hereinafter, also referred to as “liquid crystal composition”).

<Liquid crystal compound>
As the liquid crystal compound contained in the liquid crystal composition, either a low-molecular-weight liquid crystal compound or a high-molecular-weight liquid crystal compound can be used.
Here, the "small molecule liquid crystal compound" means a liquid crystal compound having no repeating unit in the chemical structure.
Further, the "polymer liquid crystal compound" means a liquid crystal compound having a repeating unit in the chemical structure.
Examples of the small molecule liquid crystal compound include those described in JP-A-2013-228706.
Examples of the polymer liquid crystal compound include thermotropic liquid crystal polymers described in JP-A-2011-237513. Further, the polymer liquid crystal compound may have a crosslinkable group (for example, an acryloyl group and a methacryloyl group) at the terminal.

<Interface improver>
The liquid crystal composition preferably contains an interface improver. By including the interface improver, the smoothness of the coated surface is improved, the degree of orientation is improved, cissing and unevenness are suppressed, and the in-plane uniformity is expected to be improved.
As the interface improver, it is preferable to make the liquid crystal compound horizontal on the coated surface side, and the compound (horizontal alignment agent) described in paragraphs [0253] to [0293] of JP-A-2011-237513 can be used. can.
When the liquid crystal composition contains the interface improver, the content of the interface improver is 0.001 to 100 parts by mass with respect to a total of 100 parts by mass of the dichroic substance and the liquid crystal compound in the liquid crystal composition. 5 parts by mass is preferable, and 0.01 to 3 parts by mass is preferable.

<Initiator of polymerization>
The liquid crystal composition may contain a polymerization initiator.
The polymerization initiator is not particularly limited, but 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. 2,376,661 and 236,670), acidoin ethers (US Pat. No. 2,448,828), and α-hydrogen-substituted aromatic acyloins. Compounds (US Pat. No. 2722512), polynuclear quinone compounds (US Pat. Nos. 3,416127 and 2951758), combinations of triarylimidazole dimers and p-aminophenylketone (US Pat. No. 3,549,677). ), Aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667 and US Pat. No. 4,239,850), oxadiazole compounds (US Pat. No. 421,970), and acylphosphine oxide compounds (Japanese Patent Laid-Open No. 421,970). No. 63-40799, Japanese Patent Application Laid-Open No. 5-29234, Japanese Patent Application Laid-Open No. 10-95788, Japanese Patent Application Laid-Open No. 10-29997) and the like can be mentioned.
As such a photopolymerization initiator, commercially available products can also be used, and examples thereof 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 with respect to a total of 100 parts by mass of the dichroic substance and the liquid crystal compound in the liquid crystal composition. 0.01 to 30 parts by mass is preferable, and 0.1 to 15 parts by mass is preferable. When the content of the polymerization initiator is 0.01 parts by mass or more, the curability of the light absorption anisotropic film is good, and when it is 30 parts by mass or less, the orientation of the light absorption anisotropic film is good. It becomes.

<Solvent>
The liquid crystal composition preferably contains a solvent from the viewpoint of workability and the like.
Examples of the solvent include ketones (eg, acetone, 2-butanone, methylisobutylketone, cyclopentanone, cyclohexanone, etc.), ethers (eg, dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, hexane, etc.). ), Alicyclic hydrocarbons (eg, cyclohexane), aromatic hydrocarbons (eg, benzene, toluene, xylene, trimethylbenzene, etc.), carbon halides (eg, dichloromethane, trichloromethane, dichloroethane, dichlorobenzene, etc.) , Chlorotoluene, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (eg, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (eg, methyl cellosolve, ethyl cellosolve, etc.), 1, , 2-Dimethoxyethane, etc.), cellosolve acetates, sulfoxides (eg, dimethylsulfoxide, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.), and organic solvents such as heterocyclic compounds (eg, pyridine, etc.). , As well as water. The solvent for this may be used alone or in combination of two or more.
Of these solvents, it is preferable to use an organic solvent, 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, more preferably 85 to 95% by mass.

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

<Formation method>
The method for forming the light absorption anisotropic film using the above-mentioned liquid crystal composition is not particularly limited, and a step of applying the above-mentioned liquid crystal composition onto a transparent support described later to form a coating film (hereinafter, "" A method including a step of orienting a liquid crystal component contained in the coating film (hereinafter, also referred to as a “orientation step”) in this order can be mentioned.
The liquid crystal component is a component that includes not only the liquid crystal compound described above but also the dichroic substance having a liquid crystal property when the dichroic substance described above has a liquid crystal property.

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

(Orientation process)
The alignment step is a step of aligning the liquid crystal component contained in the coating film. As a result, a light absorption anisotropic film is obtained.
The alignment step may have a drying process. By the drying treatment, components such as a solvent can be removed from the coating film. The drying treatment may be carried out by a method of leaving the coating film at room temperature for a predetermined time (for example, natural drying), or by a method of heating and / or blowing air.
Here, the liquid crystal component contained in the liquid crystal composition may be oriented by the above-mentioned coating film forming step or drying treatment. For example, in an embodiment in which the liquid crystal composition is prepared as a coating liquid containing a solvent, the coating film has a light absorption anisotropy by drying the coating film and removing the solvent from the coating film (that is, light). 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 later 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 and the like. When the transition temperature is 10 ° C. or higher, a cooling treatment or the like for lowering the temperature to a temperature range exhibiting a liquid crystal phase is not required, which is preferable. Further, when the transition temperature is 250 ° C. or lower, a high temperature is not required even when the isotropic liquid state is once higher than the temperature range in which the liquid crystal phase is exhibited, which wastes heat energy and causes the substrate. It is preferable because it can reduce deformation and deterioration.

The orientation step preferably has a heat treatment. As a result, 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 the light absorption anisotropic film.
The heat treatment is preferably 10 to 250 ° C., more preferably 25 to 190 ° C. from the viewpoint of manufacturing aptitude and the like. The heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.

The alignment step may have a cooling treatment performed after the heat treatment. The cooling treatment is a treatment for cooling the coated film after heating 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 can be carried out by a known method.
By the above steps, a light absorption anisotropic film can be obtained.
In this embodiment, as a method for orienting the liquid crystal component contained in the coating film, a drying treatment, a heat treatment, and the like are mentioned, but the method is not limited to this, and a known orientation treatment can be used.

(Other processes)
The method for producing a light absorption anisotropic film may include a step of curing the light absorption anisotropic film (hereinafter, also referred to as “curing step”) after the alignment step.
The curing step is carried out, for example, by heating and / or light irradiation (exposure) when the light absorption anisotropic film has a crosslinkable group (polymerizable group). Among these, it is preferable that the curing step is carried out by light irradiation.
As the light source used for curing, various light sources such as infrared rays, visible light, and ultraviolet rays can be used, but ultraviolet rays are preferable. Further, the ultraviolet rays may be irradiated while being heated at the time of curing, or the ultraviolet rays may be irradiated through a filter that transmits only a specific wavelength.
When the exposure is carried out while heating, the heating temperature at the time of exposure is preferably 25 to 140 ° C., although it depends on the transition temperature of the liquid crystal component contained in the light absorption anisotropic film to the liquid crystal phase.
Further, the exposure may be performed in a nitrogen atmosphere. When the curing of the light absorption anisotropic film proceeds by radical polymerization, the inhibition of polymerization by oxygen is reduced, so that exposure in a nitrogen atmosphere is preferable.

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 the present specification, the average refractive index ( _nave ) of the light absorption anisotropic film is represented by the following formula (R1).
Equation (R1) n _ave = (n _x + n _y + n _z ) / 3
In the formula (R1), the direction in which the maximum refractive index in the plane is maximized is the x-axis, the direction orthogonal to it is the y-axis, and the normal direction with respect to the in-plane is the z-axis, and the refractive indexes are n _x and n _y , respectively. , _Nz . Each refractive index is measured using a Woollam spectroscopic ellipsometry M-2000U.

