阅读说明：本技术 层叠体及图像显示装置 (Laminate and image display device ) 是由 柴田直也 滨口侑也 笠原健裕 小糸直希 武田淳 加藤由实 米本隆 野副宽 于 2019-10-15 设计创作，主要内容包括：本发明的课题在于提供一种层叠体及使用该层叠体的图像显示装置,所述层叠体具有支撑体、取向层及光吸收各向异性层,其中,容易仅剥离支撑体。本发明的层叠体依次具有支撑体、取向层、光吸收各向异性层、粘合层,不包括支撑体、粘合层的从支撑体至粘合层之间的厚度为5μm以下,粘合层的厚度为5μm～50μm。(The invention provides a laminate and an image display device using the same, wherein the laminate comprises a support, an orientation layer and a light absorption anisotropic layer, and only the support is easily peeled. The laminate of the present invention comprises a support, an alignment layer, a light-absorbing anisotropic layer, and an adhesive layer in this order, wherein the thickness between the support and the adhesive layer excluding the support and the adhesive layer is 5 μm or less, and the thickness of the adhesive layer is 5 to 50 μm.)

1. A laminate comprising a support, an alignment layer, a light-absorbing anisotropic layer and an adhesive layer in this order,

a thickness between the support and the adhesive layer excluding the support and the adhesive layer is 5 [ mu ] m or less,

the thickness of the adhesive layer is 5-50 μm,

the alignment layer is a photo-alignment layer formed using an alignment layer-forming composition containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond.

2. The laminate according to claim 1, wherein,

the storage modulus of the bonding layer is 100 kPa-20 MPa.

3. The laminate according to claim 2, wherein,

the storage modulus of the bonding layer is 100 kPa-2 MPa.

4. The laminate according to any one of claims 1 to 3,

the thickness of the adhesive layer is greater than 10 μm and less than 50 μm.

5. The laminate according to any one of claims 1 to 4,

the light absorption anisotropic layer contains a dichroic substance and a liquid crystalline compound.

6. The laminate according to any one of claims 1 to 5,

the light absorption anisotropic layer contains a dichroic azo compound.

7. The laminate according to any one of claims 1 to 6,

the thickness of the light absorption anisotropic layer is 0.1-3 μm.

8. The laminate according to any one of claims 1 to 7,

the thickness of the orientation layer is 0.1-2 μm.

9. The laminate according to claim 8, wherein,

the thickness of the orientation layer is more than 0.5 μm and less than 2 μm.

10. The laminate according to any one of claims 1 to 9,

the cinnamoyl compound is a photo-alignment copolymer having a repeating unit A containing a photo-alignment group represented by the following formula (A) and a repeating unit B containing a crosslinkable group represented by the following formula (B),

in the formula (A), R¹Represents a hydrogen atom or a methyl group, L¹Represents a 2-valent linking group comprising a nitrogen atom and a cycloalkane ring, a part of carbon atoms constituting the cycloalkane ring may be substituted with a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, R²、R³、R⁴、R⁵And R⁶Each independently represents a hydrogen atom or a substituent, R²、R³、R⁴、R⁵And R⁶In (2) adjacent groups may be bonded to form a ring,

in the formula (B), R⁷Represents a hydrogen atom or a methyl group, L²Represents a linking group having a valence of 2, X represents a crosslinkable group represented by the following formula (X4),

in the formula (X4), L in the formula (B) is represented by²S represents a functional group having an ethylenically unsaturated double bond。

11. The laminate according to claim 10, wherein,

l in the formula (A)¹Is a 2-valent linking group represented by any one of the following formulae (1) to (10),

in the formulae (1) to (10), 1 represents a bonding position to a carbon atom constituting the main chain in the formula (a), and 2 represents a bonding position to a carbon atom constituting the carbonyl group in the formula (a).

12. The laminate according to claim 5, wherein,

the liquid crystal compound is a polymerizable liquid crystal compound.

13. The laminate according to claim 5, wherein,

the liquid crystalline compound is a polymeric liquid crystalline compound.

14. The laminate according to claim 13, wherein,

the light absorption anisotropic layer further includes a low molecular liquid crystalline compound.

15. The laminate according to any one of claims 1 to 14, wherein a cured layer having a thickness of 100nm or less is further provided between the light absorption anisotropic layer and the adhesive layer.

16. The laminate according to claim 15, wherein,

the cured layer contains a liquid crystalline compound.

17. The laminate according to claim 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 claims 1 to 17, wherein a layer containing a polyvinyl alcohol resin having a thickness of 2 μm or less is further provided between the light-absorbing anisotropic layer and the adhesive layer.

19. The laminate according to any one of claims 1 to 18,

the support is in contact with the alignment layer.

20. The laminate according to any one of claims 1 to 19,

the alignment layer is in contact with the light-absorbing anisotropic layer.

21. A laminate having the laminate of any one of claims 1 to 20 and a surface film, and the adhesive layer is in contact with the surface film.

22. The laminate according to claim 21, wherein,

the support has been peeled off.

23. The laminate according to claim 22, further comprising a retardation film, wherein the retardation film is disposed on the alignment layer side.

24. An image display device comprising the laminate according to any one of claims 1 to 23 and an image display element.

Technical Field

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

Background

In recent years, various studies have been made on a light absorption anisotropic layer formed using a dichroic material.

For example, patent document 1 discloses "a circularly polarizing plate comprising a liquid crystal cured film, an adhesive layer, a retardation film, and an adhesive layer laminated in this order, wherein the liquid crystal cured film is a film having a thickness of 3 μm or less and containing a dichroic dye, which is obtained by curing a polymerizable liquid crystal compound in a state of being aligned in a horizontal direction in a substrate plane. "([ claim 16 ]).

On the other hand, in response to the recent demand for further reduction in thickness of display devices, a method of peeling off a support used for the circularly polarizing plate or the like to reduce the thickness has been proposed.

Further, patent document 1 has an object to provide an optically anisotropic sheet ([0004]) for providing a thin optically anisotropic film.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2016-027431

Disclosure of Invention

Technical problem to be solved by the invention

However, when the layer structure becomes complicated due to the expression of various functions, it is difficult to control at which interface the peeling occurs at the time of transfer.

In particular, when the respective layers are very thin laminates due to thinning of polarizers and the like, it is found that it is more difficult to control the peeling interface. For example, even if an attempt is made to peel off only the support from the laminate including the support, the alignment layer, and the light absorption anisotropic layer, peeling may occur at the interface between the alignment layer and the light absorption anisotropic layer.

Accordingly, an object of the present invention is to provide a laminate having a support, an alignment layer, and a light-absorbing anisotropic layer, in which the support can be easily peeled off, and an image display device using the laminate.

