JP7086210B2 - Laminates and image display devices - Google Patents

Description

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

In recent years, various studies have been conducted on a light absorption anisotropic layer formed by using a dichroic substance.
For example, Patent Document 1 states that "a circularly polarizing plate in which a liquid crystal cured film, an adhesive layer, a retardation film, and an adhesive layer are laminated in this order, and the liquid crystal cured film is described. A circularly polarizing plate having a thickness of 3 μm or less and being cured with the polymerizable liquid crystal compound oriented horizontally with respect to the surface of the substrate and containing a dichroic dye. ”Is disclosed. ([Claim 16]).

On the other hand, in recent years, there has been a demand for further thinning of display devices, and a mode has been proposed in which the support used for the above-mentioned circularly polarizing plate or the like is peeled off to make the display device thinner.
Then, in Patent Document 1, it is an object to provide an optically anisotropic sheet which gives a thin optically anisotropic film ([0004]).

Japanese Unexamined Patent Publication No. 2016-027431

However, when the layer structure is complicated due to the expression of various functions, it is very difficult to control at which interface the exfoliation occurs during transcription.
In particular, it was found that the control of the peeling interface is more difficult in the case of a laminated body in which each layer is very thin due to the reason that the stator and the like are thinned. For example, even if an attempt is made to peel off only the support from a laminate having a support, an alignment layer, and a light absorption anisotropic layer, peeling may occur at the interface between the alignment layer and the light absorption anisotropic layer. rice field.

Therefore, the present invention provides a laminated body having a support, an alignment layer, and a light absorption anisotropic layer, in which only the support can be easily peeled off, and an image display device using the same. That is the issue.

As a result of diligent studies to achieve the above problems, the present inventors have found that the peelability at other interfaces changes depending on the properties of the adhesive layer when the adhesive layer is bonded to other members.
That is, in a laminated body having a support, an alignment layer, a light absorption anisotropic layer and an adhesive layer in this order, and a thickness between the support and the adhesive layer not including the support and the adhesive layer is 5 μm or less. It has been found that by setting the thickness of the adhesive layer to a specific value, it is possible to provide a laminated body in which only the support can be easily peeled off.

That is, it was found that the above problem can be achieved by the following configuration.

[1] A support, an alignment layer, a light absorption anisotropic layer, and an adhesive layer are provided in this order.
The thickness between the support and the adhesive layer not including the support and the adhesive layer is 5 μm or less, and the thickness is 5 μm or less.
The thickness of the adhesive layer is 5 μm to 50 μm,
A laminated body in which the oriented layer is a photo-aligned layer formed by using a composition for forming an oriented layer containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond.
[2] The laminate according to [1], wherein the adhesive layer has a storage elastic modulus of 100 kPa to 20 MPa.
[3] The laminate according to [2], wherein the adhesive layer has a storage elastic modulus of 100 kPa to 2 MPa.
[4] The laminate according to any one of [1] to [3], wherein the thickness of the adhesive layer is more than 10 μm and 50 μm or less.
[5] The laminate according to any one of [1] to [4], wherein the light absorption anisotropic layer contains a dichroic substance and a liquid crystal compound.
[6] The laminate according to any one of [1] to [5], wherein the light absorption anisotropic layer contains a dichroic azo compound.
[7] The laminate according to any one of [1] to [6], wherein the thickness of the light absorption anisotropic layer is 0.1 μm to 3 μm.
[8] The laminate according to any one of [1] to [7], wherein the orientation layer has a thickness of 0.1 μm to 2 μm.
[9] The laminate according to [8], wherein the thickness of the oriented layer is more than 0.5 μm and 2 μm or less.
[10] The cinnamoyl compound has a repeating unit A containing a photo-oriented group represented by the formula (A) described later and a repeating unit B containing a crosslinkable group represented by the formula (B) described later. The laminate according to any one of [1] to [9], which is a photo-oriented copolymer.
[11] The laminate according to [10], wherein L ¹ in the formula (A) described later is a divalent linking group represented by any of the formulas (1) to (10) described later.
[12] The laminate according to [5], wherein the liquid crystal compound is a polymerizable liquid crystal compound.
[13] The laminate according to [5], wherein the liquid crystal compound is a polymer liquid crystal compound.
[14] The laminate according to [13], wherein the light absorption anisotropic layer further contains a low molecular weight liquid crystal compound.
[15] The laminate according to any one of [1] to [14], further having a cured layer having a thickness of 100 nm or less between the light absorption anisotropic layer and the adhesive layer.
[16] The laminate according to [15], wherein the cured layer contains a liquid crystal compound.
[17] The laminate according to [15], wherein the cured layer is a layer obtained by curing a composition containing a polyfunctional monomer.
[18] The laminate according to any one of [1] to [17], further comprising a layer containing a polyvinyl alcohol resin having a thickness of 2 μm or less between the light absorption anisotropic layer and the adhesive layer.
[19] The laminate according to any one of [1] to [18], wherein the support and the alignment layer are in contact with each other.
[20] The laminate according to any one of [1] to [19], wherein the oriented layer and the light absorption anisotropic layer are in contact with each other.
[21] A laminate having the laminate according to any one of [1] to [20] and a surface film, in which the adhesive layer and the surface film are in contact with each other.
[22] The laminate according to [21], wherein the support has been peeled off.
[23] The laminate according to [22], further comprising a retardation film and having the retardation film arranged on the alignment layer side.
[24] An image display device having the laminate according to any one of [1] to [23] and an image display element.

INDUSTRIAL APPLICABILITY According to the present invention, in a laminated body having a support, an alignment layer and a light absorption anisotropic layer, a laminate in which only the support can be easily peeled off, and an image display device using the same are provided. be able to.

It is a schematic sectional drawing which shows the example of the embodiment of the laminated body of this invention. It is a schematic sectional drawing which shows the example of the embodiment of the laminated body of this invention. It is a schematic sectional drawing which shows the example of the embodiment of the laminated body of this invention.

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, parallel and orthogonal do not mean parallel and orthogonal in a strict sense, but mean a range of ± 5 ° from parallel or orthogonal.

Further, in the present specification, as each component, a substance corresponding to each component may be used alone or in combination of two or more. Here, when two or more kinds of substances are used in combination for each component, the content of the component means the total content of the substances used in combination unless otherwise specified.
Further, in the present specification, "(meth) acrylate" is a notation representing "acrylate" or "methacrylate", and "(meth) acrylic" is a notation representing "acrylic" or "methacrylic". "(Meta) acrylic" is a notation representing "acryloyl" or "methacrylic acid".
Further, in the present specification, the liquid crystal composition and the liquid crystal compound include those which no longer exhibit liquid crystal property due to curing or the like as a concept.

[Laminate]
The laminate of the present invention is a laminate having a support, an alignment layer, a light absorption anisotropic layer, and an adhesive layer in this order.
Further, in the laminated body of the present invention, the thickness between the support and the adhesive layer not including the support and the adhesive layer is 5 μm or less, and the thickness of the adhesive layer is 5 μm to 50 μm.
Further, the laminate of the present invention is a photo-alignment layer formed by using a composition for forming an orientation layer, wherein the alignment layer contains a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond.
Next, the overall configuration of the laminated body of the present invention will be described with reference to FIGS. 1 to 3, and then each configuration will be described in detail.