[Transparent resin layer]
The transparent resin layer of the laminate of the present invention is a layer obtained by using a curable composition containing particles and at least one of a polymerizable compound and a polymer obtained by polymerizing the above-mentioned polymerizable compound. be.
The transparent resin layer contains particles and contains the polymerizable compound itself, a polymer obtained by polymerizing the polymerizable compound (hereinafter, also simply referred to as “polymer”), or a polymerizable compound and a polymer. Including both.

<Particles>
Examples of the particles include organic particles, inorganic particles, and organic-inorganic composite particles containing organic components and inorganic components.
The 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 thereof. Examples thereof include resin particles containing the above.
Specific examples of the inorganic particles include alumina particles, alumina hydrate particles, silica particles, zirconia particles, and inorganic oxide particles such as clay minerals (for example, smectite and mica).
Examples of the 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 silica particles, alumina particles, alumina hydrate particles or mica particles, because they are excellent in high temperature durability and wet heat durability of the laminate. Further preferred, alumina hydrate particles are particularly preferred.
The particles may be used alone or in combination of two or more.

The alumina hydrate particles may be amorphous, but preferably have at least one crystal structure of boehmite and pseudoboehmite.
Here, boehmite is a crystal of alumina hydrate represented by Al ₂ O ₃ · nH ₂ O (n = 1 to 1.5). Further, the pseudo-boehmite means a colloidal aggregate of boehmite.

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

The particles may have any shape such as spherical, needle-shaped, fiber (fiber-shaped), columnar, and plate-shaped, but columnar particles are preferable because they are more excellent in high-temperature durability and wet-heat durability of the laminate.
The average aspect ratio of the particles is preferably 1 or more, more preferably 2 or more, and particularly preferably 5 or more, from the viewpoint of being superior in high temperature durability and wet heat durability of the laminate. The average aspect ratio of the particles is preferably 1000 or less, more preferably 800 or less.
The average aspect ratio of the particles is determined by measuring the major axis and minor axis of any 100 particles observed by TEM (transmission electron microscope) or SEM (scanning electron microscope). (Major axis / minor axis) is calculated, and 100 aspect ratios are calculated by arithmetically averaging. The major axis of the particle means the length in the major axis direction of the particle, and the minor axis of the particle means the length of the particle orthogonal to the major axis direction of the particle.

The particles may be added to the curable composition in the form of a colloidal solution dispersed in a solvent (at least one of water and an organic solvent).
Commercially available products can be used as the colloidal solution, for example, AS-200 and AS-520-A (all manufactured by Nissan Chemical Industries, Ltd.), 10A, 10D, 10C, F-3000, CSA-110AD, and the like. Alumina sol such as A2, F-1000, A2K5-10 (all manufactured by Kawaken Fine Chemical Industries, Ltd.), MEK-ST-40, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP, MIBK-ST , MIBK-ST-L, CHO-ST-M, EAC-ST, PMA-ST, TOR-ST (all manufactured by Nissan Chemical Industries, Ltd.) and the like.

The refractive index of the particles at a wavelength of 550 nm is preferably 1.5 to 2.5, more preferably 1.5 to 2.0, and particularly preferably 1.5 to 1.8. When the refractive index of the particles is in the above range, it becomes easy to obtain a transparent resin layer having a small difference in refractive index from the average refractive index of the light absorption anisotropic film. As a result, it is possible to suppress the reflection of light at the interface between the transparent resin layer and the light absorption anisotropic film, so that a display device having excellent display performance can be obtained.

The content of the particles is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, based on the total mass of the total solid content of the curable composition.
The content of the particles is preferably 1.25 to 100 parts by mass, preferably 1.25 to 100 parts by mass, based on the total amount (100 parts by mass) of the polymerizable compound and the polymer obtained by using the polymerizable compound in the curable composition. From the viewpoint of excellent transparency, 1.25 to 50 parts by mass is preferable, and from the viewpoint of excellent balance between high temperature durability and moist heat durability, 2.5 to 12.5 parts by mass is more preferable.

<Polymerizable compounds and polymers>
The polymerizable compound means a compound having a polymerizable group and capable of forming a polymer by polymerization.
Examples of the polymerizable compound include a monofunctional polymerizable compound containing one polymerizable group in one molecule, and a polyfunctional polymerizable compound containing two or more of the same or different polymerizable groups in one molecule. The polymerizable compound may be a monomer, a multimer such as an oligomer or a prepolymer, or a polymer.
Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, and a radically polymerizable group is preferable. Examples of the radically polymerizable group include an ethylenically unsaturated bond group. Examples of the cationically polymerizable group include an epoxy group and an oxetane group.
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, and an acryloyl group and a methacryloyl group are preferable.

Specific examples of the polymerizable compound include the compounds described in paragraphs 0051 to 0059 of JP-A-2016-150537 and the compounds described in paragraphs 0046-0072 of JP-A-2016-056341. ) Acrylate and (meth) acrylamide are preferred.

The polymerizable compound preferably has a hydrophilic group from the viewpoint of maintaining an excellent degree of orientation.
Here, the hydrophilic group is a monovalent or divalent group, for example, an amide group, a hydroxy group, a urethane group (urethane bond), a polyoxyalkylene group (for example, a polyoxyethylene group, a polyoxypropylene). Group, polyoxyalkylene group in which oxyethylene group and oxypropylene group are blocked or randomly bonded), amino group, carboxy group, alkali metal salt of carboxy group, alkoxy group, carbamoyl group, sulfonamide group, sulfamoyl group, sulfonic acid group , Alkali metal salts of sulfonic acid groups and the like.
The presence and identification of hydrophilic groups in the transparent resin layer is determined by total reflection infrared spectroscopy (for example, Nicolet iS5 FT-IR, manufactured by Thermo Fisher Scientific Co., Ltd.) using a Fourier transform infrared spectroscope. It can be detected by measuring with ATR-IR), using a diamond crystal for the prism, and measuring at 45 degree incident (single reflection).

Specific examples of the polymerizable compound having a hydrophilic group include hydrophilic monomers HM-1 to HM-11 represented by the following formulas.

As the polymerizable compound having a hydrophilic group, a commercially available product can be used, and examples thereof include KAYARAD PET-30 (a mixture of compounds having the following structure) manufactured by Nippon Kayaku Co., Ltd.

The polymer (polymer obtained by using a polymerizable compound) preferably has a hydrophilic group. Specific examples of the hydrophilic group are as described above.
As the polymer having a hydrophilic group, a commercially available product can be used. Be done.

The total content of the polymerizable compound and the 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.

<Initiator of polymerization>
The curable composition preferably contains a polymerization initiator.
Examples of the polymerization initiator include those similar to those described in the above-mentioned liquid crystal composition.

<UV absorber>
The curable composition may contain a UV absorber. By containing a UV absorber, not only moist heat durability but also light resistance can be improved. The UV absorber preferably has no absorption in the visible region. Various UV absorbers can be used, and for example, the benzophenone type, benzotriazole type, benzothiazole type or benzodithiol type described in JP-A-2009-236617 and JP-A-2010-59235 are preferably used.

When the curable composition contains a UV absorber, the polymerizable compound is preferably a polymer. By using a polymer, the influence of polymerization inhibition on the polymerizable compound can be suppressed.

<Solvent>
The curable composition preferably contains a solvent in addition to the hydrophilic monomer from the viewpoint of workability and the like.
Examples of the solvent include the same as those described in the above-mentioned liquid crystal composition.

<Formation method>
Examples of the method for forming the transparent resin layer include a method in which the above-mentioned curable composition is applied onto the above-mentioned light absorption anisotropic film, dried, and then immobilized by polymerization.
Here, the coating method is not particularly limited, and examples thereof include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a die coating method, a wire bar coating method, and a gravure coating method.
Here, the polymerization conditions are not particularly limited, but it is preferable to use ultraviolet rays in the polymerization by light irradiation. 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 , and even more preferably 30 mJ / cm ² to 3 J / cm ² . , 50-1000 mJ / cm ² is particularly preferable. Further, 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.

