Thermosetting liquid crystal composition having photoalignment property, alignment film / retardation film and manufacturing method thereof, retardation plate and manufacturing method thereof, optical member and manufacturing method thereof, and display device

Abstract

To provide a thermosetting liquid crystal composition excellent in vertical orientation, and, excellent in the ability of orienting a directly laminated liquid crystal material, and having optical orientation capable of forming an orientation layer-cum-retardation layer and a producing method thereof, as well as, an orientation film-cum-retardation layer and a producing method thereof, a retardation plate containing the orientation layer-cum-retardation layer and a producing method thereof, an optical member and a producing method thereof, as well as, a display device.SOLUTION: A thermosetting liquid crystal composition with optical orientation comprises: a side chain type liquid crystal polymer (A) having a liquid crystalline structural unit containing a liquid crystalline moiety in its side chain and a non-liquid crystalline structural unit containing an alkylene group in its side chain; a copolymer (B) having a photoalignable structural unit containing a photoalignable group in its side chain, and a thermally crosslinkable structural unit containing a thermally crosslinkable group in its side chain, with the photoalignable structural unit not having a linear alkylene group between the photoalignable group and a monomer unit, and (C) a thermal crosslinking agent that binds with a thermal crosslinking group of the thermally crosslinkable structural unit.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a thermosetting liquid crystal composition having photoalignment properties capable of forming an alignment layer / retardation layer having the functions of both an alignment layer and a retardation layer in one layer, an alignment film / retardation film and a manufacturing method thereof, a retardation plate and a manufacturing method thereof, an optical member and a manufacturing method thereof, and a display device. [Background technology]

[0002] As an optical film applied to image display devices and the like, there is a retardation plate that imparts a desired phase difference to incident light by a retardation layer. For example, in an organic electroluminescence (organic EL) display device, a quarter-wave retardation plate is used as a circular polarizing plate in combination with a linear polarizing plate, and functions as an external light antireflection film. Conventionally, in liquid crystal display devices such as IPS mode, a retardation plate combining a positive A plate having positive A characteristics and a positive C plate having positive C characteristics has been used as a part of a polarizing plate compensation film in order to increase the contrast in a field of view from an oblique direction (for example, Patent Document 1).

[0003] Conventionally, the positive A plate and the positive C plate are laminated together using an adhesive layer or the like. As display devices become thinner, there is a demand for thinner retardation plates, such as broadband quarter-wave retardation plates that are constructed by combining retardation plates, while maintaining performance, and for more efficient manufacturing processes.

[0004] For the purpose of making the retardation plate thinner, Patent Document 2 discloses an optical film laminate in which a positive C plate and a positive A plate are laminated, the positive C plate being a plate in which the orientation of a homeotropic orientation layer formed from a first liquid crystal material having a photosensitive group is fixed, the positive A plate being a plate in which the orientation of a homogeneous orientation layer formed from a second liquid crystal material having polymerizability is fixed, the positive A plate being laminated directly on the positive C plate, and the photosensitive group in the positive C plate undergoes an anisotropic photoreaction.

[0005] On the other hand, the present inventors have disclosed in Patent Document 3 a thermosetting liquid crystal composition having high sensitivity to photoalignment, which contains a copolymer of a styrene monomer having a photoalignable group and a monomer having a thermally crosslinkable group, and a crosslinking agent, for the purpose of producing an alignment layer using the thermosetting liquid crystal composition containing a copolymer having both a photoalignment site and a thermally crosslinkable site. However, Patent Document 3 does not disclose the use of the thermosetting composition to produce a retardation layer. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 4592005 [Patent Document 2] JP 2016-004142 A [Patent Document 3] Patent No. 5626493 Summary of the Invention [Problem to be solved by the invention]

[0007] In Patent Document 2, the positive A plate is directly laminated on the positive C plate for the purpose of making the retardation plate thinner. However, the positive C plate described in Patent Document 2 is formed using a first liquid crystal material having a structure in which a photo-alignable group is bonded as a photosensitive group to the end of a liquid crystal component having vertical alignment, so that the positive C plate itself has poor vertical alignment, and further, the ability to align the liquid crystal material of the positive A plate directly laminated thereon (liquid crystal alignment ability) is also poor. In addition, the positive C plate of Patent Document 2 has insufficient durability, and there is also a problem that the vertical alignment of the positive C plate is easily changed due to heating or solvent penetration when laminating the liquid crystal material of the positive A plate on the positive C plate.

[0008] In addition, a retardation plate in which a positive A plate is directly laminated on a positive C plate, which is a cured product of a photocurable resin composition containing a polymerizable liquid crystal compound, has a problem that the adhesion between the positive C plate and the positive A plate is insufficient and the bending resistance is poor. This is because the positive C plate, which is a cured product of a photocurable resin composition, becomes hard and brittle when sufficiently cured to improve vertical alignment. If the adhesion is insufficient, the positive C plate is not transferred together with the positive A plate during transfer, and the positive C plate remains on the substrate. In addition, if the bending resistance is poor, the retardation plate is not suitable for use in a flexible display.

[0009] The present disclosure has been made in consideration of the above problems, and has as a first object to provide a thermosetting liquid crystal composition having photoalignment properties capable of forming an alignment layer / retardation layer which has excellent vertical alignment properties and excellent ability to align a directly laminated liquid crystalline material, an alignment film / retardation film and a manufacturing method thereof, a retardation plate containing the alignment layer / retardation layer and a manufacturing method thereof, an optical member and a manufacturing method thereof, and a display device.

[0010] The present disclosure has been made in consideration of the above-mentioned problems, and a second object of the present disclosure is to provide a thermosetting liquid crystal composition having good vertical alignment properties and photoalignment properties capable of forming an alignment layer / retardation layer that exhibits good vertical alignment properties and the ability to align a liquid crystalline material directly laminated thereon, and that is durable; an alignment film / retardation film and a manufacturing method thereof; a retardation plate containing the alignment layer / retardation layer and a manufacturing method thereof; an optical member and a manufacturing method thereof; and a display device.

[0011] The present disclosure has been made in consideration of the above problems, and a third object of the present disclosure is to provide a retardation plate and a manufacturing method thereof, an optical member and a manufacturing method thereof, and a display device, in which a positive C-type retardation layer and a positive A-type retardation layer are directly laminated with good adhesion to each other and have good bending resistance. [Means for solving the problem]

[0012] In order to achieve the first object, the present disclosure provides a liquid crystal polymer (A) having a liquid crystal structural unit containing a liquid crystal moiety in a side chain and a non-liquid crystal structural unit containing an alkylene group in a side chain; A copolymer (B) having a photoalignable structural unit having a structural unit represented by the following formula (1) and a thermally crosslinkable structural unit having a thermally crosslinkable group in a side chain; A thermal crosslinking agent (C) that bonds to the thermal crosslinkable group of the thermal crosslinkable structural unit; The present invention provides a thermosetting liquid crystal composition having a first photoalignment property, comprising:

[0013] [ka] (In the above formula (1), Z 1 represents at least one monomer unit selected from the group consisting of the following formulas (1-1) to (1-6), X represents a photoalignment group, L 11 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, or a combination of any of these with an arylene group.