Means for solving the technical problem

The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the releasability at other interfaces changes depending on the properties of the adhesive layer when the adhesive layer is bonded to other members.

That is, it was found that a laminate having a support, an alignment layer, a light absorption anisotropic layer, and an adhesive layer in this order and having a thickness from the support to the adhesive layer excluding the support and the adhesive layer of 5 μm or less can be provided, wherein peeling of only the support is facilitated by setting the thickness of the adhesive layer to a specific value.

That is, it has been found that the above-mentioned problems can be achieved by the following configuration.

[1] A laminate comprising a support, an alignment layer, a light-absorbing anisotropic layer and an adhesive layer in this order,

the thickness between the support and the adhesive layer excluding the support and the adhesive layer is 5 μm or less,

the thickness of the adhesive layer is 5-50 μm,

the alignment layer is a photo-alignment layer formed using an alignment layer-forming composition containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond.

[2] The laminate according to [1], wherein,

the storage modulus of the bonding layer is 100 kPa-20 MPa.

[3] The laminate according to [2], wherein,

the storage modulus of the bonding layer is 100 kPa-2 MPa.

[4] The laminate according to any one of [1] to [3], wherein,

the thickness of the adhesive layer is greater than 10 μm and not more than 50 μm.

[5] The laminate according to any one of [1] to [4], wherein,

the light absorption anisotropic layer contains a dichroic substance and a liquid crystalline 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 thickness of the orientation layer is 0.1-2 μm.

[9] The laminate according to claim [8],

the thickness of the orientation layer is more than 0.5 μm and less than 2 μm.

[10] The laminate according to any one of [1] to [9], wherein,

the cinnamoyl compound is a photo-alignment copolymer having a repeating unit a including a photo-alignment group represented by formula (a) described below and a repeating unit B including a crosslinkable group represented by formula (B) described below.

[11] The laminate according to [10], wherein,

l in the following formula (A)¹Is a 2-valent linking group represented by any one of the following formulae (1) to (10).

[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 crystalline compound is a polymeric liquid crystalline compound.

[14] The laminate according to [13], wherein,

the light absorption anisotropic layer further contains a low-molecular liquid crystalline compound.

[15] The laminate according to any one of [1] to [14], further having a cured layer having a thickness of 100nm 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 crystalline 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-absorbing anisotropic layer and the adhesive layer.

[19] The laminate according to any one of [1] to [18], wherein,

the support is in contact with the alignment layer.

[20] The laminate according to any one of [1] to [19], wherein,

the alignment layer is in contact with the light absorbing anisotropic layer.

[21] A laminate having the laminate of any one of [1] to [20] and a surface film, and an adhesive layer in contact with the surface film.

[22] The laminate according to [21], wherein,

the support has been peeled off.

[23] The laminate according to [22], further comprising a retardation film, wherein the retardation film is disposed on the alignment layer side.

[24] An image display device comprising the laminate according to any one of [1] to [23] and an image display element.

Effects of the invention

According to the present invention, a laminate comprising a support, an alignment layer, and a light-absorbing anisotropic layer, wherein only the support can be easily peeled, and an image display device using the laminate can be provided.

Drawings

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

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

Fig. 3 is a schematic cross-sectional view showing an example of an embodiment of the laminate of the present invention.

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements is made in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the present specification, the numerical range expressed by the term "to" means a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.

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

In the present specification, one kind of substance corresponding to each component may be used alone for each component, or two or more kinds may be used simultaneously. Here, when two or more substances are used together for each component, the content of the component refers to the total content of the substances used together unless otherwise specified.

In the present specification, "(meth) acrylate" is a label indicating "acrylate" or "methacrylate", "meth (acrylic acid)" is a label indicating "acrylic acid" or "methacrylic acid", and "(meth) acryloyl group" is a label indicating "acryloyl group" or "methacryloyl group".

In the present specification, the liquid crystalline composition and the liquid crystalline compound conceptually include a liquid crystalline composition and a liquid crystalline compound which do not exhibit liquid crystallinity any more after curing or the like.

[ laminate ]

The laminate of the present invention is a laminate comprising a support, an alignment layer, a light-absorbing anisotropic layer, and an adhesive layer in this order.

In the laminate of the present invention, the thickness between the support not including the support and the adhesive layer is 5 μm or less, and the thickness of the adhesive layer is 5 to 50 μm.

In the laminate of the present invention, the alignment layer is a photo-alignment layer formed using an alignment layer-forming composition containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond.

Next, the overall structure of the laminate of the present invention will be described with reference to fig. 1 to 3, and then the respective structures will be described in detail.

The laminate 10 shown in fig. 1 includes a support 1, an alignment layer 2, a light absorption anisotropic layer 3, and an adhesive layer 4 in this order.

In the laminate 10, the thickness of the support 1 and the adhesive layer 4, excluding the support 1 and the adhesive layer 4, from the support 1 to the adhesive layer 4, that is, the distance from the surface of the support 1 on the alignment layer 2 side to the surface of the adhesive layer 4 on the light absorption anisotropic layer 3 side, is 5 μm or less, preferably 1 μm to 4 μm.

In the laminate 10, the thickness of the adhesive layer 4 is 5 μm to 50 μm.

As shown in fig. 1, in the laminate of the present invention, the support 1 is preferably in contact with the alignment layer 2.

In the laminate of the present invention, as shown in fig. 1, the alignment layer 2 is preferably in contact with the light absorption anisotropic layer 3.

As shown in fig. 2, the laminate of the present invention preferably further includes a cured layer 5 having a thickness of 100nm 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 preferably further includes a layer containing a polyvinyl alcohol resin (hereinafter, also simply referred to as "PVA layer") 6 having a thickness of 2 μm or less between the light absorption anisotropic layer 3 and the adhesive layer 4.

When the laminate of the present invention includes both the cured layer 5 and the layer 6 containing a polyvinyl alcohol resin, as shown in fig. 2, it is preferable that the light absorption anisotropic layer 3, the cured layer 5, the layer 6 containing a polyvinyl alcohol resin, and the adhesive layer 4 are provided in this order.

As shown in fig. 3, the laminate of the present invention preferably further has a surface film 7. In this case, the surface film 7 is preferably in contact with the adhesive layer 4, that is, the surface film 7 is preferably bonded to another layer via the adhesive layer 4.

The laminate of the present invention can be used without the support 1 as shown in fig. 3 by peeling the support 1 shown in fig. 2.

As shown in fig. 3, the laminate of the present invention may further include a retardation film 8, and in this case, the retardation film 8 is preferably disposed on the alignment layer 2 side.

[ adhesive layer ]

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

The storage modulus of the adhesive layer used in the present invention is preferably 10kPa to 20MPa, more preferably 10kPa to 2MPa, from the viewpoint of easier adjustment of the peelability of the support.