The average refractive index of the transparent resin layer at a wavelength of 550 nm is preferably 1.5 to 2.0, more preferably 1.55 to 1.70. If the average refractive index of the transparent resin layer is within the above range, it is possible to reduce the difference in refractive index from the average refractive index of the light absorption anisotropic film. As a result, it is possible to suppress the reflection of light at the interface between the transparent resin layer and the light absorption anisotropic film, so that a display device with excellent display performance can be obtained. The average refractive index of the transparent resin layer is the light absorption anisotropic film. It can be measured by the same method as the average refractive index of.

[Transparent support]
The laminate of the present invention may have a transparent support on the side opposite to the transparent resin layer of the light absorption anisotropic film.
Examples of the material for forming the transparent support include a polycarbonate polymer; a polyester polymer such as polyethylene terephthalate (PET) and polyethylene naphthalate; an acrylic polymer such as polymethylmethacrylate; and a polystyrene and an acrylonitrile-styrene copolymer (AS). Styrene-based polymers such as resin); polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamides; imide-based polymers; Sulphonic polymers; polyether ether ketone polymers; polyphenylene sulfide polymers; vinylidene chloride polymers; vinyl alcohol polymers; vinyl butyral polymers; allylate polymers; polyoxymethylene polymers; epoxy polymers; etc.

Further, as a material for forming the transparent support, a thermoplastic norbornene-based resin can be preferably used. Examples of such thermoplastic norbornene-based resins include Zeonex and Zeonoa manufactured by Zeon Corporation, and Arton manufactured by JSR Corporation.
Further, as a material for forming the transparent support, a cellulosic polymer typified 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 further preferably 10 to 80 μm.

[Alignment film]
The laminated body of the present invention may have an alignment film between the transparent support and the light absorption anisotropic film.
Examples of the method for forming the alignment film include rubbing treatment of an organic compound (preferably a polymer) on the film surface, oblique vapor deposition of an inorganic compound, formation of a layer having microgrooves, and a Langmuir-Blojet method (LB film). ) To accumulate organic compounds (eg, ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearylate, etc.). Further, an alignment film in which an alignment function is generated by applying an electric field, applying a magnetic field, or irradiating light is also known.
Among them, in the present invention, the alignment film formed by the rubbing treatment is preferable from the viewpoint of easy control of the pretilt angle of the alignment film, and the photo-alignment film formed by light irradiation is also preferable from the viewpoint of the uniformity of orientation.

<Rubbing treatment alignment film>
The polymer material used for the alignment film formed by the rubbing treatment has been described in a large number of documents, and a large number of commercially available products can be obtained. In the present invention, polyvinyl alcohol or polyimide and its derivatives are preferably used. For the alignment film, the description on page 43, lines 24 to 49, line 8 of International Publication WO01 / 88574A1 can be referred to. The thickness of the alignment film is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm.

<Photo-alignment film>
The photo-alignment compound used for the alignment film formed by light irradiation is described in many documents and the like. In the present invention, for example, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007-121721, JP-A-2007. Azo compounds described in JP-A-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, Patent No. 3883848, Patent No. 4151746, JP-A-2002-229039. Aromatic ester compounds described in JP-A, JP-A-2002-265541, Maleimide and / or alkenyl-substituted nadiimide compounds having photoorientation units described in JP-A-2002-317013, Japanese Patent No. 4205195, Japanese Patent No. 4205198. Preferred examples thereof include the photobridgeable silane derivative described in No. 2003-520878, JP-A-2004-522220, or the photocrosslinkable polyimide, polyamide or ester described in Japanese Patent No. 4162850. More preferably, it is an azo compound, a photocrosslinkable polyimide, a polyamide, or an ester.

Of these, as the photo-alignment compound, it is preferable to use a photosensitive compound having a photoreactive group in which at least one of dimerization and isomerization is generated by the action of light.
Further, the photoreactive group has a skeleton of at least one derivative or compound selected from the group consisting of a cinnamon acid derivative, a coumarin derivative, a chalcone derivative, a maleimide derivative, an azobenzene compound, a polyimide compound, a stilbene compound and a spiropyran compound. 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 the present specification, "linearly polarized irradiation" and "non-polarized irradiation" are operations for causing a photoreaction in a photoaligned 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 required 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.

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 [eg, semiconductor lasers, heliums]. Neon lasers, argon ion lasers, helium cadmium lasers and YAG (ittrium aluminum garnet) lasers], light emitting diodes, and cathode wire tubes can be mentioned.

As a means for obtaining linear polarization, a method using a polarizing plate (for example, an iodine polarizing plate, a two-color dye polarizing plate, and a wire grid polarizing plate), a prism element (for example, a Gran Thomson prism), or a Brewster angle is used. A method using a reflected-type polarizing element or a method using light emitted from a polarized laser light source can be adopted. Further, only light having a required wavelength may be selectively irradiated by using a filter, a wavelength conversion element, or the like.

In the case of linearly polarized light, a method of irradiating the light from the upper surface or the back surface of the alignment film perpendicularly or diagonally to the surface of the alignment film is adopted. The incident angle of light varies depending on the photoalignment material, but is preferably 0 to 90 ° (vertical), preferably 40 to 90 °.
In the case of non-polarization, the alignment film is irradiated with non-polarization from an angle. The incident angle is preferably 10 to 80 °, more preferably 20 to 60 °, still more preferably 30 to 50 °.
The irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.

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

[Adhesive layer]
The laminate of the present invention is transparent as described above from the viewpoint that another functional layer (for example, a λ / 4 plate described later) is bonded to the side opposite to the light absorption anisotropic film side of the transparent resin layer described above. An adhesive layer may be provided on the side of the resin layer opposite to the light absorption anisotropic film side.
In addition, in this specification, "adhesive layer" is a concept including "adhesive layer". Here, "adhesive" is a kind of adhesive, and means that the change in the adhesive force (adhesive force) is small even after a certain period of time has passed after the adhesive is attached, and the adhesive force can be peeled off as needed. do. Further, "adhesion" is a concept including the above-mentioned "adhesion", and simply means that the objects to be attached are attached to each other in an integrated state.

The adhesive layer preferably contains an adhesive. Examples of the adhesive include rubber adhesives, (meth) acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinylpyrrolidone adhesives, and poly. Examples thereof include acrylamide-based adhesives and cellulose-based adhesives.
Of these, an acrylic pressure-sensitive adhesive (pressure-sensitive pressure-sensitive adhesive) is preferable from the viewpoint of transparency, weather resistance, heat resistance, and the like.

The adhesive layer may contain an antistatic agent. The antistatic agent diffuses into the light absorption anisotropic film and tends to cause a decrease in the degree of orientation of the dichroic substance when exposed to high temperature and after the passage of moist heat. With respect to such a problem, 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 temperature and after the passage of moist heat. That is, when the laminate of the present invention has an adhesive layer containing an antistatic agent, the effect of the present invention is more exhibited.
Examples of the antistatic agent include a compound having an organic cation and a compound having an inorganic cation. As the compound having an organic cation, for example, the ionic compound described in paragraphs [0067] to [0077] of JP-A-2011-504537 is preferably used. As the compound having an inorganic cation, for example, the metal salt described in paragraphs [0045] to [0046] of JP-A-2008-517137 is 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 is, for example, a method in which a solution of an adhesive (adhesive composition) is applied on a release sheet, dried, and then transferred to the surface of the transparent resin layer; the solution of the adhesive is applied to the surface of the transparent resin layer. It can be formed by a method of directly applying and drying; etc.
The pressure-sensitive adhesive solution (adhesive composition) is prepared as a solution of about 10 to 40% by mass in which the pressure-sensitive adhesive is dissolved or dispersed in a solvent such as toluene or ethyl acetate.
As the coating method, a roll coating method such as reverse coating and gravure coating, a spin coating method, a screen coating method, a fountain coating method, a dipping method, a spray method and the like can be adopted.
The adhesive composition may contain the above-mentioned antistatic agent, or may contain other components (for example, a curing agent, a coupling agent, etc.).