[0014] [ka] (In the above formulas (1-1) to (1-6), R 21 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 22 represents a hydrogen atom or a methyl group, and R 23 is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 24 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0015] In the first thermosetting liquid crystal composition having photoalignment property of the present disclosure, the photoalignment group of the copolymer (B) may be at least one selected from the group consisting of a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, a quinoline group, an azobenzene group, and a stilbene group.

[0016] In the first thermosetting liquid crystal composition having photoalignment property of the present disclosure, the thermally crosslinkable group may contain at least one selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group.

[0017] In the first thermosetting liquid crystal composition having photoalignment property of the present disclosure, the liquid crystalline constitutional unit of the side chain type liquid crystal polymer (A) preferably has a constitutional unit represented by the following formula (I) from the viewpoint of improving the vertical alignment property of the retardation layer:

[0018] [ka] (In general formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 is -(CH2) m - or -(C2H4O) m’ - represents a group represented by L 1 represents a single bond or a linking group represented by -O-, -OCO-, or -COO-, 1 represents an arylene group having 6 to 10 carbon atoms which may have a substituent, 1 and Ar 1may be the same or different. 3 are -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 , -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2, -R 5 -OR 5 , R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R 5 represents an alkyl group having 1 to 6 carbon atoms; a is an integer of 2 to 4, and m and m' are each independently an integer of 2 to 10.

[0019] In order to achieve the second object, the present disclosure provides a liquid crystal polymer (A) having a liquid crystal structural unit containing a liquid crystal moiety in a side chain and a non-liquid crystal structural unit containing an alkylene group in a side chain; A copolymer (B) having a photoalignable structural unit containing a photoalignable group in a side chain and a thermally crosslinkable structural unit having a structural unit represented by the following formula (2): and a thermal crosslinking agent (C) that bonds to the thermal crosslinkable group of the thermal crosslinkable structural unit, The present invention provides a thermosetting liquid crystal composition having a second photoalignment property, in which the side chain liquid crystal polymer (A) satisfies any one of the following (i) to (vi): In order to achieve the second object, the thermosetting liquid crystal composition having the first photoalignment property may have the configuration of the thermosetting liquid crystal composition having the second photoalignment property. (i) The side chain type liquid crystal polymer (A) has a non-liquid crystalline and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and the non-liquid crystalline and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to a primary carbon of an alkylene group which may have -O- in the carbon chain and which has a smaller total carbon number and oxygen number than the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain in the thermally crosslinkable constituent unit of the copolymer (B). (ii) The side chain type liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and the non-liquid crystal and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to a secondary carbon or a tertiary carbon of an alkylene group. (iii) The side chain type liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinkable constituent unit containing at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a mercapto group, and an amino group, an alkylene group, and an arylene group in the side chain, and the non-liquid crystal and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to an arylene group. (iv) The side chain type liquid crystal polymer (A) has a non-liquid crystallinity and thermal crosslinking structural unit containing at least one thermal crosslinking group selected from the group consisting of a carboxyl group, a glycidyl group, and an amide group, and an alkylene group and an arylene group in the side chain, and the non-liquid crystallinity and thermal crosslinking structural unit of the side chain type liquid crystal polymer (A) has a structure in which the thermal crosslinking group is bonded to an arylene group, and the arylene group has a structure bonded to a carbon atom or oxygen atom of an alkylene group which may have -O- in the carbon chain or at the terminal, and the total number of carbon atoms and the number of oxygen atoms is 3 or more smaller than that of the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain in the thermal crosslinking structural unit of the copolymer (B). (v) The side chain type liquid crystal polymer (A) has a thermally crosslinkable constituent unit that does not contain an alkylene group in the side chain but contains a thermally crosslinkable group in the side chain. (vi) The side chain type liquid crystal polymer (A) does not have a non-liquid crystal and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and does not have a thermally crosslinkable constituent unit containing a thermally crosslinkable group in the side chain.

[0020] [ka] (In the above formula (2), Z 2 represents at least one monomer unit selected from the group consisting of the following formulas (2-1) to (2-6), and R 50represents a linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain, and Y represents at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group.

[0021] [ka] (In the above formulas (2-1) to (2-6), R 51 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 52 represents a hydrogen atom or a methyl group, and R 53 is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 54 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 12 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-; L 12 If it is a single bond, R 50 is directly bonded to the styrene backbone.)

[0022] In the second thermosetting liquid crystal composition having photoalignment property of the present disclosure, it is preferable that the non-liquid crystal and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a constituent unit represented by the following formula (III) from the viewpoint of ease of procurement of raw materials. In the thermosetting liquid crystal composition having the first photoalignment property, a constitutional unit represented by the following formula (III) of the thermosetting liquid crystal composition having the second photoalignment property may be used.

[0023] [ka] (In the above formula (III), Z a represents at least one monomer unit selected from the group consisting of the following formulas (a-1) to (a-6), and R 16 -L 2a -R 13’ - (wherein L 2a represents a linear or branched alkylene group having 1 to 10 carbon atoms which may have -O- in the carbon chain, R 13’represents a residue obtained by removing a hydrogen atom from a methyl group which may have a substituent, a residue obtained by removing a hydrogen atom from an aryl group, or -OR 15’ R 15’ represents a residue obtained by removing a hydrogen atom from an aryl group. a represents at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group.

[0024] [ka] (In the above formulas (a-1) to (a-6), R 11 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 17 represents a hydrogen atom or a methyl group, and R 18 is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 19 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L a represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-; L a If it is a single bond, R 16 is directly bonded to the styrene backbone.)

[0025] The present disclosure also provides a first or second alignment film / retardation film that contains an alignment layer / retardation layer, wherein the alignment layer / retardation layer is a cured film of a thermosetting liquid crystal composition having the first or second photoalignment property of the present disclosure.

[0026] The present disclosure further provides a method for producing a thermosetting liquid crystal composition having the first or second photoalignment property of the present disclosure, comprising: forming a cured film having a retardation by heating the thermosetting liquid crystal composition formed into the film; and a step of imparting liquid crystal aligning ability to the cured film by irradiating the cured film having retardation with polarized ultraviolet light.