The laminated body 10 shown in FIG. 1 has a support 1, an alignment layer 2, a light absorption anisotropic layer 3, and an adhesive layer 4 in this order.
Further, the laminated body 10 has a thickness between the support 1 and the adhesive layer 4 not including the support 1 and the adhesive layer 4, that is, the light absorption anisotropic of the adhesive layer 4 from the surface of the support 1 on the alignment layer 2 side. The distance to the surface on the sex layer 3 side is 5 μm or less, preferably 1 μm to 4 μm.
Further, in the laminated body 10, the thickness of the adhesive layer 4 is 5 μm to 50 μm.

In the laminated body of the present invention, as shown in FIG. 1, it is preferable that the support 1 and the alignment layer 2 are in contact with each other.
Further, in the laminated body of the present invention, as shown in FIG. 1, it is preferable that the alignment layer 2 and the light absorption anisotropic layer 3 are in contact with each other.

As shown in FIG. 2, the laminate of the present invention preferably has a cured layer 5 having a thickness of 100 nm or less between the light absorption anisotropic layer 3 and the adhesive layer 4.

As shown in FIG. 2, the laminate of the present invention is also referred to as a layer containing a polyvinyl alcohol resin having a thickness of 2 μm or less between the light absorption anisotropic layer 3 and the adhesive layer 4 (hereinafter, also referred to as “PVA layer”). It is abbreviated.) It is preferable to have 6.
When the laminated body of the present invention contains both the cured layer 5 and the layer 6 containing the polyvinyl alcohol resin, as shown in FIG. 2, the light absorption anisotropic layer 3, the cured layer 5, and the layer containing the polyvinyl alcohol resin are contained. It is preferable to have 6 and the adhesive layer 4 in this order.

As shown in FIG. 3, the laminate of the present invention preferably further has a surface film 7. At this time, it is preferable that the surface film 7 and the adhesive layer 4 are in contact with each other, that is, the surface film 7 and the other layers are bonded by the adhesive layer 4.

The laminated body of the present invention may be used in a state where the support 1 shown in FIG. 2 is peeled off and the support 1 is not present as shown in FIG.
Further, as shown in FIG. 3, the laminate of the present invention may further have a retardation film 8, and in that case, the retardation film 8 is preferably arranged on the alignment layer 2 side.

[Adhesive layer]
The pressure-sensitive adhesive layer used in the present invention is not particularly limited as long as it has a thickness of 5 μm to 50 μm, and various known materials can be used.

The storage elastic modulus of the pressure-sensitive adhesive layer used in the present invention is preferably 10 kPa to 20 MPa, more preferably 10 kPa to 2 MPa, from the viewpoint of making it easier to adjust the peelability of the support.

<< Measurement method of storage elastic modulus >>
In the present invention, the storage elastic modulus refers to a value measured at a frequency of 1 Hz and 25 ° C. using a dynamic viscoelasticity measuring device (DVA-200) manufactured by IT Measurement Control Co., Ltd.

The thickness of the pressure-sensitive adhesive layer used in the present invention is 5 μm to 50 μm, preferably more than 10 μm and 50 μm or less.
Within the above range, it becomes easier to adjust the peelability.

<Material used for the adhesive layer>
Examples of the material contained in the adhesive layer used in the present invention include a rubber adhesive, an acrylic adhesive, a silicone adhesive, a urethane adhesive, a vinyl alkyl ether adhesive, a polyvinyl alcohol adhesive, and a polyvinyl. Examples thereof include pyrrolidone-based adhesives, polyacrylamide-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.

Examples of the acrylic pressure-sensitive adhesive include (meth) acrylate in which the alkyl group of the ester portion is an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group or a butyl group, and (meth) acrylic acid and hydroxyethyl (meth). Acrylic polymers such as copolymers with (meth) acrylic monomers having functional groups such as acrylate are preferred.
Such an adhesive containing an acrylic polymer has excellent adhesiveness, and even when it is peeled off after being attached to another member, it is relatively easy without causing adhesive residue on the display device. It is preferable because it can be peeled off.
The glass transition temperature of such an acrylic polymer is preferably 25 ° C. or lower, more preferably 0 ° C. or lower.
Further, the weight average molecular weight of such an acrylic polymer is preferably 100,000 or more.

[Support]
The support used in the present invention is not particularly limited, and various known ones can be used. The support is preferably a peelable support.

Examples of the material constituting the support used in the present invention include cellulose-based resin, acrylic-based resin, methacrylic-based resin, polycarbonate-based resin, polystyrene-based resin, polyolefin-based resin, cyclic polyolefin-based resin, and glutaric acid anhydride-based material. Examples thereof include a resin, a glutarimide-based resin, a cellulose-based resin, a polyester-based resin, and a mixed resin of a plurality of types of resins selected from these, and among them, a cellulose-based resin or a polyester-based resin is preferable.

From the viewpoint of facilitating the adjustment of the peelability, the thickness of the support is preferably 10 to 200 μm, more preferably 50 to 200 μm, and even more preferably 100 to 200 μm.

Further, by adjusting the elastic modulus of the support according to the storage elastic modulus of the adhesive layer, it is possible to more easily adjust the peelability.

Further, by selecting a support that is difficult to permeate according to the composition of the alignment layer, the adhesive force of the support / alignment layer is lowered, so that the peelability can be more easily adjusted.

[Orientation layer]
The alignment layer used in the present invention is a photoalignment layer formed by using a composition for forming an alignment layer containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond.

The thickness of the alignment layer used in the present invention is preferably 0.1 μm to 2 μm, and more preferably more than 0.5 μm and 2 μm or less.

As described above, the photo-aligned layer used in the present invention forms an oriented layer containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond (hereinafter, abbreviated as “polymerizable group” in this paragraph). It is a photo-alignment layer formed by using the composition for use, and among them, a photo-alignment layer formed by using a photo-orientation copolymer described later as a cinnamoyl compound is more preferable. A polymerizable group of the same type as that contained in the composition of the light absorption anisotropic layer (for example, a methacryloyl group or an acryloyl group) is also contained in the composition of the photoalignment layer, so that the layers are chemically bonded to each other. It is advantageous to realize a laminated body in which the interlayer adhesion of the light alignment layer / light absorption anisotropic layer is enhanced and only the support, which is the subject of the present invention, can be easily peeled off.

上記式（Ａ）中、Ｒ^１は、水素原子またはメチル基を表す。Ｌ^１は、窒素原子とシクロアルカン環とを含む２価の連結基を表し、シクロアルカン環を構成する炭素原子の一部が、窒素、酸素および硫黄からなる群から選択されるヘテロ原子で置換されていてもよい。Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立に、水素原子または置換基を表し、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６のうち、隣接する２つの基が結合して環を形成していてもよい。
上記式（Ｂ）中、Ｒ^７は、水素原子またはメチル基を表し、Ｌ^２は、２価の連結基を表し、Ｘは、下記式（Ｘ４）で表される架橋性基を表す。

上記式（Ｘ４）中、＊は、上記式（Ｂ）中のＬ^２との結合位置を表し、Ｓは、エチレン性不飽和二重結合を有する官能基を表す。<Photo-oriented copolymer>
The photo-oriented copolymer used in the present invention has a repeating unit A containing a photo-oriented group represented by the following formula (A) and a repeating unit B containing a cross-linking group represented by the following formula (B). It is a photo-oriented copolymer having and.

In the above formula (A), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a divalent linking group containing a nitrogen atom and a cycloalkane ring, and a part of carbon atoms constituting the cycloalkane ring is replaced with a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur. It may have been. R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or substituent and are two adjacent groups of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ . May be combined to form a ring.
In the above formula (B), R ⁷ represents a hydrogen atom or a methyl group, L ² represents a divalent linking group, and X represents a crosslinkable group represented by the following formula (X4).