Method for measuring storage modulus

In the present invention, the storage modulus is a value measured at 25 ℃ at a frequency of 1Hz using a dynamic viscoelasticity measuring apparatus (DVA-200) manufactured by IT Keisoku Seigyo Co., Ltd.

The thickness of the adhesive layer used in the present invention is 5 μm to 50 μm, preferably more than 10 μm and 50 μm or less.

By setting the above range, the peelability can be more easily adjusted.

< raw Material for adhesion layer >

Examples of the material to be included in the pressure-sensitive adhesive layer used in the present invention include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, polyvinyl alcohol-based pressure-sensitive adhesives, polyvinyl pyrrolidone-based pressure-sensitive adhesives, polyacrylamide-based pressure-sensitive adhesives, and cellulose-based pressure-sensitive adhesives.

Among these, acrylic adhesives (pressure-sensitive adhesives) are preferred from the viewpoint of transparency, weather resistance, heat resistance, and the like.

The acrylic pressure-sensitive adhesive is preferably an acrylic polymer such as a copolymer of a (meth) acrylate ester in which the alkyl group of the ester moiety is an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, or a butyl group, and a (meth) acrylic monomer having a functional group such as (meth) acrylic acid and hydroxyethyl (meth) acrylate.

Such an acrylic polymer-containing pressure-sensitive adhesive is preferable because it has excellent adhesion and can be peeled off relatively easily without generating a residue of slurry or the like on a display device when peeled off after being bonded to another member.

The glass transition temperature of the acrylic polymer is preferably 25 ℃ or lower, and more preferably 0 ℃ or lower.

The weight average molecular weight of the acrylic polymer is preferably 10 ten thousand or more.

[ support body ]

The support used in the present invention is not particularly limited, and various known supports can be used. The support is preferably a releasable support.

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

From the viewpoint of easier adjustment of the releasability, the thickness of the support is preferably 10 to 200 μm, more preferably 50 to 200 μm, and still more preferably 100 to 200 μm.

Further, the peelability can be more easily adjusted by adjusting the elastic modulus of the support body in accordance with the storage modulus of the adhesive layer.

Further, the support that is difficult to permeate is selected according to the composition of the alignment layer, and the adhesion between the support and the alignment layer is reduced, whereby the releasability can be more easily adjusted.

[ alignment layer ]

The alignment layer used in the present invention is a photo-alignment layer formed using an alignment layer-forming composition 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, more preferably more than 0.5 μm and 2 μm or less.

As described above, the photo-alignment layer used in the present invention is a photo-alignment layer formed using an alignment layer forming composition containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond (hereinafter, simply referred to as "polymerizable group" in this paragraph), and among them, a photo-alignment layer formed using a photo-alignment copolymer described later is more preferable as the cinnamoyl compound. When the same kind of polymerizable group (for example, a methacryloyl group or an acryloyl group) as that contained in the composition of the light absorbing anisotropic layer is also contained in the composition of the photo-alignment layer, the layers are chemically bonded to each other to increase the interlayer adhesion between the photo-alignment layer and the light absorbing anisotropic layer, which is advantageous for achieving the object of the present invention, that is, for facilitating the peeling of only the support.

< photo-alignment copolymer >

The photo-alignment copolymer used in the present invention is a photo-alignment copolymer having a repeating unit a including a photo-alignment group represented by formula (a) below and a repeating unit B including a crosslinkable group represented by formula (B) below.

[ chemical formula 1]

In the above formula (A), R¹Represents a hydrogen atom or a methyl group. L is¹Represents a 2-valent linking group comprising a nitrogen atom and a cycloalkane ring, and a part of carbon atoms constituting the cycloalkane ring may be substituted with a heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. R²、R³、R⁴、R⁵And R⁶Each independently represents a hydrogen atom or a substituent, R²、R³、R⁴、R⁵And R⁶In (2) adjacent groups may be bonded to form a ring,

in the above formula (B), R⁷Represents a hydrogen atom or a methyl group, L²Represents a 2-valent linking group, and X represents a crosslinkable group represented by the following formula (X4).

[ chemical formula 2]

In the formula (X4), L is the same as L in the formula (B)²S represents a functional group having an ethylenically unsaturated double bond.

In the present invention, by using a photo-alignment copolymer having a repeating unit a containing a photo-alignment group represented by the formula (a) and a repeating unit B containing a crosslinkable group represented by the formula (B), the solvent resistance and the liquid crystal alignment property of the obtained photo-alignment film are improved.

The present inventors speculate as follows, although the details thereof are not clear.

Namely, it is considered that L in the above formula (A) is caused by¹The 2-valent linking group represented includes a nitrogen atom and a cycloalkane ring, and the hydrogen bonding property and the molecular rigidity are improved, whereby the molecular movement is suppressed, and as a result, the solvent resistance is improved.

Similarly, it is considered that L in the above formula (A) is caused by¹The 2-valent linking group includes a nitrogen atom and a cycloalkane ring, and the glass transition temperature of the copolymer is increased, whereby the temporal stability of the photo-alignment film obtained is improvedAs a result, the liquid crystal alignment property is improved regardless of the timing of forming the optically anisotropic layer.

Next, L in the above formula (A)¹The 2-valent linking group comprising a nitrogen atom and a cycloalkane ring is illustrated. In the present invention, as described above, a part of the carbon atoms constituting the cycloalkane ring may be substituted with a heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. And, when a part of carbon atoms constituting the cycloalkane ring has been substituted with a nitrogen atom, it may not have a nitrogen atom independent of the cycloalkane ring.

And L in the above formula (A)¹The cycloalkane ring contained in the linking group having a valence of 2 represented by the formula is preferably a cycloalkane ring having 6 or more carbon atoms, and specific examples thereof include a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclododecane ring, and the like.

In the present invention, L in the formula (a) is preferable because the liquid crystal alignment property is more favorable¹Is a 2-valent linking group represented by any one of the following formulae (1) to (10).

[ chemical formula 3]

In the formulae (1) to (10), 1 represents a bonding position to a carbon atom constituting the main chain in the formula (a), and 2 represents a bonding position to a carbon atom constituting the carbonyl group in the formula (a).

Among the 2-valent linking groups represented by any one of the above formulae (1) to (10), the 2-valent linking group represented by any one of the above formulae (2), (3), (7) and (8) is preferable because the solubility in a solvent used in forming the photo-alignment film and the solvent resistance of the obtained photo-alignment film are well balanced.

L in the above formula (A)¹May be a 2-valent linking group other than the above-mentioned "2-valent linking group containing a nitrogen atom and a cycloalkane ring".