[0027] The present disclosure also provides a liquid crystal display device comprising a first retardation layer which is a cured film of a thermosetting liquid crystal composition having the first or second photoalignment property of the present disclosure; and a second retardation layer that is located directly adjacent to the first retardation layer and contains a cured product of a polymerizable liquid crystal composition.

[0028] In the first or second retardation plate of the present disclosure, it is preferable that the first retardation layer is a positive C-type retardation layer and the second retardation layer is a positive A-type retardation layer, since a retardation plate that improves the viewing angle characteristics can be efficiently prepared and the effects of the present invention can be effectively exhibited.

[0029] The present disclosure also provides a method for producing a liquid crystal display device comprising the steps of: forming a film of a thermosetting liquid crystal composition having the first or second photoalignment property of the present disclosure; forming a cured film having a retardation by heating the thermosetting liquid crystal composition formed into the film; A step of irradiating the cured film having a retardation with polarized ultraviolet light to impart liquid crystal alignment ability to the cured film, thereby forming an alignment film and a first retardation layer; a step of applying a polymerizable liquid crystal composition onto the alignment film / first retardation layer to form a coating film of the polymerizable liquid crystal composition, and heating the coating film to a phase transition temperature of the polymerizable liquid crystal composition to align liquid crystal molecules by the alignment film / retardation layer; a step of forming a second retardation layer by irradiating the coating film of the polymerizable liquid crystal composition in which the liquid crystal molecules are aligned with light and curing the coating film; The present invention provides a method for producing a first or second retardation plate having the above structure.

[0030] In order to achieve the third object, the present disclosure provides a positive C-type retardation layer which is a cured product of a thermosetting resin composition containing a photoalignment component and a thermal crosslinking agent; a positive A-type retardation layer containing a cured product of a polymerizable liquid crystal composition, the positive A-type retardation layer being located directly adjacent to the positive C-type retardation layer; A third retardation plate is provided, comprising:

[0031] In the third retardation plate of the present disclosure, the thickness direction retardation Rth at a wavelength of 550 nm may be −35 nm to 35 nm, the in-plane retardation Re at a wavelength of 550 nm may be 100 nm or more, and the total thickness of the positive C-type retardation layer and the positive A-type retardation layer may be 0.2 μm to 6 μm.

[0032] In the third retardation plate of the present disclosure, the composite elastic modulus of the positive C-type retardation layer is It may be 4.5 GPa or more and 9.0 GPa or less.

[0033] The third retardation plate of the present disclosure may contain a substrate located directly adjacent to the positive C-type retardation layer.

[0034] In the third retardation plate of the present disclosure, the positive C-type retardation layer may include a region in which a specific component contained in the positive A-type retardation layer is permeated. The specific component may include a polymerizable liquid crystal compound or a cured product thereof.

[0035] The present disclosure also provides a method for producing a thermosetting liquid crystal composition having photoalignment properties, the method comprising the steps of: forming a film of a thermosetting liquid crystal composition having photoalignment properties, the thermosetting liquid crystal composition including a side chain type liquid crystal polymer having a liquid crystal constituent unit having a liquid crystal moiety in a side chain; a copolymer having a photoalignment constituent unit and a thermocrosslinkable constituent unit having a thermocrosslinkable group in a side chain; and a thermocrosslinking agent that bonds with the thermocrosslinkable group of the thermocrosslinkable constituent unit; forming a cured film having a retardation by heating the thermosetting liquid crystal composition formed into the film; A step of forming a positive C-type retardation layer having a liquid crystal alignment ability by irradiating the cured film having a retardation with polarized ultraviolet light; A step of applying a polymerizable liquid crystal composition onto the positive C-type retardation layer to form a coating film of the polymerizable liquid crystal composition, and heating the coating film to a phase transition temperature of the polymerizable liquid crystal composition to align liquid crystal molecules by the positive C-type retardation layer; and a step of irradiating the coating film of the polymerizable liquid crystal composition in which the liquid crystal molecules are aligned with light to cure the composition, thereby forming a positive A-type retardation layer.

[0036] The present disclosure also provides an optical member containing a first, second, or third retardation plate and a polarizing plate.

[0037] The present disclosure also provides a method for producing a polarizing plate, comprising: providing a first, second, or third retarder; and laminating a retardation plate and a polarizing plate.

[0038] The present disclosure also provides a display device including the first, second, or third retardation plate, or an optical member including the retardation plate and a polarizing plate. Effect of the Invention

[0039] The first present disclosure has an effect of providing a thermosetting liquid crystal composition having photoalignment properties capable of forming an alignment layer / retardation layer which has excellent vertical alignment properties and excellent ability to align a directly laminated liquid crystalline material, an alignment film / retardation film and a manufacturing method thereof, a retardation plate containing the alignment layer / retardation layer and a manufacturing method thereof, an optical member and a manufacturing method thereof, and a display device. The second present disclosure has the effect of providing a thermosetting liquid crystal composition having photoalignment properties capable of forming an alignment layer / retardation layer that exhibits good vertical alignment properties and the ability to align a liquid crystalline material directly laminated thereon, and that has durability; an alignment film / retardation film and a manufacturing method thereof; a retardation plate containing the alignment layer / retardation layer and a manufacturing method thereof; an optical member and a manufacturing method thereof; and a display device. In addition, the third present disclosure has an effect of providing a retardation plate having good bending resistance, in which a positive C-type retardation layer and a positive A-type retardation layer are directly laminated with good adhesion, a manufacturing method thereof, an optical member using the retardation plate, a manufacturing method thereof, and a display device. [Brief description of the drawings]

[0040] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an alignment film / retardation film according to the present disclosure. [Diagram 2] FIG. 1 is a schematic cross-sectional view showing an example of an alignment film / retardation film according to the present disclosure. [Diagram 3] FIG. 1 is a schematic cross-sectional view showing an example of an alignment film / retardation film according to the present disclosure. [Figure 4] FIG. 1 is a schematic cross-sectional view illustrating an example of a retardation plate according to the present disclosure. [Diagram 5] FIG. 1 is a schematic cross-sectional view illustrating an example of a retardation plate according to the present disclosure. [Figure 6] FIG. 1 is a schematic cross-sectional view illustrating an example of an optical member according to the present disclosure. [Figure 7] FIG. 1 is a diagram for explaining a method of a dynamic bending test. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0041] Hereinafter, the embodiments and examples of the present disclosure will be described with reference to the drawings. However, the present disclosure can be implemented in many different forms, and is not to be interpreted as being limited to the description of the embodiments and examples exemplified below. In addition, in order to make the explanation clearer, the drawings may be schematic in terms of the width, thickness, shape, etc. of each part compared to the actual form, but these are merely examples and do not limit the interpretation of the present disclosure. In addition, in this specification and each figure, elements similar to those described above with respect to the previous figures may be given the same reference numerals, and detailed explanations may be omitted as appropriate. In addition, for convenience of explanation, the terms "upper" and "lower" may be used in the explanation, but the up-down direction may be reversed. "In this specification, when a certain component or region is described as being "on (or under)" another component or region, unless otherwise specified, this includes not only the case where it is directly on (or directly under) the other component, but also the case where it is above (or below) the other component, i.e., the case where another component is included between the other component and the component above (or below) the other component.