As the constituent material of the release sheet, for example, a synthetic resin film such as polyethylene, polypropylene, polyethylene terephthalate; rubber sheet; paper; cloth; non-woven fabric; net; foam sheet; metal leaf; 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 having a λ / 4 function, and specifically, a function of converting linear polarization of a specific wavelength into circular polarization (or circular polarization into linear polarization). It is a plate having.
Specific examples of the λ / 4 plate include, for example, US Patent Application Publication No. 2015/0277006.
For example, examples of the embodiment in which the λ / 4 plate has a single-layer structure include a stretched polymer film and a retardation film in which an optically anisotropic layer having a λ / 4 function is provided on a support. Further, as an embodiment in which the λ / 4 plate has a multi-layer structure, specifically, a wide band λ / 4 plate formed by laminating a λ / 4 plate and a λ / 2 plate can be mentioned.

[Use]
The laminate of the present invention can be used as a polarizing element (polarizing plate), and specifically, for example, it can be used as a linear polarizing plate or a circular polarizing plate.
When the laminate of the present invention does not have an optically anisotropic layer such as the 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 circular polarizing plate.

[Manufacturing method of laminated body]
The method for producing the laminate of the present invention is the method for producing the laminate of the present invention described above.
In the method for producing a laminate of the present invention, a composition containing a dichroic substance (specific dichroic substance) represented by the above-mentioned formula (1) on the above-mentioned transparent support is used for different light absorption. The process of forming a light absorption anisotropic film that forms a square film,
A transparent resin layer using a curable composition containing the above-mentioned particles and at least one of the above-mentioned polymerizable compound and at least one of the polymers obtained by polymerizing the above-mentioned polymerizable compound on a light absorption anisotropic film. It has a transparent resin layer forming step of forming the above.

[Light absorption anisotropic film forming step]
In the light absorption anisotropic film forming step, a composition containing a dichroic substance (specific dichroic substance) represented by the above-mentioned formula (1) on the above-mentioned transparent support is used for different light absorption. This is the process of forming an anisotropic film.
Here, the composition is preferably the liquid crystal composition described in the light absorption anisotropic film of the laminate of the present invention.
Further, as a method for forming the light absorption anisotropic film using the composition, the same method as the forming method described for the light absorption anisotropic film possessed by the laminate of the present invention, that is, the above-mentioned coating film forming step. And a forming method having an orientation step.

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

[Image display device]
The image display device of the present invention has the above-mentioned laminate of the present invention and a display element installed on the side opposite to the light absorption anisotropic film side of the transparent resin layer in the above-mentioned laminate.
The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, and a plasma display panel.
Of 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 and an organic EL display device using an organic EL display panel as a display element, and the liquid crystal display device is preferable. More preferred.

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

<LCD cell>
The liquid crystal cell used in the liquid crystal display device is preferably a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. It is not limited to these.
In the liquid crystal cell in the TN mode, the rod-shaped liquid crystal molecules are substantially horizontally oriented when no voltage is applied, and are further twisted to 60 to 120 °. The TN mode liquid crystal cell is most often used as a color TFT (Thin Film Transistor) liquid crystal display device, and has been described in many documents.
In the VA mode liquid crystal cell, the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied. In the VA mode liquid crystal cell, (1) a VA mode liquid crystal cell in a narrow sense (1) in which rod-shaped liquid crystal molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. 2-). In addition to (described in Japanese Patent Publication No. 176625), (2) a liquid crystal cell (SID97, Digital of technique. Papers (Proceedings) 28 (1997) 845 in which the VA mode is multi-domainized for expanding the viewing angle). ), (3) Liquid crystal cells in a mode (n-ASM mode) in which rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted and multi-domain oriented when a voltage is applied. (1998)) and (4) SURVIVAL mode liquid crystal cells (announced at LCD International 98) are included. Further, it may be any of PVA (Patternized Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Stained Alignment). Details of these modes are described in Japanese Patent Application Laid-Open No. 2006-215326 and Japanese Patent Application Laid-Open No. 2008-538819.
In the IPS mode liquid crystal cell, the rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond in a plane by applying an electric field parallel to the substrate surface. In the IPS mode, the display is black when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other. Methods for reducing leakage light when displaying black in an oblique direction and improving the viewing angle by using an optical compensation sheet are described in JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522. It is disclosed in JP-A-11-133408, JP-A-11-305217, JP-A-10-307291, and the like.

[Organic EL display device]
The organic EL display device, which is an example of the image display device of the present invention, includes, for example, the above-mentioned laminate of the present invention (however, including a transparent support, an alignment film, an adhesive layer, and a λ / 4 plate) from the visual inspection side. , And an organic EL display panel in this order are preferable. In this case, the laminated body is arranged in the order of the transparent support, the alignment film, the light absorption anisotropic film, the transparent resin layer, the adhesive layer, and the λ / 4 plate from the visual recognition side.
Further, the organic EL display panel is a display panel configured by using an organic EL element formed by sandwiching an organic light emitting layer (organic electroluminescence layer) between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

[Example 1]
<Manufacturing of transparent support 1>
On a TAC substrate (TG40, manufactured by Fujifilm Corporation) having a thickness of 40 μm, an alignment film coating solution having the following composition was continuously applied with a # 8 wire bar. Then, by drying with warm air at 100 ° C. for 2 minutes, a transparent support 1 having a polyvinyl alcohol (PVA) alignment film having a thickness of 0.8 μm formed on the TAC substrate was obtained.
The modified polyvinyl alcohol was added to the alignment film coating liquid so that the solid content concentration was 4 wt%.
――――――――――――――――――――――――――――――――
Composition of alignment film coating liquid ――――――――――――――――――――――――――――――――
The following modified polyvinyl alcohol water 70 parts by mass 30 parts by mass of methanol ――――――――――――――――――――――――――――――――

Modified polyvinyl alcohol

<Formation of alignment film 1>
To 1 part by mass of the photoalignment material E-1 having the following structure, 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, and the obtained solution was added. The composition 1 for forming an alignment film was prepared by pressure filtration with a 0.45 μm membrane filter.
Next, the obtained composition for forming an alignment film 1 was applied onto the transparent support 1 and dried at 60 ° C. for 1 minute. Then, 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 the alignment film 1 (Azo (E-1 in Table 1 below). ) Was produced.

<Formation of light absorption anisotropic film 1>
The following liquid crystal composition 1 (abbreviated as "composition 1" in Table 1 below) was continuously applied onto the obtained alignment film 1 with a wire bar of # 4 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.).
It was then heated at 80 ° C. for 60 seconds and cooled again to room temperature.
Then, the light absorption anisotropic film 1 was produced on the alignment film 1 by irradiating with a high-pressure mercury lamp under an irradiation condition of an illuminance of 28 mW / cm ² for 60 seconds.
――――――――――――――――――――――――――――――――
Composition of Liquid Crystal Composition 1 ――――――――――――――――――――――――――――――――
The following yellow azo dye Y-1 7.1 parts by mass The following cyan azo dye D-55 9.1 parts by mass The following polymer liquid crystal compound P-1 101.1 parts by mass Polymerization initiator IRGACURE819 (manufactured by BASF) 1.0 mass Part The following surfactant F-1 0.3 parts by mass Cyclopentanone 617.0 parts by mass tetrahydrofuran 264.4 parts by mass ――――――――――――――――――――――― ―――――――――

Yellow azo dye Y-1

Cyanazo dye D-55

Polymer liquid crystal compound P-1

Interface improver F-1

<Formation of transparent resin layer 1>
The following curable composition 1 was continuously applied onto the light absorption anisotropic film 1 with a wire bar of # 2, and dried at 60 ° C. for 5 minutes.
Then, the curable composition 1 was cured by irradiating it with a high-pressure mercury lamp under an irradiation condition of an illuminance of 28 mW / cm ² for 60 seconds to form a laminate in which the transparent resin layer 1 was formed on the light absorption anisotropic film 1. Made. In this way, the laminated body of Example 1 was obtained.
When the cross section of the transparent resin layer 1 was cut using a microtome cutting machine and the film thickness was measured by observation with a scanning electron microscope (SEM), the film thickness was about 1.0 μm.
Further, the reaction rate of the polymerizable compound in the transparent resin layer 1 was calculated by the following formula (Re). As a result, the reaction rate of the polymerizable compound was 60%.
The following formula (Re) is a formula based on the consumption rate of photopolymerizable groups by light irradiation.
Reaction rate (%) = [1-{Peak area of carbon-carbon unsaturated double bond after light irradiation} / {Peak area of carbon-carbon unsaturated double bond before light irradiation}] x 100 formula (Re )
More specifically, using the NICOLET 6700 FT-IR (Fourier transform infrared spectrophotometer) of Thermo electron corporation, the pre-curable composition (excluding particles) is coated with a pre-cured coating. KBr-IR measurement is performed to determine the peak area (808 cm ^-1 ) of the polymerizable carbon-carbon unsaturated double bond. In addition, the cure rate is determined by determining the peak area of the polymerizable carbon-carbon unsaturated double bond from the KBr-IR measurement of one-time reflection after light irradiation and determining the rate of change in the peak area before and after light irradiation. calculate.