In the above formula (X4), * represents a bond position with L ² in the above formula (B), and S represents a functional group having an ethylenically unsaturated double bond.

In the present invention, the photo-oriented co-weight having a repeating unit A containing a photo-oriented group represented by the above formula (A) and a repeating unit B containing a cross-linking group represented by the above formula (B). By using the coalescence, the solvent resistance and the liquid crystal orientation of the obtained photoalignment film are improved.
This is not clear in detail, but the present inventors speculate as follows.
That is, when the divalent linking group represented by L1 in the above formula ( ^A ) contains a nitrogen atom and a cycloalkane ring, hydrogen bonding property and molecular rigidity are enhanced, so that molecular motion is suppressed. As a result, it is considered that the solvent resistance is improved.
Similarly, when the divalent linking group represented by L1 in the above formula ( ^A ) contains a nitrogen atom and a cycloalkane ring, the glass transition temperature of the copolymer rises, and the obtained photoalignment is obtained. As a result of improving the stability of the film over time, it is considered that the liquid crystal orientation is improved regardless of the timing of forming the optically anisotropic layer.

Next, a divalent linking group containing a nitrogen atom and ^a cycloalkane ring represented by L1 in the above formula (A) will be described. In the present invention, as described above, a part of the carbon atom constituting the cycloalkane ring may be substituted with a heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. Further, when a part of the carbon atom constituting the cycloalkane ring is substituted with a nitrogen atom, it does not have to have a nitrogen atom separately from the cycloalkane ring.

Further, the cycloalkane ring contained in the divalent linking group represented by L ¹ in the above formula (A) is preferably a cycloalkane ring having 6 or more carbon atoms, and specific examples thereof include a cyclohexane ring and a cyclopeptane. Examples thereof include a ring, a cyclooctane ring, a cyclododecane ring, a cyclodocosane ring and the like.

上記式（１）～（１０）中、＊１は、上記式（Ａ）中の主鎖を構成する炭素原子との結合位置を表し、＊２は、上記式（Ａ）中のカルボニル基を構成する炭素原子との結合位置を表す。In the present invention, L ¹ in the above formula (A) is a divalent linking group represented by any of the following formulas (1) to (10) for the reason that the liquid crystal orientation becomes better. Is preferable.

In the above formulas (1) to (10), * 1 represents a bond position with a carbon atom constituting the main chain in the above formula (A), and * 2 represents a carbonyl group in the above formula (A). Represents the bond position with the constituent carbon atoms.

Among the divalent linking groups represented by any of the above formulas (1) to (10), the solubility in the solvent used for forming the photoalignment film and the solvent resistance of the obtained photoalignment film. A divalent linking group represented by any of the above formulas (2), (3), (7) and (8) is preferable for the reason that the balance is good.

In addition, L ¹ in the above formula (A) may be a divalent linking group other than the above-mentioned "divalent linking group containing a nitrogen atom and a cycloalkane ring".
As such a divalent linking group, even if it has a substituent, the photo-orientation group easily interacts with the liquid crystal compound and the liquid crystal orientation of the adjacent liquid crystal layer becomes better. A good linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, an arylene group having 6 to 12 carbon atoms which may have a substituent, an ether group (—O—), a carbonyl group (—C). It is preferably a divalent linking group in which at least two or more groups selected from the group consisting of (= O)-) and an imino group (-NH-) which may have a substituent are combined. ..

Next, the substituent represented by one aspect of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula (A) will be described. As described above, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula (A) may be hydrogen atoms instead of substituents.

ここで、上記式（１１）中、＊は、上記式（Ａ）中のベンゼン環との結合位置を表し、Ｒ^９は、１価の有機基を表す。In the substituent represented by one aspect of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the above formula (A), the photo-orientation group easily interacts with the liquid crystal compound, and the liquid crystal orientation becomes higher. For good reasons, each independently has a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. It is preferably an alkoxy group of 20, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a cyano group, an amino group, or a group represented by the following formula (11).

Here, in the above formula (11), * represents a bond position with the benzene ring in the above formula (A), and R ⁹ represents a monovalent organic group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom and a chlorine atom are preferable.

Regarding the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, the linear alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and specifically, for example, a methyl group or ethyl. Groups, n-propyl groups and the like can be mentioned.
As the branched alkyl group, an alkyl group having 3 to 6 carbon atoms is preferable, and specific examples thereof include an isopropyl group and a tert-butyl group.
As the cyclic alkyl group, an alkyl group having 3 to 6 carbon atoms is preferable, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

As the linear alkyl halide group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms is preferable, and specifically, for example, a trifluoromethyl group, a perfluoroethyl group and a perfluoropropyl group. , Perfluorobutyl group and the like, and among them, a trifluoromethyl group is preferable.

As the alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 6 to 18 carbon atoms is more preferable, and an alkoxy group having 6 to 14 carbon atoms is further preferable. Specifically, for example, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, n-tetradecyloxy. Groups and the like are preferably mentioned, and among them, n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group and n-tetradecyloxy group are more preferable.

As the aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms is preferable, and specific examples thereof include a phenyl group, an α-methylphenyl group, a naphthyl group and the like, and among them, the phenyl group is used. preferable.

The aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and specific examples thereof include a phenyloxy group and a 2-naphthyloxy group. Among them, a phenyloxy group. Is preferable.

Examples of the amino group include a primary amino group (-NH ₂ ); a secondary amino group such as a methylamino group; a dimethylamino group, a diethylamino group, a dibenzylamino group, and a nitrogen-containing heterocyclic compound (for example, pyrrolidine). , Piperidine, piperazine, etc.), such as a tertiary amino group having a nitrogen atom as a bond.

Regarding the group represented by the above formula (11), examples of the monovalent organic group represented by R ⁹ in the above formula (11) include a linear or cyclic alkyl group having 1 to 20 carbon atoms. ..
As the linear alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group and the like, and among them, a methyl group or an ethyl group is used. preferable.
As the cyclic alkyl group, an alkyl group having 3 to 6 carbon atoms is preferable, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and the like, and among them, a cyclohexyl group is preferable.
The monovalent organic group represented by R ⁹ in the above formula (11) may be a combination of a plurality of the above-mentioned linear alkyl group and cyclic alkyl group directly or via a single bond. good.

In the present invention, R ² , R ³ , R ⁴ , R ⁵ and R 5 in the above formula (A) are used because the photo-oriented group easily interacts with the liquid crystal compound and the liquid crystal orientation becomes better. Of R ⁶ , it is preferable that at least R ⁴ represents the above-mentioned substituent, and further, the linearity of the obtained photo-oriented copolymer is improved, and it becomes easy to interact with the liquid crystal compound, so that the liquid crystal orientation is achieved. It is more preferable that R ² , R ³ , R ⁵ and R ⁶ all represent a hydrogen atom for the reason that the properties are further improved.

In the present invention, ^R4 in the above formula (A) is preferably an electron-donating substituent because the reaction efficiency is improved when the obtained photoalignment film is irradiated with light.
Here, the electron-donating substituent (electron-donating group) means a substituent having a Hammett value (Hammett substituent constant σp) of 0 or less, and for example, among the above-mentioned substituents, an alkyl group, Examples thereof include an alkyl halide group and an alkoxy group.
Of these, an alkoxy group is preferable, and an alkoxy group having 6 to 16 carbon atoms is more preferable, and an alkoxy group having 7 to 10 carbon atoms is preferable because the liquid crystal orientation is better. Is more preferable.

Next, the divalent linking group represented by L ² in the above formula (B) will be described.