The 2-valent linking group is preferably a 2-valent linking group in which at least two or more groups selected from the group consisting of a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms which may have a substituent, an arylene group having 6 to 12 carbon atoms which may have a substituent, an ether group (-O-), a carbonyl group (-C (═ O) -), and an imino group (-NH-) which may have a substituent are combined, because the photoalignment group easily interacts with a liquid crystal compound and the liquid crystal alignment properties of the adjacent liquid crystal layer become better.

Then, for R in the above formula (A)²、R³、R⁴、R⁵And R⁶The substituent represented by the first embodiment of (1) is described. As described above, R in the above formula (A)²、R³、R⁴、R⁵And R⁶May be a hydrogen atom instead of a substituent.

R in the formula (A) is R because the photo-alignment group easily interacts with the liquid crystalline compound to improve the liquid crystal alignment²、R³、R⁴、R⁵And R⁶The substituent represented by the above-mentioned one mode is preferably a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 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).

[ chemical formula 4]

Wherein in the formula (11), R represents a bonding position with the benzene ring in the formula (A)⁹Represents an organic group having a valence of 1.

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 linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferred is an alkyl group having 1 to 6 carbon atoms as the linear alkyl group, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group and the like.

The branched alkyl group is preferably an alkyl group having 3 to 6 carbon atoms, and specific examples thereof include an isopropyl group, a tert-butyl group and the like.

The cyclic alkyl group is preferably an alkyl group having 3 to 6 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The linear haloalkyl group having 1 to 20 carbon atoms is preferably a fluoroalkyl group having 1 to 4 carbon atoms, and specific examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group and the like, and among them, a trifluoromethyl group is preferable.

The alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 6 to 18 carbon atoms, and still more preferably an alkoxy group having 6 to 14 carbon atoms. Specific examples thereof include preferably methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, and n-tetradecyloxy group, and among these, n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, and n-tetradecyloxy group are more preferable.

The aryl group having 6 to 20 carbon atoms is preferably 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 among them, a phenyl group is 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 phenoxy group, a 2-naphthoxy group and the like, and among them, a phenoxy group is preferable.

Examples of the amino group include a primary amino group (-NH)₂) (ii) a Secondary amino groups such as methylamino; a tertiary amino group such as a dimethylamino group, a diethylamino group, a dibenzylamino group, or a group having a nitrogen atom of a nitrogen-containing heterocyclic compound (e.g., pyrrolidine, piperidine, or piperazine) as a connecting bond.

The group represented by the above formula (11) is R in the above formula (11)⁹Examples of the 1-valent organic group include linear or cyclic alkyl groups having 1 to 20 carbon atoms.

The linear alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, and an n-propyl group, and among them, a methyl group and an ethyl group are preferable.

The cyclic alkyl group is preferably an alkyl group having 3 to 6 carbon atoms, 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.

R in the above formula (11) is⁹The 1-valent organic group represented may be a group obtained by combining a plurality of the above-mentioned linear alkyl groups and cyclic alkyl groups directly or through a single bond.

In the present invention, R in the formula (a) is R because the photo-alignment group easily interacts with the liquid crystalline compound and the liquid crystal alignment property is more excellent²、R³、R⁴、R⁵And R⁶Among them, at least R is preferable⁴The substituent is more preferably represented, and R is more preferably selected from the group consisting of the substituents mentioned above, because the obtained photo-alignment copolymer has improved linearity, and easily interacts with a liquid crystalline compound to further improve liquid crystal alignment²、R³、R⁵And R⁶All represent hydrogen atoms.

In the present invention, R in the formula (a) is preferable because the reaction efficiency is improved when the obtained photo-alignment film is irradiated with light⁴Are substituents which are electron donating.

Here, the electron donating substituent (electron donating group) means a substituent having a Hammett value (Hammett substituent constant σ p) of 0 or less, and examples thereof include an alkyl group, a halogenated alkyl group, and an alkoxy group among the substituents.

Among these, alkoxy groups are preferable, and alkoxy groups having 6 to 16 carbon atoms are more preferable, and alkoxy groups having 7 to 10 carbon atoms are even more preferable, because the liquid crystal alignment properties are more excellent.

Next, L in the above formula (B)²Is shown inThe 2-valent linking group is illustrated.

The 2-valent linking group is preferably a 2-valent linking group in which at least two or more groups selected from the group consisting of a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms which may have a substituent, an arylene group having 6 to 12 carbon atoms which may have a substituent, an ether group (-O-), a carbonyl group (-C (-O-) and an imino (-NH-) which may have a substituent are combined, because the photo-alignment group easily interacts with the liquid crystalline compound and the liquid crystal alignment property is more excellent.

Examples of the substituent which 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 carboxyl group, an alkoxycarbonyl group and a hydroxyl 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.

The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, etc.), still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (e.g., methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.), even more preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.

Examples of the aryl group include aryl groups having 6 to 12 carbon atoms, and specific examples thereof include phenyl, α -methylphenyl, naphthyl and the like, and among them, phenyl is preferable.

Examples of the aryloxy group include a phenoxy group, a naphthoxy group, an imidazolyloxy group, a benzimidazolyloxy group, a pyridin-4-yloxy group, a pyrimidyloxy group, a quinazolinyloxy group, a purinyloxy group, and a thiophen-3-yloxy group.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

Examples of the linear alkylene group include a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a decylene group, an undecylene group, a dodecenyl group, a tridecylene group, a tetradecylene group, a pentadecenyl group, a hexadecylene group, a heptadecenyl group, and an octadecenyl group.

Specific examples of the branched alkylene group include dimethylmethylene, methylethylene, 2-dimethylpropylene, and 2-ethyl-2-methylpropylene.

Specific examples of the cyclic alkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, adamantane-diyl, norbornane-diyl, exo-tetrahydrodicyclopentadiene-diyl, and the like, and among them, cyclohexylene is preferable.

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

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

The X (crosslinkable group) in the formula (B) is a crosslinkable group represented by the following formula (X4) among the crosslinkable groups represented by the following formulae (X1) to (X4).

[ chemical formula 5]

In the formulae (X1) to (X4), L in the formula (B) is the same as L in the formula (B)²Bonding position of R⁸Represents any of a hydrogen atom, a methyl group and an ethyl group, and in the formula (X4), S represents a functional group having an ethylenically unsaturated double bond.

Specific examples of the functional group having an ethylenically unsaturated double bond include a vinyl group, an allyl group, a styryl group, an acryloyl group, and a methacryloyl group, and an acryloyl group or a methacryloyl group is preferable.

In the present invention, it is preferable that the repeating unit B includes a repeating unit in which X in the formula (B) is a crosslinkable group represented by any one of the formulae (X1) to (X3) (hereinafter, also simply referred to as "repeating unit B1") and a repeating unit in which X in the formula (B) is a crosslinkable group represented by the formula (X4) (hereinafter, also simply referred to as "repeating unit B2") because the strength of the optical laminate of the present invention described later becomes high and the handleability when another layer is formed using the optical laminate of the present invention described later becomes good.