――――――――――――――――――――――――――――――――
Curable composition 1
――――――――――――――――――――――――――――――――
Polymerizable compound KAYARAD PET-30
(Manufactured by Nippon Kayaku Co., Ltd.) 29 parts by mass Polymerization initiator IRGACURE819 (manufactured by BASF) 1 part by mass Alumina ethanol sol A2K5-10
(Made by Kawaken Fine Chemicals, a colloidal liquid in which columnar alumina hydrate particles are dispersed in the liquid) 70 parts by mass ―――――――――――――――――――――――― ――――――――

KAYARAD PET-30 (A mixture of the following compounds. In Table 1 below, it is abbreviated as "PET-30").

[Example 2]
<Formation of adhesive layer A>
Acrylic resin solution (trade name "SK Dyne 2147", manufactured by Soken Chemical Co., Ltd.) 100 parts by mass, curing agent (trade name "TD-75", manufactured by Soken Chemical Co., Ltd.) 0.05 parts by mass, and coupling agent (product) Name "A-50", manufactured by Soken Chemical Co., Ltd.) 0.05 parts by mass was mixed to obtain an adhesive composition A.
The obtained resin solution was applied to a mold release sheet (a sheet in which one side of PET was subjected to a silicone mold release treatment) to a thickness of 170 μm, and dried at 90 ° C. for 3 minutes. Then, the adhesive layer A was prepared on one side of the glass by laminating it on one side of the glass (EagleXG, 0.3t) and further allowing it to stand in an environment of 25 ° C. and 60% RH for 3 days for aging.

The release sheet of the adhesive layer A was peeled off, and the adhesive layer A and the transparent resin layer 1 in the laminate prepared in Example 1 were bonded together. In this way, the laminated body of Example 2 was obtained.

[Example 3]
<Formation of adhesive layer B>
Adhesive composition B was prepared in the same manner except that 0.5 parts by mass of an antistatic agent (lithium bis (trifluorosulfonyl) imide, trade name "LiTFSI", manufactured by Wako Chemical Co., Ltd.) was mixed with the adhesive composition A. Prepared.
The laminated body of Example 3 in the same manner as in Example 2 except that the adhesive layer A formed by using the adhesive composition A was changed to the adhesive layer B formed by using the adhesive composition B. Got

The structure of the antistatic agent used above is shown below.

[Example 4]
Example 4 in the same manner as in Example 2 except that the curable composition 1 used for forming the transparent resin layer 1 was changed to the curable composition 2 having the following composition to form the transparent resin layer 2. Was obtained.
――――――――――――――――――――――――――――――――
Curable composition 2
――――――――――――――――――――――――――――――――
Polymerizable compound KAYARAD PET-30
(Manufactured by Nippon Kayaku Co., Ltd.) 29 parts by mass Polymerization initiator IRGACURE819 (manufactured by BASF) 1 part by mass Alumina ethanol sol 5SK5-10
(Made by Kawaken Fine Chemicals, a colloidal liquid in which plate-shaped alumina hydrate particles are dispersed in the liquid) 70 parts by mass ――――――――――――――――――――――― ―――――――――

[Example 5]
Example 5 in the same manner as in Example 2 except that the curable composition 1 used for forming the transparent resin layer 1 was changed to the curable composition 3 having the following composition to form the transparent resin layer 3. Was obtained.
――――――――――――――――――――――――――――――――
Curable composition 3
――――――――――――――――――――――――――――――――
Polymerizable compound KAYARAD PET-30
(Manufactured by Nippon Kayaku Co., Ltd.) 29 parts by mass Polymerization initiator IRGACURE819 (manufactured by BASF) 1 part by mass Lucentite STN
(Layered Viscosity Mineral (Smectite) manufactured by CO-OP CHEMICAL CO., LTD.) 7 parts by mass Ethanol 63 parts by mass ―――――――――――――――――――――――――――――― ――

[Example 6]
Example 6 in the same manner as in Example 2 except that the curable composition 1 used for forming the transparent resin layer 1 was changed to the curable composition 4 having the following composition to form the transparent resin layer 4. Was obtained.
――――――――――――――――――――――――――――――――
Curable composition 4
――――――――――――――――――――――――――――――――
Polymerizable compound KAYARAD PET-30
(Manufactured by Nippon Kayaku Co., Ltd.) 29 parts by mass Polymerization initiator IRGACURE819 (manufactured by BASF) 1 part by mass Organosilica sol MIBK-ST
(Manufactured by Nissan Chemical Industries, Ltd., a colloidal liquid in which substantially spherical silica particles are dispersed in the liquid)
23 parts by mass ethanol 47 parts by mass ――――――――――――――――――――――――――――――――

[Examples 7 to 10]
Examples of the formation of the transparent resin layer, except that a curable composition in which the mixing ratio (solid content ratio) of the alumina ethanol sol A2K5-10 and KAYARAD PET-30 was changed to the ratio shown in Table 1 below was used. In the same manner as in 2, the laminates of Examples 7 to 10 were obtained.

[Examples 11 to 13]
In the formation of the transparent resin layer, the laminates of Examples 11 to 13 were prepared in the same manner as in Example 2 except that the irradiation conditions were adjusted so that the reaction rate of the polymerizable compound was the reaction rate shown in Table 1 below. Obtained.

[Examples 14 to 19]
In the formation of the transparent resin layer, the same as in Example 2 except that the curable composition prepared in the same manner as in Example 1 was used except that KAYARAD PET-30 was changed to various polymerizable compounds shown in Table 1 below. By the method, the laminated body of Examples 14 to 19 was obtained.
The structures of the various polymerization initiators used to form the transparent resin layer in Examples 14 to 19 are shown below.
DPHA: Dipentaerythritol hexaacrylate A-DCP: Product name, manufactured by Shin Nakamura Chemical Industry Co., Ltd., tricyclodecanedimethanol diacrylate hydroxyethyl acrylate: See structure below Hydroxyethyl acrylamide: See structure below PEO (polyethylene oxide) Monomer: Below Structural reference KS-10: Manufactured by Sekisui Chemical Industry Co., Ltd., trade name "Eslek KS-10", polyvinyl butyral