As the divalent linking group, a direct group having 1 to 18 carbon atoms which may have a substituent may have a substituent because the photo-orientation group easily interacts with the liquid crystal compound and the liquid crystal orientation becomes better. A chain, branched or cyclic alkylene group, an arylene group having 6 to 12 carbon atoms which may have a substituent, an ether group (-O-), a carbonyl group (-C (= O)-), and a group. , It is preferable that the divalent linking group is a combination of at least two or more groups selected from the group consisting of imino groups (-NH-) which may have a substituent.

Here, examples of the substituent that the alkylene group, arylene group and imino group may have include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, a carboxy group and an alkoxycarbonyl group. And hydroxyl groups and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom and a chlorine atom are preferable.
As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group or an isopropyl group) is preferable. , N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is used. Is particularly preferable.
As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable, and carbon is more preferable. It is more preferably an alkoxy group having the number 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
Examples of the aryl group include an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α-methylphenyl group, a naphthyl group and the like, and a phenyl group is preferable.
Examples of the aryloxy group include phenoxy, naphthoxy, imidazoliyloxy, benzoimidazoliyloxy, pyridine-4-yloxy, pyrimidinyloxy, quinazolinyloxy, prynyloxy, thiophene-3-yloxy and the like.
Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.

Regarding the linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, specific examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group and a pentylene group. Examples thereof include a hexylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group and an octadecylene group.
Specific examples of the branched alkylene group include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group and a 2-ethyl-2-methylpropylene group.
Specific examples of the cyclic alkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantan-diyl group, and a norbornane-diyl group. , Exo-tetrahydrodicyclopentadiene-diyl group and the like, and among them, the cyclohexylene group is preferable.

Specific examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, a 2,2'-methylenebisphenyl group and the like, and a phenylene group is preferable. ..

Next, the crosslinkable group represented by X in the above formula (B) will be described.

上記式（Ｘ１）～（Ｘ４）中、＊は、上記式（Ｂ）中のＬ^２との結合位置を表し、Ｒ^８は、水素原子、メチル基およびエチル基のいずれかを表し、上記式（Ｘ４）中、Ｓは、エチレン性不飽和二重結合を有する官能基を表す。
ここで、エチレン性不飽和二重結合を有する官能基としては、具体的には、例えば、ビニル基、アリル基、スチリル基、アクリロイル基、メタクリロイル基が挙げられ、アクリロイル基またはメタクリロイル基であることが好ましい。The X (crosslinkable group) in the above formula (B) is a crosslinkable group represented by the following formula (X4) among the crosslinkable groups represented by the following formulas (X1) to (X4).

In the above formulas (X1) to (X4), * represents the bond position with L ² in the above formula (B), and R ⁸ represents any of a hydrogen atom, a methyl group and an ethyl group, and the above formula. In (X4), S represents a functional group having an ethylenically unsaturated double bond.
Here, examples of the functional group having an ethylenically unsaturated double bond include, for example, a vinyl group, an allyl group, a styryl group, an acryloyl group, and a methacryloyl group, and the functional group is an acryloyl group or a methacryloyl group. Is preferable.

In the present invention, the repeating unit B is for the reason that the strength of the optical laminate of the present invention described later becomes high and the handleability when forming another layer using the optical laminate of the present invention described later becomes good. However, the repeating unit (hereinafter, also abbreviated as "repeating unit B1") in which X in the above formula (B) is a crosslinkable group represented by any of the above formulas (X1) to (X3) and the above formula. It is preferable that X in (B) contains a repeating unit (hereinafter, also abbreviated as “repeating unit B2”) which is a crosslinkable group represented by the above formula (X4).

Specific examples of the repeating unit A containing the photooriented group represented by the above formula (A) include the repeating units A-1 to A-44 shown below. In the following formula, Me represents a methyl group and Et represents an ethyl group. In the following specific examples, the "1,4-cyclohexyl group" contained in the divalent linking group of the repeating units A-1 to A-10 may be either a cis form or a trans form. It is preferably a transformer body.

On the other hand, as the repeating unit B (repeating unit B1) containing the crosslinkable group represented by the above formula (B), specifically, for example, the repeating units B-1 to B-17 shown below can be mentioned.

Specific examples of the repeating unit B (repeating unit B2) containing the crosslinkable group represented by the above formula (B) include the repeating units B-18 to B-47 shown below.

In the photoorientation copolymer used in the present invention, the content a of the repeating unit A described above and the content b of the repeating unit B described above satisfy the following formula (12) in terms of mass ratio. It is more preferable that the following formula (13) is satisfied, further preferably the following formula (14) is satisfied, and particularly preferably the following formula (15) is satisfied.
0.03 ≤ a / (a + b) ≤ 0.5 ... (12)
0.03 ≤ a / (a + b) ≤ 0.3 ... (13)
0.03 ≤ a / (a + b) ≤ 0.2 ... (14)
0.05 ≤ a / (a + b) ≤ 0.2 ... (15)

Further, when the photo-orientation copolymer used in the present invention has the above-mentioned repeating unit B1 together with the above-mentioned repeating unit B1, the optical difference including the photo-alignment film while maintaining good liquid crystal orientation and adhesion. For the reason that the strength of the rectangular layer can be further increased, the above-mentioned content a of the repeating unit A, the above-mentioned content b1 of the repeating unit B1 and the above-mentioned content b2 of the repeating unit B2 are described below in terms of mass ratio. It is preferable that the formula (16) is satisfied, and it is more preferable that the following formula (17) is satisfied.
0.05 ≤ b2 / (a + b1 + b2) ≤ 0.7 ... (16)
0.10 ≤ b2 / (a + b1 + b2) ≤ 0.5 ... (17)

The photoorientation copolymer used in the present invention may have other repeating units in addition to the above-mentioned repeating unit A and repeating unit B as long as the effects of the present invention are not impaired.
Examples of the monomer (radical polymerizable monomer) forming such another repeating unit include an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic acid anhydride, and a styrene compound. Examples include vinyl compounds.

The method for synthesizing the photoorientable copolymer used in the present invention is not particularly limited, and for example, the above-mentioned monomer forming the repeating unit A, the above-mentioned monomer forming the repeating unit B, and any other repeating unit. It can be synthesized by mixing the monomers forming the above and polymerizing in an organic solvent with a radical polymerization initiator.

The weight average molecular weight (Mw) of the photo-oriented copolymer used in the present invention is preferably 10,000 to 500,000, more preferably 30,000 to 300,000 for the reason that the liquid crystal orientation is further improved.
Here, the weight average molecular weight and the number average molecular weight in the present invention are values measured by the gel permeation chromatograph (GPC) method under the conditions shown below.
-Solvent (eluent): THF (tetrahydrofuran)
-Device name: TOSOH HLC-8320GPC
-Column: TOSOH TSKgel Super HZM-H (4.6 mm x 15 cm)
) Are connected and used. ・ Column temperature: 40 ° C
-Sample concentration: 0.1% by mass
-Flow velocity: 1.0 ml / min
-Calibration curve: Use a calibration curve with 7 samples from TSK standard polystyrene Mw = 2800000 to 1050 (Mw / Mn = 1.03 to 1.06) manufactured by TOSOH.

[Light absorption anisotropic layer]
The light absorption anisotropic layer used in the present invention is a layer having a different degree of light absorption depending on the direction, and usually has an absorption axis and a polarization axis (transmission axis).

The thickness of the light absorption anisotropic layer used in the present invention is preferably 0.1 μm to 3 μm, more preferably 0.1 μm to 2 μm.