[0042] In the present disclosure, the alignment regulation force refers to the action of aligning liquid crystal compounds in the retardation layer in a specific direction. In the present disclosure, (meth)acrylic refers to either acrylic or methacrylic, and (meth)acrylate refers to either acrylate or methacrylate. In addition, in this specification, the terms "plate," "sheet," and "film" are not distinguished from one another solely based on the difference in name, and a "film surface (plate surface, sheet surface)" refers to a surface that coincides with the planar direction of the target film-like (plate-like, sheet-like) member when viewed overall and globally. In addition, in the present disclosure, the use of "to" indicating a numerical range means that the numerical values ​​before and after it are included as the lower limit and upper limit. In the present disclosure, the "alignment layer / retardation layer" is a layer that is a retardation layer itself and has the ability to align a liquid crystal material that is directly laminated thereon, and can be rephrased as "a retardation layer to which liquid crystal alignment ability has been imparted." In the present disclosure, the "alignment layer / retardation layer" is a single layer that also functions as an alignment layer, and can be rephrased as "a retardation layer that functions as an alignment layer." In the present disclosure, the "alignment film / retardation film" can be rephrased as "a retardation film that functions as an alignment film" or "a retardation film to which a liquid crystal aligning ability has been imparted".

[0043] Furthermore, in the present disclosure, "an alkylene group... which may have -O- in the carbon chain" means "an alkylene group... which may have -O- in the carbon chain, i.e., other than at the terminals, and both terminals of the alkylene group are carbon atoms", and "an alkylene group... which may have -O- in the carbon chain or at the terminal" means "an alkylene group... which may have -O- not only in the carbon chain but also at the terminals, and both terminals of the alkylene group are carbon atoms or oxygen atoms".

[0044] Hereinafter, first, a thermosetting liquid crystal composition having photoalignment properties according to the present disclosure, an alignment film / retardation film using the same and a method for producing the same, and a retardation plate and a method for producing the same will be described in detail.

[0045] I. First Present Disclosure A. Photo-alignable thermosetting liquid crystal composition The thermosetting liquid crystal composition having photoalignment properties of the present disclosure comprises a side chain type liquid crystal polymer (A) having a liquid crystal constituent unit having a liquid crystal moiety in a side chain and a non-liquid crystal constituent unit having an alkylene group in a side chain; A copolymer (B) having a photoalignable structural unit having a structural unit represented by the following formula (1) and a thermally crosslinkable structural unit having a thermally crosslinkable group in a side chain; A thermal crosslinking agent (C) that bonds to the thermal crosslinkable group of the thermal crosslinkable structural unit; The present invention is characterized in that it contains:

[0046] [ka] (In the above formula (1), Z 1 represents at least one monomer unit selected from the group consisting of the following formulas (1-1) to (1-6), X represents a photoalignment group, L 11 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, or a combination of any of these with an arylene group.

[0047] [ka] (In the above formulas (1-1) to (1-6), R 21 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 22 represents a hydrogen atom or a methyl group, and R 23 is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 24 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0048] The thermosetting liquid crystal composition having photoalignment properties of the present disclosure contains the side-chain liquid crystal polymer (A), a copolymer (B) having a photoalignment structural unit and a thermally crosslinkable structural unit that exhibit the ability to align a liquid crystal material that is directly laminated thereon, and a thermal crosslinking agent (C) that bonds to the thermally crosslinkable group of the thermally crosslinkable structural unit. Therefore, by forming a cured film of the composition, it is possible to form an alignment layer / retardation layer that has the functions of both an alignment layer and a retardation layer in a single layer, has excellent vertical alignment properties, and is excellent in the ability to align a liquid crystal material that is directly laminated thereon. In the thermosetting liquid crystal composition having photo-alignment property of the present disclosure, in the copolymer (B) having a photo-alignment structural unit, the photo-alignment structural unit has a structure having no alkylene chain between the photo-alignment group and the main chain of the copolymer. Since the photo-alignment structural unit of the copolymer (B) has a structure having no alkylene chain, it becomes more non-liquid crystal, and it is presumed that the compatibility with the side chain type liquid crystal polymer (A) decreases and the phase separation from the side chain type liquid crystal polymer (A) becomes easy. Furthermore, since the photo-alignment structural unit of the copolymer (B) has a structure having no alkylene chain, it is presumed that the rigidity increases, the distance between the photo-alignment groups tends to become small, and the photo-alignment property (liquid crystal alignment ability) is improved. Furthermore, unlike a polymerizable liquid crystal compound of a low molecular weight compound, the side chain type liquid crystal polymer (A) is easily arranged on the substrate side even when mixed with the copolymer (B), and the vertical alignment property is easily improved, and as a result, the copolymer (B) is also easily arranged on the air interface side, and the photo-alignment property is easily improved. Due to these synergistic effects, in the thermosetting liquid crystal composition having photoalignment properties disclosed herein, the side-chain liquid crystal polymer (A) that is vertically aligned to exhibit retardation, and the copolymer (B) having photoalignable structural units that exhibits the alignment property of the directly laminated liquid crystal material, are less likely to interfere with each other's performance, and it is considered that by forming a cured film of the composition, it is possible to realize a single layer that serves as both an alignment layer and a retardation layer, which has excellent vertical alignment properties and the ability to align the directly laminated liquid crystal material.

[0049] In addition, the thermosetting liquid crystal composition having photoalignment properties disclosed herein contains a copolymer having both a photoalignment constituent unit and a thermally crosslinkable constituent unit, and a thermal crosslinking agent. Therefore, when thermally cured, the crosslinked structure improves the heat resistance and solvent resistance of the film, and a highly durable alignment layer / retardation layer can be obtained.