Specific examples of the repeating unit a containing a photo-alignment group represented by the formula (a) include the following repeating units a-1 to a-44. In the following formulae, Me represents a methyl group and Et represents an ethyl group. In the following specific examples, "1, 4-cyclohexyl" contained in the linking group having a valence of 2 in the repeating units a-1 to a-10 may be either cis-isomer or trans-isomer, but is preferably trans-isomer.

[ chemical formula 6]

[ chemical formula 7]

On the other hand, as the repeating unit B (repeating unit B1) containing a crosslinkable group represented by the above formula (B), specific examples thereof include the following repeating units B-1 to B-17.

[ chemical formula 8]

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

[ chemical formula 9]

The content a of the repeating unit a and the content B of the repeating unit B in the photo-alignment copolymer used in the present invention preferably satisfy the following formula (12), more preferably satisfy the following formula (13), further preferably satisfy the following formula (14), and particularly preferably satisfy the following formula (15) in a mass ratio.

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)

In addition, when the photo-alignment copolymer used in the present invention has the repeating unit B1 and the repeating unit B2, the content a of the repeating unit a, the content B1 of the repeating unit B1, and the content B2 of the repeating unit B2 preferably satisfy the following formula (16) and more preferably satisfy the following formula (17) in terms of mass ratio, for the reason that the strength of the optically anisotropic layer including the photo-alignment film is further improved while maintaining good liquid crystal alignment properties and adhesion.

0.05≤b2/(a+b1+b2)≤0.7……(16)

0.10≤b2/(a+b1+b2)≤0.5……(17)

The photo-alignment copolymer used in the present invention may have other repeating units in addition to the repeating unit a and the repeating unit B as long as the effects of the present invention are not hindered.

Examples of the monomer (radical polymerizable monomer) forming such another repeating unit include an acrylate compound, a methacrylate compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

The method for synthesizing the photo-alignment copolymer used in the present invention is not particularly limited, and for example, the photo-alignment copolymer can be synthesized by mixing a monomer forming the repeating unit a, a monomer forming the repeating unit B, and a monomer forming any other repeating unit and polymerizing the mixture in an organic solvent using a radical polymerization initiator.

The weight average molecular weight (Mw) of the photo-alignment copolymer used in the present invention is preferably 10000 to 500000, more preferably 30000 to 300000, for the reason that the liquid crystal alignment property is further improved.

Here, the weight average molecular weight and the number average molecular weight in the present invention are values measured by a Gel Permeation Chromatography (GPC) method under the conditions shown below.

Solvent (eluent): THF (tetrahydrofuran)

Device name: TOSOH HLC-8320GPC

Column: 3 TOSOH TSKgel Super HZM-H (4.6 mm. times.15 cm) were used in a ligation

Column temperature: 40 deg.C

Sample concentration: 0.1% by mass

Flow rate: 1.0ml/min

Calibration curve: calibration curves obtained using 7 samples of TSK standard polystyrene Mw 2800000-1050 (Mw/Mn 1.03-1.06) manufactured by TOSOH

[ light-absorbing anisotropic layer ]

The light absorption anisotropic layer used in the present invention is a layer that absorbs light to a different degree depending on the direction, and generally 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 to 3 μm, more preferably 0.1 to 2 μm.

The light absorption anisotropic layer used in the present invention preferably contains a dichroic substance.

The light absorption anisotropic layer used in the present invention preferably contains a liquid crystalline compound together with a dichroic material.

Also, the light absorption anisotropic layer used in the present invention preferably contains a dichroic azo compound.

< dichroic substance >

The dichroic substance used in the present invention is not particularly limited, and visible light absorbing substances (dichroic dye, dichroic azo compound), luminescent substances (fluorescent substance, phosphorescent substance), ultraviolet absorbing substances, infrared absorbing substances, nonlinear optical substances, carbon nanotubes, inorganic substances (e.g., quantum rod), and the like can be mentioned, and conventionally known dichroic substances (dichroic dye) can be used. Further, a dichroic material having liquid crystallinity is also preferable.

Specifically, for example, there are sections [0067] to [0071] of Japanese patent laid-open publication No. 2013-228706, sections [0008] to [0026] of Japanese patent laid-open publication No. 2013-227532, sections [0008] to [0015] of Japanese patent laid-open publication No. 2013-209367, [0045] to [0058] of Japanese patent laid-open publication No. 2013-014883, sections [0012] to [0029] of Japanese patent laid-open publication No. 2013-109090, sections [0009] to [0017] of Japanese patent laid-open publication No. 2013-101328, [0011] to [0065] of Japanese patent laid-open publication No. 2013-037353, sections [0049] to [ 0023 ] of Japanese patent laid-open publication No. 0049] and sections [0016] to [ 00769 ] of Japanese patent laid-open publication No. 11-033056, sections [ 0019 ] to [ 007242 ] of Japanese patent laid-0011 ] and [ 007242 ] of Japanese patent laid-036969 ], sections [ 2010 ] and [ 007242 ] of Japanese patent laid-007242, paragraphs [ 007242, and [ 007242 ] of Japanese patent laid-1061 ] of Japanese patent laid-0031 ] of, The dichroic substances described in paragraphs [0011] to [0025] of Japanese patent laid-open No. 2010-215846, paragraphs [0017] to [0069] of Japanese patent laid-open No. 2011-048311, paragraphs [0013] to [0133] of Japanese patent laid-open No. 2011-213610, paragraphs [0074] to [0246] of Japanese patent laid-open No. 2011-237513, paragraphs [0005] to [0051] of Japanese patent laid-open No. 2016-006502, paragraphs [0005] to [0041] of International publication No. 2016/060173, paragraphs [0008] to [0062] of International publication No. 2016/136561, paragraphs [0014] to [0033] of International publication No. 2017/154835, paragraphs [0014] to [0033] of International publication No. 2017/154695, and paragraphs [0013] to [0037] of International publication No. 2017/195833.

In the present invention, two or more dichroic substances may be used simultaneously, and for example, from the viewpoint of making the polarizer black-like, it is preferable to use at least one dichroic substance having a maximum absorption wavelength in the wavelength range of 370 to 550nm and at least one dichroic substance having a maximum absorption wavelength in the wavelength range of 500 to 700nm simultaneously.

The dichroic substance may have a crosslinkable group.

Specific examples of the crosslinkable group include a (meth) acryloyl group, an epoxy group, an oxetanyl group, and a styryl group, and among them, a (meth) acryloyl group is preferable.

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

< liquid crystalline Compound >

As the liquid crystalline compound used in the present invention, both a low molecular liquid crystalline compound and a high molecular liquid crystalline compound can be used.