The light absorption anisotropic layer used in the present invention preferably contains a dichroic substance.
Further, the light absorption anisotropic layer used in the present invention preferably contains a liquid crystal compound together with a dichroic substance.
Further, the light absorption anisotropic layer used in the present invention preferably contains a dichroic azo compound.

<Dichroic substance>
The bicolor substance used in the present invention is not particularly limited, and is a visible light absorbing substance (bicolor dye, bicolor azo compound), a light emitting substance (fluorescent substance, phosphorescent substance), an ultraviolet absorbing substance, and an infrared absorbing substance. , Non-linear optical substances, carbon nanotubes, inorganic substances (for example, quantum rods), and the like, and conventionally known bicolor substances (bicolor dyes) can be used. Further, a dichroic substance having a liquid crystal property is also preferable.

Specifically, for example, paragraphs [0067] to [0071] of JP2013-228706, paragraphs [0008] to [0026] of JP2013-227532A, and paragraphs [0008] to [0026] of JP2013-209367, [Japanese Patent Laid-Open No. 2013-209367]. 0008]-[0015] paragraphs, Japanese Patent Application Laid-Open No. 2013-14883 [0045]-[0058] paragraphs, Japanese Patent Application Laid-Open No. 2013-109090 [0012]-[0029] paragraphs, Japanese Patent Application Laid-Open No. 2013-101328 Paragraphs [0009] to [0017], paragraphs [0051] to [0065] of JP2013-37353, paragraphs [0049] to [0073] of JP2012-63387, JP-A-11-305036. Paragraphs [0016] to [0018], paragraphs [0009] to [0011] of JP-A-2001-133630, JP-A-2011-215337, [0030]-[0169], JP-A-2010-106242. Paragraphs [0021] to [0075], paragraphs [0011] to [0025] of JP2010-215846A, paragraphs [0017] to [0069] of JP2011-048311A, JP2011-213610. Paragraphs [0013] to [0133] of JP-A, paragraphs [0074] to [0246] of JP-A-2011-237513, paragraphs [0005]-[0051] of JP-A-2016-006502, International Publication No. 2016 / Paragraphs 060173 [0005] to [0041], paragraphs [0008] to [0062] of International Publication No. 2016/136561, paragraphs [0014] to [0033] of International Publication No. 2017/154835, International Publication No. 2017. Examples thereof include those described in paragraphs [0014] to [0033] of No. 154695 and paragraphs [0013] to [0037] of International Publication No. 2017/195833.

In the present invention, two or more kinds of dichroic substances may be used in combination. For example, from the viewpoint of bringing the polarizing element closer to black, at least one kind of dichroism having a maximum absorption wavelength in the wavelength range of 370 to 550 nm. It is preferable to use the substance in combination with at least one dichroic substance having a maximum absorption wavelength in the wavelength range of 500 to 700 nm.

The dichroic substance may have a crosslinkable group.
Specific examples of the crosslinkable group include (meth) acryloyl group, epoxy group, oxetanyl group, styryl group and the like, and among them, (meth) acryloyl group is preferable.

The dichroic substance is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, still more preferably 10 to 30% by mass, based on the solid content of the light absorption anisotropic layer.

<Liquid crystal compound>
As the liquid crystal compound used in the present invention, 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 the liquid crystal compound described in Japanese Patent Application Laid-Open No. 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.

The liquid crystal compound used in the present invention is preferably a liquid crystal compound having a polymerizable group (polymerizable liquid crystal compound).
Here, examples of the polymerizable group include, for example, a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Of these, the (meth) acryloyl group is preferable.

In the present invention, the liquid crystal compound may be used alone or in combination of two or more.
Further, in the present invention, it is preferable to contain a high molecular weight liquid crystal compound, and it is more preferable to use a low molecular weight liquid crystal compound together with the high molecular weight liquid crystal compound.

The content of the liquid crystal compound is preferably 25 to 2000 parts by mass, more preferably 33 to 1000 parts by mass, and even more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the content of the dichroic substance. When the content of the liquid crystal compound is within the above range, the degree of orientation of the substituent is further improved.

[Hardened layer]
Any cured layer used in the present invention is preferably a cured layer having a thickness of 100 nm or less.
As the cured layer, various known ones can be used. For example, a layer containing a liquid crystal compound and a layer obtained by curing a composition containing a polyfunctional monomer can be mentioned. It is preferable to have a refractive index capable of performing index matching with the light absorption anisotropic layer.

[Layer containing polyvinyl alcohol resin]
The layer containing any polyvinyl alcohol resin (PVA layer) used in the present invention is preferably a layer containing a polyvinyl alcohol resin having a thickness of 2 μm or less.

[Surface film]
Any surface film used in the present invention is usually preferably placed on the outermost side of the resulting optical laminate.
The surface film is not particularly limited, and various known ones can be used. For example, an embodiment in which the surface film has a hard coat layer and a base material can be mentioned.

Examples of the material constituting the surface film include (meth) acrylic resin, polycarbonate resin, polystyrene resin, polyolefin resin, cyclic polyolefin resin, glutaric acid anhydride-based resin, glutarimide-based resin, and cellulose-based resin. , Polyester resin, Polyimide resin, and mixed resin of multiple kinds of resins selected from these, among them, cyclic polyolefin resin, (meth) acrylic resin, polyimide resin, or polyester resin. Is preferable. Further, a polyimide resin is preferable from the viewpoint of excellent flexibility.
The surface film may contain an ultraviolet absorber.

Examples of the (meth) acrylic resin include a methacrylic resin and an acrylic resin, as well as a (meth) acrylic polymer having a ring structure in the main chain, that is, a polymer having a lactone ring and a maleic anhydride ring. Examples thereof include a maleic anhydride-based polymer having a maleic anhydride, a polymer having a glutaric anhydride ring, and a glutarimide ring-containing polymer.

The hardcoat layer is a layer for imparting hardness or scratch resistance to the laminate.
The hardcoat layer can be formed, for example, by applying a composition for forming a hardcoat layer onto a substrate and curing it.
Further, for the purpose of adding other functions, another functional layer may be laminated on the hard coat layer.
Further, by adding a filler or an additive to the hard coat layer, it is possible to impart mechanical, electrical or optical physical performance, or chemical performance such as water repellency or oil repellency to the hard coat layer itself. ..
The hardcoat layer preferably has excellent scratch resistance. Specifically, it is preferable to achieve 3H or more when a pencil hardness test, which is an index of scratch resistance, is carried out.
The thickness of the hard coat layer is preferably 0.1 to 6 μm, more preferably 3 to 6 μm.

The hardcourt layer is preferably formed by curing the curable composition.
The curable composition is preferably prepared as a liquid coating composition.
An example of a curable composition comprises a monomer, oligomer, or polymer for a matrix-forming binder and an organic solvent.

In the present invention, the surface film is not limited to the embodiment having the base material and the hard coat layer, and may be, for example, only the base material or only the hard coat layer.

[Phase difference film]
As any retardation film used in the present invention, various known films can be used. The value of the in-plane retardation of the retardation film is not particularly limited, and the retardation film may be a λ / 4 plate or a λ / 2 plate. Further, a retardation film composed of a plurality of layers may be used.

In the present specification, the "λ / 4 plate" is a plate having a λ / 4 function, and specifically, it converts linear polarization of a specific wavelength into circular polarization (or circular polarization into linear polarization). It is a plate having a function to carry out.
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.

The material constituting the retardation film is not particularly limited, and examples thereof include various polymer films and layers containing various liquid crystal compounds.