[0050] In addition, the alignment layer / retardation layer, which is a cured product of the thermosetting liquid crystal composition having photoalignment property of the present disclosure, crosslinks the polymers with each other by a thermal crosslinking agent, and is less likely to harden and has flexibility, and has good adhesion to the liquid crystal material directly laminated thereto, compared with the cured product of the photosetting resin composition containing a polymerizable liquid crystal compound. Therefore, according to the alignment layer / retardation layer, which is a cured product of the thermosetting liquid crystal composition having photoalignment property of the present disclosure, a thin retardation plate having good bending resistance in which the first retardation layer and the second retardation layer are directly laminated with good adhesion can be obtained, as in the third disclosure described later.

[0051] Hereinafter, each component in the thermosetting liquid crystal composition having photoalignment properties of the present disclosure will be described. 1. Side-chain liquid crystal polymer (A) The side chain liquid crystal polymer (A) used in the present disclosure has a liquid crystal constituent unit containing a liquid crystal moiety in the side chain, and a non-liquid crystal constituent unit containing an alkylene group in the side chain. Each of the structural units in the side chain type liquid crystal polymer (A) will be described below.

[0052] (1) Liquid crystal structural unit In an embodiment of the present disclosure, the liquid crystal constitutional unit has a side chain including a liquid crystal portion, i.e., a portion exhibiting liquid crystallinity. The liquid crystal constitutional unit is preferably a constitutional unit including a mesogen exhibiting liquid crystallinity in a side chain. The liquid crystal constitutional unit is preferably a constitutional unit derived from a compound exhibiting liquid crystallinity in which a polymerizable group is bonded to a mesogen group via a spacer. In the present disclosure, the mesogen refers to a highly rigid portion exhibiting liquid crystallinity, for example, a partial structure having two or more ring structures, preferably three or more ring structures, in which the ring structures are connected to each other by direct bonds, or the ring structures are connected via one to three atoms. By having such a portion exhibiting liquid crystallinity in the side chain, the liquid crystal constitutional unit is easily aligned vertically. The ring structure may be an aromatic ring such as benzene, naphthalene, or anthracene, or may be a cyclic aliphatic hydrocarbon such as cyclopentyl or cyclohexyl. Furthermore, when the ring structure is linked via 1 to 3 atoms, examples of the structure of the linking portion include -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)-O-, -NR-C(=O)-, -C(=O)-NR-, -OC(=O)-NR-, -NR-C(=O)-O-, -NR-C(=O)-NR-, -O-NR-, -NR-O- (R is a hydrogen atom or a hydrocarbon group), and the like. Among them, the mesogen is preferably a rod-shaped mesogen in which the ring structures are connected in a rod shape at the para position in the case of benzene, or at the 2,6 position in the case of naphthalene.

[0053] In addition, when the liquid crystal structural unit is a structural unit containing a mesogen exhibiting liquid crystallinity in the side chain, it is preferable that the terminal of the side chain of the structural unit is a polar group or has an alkyl group from the viewpoint of vertical alignment. Specific examples of such polar groups include -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHC(=O)-R', -C(=O)-OR', -OH, -SH, -CHO, -SO3H, -NR'2, -R ” -OR ” (R' is a hydrogen atom or a hydrocarbon group, R ”is an alkyl group).

[0054] The liquid crystal structural unit has a side chain of -R 2 -(L 1 -Ar 1 ) a -R 3 (wherein R 2 is -(CH2) m - or -(C2H4O) m’ - represents a group represented by L 1 represents a single bond or a linking group represented by -O-, -OCO-, or -COO-, 1 represents an arylene group having 6 to 10 carbon atoms which may have a substituent, 1 and Ar 1 may be the same or different. 3 are -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 , -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2, -R 5 -OR 5 , R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R 5 represents an alkyl group having 1 to 6 carbon atoms. a is an integer of 2 to 4, and m and m' are each independently an integer of 2 to 10.) are examples of structural units having these structures.

[0055] R 2 In the formula, m and m' are each independently an integer of 2 to 10. In terms of vertical alignment, m and m' are preferably 2 to 8, and more preferably 2 to 6.

[0056] Ar 1 In the formula (I), examples of the arylene group having 6 to 10 carbon atoms which may have a substituent include a phenylene group and a naphthylene group, and among these, a phenylene group is more preferable. 3Examples of the substituent other than the above include an alkyl group having 1 to 5 carbon atoms, and halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom.

[0057] R 3 In R 4 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 3 In R 5 is an alkyl group having 1 to 6 carbon atoms, and among these, an alkyl group having 1 to 5 carbon atoms is preferable.

[0058] The liquid crystal structural unit is preferably a structural unit derived from a monomer having a polymerizable ethylenic double bond-containing group. Examples of such a monomer having an ethylenic double bond-containing group include derivatives such as (meth)acrylic acid ester, styrene, (meth)acrylamide, maleimide, vinyl ether, or vinyl ester. In terms of vertical alignment, the liquid crystal structural unit is preferably a structural unit derived from a (meth)acrylic acid ester derivative.

[0059] In the embodiment of the present disclosure, the liquid crystal constitutional unit preferably contains a constitutional unit represented by the following general formula (I) in terms of vertical alignment properties.

[0060] [ka] (In general formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 is -(CH2) m - or -(C2H4O) m’ - represents a group represented by L 1 represents a single bond or a linking group represented by -O-, -OCO-, or -COO-, 1 represents an arylene group having 6 to 10 carbon atoms which may have a substituent, 1 and Ar 1 may be the same or different. 3are -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 , -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2, -R 5 -OR 5 , R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R 5 represents an alkyl group having 1 to 6 carbon atoms; a is an integer of 2 to 4, and m and m' are each independently an integer of 2 to 10.

[0061] In the structural unit represented by formula (I), -R 2 -(L 1 -Ar 1 ) a -R 3 The group represented by the formula (I) may be the same as above.

[0062] Suitable specific examples of the liquid crystal constituent unit represented by general formula (I) include, but are not limited to, those represented by the following general formulae (I-1), (I-2) and (I-3).

[0063] [ka]

[0064] In the constitutional units represented by the above general formulas (I-1) to (I-3), R 2 , and R 3 are R in general formula (I), 2 , and R 3 is the same as:

[0065] In the embodiments of the present disclosure, the liquid crystal structural units may be used alone or in combination of two or more.

[0066] In the synthesis of the copolymer, a monomer such as a (meth)acrylic acid ester derivative that induces a liquid crystal constitutional unit can be used. The monomer such as a (meth)acrylic acid ester derivative that induces a liquid crystal constitutional unit can be used alone or in combination of two or more kinds.