Here, the "low-molecular liquid crystalline compound" refers to a liquid crystalline compound having no repeating unit in its chemical structure.

The "polymeric liquid crystalline compound" refers to a liquid crystalline compound having a repeating unit in its chemical structure.

Examples of the low-molecular liquid crystalline compound include liquid crystalline compounds described in jp 2013-a 228706.

Examples of the polymer liquid crystalline compound include thermotropic liquid crystalline polymers described in Japanese patent application laid-open No. 2011-237513.

The liquid crystalline polymer compound may have a crosslinkable group (for example, an acryloyl group or a methacryloyl group) at the end.

The liquid crystalline compound used in the present invention is preferably a liquid crystalline compound having a polymerizable group (polymerizable liquid crystalline compound).

Specific examples of the polymerizable group include a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

In the present invention, one liquid crystalline compound may be used alone, or two or more liquid crystalline compounds may be used simultaneously.

In the present invention, the liquid crystal composition preferably contains a polymeric liquid crystalline compound, and more preferably contains both a polymeric liquid crystalline compound and a low molecular liquid crystalline compound.

The content of the liquid crystalline compound is preferably 25 to 2000 parts by mass, more preferably 33 to 1000 parts by mass, and further preferably 50 to 500 parts by mass, based on 100 parts by mass of the dichroic material. When the content of the liquid crystalline compound is within the above range, the degree of orientation of the polarizer is further improved.

[ solidified layer ]

Any cured layer used in the present invention is preferably a cured layer having a thickness of 100nm or less.

As the cured layer, various known cured layers can be used. For example, a layer containing a liquid crystalline compound or a layer obtained by curing a composition containing a polyfunctional monomer can be given. It is preferable to have a refractive index that can be index-matched with the light absorption anisotropic layer.

[ layer containing polyvinyl alcohol resin ]

The layer containing an arbitrary 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 ]

It is generally preferable that an arbitrary surface film used in the present invention is disposed on the outermost side in the optical laminate obtained.

The surface film is not particularly limited, and various known surface films can be used. For example, a surface film having a hard coat layer and a base material is given.

Examples of the material constituting the surface film include a (meth) acrylic resin, a polycarbonate resin, a polystyrene resin, a polyolefin resin, a cyclic polyolefin resin, a glutaric anhydride resin, a glutarimide resin, a cellulose resin, a polyester resin, a polyimide resin, and a mixed resin of a plurality of resins selected from these resins, and among them, a cyclic polyolefin resin, a (meth) acrylic resin, a polyimide resin, or a polyester resin is preferable. Further, a polyimide-based resin is preferable from the viewpoint of excellent flexibility.

The surface film may contain an ultraviolet absorber.

Examples of the (meth) acrylic resin include, in addition to methacrylic resins and acrylic resins, (meth) acrylic polymers having a ring structure in the main chain, that is, polymers having a lactone ring, maleic anhydride polymers having a succinic anhydride ring, polymers having a glutaric anhydride ring, and glutarimide ring-containing polymers.

The hard coat layer is a layer for imparting hardness or scratch resistance to the laminate.

The hard coat layer can be formed, for example, by applying a composition for forming a hard coat layer to a substrate and curing the composition.

In addition, other functional layers may be laminated on the hard coat layer in order to provide other functions.

Further, by adding a filler or an additive to the hard coat layer, mechanical, electrical, or optical physical properties, or chemical properties such as water-repellency or oil-repellency can be imparted to the hard coat layer itself.

The hard coat layer is preferably excellent in scratch resistance 20663. Specifically, when a pencil hardness test which is an index of the scratch resistance 20663is performed, it is preferably 3H or more.

The thickness of the hard coating layer is preferably 0.1 to 6 μm, and more preferably 3 to 6 μm.

The hard coat layer is preferably formed by curing the curable composition.

The curable composition is preferably prepared as a liquid coating composition.

One example of the curable composition includes a monomer, oligomer, or polymer for forming a matrix binder and an organic solvent.

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

[ retardation film ]

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

In the present specification, the "λ/4 plate" refers to a plate having a λ/4 function, specifically, a plate having a function of converting linearly polarized light of a certain specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light).

For example, as an embodiment in which the λ/4 plate has a single-layer structure, a stretched polymer film or a retardation film having an optically anisotropic layer having a λ/4 function provided on a support can be specifically mentioned, and as an embodiment in which the λ/4 plate has a multilayer structure, a broadband λ/4 plate in which a λ/4 plate and a λ/2 plate are laminated can be specifically mentioned.

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

[ image display apparatus ]

An image display device of the present invention includes the laminate 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.

Among these, a liquid crystal cell or an organic EL display panel is preferable, and a liquid crystal cell is more preferable. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as an image display element, an organic EL display device using an organic EL display panel as a display element, and more preferably an organic EL display device.

[ liquid Crystal cell ]

The liquid crystal cell used In the liquid crystal display device is preferably a VA (Vertical Alignment: Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode, but is not limited thereto.

In the TN-mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied, and further are twisted and aligned at 60 to 120 °. Liquid crystal cells of TN mode are most often used as color TFT (Thin Film Transistor) liquid crystal display devices and are described in many documents.

In the VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied. In addition to a VA mode liquid crystal cell (described in japanese patent application laid-open No. h 2-176625) in a narrow sense in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and aligned substantially horizontally when a voltage is applied, a VA mode liquid crystal cell (described in SID97, Digest of tech. papers 28 (1997)) and (845) in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied and the alignment is distorted when a voltage is applied (n-ASM mode) are included in VA mode liquid crystal cells (described in japanese patent application laid-open No. 58-59 (1998)) and (4) in a liquid crystal cell in a suival mode (published in LCD international 98). Further, any of a PVA (Patterned Vertical Alignment) type, a photo-Alignment type (Optical Alignment) and a PSA (Polymer-stabilized Alignment) type may be used. The details of these modes are described in detail in Japanese patent laid-open Nos. 2006-215326 and 2008-538819.

In the IPS mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in plane by applying an electric field parallel to the substrate surface. The IPS mode displays black in a state where no electric field is applied, and absorption axes of the upper and lower pair of polarizing plates are orthogonal to each other. Methods for improving the viewing angle by reducing light leakage in black display in an oblique direction using an optical compensation sheet are disclosed in japanese patent application laid-open nos. 10-054982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

(organic EL display device)

As an example of the image display device of the present invention, an organic EL display device is preferably provided with the laminate and the organic EL display panel of the present invention in this order from the viewing side.

More preferably, the laminate of the present invention and the organic EL display panel are provided in this order from the viewing side with a λ/4 plate. In this case, the laminate is arranged in the order of the surface film, the adhesive layer, the light absorbing anisotropic layer, the alignment layer, and the retardation film as necessary from the viewing side.