[Example 20]
<Formation of alignment film 2>
(Synthesis of polymer E-2)
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 100.0 parts by mass of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 parts by mass of methylisobutylketone, and 10 parts of triethylamine. 9.0 parts by mass were charged and the mixture was stirred at room temperature. Next, 100 parts by mass of deionized water was added dropwise to the mixture obtained over 30 minutes from a dropping funnel, and then the mixture was reacted at 80 ° C. for 6 hours while mixing the mixture under reflux. After completion of the reaction, the organic phase was taken out, and the organic phase was washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral. Then, 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 oxylanyl group was obtained near chemical shift (δ) = 3.2 ppm according to the theoretical intensity, and the reaction was carried out. It was confirmed that no side reaction of the epoxy group occurred inside. The weight average molecular weight Mw of the polyorganosiloxane having an epoxy group was 2,200, and the epoxy equivalent was 186 g / mol.
Next, in a 100 mL three-necked flask, 10.1 parts by mass of the polyorganosiloxane having the epoxy group obtained above, an acrylic group-containing carboxylic acid (Toa Synthetic Co., Ltd., trade name "Aronix M-5300", acrylic acid ω- Carboxylic acid prolactone (polymerization degree n≈2)) 0.5 parts by mass, butyl acetate 20 parts by mass, 1.5 parts by mass of the lauric acid derivative obtained by the method of Synthesis Example 1 of JP-A-2015-26050, and , Tetrabutylammonium bromide 0.3 parts by mass was charged, and the obtained mixture was stirred at 90 ° C. for 12 hours. After stirring, the mixture was diluted with the same amount (mass) of butyl acetate as the obtained mixture, and the further diluted mixture was washed with water three times. The operation of concentrating the obtained mixture and diluting it with butyl acetate was repeated twice, and finally, a solution containing a polyorganosiloxane having a photo-oriented group (polymer E-2 below) was obtained. The weight average molecular weight Mw of this polymer E-2 was 9,000. Further, as a result of ^{1 1} H-NMR analysis, the component having a cinnamate group in the polymer E-2 was 23.7% by mass.

(Preparation of Composition 2 for Forming Alignment Film)
The following components were mixed to prepare a composition 2 for forming an alignment film.
――――――――――――――――――――――――――――――――
Composition of composition 2 for forming an alignment film ――――――――――――――――――――――――――――――――
Polymer E-2 10.67 parts by mass The following low molecular weight 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 San-Apro Co., Ltd. (hereinafter, refer to the structural formula).

The alignment film forming composition 2 is applied onto the PET support by a spin coating method, and the support coated with the alignment film forming composition 2 is dried on a hot plate at 80 ° C. for 5 minutes to remove the solvent. And formed a coating film.
The obtained coating film was irradiated with polarized ultraviolet rays (25 mJ / cm ² , ultrahigh pressure mercury lamp) to prepare an alignment film 2 (denoted as cinnamoyl (E-2) in Table 1 below).

The laminate of Example 20 was obtained by the same method as in Example 2 except that the alignment film 2 was used instead of the alignment film 1.

[Example 21]
A laminate of Example 21 was obtained in the same manner as in Example 20 except that the curable composition 1 was changed to the curable composition 5 in the formation of the light absorption anisotropic film.
――――――――――――――――――――――――――――――――
Curable composition 5
――――――――――――――――――――――――――――――――
PVA (manufactured by Kuraray, product name "Kuraray Poval PVA-103")
30 parts by mass alumina sol AS-200
(Made by Nissan Chemical Industries, Ltd., a colloidal liquid in which needle-shaped alumina hydrate particles are dispersed in the liquid) 70 parts by mass ―――――――――――――――――――――――― ――――――――

[Example 22]
A laminate of Example 22 was obtained in the same manner as in Example 20 except that the curable composition 1 was changed to the curable composition 6 in the formation of the light absorption anisotropic film.
――――――――――――――――――――――――――――――――
Curable composition 6
――――――――――――――――――――――――――――――――
PVA (manufactured by Kuraray, product name "Kuraray Poval PVA-103")
30 parts by mass alumina sol F-1000
(Made by Kawaken Fine Chemicals, a colloidal liquid in which fibrous alumina hydrate particles are dispersed in the liquid) 70 parts by mass ――――――――――――――――――――――― ―――――――――

[Example 23]
A laminate of Example 23 was obtained in the same manner as in Example 20 except that the curable composition 1 was changed to the curable composition 7 in the formation of the light absorption anisotropic film.
――――――――――――――――――――――――――――――――
Curable composition 7
――――――――――――――――――――――――――――――――
PVA (manufactured by Kuraray, product name "Kuraray Poval PVA-103")
30 parts by mass alumina sol F-3000
(Made by Kawaken Fine Chemicals, a colloidal liquid in which fibrous alumina hydrate particles are dispersed in the liquid) 70 parts by mass ――――――――――――――――――――――― ―――――――――

[Example 24]
<Formation of alignment film 3>
The alignment film forming composition 3 is applied onto the PET support after drying using the bar of # 4, the applied alignment film forming composition 3 is dried at 80 ° C. for 15 minutes, and then heated at 250 ° C. for 1 hour. Then, a coating film was formed on the PET support.
The obtained coating film was irradiated with polarized ultraviolet rays (1 J / cm ² , ultrahigh pressure mercury lamp) once to prepare an alignment film 3 (denoted as polyimide in Table 1 below) on a PET support.

――――――――――――――――――――――――――――――――
Composition of Composition 3 for Forming Alignment Film ――――――――――――――――――――――――――――――――
Polyimide alignment film material (SE-130, manufactured by Nissan Chemical Industries, Ltd.) 2.0 parts by mass N-methylpyrrolidone 98.0 parts by mass ―――――――――――――――――――――― ――――――――――

The laminate of Example 24 was obtained by the same method as in Example 2 except that the alignment film 3 was used instead of the alignment film 1.

[Example 25]
<Synthesis of liquid crystal compounds>
Lube et al. Recl. Trav. Chim. The 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).

Then, the liquid crystal compound (1-7) represented by the following formula (1-7) was synthesized with reference to the method for synthesizing the compound (1-6).

<Preparation of liquid crystal composition 2>
The liquid crystal composition 2 (abbreviated as "composition 2" in Table 1 below) was prepared by mixing the following components and stirring at 80 ° C. for 1 hour.

――――――――――――――――――――――――――――――――
Composition of Liquid Crystal Composition 2 ――――――――――――――――――――――――――――――――
Liquid crystal compound (1-6) 50 parts by mass Liquid crystal compound (1-7) 50 parts by mass Azo dye (NKX2029; manufactured by Hayashihara Biochemical Research Institute) 2.5 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 25 was obtained in the same manner as in Example 2 except that the liquid crystal composition 1 was changed to the liquid crystal composition 2 to form a light absorption anisotropic film according to the following forming method. ..

<Formation method>
The liquid crystal composition 2 was applied onto the alignment film 1 by a spin coating method so that the film thickness was 0.7 μm. Then, after heating and drying on a hot plate at 120 ° C. for 3 minutes, the mixture is quickly cooled to 70 ° C. or lower, and then irradiated with an exposure amount of 2400 mJ / cm ² (365 nm standard) using an ultraviolet irradiation device to cure. rice field.

[Example 26]
A laminate of Example 26 was obtained in the same manner as in Example 2 except that the liquid crystal composition 1 was changed to the liquid crystal composition 3 (abbreviated as “composition 3” in Table 1 below).

――――――――――――――――――――――――――――――――
Composition of Liquid Crystal Composition 3 ――――――――――――――――――――――――――――――――
The following cyanazo dye D-55 16.2 parts by mass The polymer liquid crystal compound P-1 101.1 parts by mass Polymerization initiator IRGACURE819 (manufactured by BASF) 1.0 part by mass The interface improver F-1 0.3 parts by mass Part cyclopentanone 617.0 parts by mass Tetrahydrofuran 264.4 parts by mass ――――――――――――――――――――――――――――――――

Cyanazo dye D-55

[Example 27]
A laminate of Example 27 was obtained in the same manner as in Example 2 except that the liquid crystal composition 1 was changed to the liquid crystal composition 4 (abbreviated as “composition 4” in Table 1 below).

――――――――――――――――――――――――――――――――
Composition of Liquid Crystal Composition 4 ――――――――――――――――――――――――――――――――
The following yellow azo dye Y-2 7.1 parts by mass The following cyan azo dye D-56 9.1 parts by mass The above polymer liquid crystal compound P-1 101.1 parts by mass Polymerization initiator IRGACURE819 (manufactured by BASF) 1.0 mass Part The above-mentioned surface improver F-1 0.3 parts by mass Cyclopentanone 617.0 parts by mass tetrahydrofuran 264.4 parts by mass ――――――――――――――――――――――― ―――――――――

Yellow azo dye Y-2

Cyanazo dye D-56

[Comparative Examples 1 to 3]
The laminates of Comparative Examples 1 to 3 were produced in the same manner as in Examples 1 to 3 except that the transparent resin layer was not provided.