[0067] In order to improve the vertical alignment of the liquid crystalline constituent units and to provide sufficient liquid crystal alignment, the content of the liquid crystalline constituent units in the copolymer is preferably set within the range of 40 mol% to 90 mol%, more preferably within the range of 40 mol% to 80 mol%, even more preferably within the range of 45 mol% to 70 mol%, and particularly preferably within the range of 50 mol% to 65 mol%, when the amount of the constituent units contained in the entire copolymer is taken as 100 mol%. The content ratio of each structural unit in the copolymer is as follows: 1 It can be calculated from the integral value obtained by H-NMR measurement.

[0068] (2) Non-liquid crystal structural unit containing an alkylene group in the side chain The non-liquid crystal structural unit containing an alkylene group in the side chain has the effect of promoting vertical alignment (homeotropic alignment) of the part (mesogen) exhibiting liquid crystallinity in the side chain of the liquid crystal structural unit when the side chain type liquid crystal polymer becomes liquid crystal. By including the non-liquid crystal structural unit containing an alkylene group in the side chain, the vertical alignment property of the side chain type liquid crystal polymer (A) is improved, and the solvent solubility is also improved. The non-liquid crystal structural unit having an alkylene group in the side chain has -L 2 -R 13 , or -L 2’ -R 14 (wherein L 2 Ha-(CH2) n - represents L 2’ Ha-(C2H4O) n’ - represents a linking group represented by R 13 represents a methyl group which may have a substituent, an aryl group which may have an alkyl group, or -OR 15 R 14 and R 15each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and n and n′ each independently represents an integer of 1 to 18.

[0069] L 2 Ha-(CH2) n - represents L 2’ Ha-(C2H4O) n’ Among them, -(CH2) is preferably used because it tends to provide good vertical alignment. n n is an integer of 1 to 18, and preferably an integer of 2 to 18. 13 When is a methyl group having a substituent or an alkyl group having a substituent, n is preferably an integer of 1. Furthermore, n' is an integer of 1 to 18, preferably an integer of 1 to 8, and more preferably an integer of 2 to 8.

[0070] R 14 and R 15 The alkyl group in may be linear, branched, or cyclic, and is preferably linear. R 14 , and R 15 The alkyl group in is preferably an alkyl group having 1 to 20 carbon atoms, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl groups, branched alkyl groups such as i-propyl, i-butyl, and t-butyl groups, alkenyl groups such as 1-propenyl and 1-butenyl groups, alkynyl groups such as ethynyl and 2-propynyl groups, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl, and adamantyl groups, and cycloalkenyl groups such as 1-cyclohexenyl groups. In the case of the above cycloalkyl groups, it is preferable that the linear alkyl group is substituted with a cycloalkyl group.

[0071] R 14 and R15 The alkyl group in is not particularly limited, but is preferably an alkyl group having 1 to 12 carbon atoms in terms of the in-plane uniformity of retardation.

[0072] R 13 , R 14 , and R 15 The aryl group in is preferably an aryl group having 6 to 20 carbon atoms, specifically, a phenyl group, a naphthyl group, an anthracenyl group, etc., among which a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. In the case of the above aryl group, it is preferable that the aryl group is substituted with a linear alkyl group.

[0073] The non-liquid crystal structural unit having an alkylene group in a side chain may have, as a substituent, a reactive group that reacts with other components, and may have, for example, a thermally crosslinkable group similar to that of the copolymer (B) described later. The non-liquid crystal structural unit having an alkylene group in the side chain may include a non-liquid crystal non-crosslinkable structural unit and a non-liquid crystal thermal crosslinkable structural unit. The non-liquid crystal structural unit having an alkylene group in the side chain may include only a non-liquid crystal non-crosslinkable structural unit or may include only a non-liquid crystal thermal crosslinkable structural unit. The non-liquid crystalline structural unit having an alkylene group in a side chain preferably contains at least a non-liquid crystalline and non-crosslinkable structural unit, since this tends to result in good vertical alignment, and more preferably contains a non-liquid crystalline and non-crosslinkable structural unit and a non-liquid crystalline and thermally crosslinkable structural unit, since this tends to result in good vertical alignment and improved durability.

[0074] In the non-liquid crystalline and non-crosslinkable constitutional unit containing an alkylene group in the side chain, R 13 The substituents that the methyl group in 14 and R 15 Examples of the substituent that the alkyl group in the formula (I) may have include non-crosslinkable substituents, such as halogen atoms, e.g., fluorine atom, chlorine atom, bromine atom, etc., alkoxy groups, nitro groups, etc. Among these, halogen atoms, e.g., fluorine atom, chlorine atom, bromine atom, etc., are preferred.

[0075] In the non-liquid crystalline and non-crosslinkable constitutional unit containing an alkylene group in the side chain, R 13 , R 14 , and R 15 The substituent that the aryl group in the formula (I) may have includes non-crosslinkable substituents, such as halogen atoms, such as fluorine atoms, chlorine atoms, and bromine atoms, alkyl groups, alkoxy groups, and nitro groups. The alkyl groups include alkyl groups having 1 to 12 carbon atoms, such as alkyl groups having 1 to 9 carbon atoms, and may be linear alkyl groups or alkyl groups having a branched or ring structure. Among these, halogen atoms, such as fluorine atoms, chlorine atoms, and bromine atoms, and alkyl groups having 1 to 9 carbon atoms are preferred. Specific examples of the alkyl group include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, cyclopentyl groups, cyclohexyl groups, cyclohexylmethyl groups, cyclohexylethyl groups, and cyclohexylpropyl groups. The hydrogen atoms in the alkyl groups may be substituted with halogen atoms.

[0076] In the non-liquid crystalline and thermally crosslinkable constitutional unit containing an alkylene group in the side chain, R 13 The methyl group, R 14 and R 15 The alkyl group in R 13 , R 14 , and R 15 The substituent that the aryl group in R may have is preferably a thermally crosslinkable group, and examples thereof include the same thermally crosslinkable groups as those in the copolymer (B) described below, and may be, for example, at least one selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, an amide group, a hydroxymethyl group, an alkoxymethyl group, a trialkoxysilyl group, a blocked isocyanate group, and an alkoxy group substituted with a methyl group. The hydroxymethyl group and the alkoxymethyl group, which are self-crosslinking groups, are represented by R 13 The methyl group in the formula (I) may be substituted with a hydroxy group or an alkoxy group to form a hydroxymethyl group or an alkoxymethyl group. Among them, from the viewpoint of reactivity, the thermally crosslinkable group is preferably a hydroxy group, and more preferably a primary hydroxy group, where the carbon atom to which the hydroxy group is bonded is a primary carbon atom.