[Image display device]
The image display device of the present invention includes the above-mentioned laminated body and an image display element.
The image 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 an image display element and an organic EL display device using an organic EL display panel as a display element, and is an organic EL display device. Is more preferable.

[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, Voltage of technique. Papers (Proceedings) 28 (1997) 845 in which the VA mode is multi-domainized for the purpose of 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 LCD cells (presented at LCD International 98). 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]
As the organic EL display device which is an example of the image display device of the present invention, for example, an embodiment having the above-mentioned laminate of the present invention and the organic EL display panel in this order is preferably mentioned from the visual inspection side.
More preferably, from the visual recognition side, the above-mentioned laminate of the present invention having a λ / 4 plate and the organic EL display panel are provided in this order. In this case, the laminated body is arranged in the order of the surface film, the adhesive layer, the light absorption anisotropic layer, the alignment layer, and the retardation film from the visual recognition side, if necessary.
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]
<Formation of photoalignment layer PA1>
As a support, a TAC (triacetyl cellulose) film (TJ40UL, thickness 40 μm, manufactured by FUJIFILM Corporation) was used.
Next, the alignment layer forming composition PA1, which will be described later, was continuously applied onto the support with a wire bar. The support on which the coating film was formed was dried with warm air at 140 ° C. for 120 seconds, and then the coating film was irradiated with polarized ultraviolet rays (10 mJ / cm ² , using an ultrahigh pressure mercury lamp) to obtain a photoalignment layer. PA1 was formed to obtain a TAC film with a photoalignment layer.
The film thickness of the photoalignment layer PA1 was 1.0 μm.

────────────────────────────────
Composition for forming an oriented layer PA1
────────────────────────────────
・ The following polymer PA-1 100.00 parts by mass ・ The following acid generator PAG-1 5.00 parts by mass ・ The following acid generator CPI-110TF 0.005 parts by mass ・ Xylene 1220.00 parts by mass ・ Methyl isobutyl ketone 122.00 parts by mass ────────────────────────────────

Polymer PA-1

Acid generator PAG-1

Acid generator CPI-110F

<Formation of light absorption anisotropic layer P1>
On the obtained photo-alignment layer PA1, the composition P1 for forming a light absorption anisotropic layer having the following composition was continuously coated with a wire bar to form the coating layer P1.
Then, the coating layer P1 was heated at 140 ° C. for 90 seconds, and the coating layer P1 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 layer P1 was formed on the light alignment layer PA1 by irradiating with a high-pressure mercury lamp under an irradiation condition of an illuminance of 28 mW / cm ² for 60 seconds.
The film thickness of the light absorption anisotropic layer P1 was 0.4 μm.

――――――――――――――――――――――――――――――――
Composition for forming a light absorption anisotropic layer P1
――――――――――――――――――――――――――――――――
-The following azo dye Y-1 0.25 parts by mass-The following azo dye M-1 0.27 parts by mass-The following azo dye C-1 0.65 parts by mass-The following polymer liquid crystal compound P-1 3.59 mass Parts ・ The following liquid crystal compound L-1 0.12 parts by mass ・ Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.200 parts by mass ・ The following interface improver F-1 0.026 parts by mass ・ Cyclopentanone 47.50 Parts by mass ・ tetrahydrofuran 47.50 parts by mass ――――――――――――――――――――――――――――――――

Azo dye Y-1

Azo dye M-1

Azo dye C-1

Polymer liquid crystal compound P-1

Liquid crystal compound L-1

Interface improver F-1

<Formation of hardened layer L1>
On the obtained light absorption anisotropic layer P1, the cured layer forming composition L1 having the following composition was continuously applied with a wire bar to form the composition layer L1.
Next, the composition layer L1 was dried at room temperature, and then irradiated for 10 seconds under an irradiation condition of an illuminance of 28 mW / cm ² using a high-pressure mercury lamp to form a cured layer L1 on the light absorption anisotropic layer P1.
The film thickness of the cured layer L1 was 30 nm.
――――――――――――――――――――――――――――――――
Composition for forming a hardened layer L1
――――――――――――――――――――――――――――――――
-Mix of the following rod-shaped liquid crystal compound L-2 2.43 parts by mass-The following modified trimethylol propantriacrylate 0.98 parts by mass-The following photopolymerization initiator I-1 0.20 parts by mass-The above-mentioned interface improver F- 1 0.14 parts by mass, 1,4-phenylenedidiboronic acid (Tokyo Kasei Kogyo) 0.10 parts by mass, methyl ethyl ketone 371 parts by mass ―――――――――――――――――――― ――――――――――――

Mixture of rod-shaped liquid crystal compounds L-2 (The numerical value in the following formula represents mass%, and R represents a group bonded with an oxygen atom).

Modified trimethylolpropane triacrylate

The following photopolymerization initiator I-1

<Formation of PVA layer B1>
A coating liquid B1 for forming a polyvinyl alcohol (PVA) layer having the following composition was continuously coated on the cured layer L1 with a wire bar.
Then, the PVA layer having a thickness of 1.0 μm was formed on the cured layer L1 by drying with warm air at 100 ° C. for 2 minutes.
――――――――――――――――――――――――――――――――
Coating liquid B1 for forming a PVA layer
――――――――――――――――――――――――――――――――
・ The following modified polyvinyl alcohol 3.80 parts by mass ・ Initiator Irg2959 0.20 parts by mass ・ 70 parts by mass of water ・ 30 parts by mass of methanol ―――――――――――――――――――― ――――――――――――

Modified polyvinyl alcohol

<Manufacturing of laminated body 1>
The adhesive layer N1 side of the adhesive sheet N1 produced below was pressure-bonded onto the PVA layer B1 to complete the laminated body 1 of Example 1. The thickness of the adhesive layer was 20 μm.
(Preparation of adhesive sheet N1)
Nitrogen gas was introduced into a reaction device equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the air in the reaction device was replaced with nitrogen gas.
Then, in this reaction apparatus, 70 parts by mass of butyl acrylate, 30 parts by mass of methyl acrylate, 4 parts by mass of acrylic acid, 2 parts by mass of N, N-dimethylmethacrylate, 0.1 part by mass of azobisisobutyronitrile and acetic acid. 120 parts by mass of ethyl was added.
While stirring this, the reaction was carried out at 60 ° C. for 8 hours in a nitrogen gas stream to obtain a solution of an acrylic copolymer having a weight average molecular weight of 1.5 million. Further, it was diluted with ethyl acetate to obtain a copolymer solution 1 having a solid content of 15%.
Next, with respect to 100 parts by mass of the solid content of the copolymer solution 1, 3 parts by mass of polyisocyanate (Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 0 parts of aluminum trisacetylacetonate (Aluminum chelate A, manufactured by Kawaken Fine Chemical Co., Ltd.). A solution (adhesive composition N1) was prepared by mixing 2 parts by mass and 0.1 parts by mass of γ-mercaptopropylmethyldimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
Next, the prepared pressure-sensitive adhesive composition N1 was applied onto a silicone resin-coated PET film (hereinafter, also abbreviated as "release film"), and dried at 90 ° C. to remove the solvent to a thickness of 20 μm. An adhesive sheet N1 having an adhesive layer N1 was produced. The storage elastic modulus of the adhesive layer N1 was 0.3 MPa.

[Example 2]
A laminated body of Example 2 was obtained by the same method as in Example 1 except that the support was changed to PET (thickness 40 μm) in the formation of the light absorption anisotropic layer of Example 1.

[Example 3]
In the formation of the light absorption anisotropic layer of Example 1, the same method as in Example 1 was used except that the support was changed to the cellulose acylate film TJ100UL (thickness 100 μm, manufactured by FUJIFILM Corporation). Was obtained.