[Comparative Examples 4 and 5]
The laminates of Comparative Examples 4 and 5 were prepared in the same manner as in Examples 1 and 2, respectively, except that the curable composition 1 was changed to the curable composition 6 below.
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Curable composition 6
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KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd.) 29 parts by mass Polymerization initiator IRGACURE819 (manufactured by BASF) 1 part by mass Ethanol 70 parts by mass ―――――――――――――――――――― ――――――――――――

<Degree of orientation>
With the linear spectrometer inserted on 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 a sample table, and a multi-channel spectroscope (Ocean) was set. The absorbance of the laminate in the wavelength range of 400 to 700 nm was measured using a product name “QE65000” manufactured by Optics, and the degree of orientation was calculated by the following formula. The results are shown in Table 1 below.
Degree of orientation: S = [(Az0 / Ay0) -1] / [(Az0 / Ay0) +2]
Az0: Absorbance for polarization in the absorption axis direction of the laminate Ay0: Absorbance for polarization in the polarization axis direction of the laminate

<High temperature durability>
A durability test was conducted at 80 ° C. (dry) for 500 hours with glass bonded to the surface of the adhesive layer in the produced laminate. The transmittance before and after this durability test was measured and evaluated according to the following criteria. For the laminated bodies of Example 1 and Comparative Example 4, the above test was carried out in a state where an adhesive layer was formed on the surface of the transparent resin layer and a glass plate was attached to the surface of the adhesive layer. Further, for the laminated body of Comparative Example 1, the above test was carried out in a state where an adhesive layer was formed on the surface of the light absorption anisotropic film and a glass plate was bonded to the surface of the adhesive layer. The results are shown in Table 1 below.
7: Transmittance change is less than 1% 6: Transmittance change is 1% or more and less than 2% 5: Transmittance change is 2% or more and less than 3% 4: Transmittance change is 3% or more and less than 5% 3: Transmittance change Is 5% or more and less than 10% 2: Transmittance change is 10% or more and less than 15% 1: Transmittance change is 15% or more

<Moist heat durability>
A durability test was conducted at 60 ° C., a relative humidity of 90%, and 500 hours with glass bonded to the surface of the adhesive layer in the produced laminate. The transmittance before and after this durability test was measured and evaluated according to the following criteria. For the laminated bodies of Example 1 and Comparative Example 4, the above test was carried out in a state where an adhesive layer was formed on the surface of the transparent resin layer and a glass plate was attached to the surface of the adhesive layer. Further, for the laminated body of Comparative Example 1, the above test was carried out in a state where an adhesive layer was formed on the surface of the light absorption anisotropic film and a glass plate was bonded to the surface of the adhesive layer. The results are shown in Table 1 below.
7: Transmittance change is less than 1% 6: Transmittance change is 1% or more and less than 2% 5: Transmittance change is 2% or more and less than 3% 4: Transmittance change is 3% or more and less than 5% 3: Transmittance change Is 5% or more and less than 10% 2: Transmittance change is 10% or more and less than 15% 1: Transmittance change is 15% or more

<Display performance evaluation>
In the laminated bodies of Examples 2 to 27, Comparative Examples 2 to 3 and Comparative Example 5 produced above, Pure Ace WR (manufactured by Teijin Limited), which is a λ / 4 plate, is bonded to a circular polarizing plate via an adhesive layer. Was produced.

The GALAXY S5 manufactured by SAMSUNG equipped with an organic EL panel (organic EL display element) is disassembled, the touch panel with a circular polarizing plate is peeled off from the organic EL display device, and the circular polarizing plate is further peeled off from the touch panel. And the circular plate plate were isolated respectively. Subsequently, the isolated touch panel was reattached to the organic EL display element, and the circular polarizing plate produced above was attached onto the touch panel so as not to allow air to enter, thereby producing an organic EL display device.

The organic EL display device produced was evaluated for visibility and display quality under bright light. The display device was set to white, and the reflected light was observed when the fluorescent lamp was projected from the front and the polar angle of 45 degrees. The display quality was evaluated according to the following criteria. The evaluation results are summarized in Table 1.
A: It is black and the coloring is not visible at all.
B: Slight coloring is visible.
C: Coloring is visible and the reflectance is high.

In Table 1, the "addition amount ratio" means the content of the polymerizable compound or the polymer with respect to the content of the particles in the curable composition.
Further, in Table 1, the methods for measuring the refractive index of the film, the refractive index of the particles, the particle diameter of the particles, and the average aspect ratio of the particles are as described above. The refractive index of the film means the in-plane refractive index of the light absorption anisotropic film.

From the evaluation results in Table 1, a polymer obtained by polymerizing particles with a polymerizable compound and the above-mentioned polymerizable compound together with a light absorption anisotropic film containing the dichroic substance represented by the above-mentioned formula (1). The laminate having the transparent resin layer obtained by using the curable composition containing at least one of them maintains the excellent orientation of the dichroic substance, and has good high temperature durability and wet heat durability. It turned out to be.

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

<Preparation of coating liquid for optically anisotropic layer>
A coating liquid for an optically anisotropic layer having the following composition was prepared.
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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 weight compound B-2 6.00 parts by mass The following polymerization Initiator S-1 (Oxim type) 0.50 parts by mass The following leveling agent G-1 0.20 parts by mass High solve MTEM (manufactured by Toho Chemical Industry Co., Ltd.) 2.00 parts by mass NK ester A-200 (New Nakamura Chemical Industry Co., Ltd.) 1.00 parts by mass Methyl ethyl ketone 424.8 parts by mass ――――――――――――――――――――――――――――――――
The group adjacent to the acryloyloxy group of the following liquid crystal compounds L-3 and L-4 represents a propylene group (a group in which a methyl group is replaced with an ethylene group), and the following liquid crystal compounds L-3 and L-4 are represented. Represents a mixture of positional isomers with different positions of methyl groups.

[Preparation of Cellulose Achillate 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.
───────────────────────────────
Core layer Cellulose acylate dope ───────────────────────────────
100 parts by mass of cellulose acetate having an acetyl substitution degree of 2.88 12 parts by mass of the polyester compound B described in Examples of JP-A-2015-227955, 2 parts by mass of the following compound F 2 parts by mass of methylene chloride (first solvent) 430 parts by mass of 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 above-mentioned core layer cellulose acylate dope to prepare a cellulose acetate solution to be used as the outer layer cellulose acylate dope.
───────────────────────────────
Matte solution ───────────────────────────────
Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass Methylene chloride (first solvent) 76 parts by mass Methanol (second solvent) 11 parts by mass 1 part by mass of the above core layer cellulose acylate dope Department ───────────────────────────────

(Preparation of Cellulose Achillate Film 1)
After filtering the core layer cellulose acylate dope and the outer layer cellulose acylate dope with a filter paper having an average pore diameter of 34 μm and a sintered metal filter having an average pore diameter of 10 μm, the core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides thereof. And three layers were simultaneously spread on a drum at 20 ° C. from the spreading port (band spreading machine).
Then, the film was peeled off with a solvent content of about 20% by mass, both ends of the film in the width direction were fixed with tenter clips, and the film was dried while being stretched laterally at a stretching ratio of 1.1 times.
Then, it was further dried by transporting it between the rolls of the heat treatment apparatus to prepare 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.