The organic EL display panel is a display panel configured using an organic EL element in which an organic light-emitting layer (organic electroluminescent layer) is sandwiched between electrodes (between a cathode and an anode). The structure of the organic EL display panel is not particularly limited, and a known structure may be employed.

Examples

The present invention will be described in further detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing steps and the like shown in the following examples can be appropriately modified without departing from the spirit of the present invention. The scope of the invention should therefore not be construed in a limiting sense by the examples shown below.

[ example 1]

< formation of photo-alignment layer PA1 >

As the support, a TAC (triacetyl cellulose) film (TJ40UL, thickness 40 μm, manufactured by FUJIFILM Corporation) was used.

Subsequently, the alignment layer forming composition PA1 described later was continuously applied to a support by a wire bar. The support having the coating film formed thereon was dried with warm air at 140 ℃ for 120 seconds, and then the coating film was irradiated with polarized ultraviolet rays (10 mJ/cm)²Ultra-high pressure mercury lamp was used) to form a photo-alignment layer PA1, thereby obtaining a TAC film with a photo-alignment layer.

The thickness of the photo-alignment layer PA1 was 1.0. mu.m.

Polymer PA-1

[ chemical formula 10]

Acid generator PAG-1

[ chemical formula 11]

Acid generator CPI-110F

[ chemical formula 12]

< formation of light absorption Anisotropic layer P1 >

The light-absorbing anisotropic layer-forming composition P1 having the following composition was continuously applied to the obtained photo-alignment layer PA1 with a wire bar, thereby forming a coating layer P1.

Subsequently, the coating layer P1 was heated at 140 ℃ for 90 seconds, and the coating layer P1 was cooled to room temperature (23 ℃).

Subsequently, the mixture was heated at 80 ℃ for 60 seconds and cooled again to room temperature.

Then, a high-pressure mercury lamp was used at an illuminance of 28mW/cm²Is irradiated under the irradiation conditions of (1) for 60 seconds, thereby forming a light absorption anisotropic layer P1 on the photo-alignment layer PA 1.

The thickness of the light absorption anisotropic layer P1 was 0.4 μm.

Azo dye Y-1

[ chemical formula 13]

Azo pigment M-1

[ chemical formula 14]

Azo pigment C-1

[ chemical formula 15]

Polymer liquid crystalline compound P-1

[ chemical formula 16]

Liquid crystalline Compound L-1

[ chemical formula 17]

Surface modifier F-1

[ chemical formula 18]

< formation of cured layer L1 >

On the obtained light absorption anisotropic layer P1, a cured layer-forming composition L1 having the following composition was continuously applied with a wire bar, thereby forming a composition layer L1.

Next, the composition layer L1 was dried at room temperature, and then, the illuminance was 28mW/cm using a high-pressure mercury lamp²Is irradiated under the irradiation conditions of (1) for 10 seconds, thereby forming a cured layer L1 on the light-absorbing anisotropic layer P1.

The cured layer L1 had a film thickness of 30 nm.

Mixture L-2 of rod-shaped liquid crystalline Compounds (numerical values in the following formula represent mass%, and R represents a group bonded through an oxygen atom.)

[ chemical formula 19]

Modified trimethylolpropane triacrylate

[ chemical formula 20]

The following photopolymerization initiator I-1

[ chemical formula 21]

< formation of PVA layer B1 >

A coating liquid B1 for forming a polyvinyl alcohol (PVA) layer having the following composition was continuously applied to the cured layer L1 with a wire bar.

Then, by drying at 100 ℃ for 2 minutes under warm air, a PVA layer having a thickness of 1.0 μm was formed on the cured layer L1.

Modified polyvinyl alcohol

[ chemical formula 22]

< production of laminate 1 >

The psa sheet N1 produced below was laminated on the PVA layer B1 on the psa layer N1 side to complete the laminate 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 apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, and the air in the reaction apparatus was replaced with nitrogen gas.

Then, to the reaction apparatus were added 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-dimethylmethacrylamide, 0.1 part by mass of azobisisobutyronitrile, and 120 parts by mass of ethyl acetate.

This was reacted at 60 ℃ for 8 hours in a nitrogen stream with stirring to obtain a solution of an acrylic copolymer having a weight average molecular weight of 150 ten thousand. Further, the mixture was diluted with ethyl acetate to obtain a copolymer solution 1 having a solid content of 15%.

Subsequently, a solution (adhesive composition N1) in which 3 parts by mass of polyisocyanate (Coronate-L, Nippon Polyurethane Industry Co., Ltd.) and 0.2 part by mass of aluminum triacetylacetonate (aluminum chelate A, Kawaken Fine Chemicals Co., Ltd.) and 0.1 part by mass of γ -mercaptopropylmethyldimethoxysilane (KBM-803, Shin-Etsu Chemical Co., Ltd.) were mixed with 100 parts by mass of the solid content of the copolymer solution 1 was prepared.

Next, the prepared adhesive composition N1 was applied to a PET film coated with a silicone resin (hereinafter, also simply referred to as a "release film"), and the solvent was removed by drying at 90 ℃. The storage modulus of the adhesive layer N1 was 0.3 MPa.

[ example 2]

In the same manner as in example 1 except that the support was changed to PET (thickness: 40 μm) in the formation of the light absorption anisotropic layer in example 1, a laminate of example 2 was obtained.

[ example 3]

In the formation of the light absorption anisotropic layer of example 1, a laminate of example 3 was obtained in the same manner as in example 1 except that the support was changed to a cellulose acylate film TJ100UL (thickness 100 μm, manufactured by FUJIFILM Corporation).

[ examples 4 to 7]

Laminates of examples 4 to 7 were obtained in the same manner as in example 1 except that the thicknesses of the composition for forming a light-absorbing anisotropic layer and the photo-alignment layer were changed as shown in table 2 below in the formation of the light-absorbing anisotropic layer in example 1.

In table 2 below, the details of the compositions P2 and P3 for forming a light-absorbing anisotropic layer are as follows.

Azo pigment C-2

[ chemical formula 23]

Polymer liquid crystalline compound P-2

[ chemical formula 24]

Composition P3 for forming light-absorbing anisotropic layer

Azo dye Y-2

[ chemical formula 25]

Azo pigment M-2

[ chemical formula 26]

Azo pigment C-3

[ chemical formula 27]

[ example 8]

< formation of light absorption Anisotropic layer P4 >

A 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 P4 for forming a light-absorbing anisotropic layer, which was prepared below, was continuously coated on the obtained photo-alignment layer PA1 with a wire bar, thereby forming a coating layer P4.

Subsequently, the coating layer P4 was heated at 120 ℃ for 60 seconds, and the coating layer P4 was cooled to room temperature (23 ℃).