[Examples 4 to 7]
In the formation of the light absorption anisotropic layer of Example 1, the thickness of the composition for forming the light absorption anisotropic layer and the thickness of the light alignment layer were changed as shown in Table 2 below, except that the thickness was changed from that of Example 1. In the same manner, the laminates of Examples 4 to 7 were obtained.
In Table 2 below, the details of the compositions P2 and P3 for forming the light absorption anisotropic layer are as follows.

――――――――――――――――――――――――――――――――
Composition for forming a light absorption anisotropic layer P2
――――――――――――――――――――――――――――――――
-The above azo dye Y-1 0.25 parts by mass-The above azo dye M-1 0.27 parts by mass-The following azo dye C-2 0.65 parts by mass-The following polymer liquid crystal compound P-2 3.71 parts by mass Part ・ Polymerization initiator IRGACUREOXE-03 (manufactured by BASF) 0.151 parts by mass ・ The above-mentioned interface improver F-1 0.026 parts by mass ・ Cyclopentanone 47.50 parts by mass ・ tetrahydrofuran 47.50 parts by mass --- ―――――――――――――――――――――――――――――

Azo dye C-2

Polymer liquid crystal compound P-2

――――――――――――――――――――――――――――――――
Composition for forming a light absorption anisotropic layer P3
――――――――――――――――――――――――――――――――
-The following azo dye Y-2 0.17 parts by mass-The following azo dye M-2 0.19 parts by mass-The following azo dye C-3 0.45 parts by mass-The polymer liquid crystal compound P-2 4.07 mass Part ・ Polymerization initiator IRGACUREOXE-03 (manufactured by BASF) 0.151 parts by mass ・ The above-mentioned interface improver F-1 0.026 parts by mass ・ Cyclopentanone 47.50 parts by mass ・ tetrahydrofuran 47.50 parts by mass --- ―――――――――――――――――――――――――――――

Azo dye Y-2

Azo dye M-2

Azo dye C-3

[Example 8]
<Formation of light absorption anisotropic layer P4>
The photo-alignment layer PA1 was formed in the same manner as in Example 1 to obtain a TAC film with a photo-alignment layer.
The composition for forming a light absorption anisotropic layer P4 prepared below was continuously coated on the obtained photoalignment layer PA1 with a wire bar to form a coating layer P4.
Then, the coating layer P4 was heated at 120 ° C. for 60 seconds, and the coating layer P4 was cooled to room temperature (23 ° C.).
Then, the light absorption anisotropic layer P4 was formed on the light alignment layer PA1 by irradiating with a high-pressure mercury lamp under an irradiation condition of an illuminance of 28 mW / cm ² for 60 seconds.
The film thickness of the light absorption anisotropic layer P4 was 1.7 μm.

A composition for forming a light absorption anisotropic layer P4 was prepared with the following composition, dissolved by heating at 50 ° C. for 3 hours with stirring, and filtered through a 0.45 μm filter.
――――――――――――――――――――――――――――――――
Composition for forming a light absorption anisotropic layer P4
――――――――――――――――――――――――――――――――
-The following azo dye Y-3 2.7 parts by mass-The following azo dye M-3 2.7 parts by mass-The following azo dye C-4 2.7 parts by mass-The following liquid crystal compound P-3 75.5 parts by mass-Polymerization Initiator IRGACURE819 (manufactured by BASF) 0.8 parts by mass ・ The above-mentioned interface improver F-1 0.6 parts by mass ・ Cyclopentanone 274.5 parts by mass ・ tetrahydrofuran 640.5 parts by mass ―――――――― ――――――――――――――――――――――――

Azo dye M-3

Azo dye Y-3

Azo dye C-4

Liquid crystal compound P-3 (mixed with the following compound A / the following compound B = 75/25)

Compound A

Compound B

<Preparation of laminated body 8>
The PVA layer B1 and the adhesive layer were formed on the light absorption anisotropic layer P4 in the same manner as in Example 1, and the laminated body 8 of Example 8 was completed.

[Examples 9 to 16]
In the formation of the pressure-sensitive adhesive layer of Example 1, among the pressure-sensitive adhesive layers in the pressure-sensitive adhesive sheet N1 described above and the pressure-sensitive adhesive sheets N2 to N6 described later, the pressure-sensitive adhesive layer shown in Table 2 below was used, except that the thickness was changed to the thickness shown in Table 2 below. , The laminated body of Examples 9 to 16 was obtained by the same method as in Example 1.

<Preparation of adhesive sheet N2>
Similar to the pressure-sensitive adhesive sheet N1, 95 parts by mass of butyl acrylate and 5 parts by mass of acrylic acid are polymerized by a solution polymerization method to have an average molecular weight of 2 million and an acrylic weight distribution (Mw / Mn) of 3.0. Combined 2 was obtained.
Next, with respect to 100 parts by mass of the solid content of the acrylic copolymer 2, 10 parts by mass of a polyfunctional acrylate-based monomer (Aronix M-315, manufactured by Toa Synthetic Co., Ltd.) and a photopolymerization initiator (Irgacure 500, manufactured by BASF). A solution obtained by mixing 1 part by mass of 1 part by mass of trimesterolpropane tolylene diisocyanate (Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) and 0.2 part by mass of a silane coupling agent (KBM-403, manufactured by Shinetsu Chemical Industry Co., Ltd.). The pressure-sensitive adhesive composition N2) was prepared.
Next, the prepared pressure-sensitive adhesive composition N2 is applied onto a PET film (release film) coated with a silicone resin, dried at 90 ° C. to remove the solvent, and irradiated with ultraviolet rays (UV) under the following conditions. , A pressure-sensitive adhesive sheet N2 having a pressure-sensitive adhesive layer N2 having a thickness of 20 μm was produced. The storage elastic modulus of the adhesive layer N2 was 0.6 MPa.
(UV irradiation conditions)
・ Fusion electrodeless lamp H bulb ・ Illuminance: 600mW / cm ²
・ Light intensity: 150mJ / cm ²
The UV illuminance and the amount of light were measured using "UVPF-36" manufactured by Eye Graphics.

<Manufacturing of adhesive sheets N3 to N5>
First, an acrylic polymer was prepared according to the following procedure.
A solution of 70 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of ethyl acrylate, 6 parts by mass of hydroxyethyl methacrylate, and 4 parts by mass of acrylic acid in a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer. Polymerization was carried out by a polymerization method to obtain an acrylic polymer A1 having an average molecular weight of 300,000.
Next, using the obtained acrylic polymer A1, pressure-sensitive adhesive sheets N3 to N5 were prepared according to the following procedure.
Specifically, trimethylolpropane tolylene diisocyanate (Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) in parts by mass shown in Table 1 below is added to 100 parts by mass of the solid content of the acrylic polymer A1 to form a pressure-sensitive adhesive composition. Was prepared.
Next, the prepared pressure-sensitive adhesive composition is applied to a PET film (release film) coated with a silicone resin using a die coater, dried at 150 ° C. for 3 hours, and has a pressure-sensitive adhesive layer N3 to 5 having a desired thickness. Sheets N3 to N5 were produced. The storage elastic moduli of the adhesive layers N3 to N5 were as shown in Table 1 below.