[0077] The non-liquid crystal structural unit is preferably a structural unit derived from a monomer having a polymerizable ethylenic double bond-containing group. Examples of such a monomer having an ethylenic double bond-containing group include derivatives such as (meth)acrylic acid ester, styrene, (meth)acrylamide, maleimide, vinyl ether, or vinyl ester. From the viewpoint of vertical alignment, the non-liquid crystal structural unit is preferably a structural unit derived from a (meth)acrylic acid ester derivative or styrene, and more preferably a structural unit derived from a (meth)acrylic acid ester derivative.

[0078] In an embodiment of the present disclosure, the non-liquid crystal structural unit preferably has a structural unit represented by the following formula (II).

[0079] [ka] (In general formula (II), R 11 represents a hydrogen atom or a methyl group, R 12 -L 2 -R 13 , or -L 2’ -R 14 L represents a group represented by 2 Ha-(CH2) n - represents L 2’ Ha-(C2H4O) n’ - represents a linking group represented by R 13 represents a methyl group which may have a substituent, an aryl group which may have an alkyl group, or -OR 15 R 14 and R 15 each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and n and n' each independently represent an integer of 1 to 18.

[0080] In the constitutional unit represented by formula (II), -L 2 -R 13 , or -L 2’ -R 14 The group represented by the formula (I) may be the same as above.

[0081] In an embodiment of the present disclosure, when the non-liquid crystal structural unit is a non-liquid crystal and non-crosslinkable structural unit, examples of the optional substituent contained in the structural unit represented by formula (II) include the above-mentioned non-crosslinkable substituents. In the embodiment of the present disclosure, when the non-liquid crystal structural unit is a non-liquid crystal and thermally crosslinkable structural unit, the optional substituent contained in the structural unit represented by formula (II) includes the above-mentioned thermally crosslinkable group. It is preferable that one non-liquid crystal and thermally crosslinkable structural unit has one thermally crosslinkable group, but it may have two or more thermally crosslinkable groups.

[0082] In an embodiment of the present disclosure, when the non-liquid crystal structural unit contains a non-liquid crystal and thermally crosslinkable structural unit, it is preferable that the non-liquid crystal structural unit has a structural unit represented by the following formula (III) from the viewpoints of improving reactivity and durability.

[0083] [ka] (In the above formula (III), Z a represents at least one monomer unit selected from the group consisting of the following formulas (a-1) to (a-6), and R 16 is a linear alkylene group having 1 to 11 carbon atoms which may have -O- in the carbon chain, and Y a represents a thermally crosslinkable group.

[0084] [ka] (In the above formulas (a-1) to (a-6), R 11 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 17 represents a hydrogen atom or a methyl group, and R 18is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 19 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L a represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-; L a If it is a single bond, R 16 is directly bonded to the styrene backbone.)

[0085] R 16 is a linear alkylene group having 1 to 11 carbon atoms which may have -O- in the carbon chain, but -(CH2) n” -or-(C2H4O) m” It is preferably -C2H4- (n" is 1 to 11, m" is 1 to 4), it is preferably 2 to 11, m" is 1 to 4, it is preferably 4 to 11, m" is 2 to 4. If n" and m" are too small, the distance between the thermally crosslinkable group and the main skeleton of the copolymer in the thermally crosslinkable constituent unit becomes short, so that the thermal crosslinking agent is difficult to bond to the thermally crosslinkable group, and the reactivity between the thermally crosslinkable constituent unit and the thermal crosslinking agent may decrease. On the other hand, if n" and m" are too large, the chain length of the linking group in the thermally crosslinkable constituent unit becomes long, so that the thermally crosslinkable group at the terminal is difficult to come out to the surface, it is difficult for the thermal crosslinking agent to bond to the thermally crosslinkable group, and the reactivity between the thermally crosslinkable constituent unit and the thermal crosslinking agent may decrease. Y a The thermally crosslinkable group may be the same as the thermally crosslinkable group described above, and may be, for example, at least one selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, an amide group, a hydroxymethyl group, an alkoxymethyl group, a trialkoxysilyl group, a blocked isocyanate group, and an alkoxy group substituted with a methyl group. The hydroxymethyl group and the alkoxymethyl group, which are self-crosslinking groups, are substituted with a methyl group (R 16 The methylene group in the formula (I) may be substituted with a hydroxy group or an alkoxy group to form a hydroxymethyl group or an alkoxymethyl group.

[0086] In addition, in an embodiment of the present disclosure, when the non-liquid crystal structural unit includes a non-liquid crystal and thermally crosslinkable structural unit, the non-liquid crystal and thermally crosslinkable structural unit may be the same as the structural unit represented by formula (III) described later in the side chain type liquid crystal polymer (A) of the second present disclosure described later.

[0087] The non-liquid crystal structural unit contained in the copolymer may be of one type or of two or more types. Among the constitutional units represented by general formula (II), examples of the non-liquid crystal and non-crosslinkable constitutional units include the following chemical formulas (II-1) to (II-10). Among the structural units represented by general formula (II), examples of the non-liquid crystallinity and thermal crosslinking structural units include structures in which one of the hydrogen atoms of the hydrocarbon groups of the following chemical formulae (II-1) to (II-10) is substituted with the thermal crosslinking group. Further, examples of the non-liquid crystallinity and thermal crosslinking structural units include the following chemical formulae (III-1) to (III-11).

[0088] [ka]

[0089] [ka]

[0090] In addition, constitutional units represented by chemical formulas (III-1) to (III-12) of the second disclosure of the present invention, which are explained in the side chain type liquid crystal polymer (A) of the second disclosure of the present invention described later, can also be used.

[0091] In the synthesis of the copolymer, a monomer such as a (meth)acrylic acid ester derivative that derives the non-liquid crystal structural unit can be used. The monomer such as a (meth)acrylic acid ester derivative that derives the non-liquid crystal structural unit can be used alone or in combination of two or more.

[0092] In order to improve the vertical alignment of the liquid crystalline structural units and to provide sufficient liquid crystal alignment, the content of the non-liquid crystal structural units in the copolymer is preferably set within the range of 10 mol % to 60 mol %, more preferably within the range of 15 mol % to 50 mol %, further preferably within the range of 15 mol % to 45 mol %, and particularly preferably within the range of 20 mol % to 40 mol %, when the amount of the structural units contained in the entire copolymer is taken as 100 mol %.

[0093] When the copolymer contains both a non-liquid crystalline, non-crosslinkable constituent unit and a non-liquid crystalline, thermally crosslinkable constituent unit as the non-liquid crystalline constituent unit, the content of the non-liquid crystalline, thermally crosslinkable constituent unit is preferably set in the range of 10 mol % to 70 mol %, and more preferably set in the range of 30 mol % to 50 mol %, when the total amount of the non-liquid crystalline constituent units contained in the entire copolymer is taken as 100 mol %. The content ratio of each structural unit in the copolymer is as follows: 1 It can be calculated from the integral value obtained by H-NMR measurement.