Then, a high-pressure mercury lamp was used at an illuminance of 28mW/cm²Is irradiated under the irradiation conditions of (1) for 60 seconds, thereby forming a light absorption anisotropic layer P4 on the photo-alignment layer PA 1.

The thickness of the light absorption anisotropic layer P4 was 1.7 μm.

A composition P4 for forming a light-absorbing anisotropic layer was prepared in the following composition, and was dissolved by heating at 50 ℃ for 3 hours while stirring, and was filtered through a 0.45 μm filter.

Azo pigment M-3

[ chemical formula 28]

Azo dye Y-3

[ chemical formula 29]

Azo pigment C-4

[ chemical formula 30]

Liquid crystal compound P-3 (compound a/compound B. 75/25 blend)

Compound A

[ chemical formula 31]

Compound B

[ chemical formula 32]

< production of laminate 8 >

A PVA layer B1, an adhesive layer, was formed on the above-described light absorption anisotropic layer P4 in the same manner as in example 1, thereby completing a laminate 8 of example 8.

(examples 9 to 16)

Laminates of examples 9 to 16 were obtained in the same manner as in example 1 except that adhesive layers shown in table 2 below were used as the adhesive layers in the adhesive sheet N1 and the adhesive sheets N2 to N6 described later in the formation of the adhesive layer in example 1 and the thicknesses thereof were changed to those shown in table 2 below.

< production of adhesive sheet N2 >

In the same manner as in the adhesive sheet N1, 95 parts by mass of butyl acrylate and 5 parts by mass of acrylic acid were polymerized by solution polymerization to obtain an acrylic copolymer 2 having an average molecular weight of 200 ten thousand and a molecular weight distribution (Mw/Mn) of 3.0.

Subsequently, a solution (adhesive composition N2) was prepared by mixing 10 parts by mass of a polyfunctional acrylate monomer (ARONIX M-315, TOAGOSEI CO., LTD., manufactured by LTD.) with 1 part by mass of a photopolymerization initiator (Irgacure500, manufactured by BASF corporation), 1 part by mass of trimethylolpropane toluene diisocyanate (Coronate-L, Nippon Polyurethane Industry Co., manufactured by Ltd.) and 0.2 part by mass of a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., manufactured by Ltd.) with respect to 100 parts by mass of the solid content of the acrylic copolymer 2.

Next, the prepared adhesive composition N2 was applied to a PET film (release film) coated with a silicone resin, dried at 90 ℃ to remove the solvent, and irradiated with Ultraviolet (UV) rays under the following conditions, thereby producing an adhesive sheet N2 having an adhesive layer N2 with a thickness of 20 μm. The storage modulus of the adhesive layer N2 was 0.6 MPa.

(UV irradiation conditions)

Fusion co, ltd. electrodeless lamp H bulb

Illuminance: 600mW/cm²

Light amount: 150mJ/cm²

The UV illuminance and the amount of light were measured using EYE GRAPHICS co, "UVPF-36" manufactured by ltd.

< preparation of adhesive sheets N3-N5 >

First, an acrylic polymer was prepared according to the following procedure.

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 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 were polymerized by solution polymerization to obtain an acrylic polymer a1 having an average molecular weight of 30 ten thousand.

Next, using the obtained acrylic polymer a1, adhesive sheets N3 to N5 were produced according to the following procedure.

Specifically, trimethylolpropane toluene diisocyanate (Coronate-L, Nippon Polyurethane Industry co., ltd.) was added in an amount of the following table 1 based on 100 parts by mass of the solid content of the acrylic polymer a1 to prepare a pressure-sensitive adhesive composition.

Then, the prepared adhesive composition was applied to a silicone resin-coated PET film (release film) using a die coater, and dried at 150 ℃ for 3 hours, thereby producing adhesive sheets N3 to 5 having adhesive layers N3 to 5 of desired thickness. The storage modulus of the adhesive layers N3 to N5 is shown in table 1 below.

[ Table 1]

< production of adhesive sheet N6 >

Acrylic copolymer 2 was obtained in the same manner as in the adhesive sheet N2.

Subsequently, a solution (adhesive composition N6) obtained by mixing 1 part by mass of trimethylolpropane toluene diisocyanate (Coronate-L, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 0.2 part by mass of a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts by mass of the solid content of the acrylic copolymer 2 was prepared.

Next, the prepared adhesive composition N6 was applied to a PET film (release film) coated with a silicone resin, and the solvent was removed by drying at 90 ℃, thereby producing an adhesive sheet N6 having an adhesive layer N6 with a thickness of 25 μm. The storage modulus of the adhesive layer N6 was 0.1 MPa.

[ example 17]

A laminate of example 17 was obtained in the same manner as in example 15, except that TJ100UL (thickness 100 μm, manufactured by FUJIFILM Corporation) was used as the support instead of TJ40 UL.

Comparative example 1

A laminate of comparative example 1 was obtained in the same manner 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 in the same manner as in example 1, except that the composition PA1 for an alignment layer was changed to the composition PA2 for an alignment layer having the following composition.

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Composition PA2 for Forming alignment layer

Polymer PA-2

[ chemical formula 33]

[ evaluation ]

Evaluation of peeling

The obtained laminate was cut into a size of 25mm × 150mm, and after peeling the release film, the adhesive layer side was laminated on a glass substrate (Corning inc.

Then, a tape was attached to the support of the laminate and peeled off.

The peeled surface of the support was observed and evaluated according to the following criteria. The results are shown in table 2 below.

AA: the peel surface has no roughness

A: rough peel surface

B: peeling residue due to the alignment layer was observed, and the area of the peeling residue was less than 5% with respect to the area of the peeled surface

C: peeling residue due to the alignment layer is observed, and the area of the peeling residue is 5% or more of the area of the peeling surface

[ Table 2]

From the results shown in table 2, it was found that when the thickness from the support to the adhesive layer excluding the thicknesses of the support and the adhesive layer was 5 μm or less, it was difficult to peel only the support when the thickness of the adhesive layer was less than 5 μm (comparative example 1).

Further, it is 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 peel only the support (comparative example 2).

On the other hand, when the thickness from the support to the adhesive layer excluding the thicknesses of the support and the adhesive layer is 5 μm or less, the support is easily peeled off when the thickness of the adhesive layer is 5 to 50 μm, the alignment layer is a photo-alignment layer formed using an alignment layer forming composition containing a cinnamoyl compound having a functional group having an ethylenically unsaturated double bond (examples 1 to 17).

Description of the symbols

1-support, 2-orientation layer, 3-light absorption anisotropic layer, 4-adhesive layer, 5-cured layer, 6-layer comprising polyvinyl alcohol resin, 7-surface film, 8-phase difference film, 10-laminate.