<Preparation of adhesive sheet N6>
An acrylic copolymer 2 was obtained in the same manner as the pressure-sensitive adhesive sheet N2.
Next, 1 part by mass of trimethylolpropane tolylene diisocyanate (Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) and a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) were added to 100 parts of the solid content of the acrylic copolymer 2. A solution (adhesive composition N6) in which 0.2 parts by mass was mixed was prepared.
Next, the prepared pressure-sensitive adhesive composition N6 is applied onto a PET film (release film) coated with a silicone resin, and the solvent is removed by drying at 90 ° C., and the pressure-sensitive adhesive sheet has a pressure-sensitive adhesive layer N6 having a thickness of 25 μm. N6 was prepared. The storage elastic modulus of the adhesive layer N6 was 0.1 MPa.

[Example 17]
The laminate of Example 17 was obtained by the same method as in Example 15 except that TJ100UL (thickness 100 μm, manufactured by Fujifilm Corporation) was used instead of TJ40UL as the support.

[Comparative Example 1]
The laminated body of Comparative Example 1 was obtained by the same method as in Example 10 except that the thickness of the adhesive layer was changed to the value shown in Table 2 below.

[Comparative Example 2]
A laminate of Comparative Example 2 was obtained by the same method as in Example 1 except that the composition PA1 for forming an oriented layer was changed to the composition PA2 for forming an oriented layer having the following composition.

────────────────────────────────
Composition for forming an oriented layer PA2
────────────────────────────────
・ Polymer PA-2 100.00 parts by mass ・ Acid generator PAG-1 5.00 parts by mass ・ Acid generator CPI-110TF 0.005 parts by mass ・ Xylene 1220.00 parts by mass ・ Methyl isobutyl ketone 122.00 parts by mass ────────────────────────────────

Polymer PA-2

[evaluation]
<< Peeling evaluation >>
The obtained laminate was cut into a size of 25 mm × 150 mm, the release film was peeled off, and then the adhesive layer side was pressure-bonded onto a glass substrate (Eagle XG, Corning Inc.).
After that, a tape was attached to the support of the laminated body and peeled off.
The peeled surface of the peeled support was observed and evaluated according to the following criteria. The results are shown in Table 2 below.
AA: No roughness of the peeled surface A: The peeled surface is rough B: Peeling residue due to the alignment layer is observed, and the peeling residue area is less than 5% of the area of the peeling surface C: Peeling residue due to the alignment layer Is observed, and the area remaining after peeling is 5% or more of the area of the peeled surface.

From the results shown in Table 2, when the thickness between the support and the adhesive layer excluding the thickness of the support and the adhesive layer is 5 μm or less and the thickness of the adhesive layer is less than 5 μm, only the support is used. It was found that it was difficult to peel off (Comparative Example 1).
It was also found that when the cinnamoyl compound used to form the alignment layer does not have a functional group having an ethylenically unsaturated double bond, it is difficult to exfoliate only the support (Comparative Example 2). ..
On the other hand, when the thickness between the support and the adhesive layer excluding the thickness of the support and the adhesive layer is 5 μm or less, the thickness of the adhesive layer is 5 to 50 μm, and the oriented layer is not ethylenically. It was found that the support can be easily peeled off when the photo-aligned layer is formed by using the composition for forming an oriented layer containing a cinnamoyl compound having a functional group having a saturated double bond (Example). 1-17).

1 Support 2 Orientation layer 3 Light absorption anisotropic layer 4 Adhesive layer 5 Curing layer 6 Layer containing polyvinyl alcohol resin 7 Surface film 8 Phase difference film 10 Laminated body

Claims (23)

It has a support, an alignment layer, a light absorption anisotropic layer, and an adhesive layer in this order.
The light absorption anisotropic layer contains a dichroic substance and a liquid crystal compound, and contains.
The thickness between the support and the support not including the adhesive layer and the adhesive layer is 5 μm or less.
The thickness of the adhesive layer is 5 μm to 50 μm, and the thickness is 5 μm to 50 μm.
A laminate in which the alignment layer is a photoalignment layer formed by using a composition for forming an orientation layer containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond. It has a support, an alignment layer, a light absorption anisotropic layer, and an adhesive layer in this order.
The light absorption anisotropic layer contains a dichroic azo compound and contains.
The thickness between the support and the support not including the adhesive layer and the adhesive layer is 5 μm or less.
The thickness of the adhesive layer is 5 μm to 50 μm, and the thickness is 5 μm to 50 μm.
A laminate in which the alignment layer is a photoalignment layer formed by using a composition for forming an orientation layer containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond. The laminate according to claim 1 or 2 , wherein the adhesive layer has a storage elastic modulus of 100 kPa to 20 MPa. The laminate according to claim 3 , wherein the adhesive layer has a storage elastic modulus of 100 kPa to 2 MPa. The laminate according to any one of claims 1 to 4 , wherein the thickness of the adhesive layer is more than 10 μm and 50 μm or less. The laminate according to any one of claims 1 to 5 , wherein the light absorption anisotropic layer has a thickness of 0.1 μm to 3 μm. The laminate according to any one of claims 1 to 6 , wherein the alignment layer has a thickness of 0.1 μm to 2 μm. The laminate according to claim 7 , wherein the alignment layer has a thickness of more than 0.5 μm and 2 μm or less. The cinnamoyl compound has a repeating unit A containing a photo-oriented group represented by the following formula (A) and a repeating unit B containing a cross-linking group represented by the following formula (B). The laminate according to any one of claims 1 to 8 , which is a polymer.

In the formula (A), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a divalent linking group containing a nitrogen atom and a cycloalkane ring, and a part of the carbon atoms constituting the cycloalkane ring is a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur. It may be replaced. R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or substituent and are two adjacent groups of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ . May be combined to form a ring.
In the formula (B), R ⁷ represents a hydrogen atom or a methyl group, L ² represents a divalent linking group, and X represents a crosslinkable group represented by the following formula (X4).

In the formula (X4), * represents a bond position with L ² in the formula (B), and S represents a functional group having an ethylenically unsaturated double bond. The laminate according to claim 9 , wherein L ¹ in the formula (A) is a divalent linking group represented by any of the following formulas (1) to (10).

In the formulas (1) to (10), * 1 represents a bond position with a carbon atom constituting the main chain in the formula (A), and * 2 represents a carbonyl group in the formula (A). Represents the bond position with the constituent carbon atoms. The laminate according to claim 1 , wherein the liquid crystal compound is a polymerizable liquid crystal compound. The laminate according to claim 1 , wherein the liquid crystal compound is a polymer liquid crystal compound. The laminate according to claim 12 , wherein the light absorption anisotropic layer further contains a small molecule liquid crystal compound. The laminate according to any one of claims 1 to 13 , further comprising a cured layer having a thickness of 100 nm or less between the light absorption anisotropic layer and the adhesive layer. The laminate according to claim 14 , wherein the cured layer contains a liquid crystal compound. The laminate according to claim 14 , wherein the cured layer is a layer obtained by curing a composition containing a polyfunctional monomer. The laminate according to any one of claims 1 to 16 , further comprising a layer containing a polyvinyl alcohol resin having a thickness of 2 μm or less between the light absorption anisotropic layer and the adhesive layer. The laminate according to any one of claims 1 to 17 , wherein the support and the alignment layer are in contact with each other. The laminate according to any one of claims 1 to 18 , wherein the alignment layer and the light absorption anisotropic layer are in contact with each other. A laminate having the laminate according to any one of claims 1 to 19 and a surface film, in which the adhesive layer and the surface film are in contact with each other. The laminate according to claim 20 , wherein the support is peeled off. The laminate according to claim 21 , further comprising a retardation film, wherein the retardation film is arranged on the alignment layer side. An image display device having the laminate according to any one of claims 1 to 22 and an image display element.

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