[Manufacturing of λ / 4 retardation film 1]
The composition for each photoalignment film prepared above was applied to one side of the prepared cellulose acylate film 1 with a bar coater.
After coating, it was dried on a hot plate at 120 ° C. for 1 minute to remove the solvent, and a photoisomerized composition layer having a thickness of 0.3 μm was formed.
The obtained photoisomerization composition layer was irradiated with polarized ultraviolet rays (10 mJ / cm ² , using an ultrahigh pressure mercury lamp) to form a photoalignment film.
Next, the coating solution for the optically anisotropic layer prepared above was applied onto the photoalignment film with a bar coater to form a composition layer.
The formed composition layer was once heated to 110 ° C. on a hot plate and then cooled to 60 ° C. to stabilize the orientation.
After that, the orientation was fixed by UV irradiation (500 mJ / cm ² , using an ultrahigh pressure mercury lamp) under a nitrogen atmosphere (oxygen concentration 100 ppm) at 60 ° C. 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 FUJIFILM Corporation) was used (this is referred to as cellulose acylate film 2). After passing the cellulose acylate film 2 through a dielectric heating roll having a temperature of 60 ° C. and raising the film surface temperature to 40 ° C., an alkaline solution having the composition shown below is applied to one side of the film using a bar coater. The film was applied at 14 ml / m ² , heated to 110 ° C., and conveyed under a steam-type far-infrared heater manufactured by Noritake Co., Ltd. Limited for 10 seconds.
Then, using the same bar coater, 3 ml / m ² of pure water was applied.
Then, after repeating washing with water 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 and dried to prepare a cellulose acylate film 2 subjected to alkali saponification treatment.
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Alkaline solution composition (parts by mass)
───────────────────────────────
Potassium hydroxide 4.7 parts by mass Water 15.8 parts by mass Isopropanol 63.7 parts by mass Fluorosurfactant SF-1
(C ₁₄ H ₂₉ O (CH ₂ CH _2O ) ₂₀ H) 1.0 part by mass Propylene glycol 14.8 parts by mass ────────────────────── ─────────

Using the above-mentioned alkali-saponified cellulose acylate film 2, the coating liquid for forming an alignment film having the following composition was continuously applied with a wire bar of # 8. It was dried with warm air at 60 ° C. for 60 seconds and further with warm air at 100 ° C. for 120 seconds to form an alignment film.
───────────────────────────────
Composition of coating liquid for forming alignment film ───────────────────────────────
PVA (manufactured by Kuraray, 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 liquid N is applied onto the cellulose acylate film 2 having the alignment film prepared above, and after aging at 60 ° C. for 60 seconds, an air-cooled metal halide lamp of 70 mW / cm ² (eye graphics (eye graphics). The polymerizable rod-shaped liquid crystal compound was vertically oriented by irradiating with ultraviolet rays of 1000 mJ / cm ² using (manufactured by Co., Ltd.) to fix the orientation state, and a positive C plate film 1 was prepared. Rth was -60 nm at a wavelength of 550 nm.

───────────────────────────────
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 distribution liquid crystal compound target (S01) 1 part by mass Ethylene oxide modified trimethyl propantriacrylate (V # 360, Osaka Organic Chemistry (V # 360, Osaka Organic Chemistry) (Manufactured by 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 ──── ────────────────────────────

<Manufacturing of circular 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 prepared in Example 1 was bonded to the cellulose acylate film 1 side of the λ / 4 retardation film via an adhesive to obtain a circular polarizing plate.

The GALAXY S5 manufactured by SAMSUNG equipped with an organic EL panel (organic EL display element) is disassembled, the touch panel with a circular polarizing plate is peeled off from the organic EL display device, and the circular polarizing plate is further peeled off from the touch panel. And the circular plate plate were isolated respectively. Next, the isolated touch panel was reattached to the organic EL display element, and the circular polarizing plate produced above was further attached to the touch panel so that the positive C plate side was on the panel side to prepare 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 Limited) was used as the λ / 4 plate, and the λ / 4 plate was the λ / 4 retardation film 1. It was confirmed that the same effect was exhibited even when the laminated body of the positive C plate film 2 was used.

10, 20, 30, 40 Laminated body 12 Transparent support 14 Alignment film 16 Light absorption anisotropic film 18 Transparent resin layer 19 Adhesive layer

Claims (16)

A laminate having a light absorption anisotropic film and a transparent resin layer.
The transparent resin layer is directly formed on the light absorption anisotropic film, and the transparent resin layer is formed directly on the light absorption anisotropic film.
The light absorption anisotropic film is a film obtained by using a composition containing a dichroic substance represented by the following formula (1).
The transparent resin layer is a layer obtained by using a curable composition containing particles and at least one of a polymerizable compound and a polymer obtained by polymerizing the polymerizable compound.
The particles are alumina hydrate particles, and the particles are
A laminate in which the average aspect ratio of the particles is 2 or more.

In the formula (1), A ¹ , A ² and A ³ each independently represent a divalent aromatic group which may have a substituent.
In the above formula (1), L ¹ and L ² each independently represent a substituent.
In the above equation (1), m represents an integer of 1 to 4, and when m is an integer of 2 to 4, a plurality of A ^2s may be the same or different from each other. The laminate according to claim 1 , wherein the average particle size of the particles is 5 to 300 nm. The laminate according to claim 1 or 2 , wherein the transparent resin layer has a refractive index of 1.5 to 2.0 at a wavelength of 550 nm. The laminate according to any one of claims 1 to 3 , wherein the composition further contains a liquid crystal compound. A transparent support is provided on the side of the light absorption anisotropic film opposite to the transparent resin layer.
The laminate according to any one of claims 1 to 4 , which has an alignment film between the transparent support and the light absorption anisotropic film. The alignment film is a photo-alignment film formed by using a composition containing a photo-alignment compound.
The photo-alignment compound is a photosensitive compound having a photoreactive group in which at least one of dimerization and isomerization is generated by the action of light.
The photoreactive group has a skeleton of at least one derivative or compound selected from the group consisting of a cinnamon acid derivative, a coumarin derivative, a chalcone derivative, a maleimide derivative, an azobenzene compound, a polyimide compound, a stilben compound and a spiropyran compound. The laminate according to claim 5 . The laminate according to any one of claims 1 to 6 , wherein the dichroic substance has a structure represented by the following formula (2).

In the formula ( ² ), A4 represents a divalent aromatic group which may have a substituent.
In the above formula (2), L ³ and L ⁴ each independently represent a substituent.
In the formula (2), E represents any atom of nitrogen atom, oxygen atom and sulfur atom.
In the formula (2), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.
In the formula (2), R ² represents an alkyl group which may have a hydrogen atom or 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 laminate according to claim 7 , wherein A4 is a phenylene group in the above formula ( ² ). The laminate according to claim 7 or 8 , wherein in the formula (2), at least one of L ³ and L ⁴ contains a crosslinkable group. The laminate according to any one of claims 6 to 9 , wherein both L ³ and L ⁴ contain a crosslinkable group in the above formula (2). The laminate according to claim 9 or 10 , wherein the crosslinkable group is an acryloyl group or a methacryloyl group. The laminate according to any one of claims 1 to 11 , further comprising an adhesive layer on the side of the transparent resin layer opposite to the light absorption anisotropic film side. The laminate according to claim 12 , wherein the adhesive layer contains an antistatic agent. The laminate according to claim 12 or 13 , further comprising a λ / 4 plate on the side of the adhesive layer opposite to the transparent resin layer side. The method for manufacturing a laminate according to any one of claims 1 to 14 .
A light absorption anisotropic film forming step of forming a light absorption anisotropic film using a composition containing a dichroic substance represented by the following formula (1).
A transparent resin layer is formed on the light absorption anisotropic film by using a curable composition containing particles and at least one of a polymerizable compound and a polymer obtained by polymerizing the polymerizable compound. A method for producing a laminate, which comprises a transparent resin layer forming step.

In the formula (1), A ¹ , A ² and A ³ each independently represent a divalent aromatic group which may have a substituent.
In the above formula (1), L ¹ and L ² each independently represent a substituent.
In the above equation (1), m represents an integer of 1 to 4, and when m is an integer of 2 to 4, a plurality of A ^2s may be the same or different from each other. An image display device comprising the laminate according to any one of claims 1 to 14 and a display element installed on the side opposite to the light absorption anisotropic film side of the transparent resin layer in the laminate. ..

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