[0094] (3) Other constituent units The side chain liquid crystal polymer (A) used in the present disclosure has at least the liquid crystal constituent unit and the non-liquid crystal constituent unit containing an alkylene group in the side chain, and may further have other constituent units. Examples of other structural units include a thermally crosslinkable structural unit that does not contain an alkylene group in the side chain but has the thermally crosslinkable group, and a photoalignable structural unit that contains a photoalignable group in the side chain of the copolymer (B) described below. Examples of the thermally crosslinkable constituent unit that does not contain an alkylene group in the side chain and has the thermally crosslinkable group include (meth)acrylic acid, 4-hydroxystyrene, and 4-carboxystyrene. The side chain type liquid crystal polymer (A) used in the present disclosure preferably has at least one type of thermally crosslinkable structural unit having a thermally crosslinkable group in a side chain selected from the group consisting of a non-liquid crystal and thermally crosslinkable structural unit having an alkylene group in a side chain, and a thermally crosslinkable structural unit having no alkylene group in a side chain and the thermally crosslinkable group, from the viewpoint of improving the durability and reliability of the retardation layer. The photoalignable constituent unit may be the same as the photoalignable constituent unit containing a photoalignable group in the side chain contained in the copolymer (B) described below.

[0095] The content ratio of the above-mentioned other structural units in the copolymer is preferably set within the range of 30 mol % or less, and more preferably within the range of 20 mol % or less, when the amount of structural units contained in the entire copolymer is taken as 100 mol %, in order to improve the vertical alignment property of the liquid crystalline structural units and to have sufficient liquid crystal alignment property.

[0096] (4) Copolymer of side-chain liquid crystal polymer (A) In an embodiment of the present disclosure, the side chain type liquid crystal polymer (A) may be a block copolymer having a block portion consisting of a liquid crystal constitutional unit and a block portion consisting of a non-liquid crystal constitutional unit containing an alkylene group in the side chain, or may be a random copolymer in which the liquid crystal constitutional unit and the non-liquid crystal constitutional unit containing an alkylene group in the side chain are irregularly arranged. In this embodiment, it is preferable that the side chain type liquid crystal polymer is a random copolymer from the viewpoint of improving the vertical alignment property and the in-plane uniformity of the retardation value.

[0097] The mass average molecular weight Mw of the side chain type liquid crystal polymer, which is a copolymer, is not particularly limited, but is preferably within a range of 5000 to 80000, more preferably within a range of 8000 to 50000, and further preferably within a range of 10000 to 36000. By being within the above range, the stability of the liquid crystal composition is excellent, and the handling during the formation of the retardation layer is excellent.

[0098] The mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). The measurement was performed using HLC-8120GPC manufactured by Tosoh Corporation, N-methylpyrrolidone containing 0.01 mol / L lithium bromide as an elution solvent, polystyrene standards for calibration curve Mw 377400, 210500, 96000, 50400, 206500, 10850, 5460, 2930, 1300, 580 (all manufactured by Polymer Laboratories, Easi PS-2 series) and Mw 1090000 (manufactured by Tosoh Corporation), and two TSK-GEL ALPHA-M columns (manufactured by Tosoh Corporation).

[0099] A method for synthesizing the copolymer of the side chain type liquid crystal polymer (A) includes a method in which a monomer that derives a liquid crystal constituent unit and a monomer that derives a non-liquid crystal constituent unit containing an alkylene group in the side chain are copolymerized by a conventionally known production method. The side chain type liquid crystal polymer (A) may be used in the form of a solution obtained when the copolymer is synthesized, or in the form of a powder, or in the form of a solution obtained by redissolving the purified powder in a solvent described below.

[0100] The side chain liquid crystal polymer (A) may be used alone or in combination of two or more. In the present embodiment, in order to exert vertical alignment properties, the content of the side chain liquid crystal polymer is preferably 20 parts by mass to 80 parts by mass, more preferably 25 parts by mass to 70 parts by mass, and even more preferably 30 parts by mass to 60 parts by mass, based on 100 parts by mass of the solid content of the liquid crystal composition. In the present disclosure, the solid content refers to all components excluding the solvent. For example, even if a polymerizable liquid crystal compound described below is in a liquid state, it is included in the solid content.

[0101] 2.Copolymer (B) The copolymer (B) used in the present disclosure has a photoalignable constituent unit having a photoalignable group in a side chain with a specific structure, and a thermally crosslinkable constituent unit having a thermally crosslinkable group in a side chain. The copolymer (B) is a photoalignable copolymer. Each of the structural units in the copolymer will be described below.

[0102] (1) Photo-orientable building block The photoalignable structural unit of the present disclosure has a structural unit represented by the following formula (1).

[0103] [ka] (In the above formula (1), Z 1 represents at least one monomer unit selected from the group consisting of the following formulas (1-1) to (1-6), X represents a photoalignment group, L 11 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, or a combination of any of these with an arylene group.

[0104] [ka] (In the above formulas (1-1) to (1-6), R 21 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 22 represents a hydrogen atom or a methyl group, and R 23 is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 24 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0105] The monomer unit constituting the photoalignment structural unit may be at least one selected from the group consisting of the above formulas (1-1) to (1-6). 1 is at least one selected from the group consisting of formula (1-2), -L 11 -X may be bonded to any of the ortho, meta, and para positions, but -L 11 It is preferable that -X is bonded to the para position, since the distance between the photoalignable groups tends to be small and photoalignment is easily obtained. As the monomer unit constituting the photo-alignable structural unit, at least one selected from the group consisting of formulas (1-1) and (1-2) is preferred from the viewpoint of easiness of procurement of raw materials. Furthermore, at least one selected from the group consisting of formula (1-2) is more preferred because the copolymer (B) is more likely to be non-liquid crystal, it is more likely to be phase separated from the side chain type liquid crystal polymer (A), the vertical alignment property of the side chain type liquid crystal polymer (A) is improved, and the rigidity of the photo-alignable structural unit of the copolymer (B) is increased, so the distance between the photo-alignable groups is more likely to be small, and excellent photo-alignment is more likely to be obtained.

[0106] In addition, when the copolymer has a styrene skeleton and contains a large amount of π electron systems, it is considered that, due to the interaction of the π electron systems, the alignment layer / retardation layer formed from the thermosetting liquid crystal composition having photoalignment properties of the present disclosure also has high adhesion to the liquid crystal material directly laminated on this alignment layer / retardation layer.

[0107] L 11 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, or a combination of these with an arylene group, and links the monomer unit with the photoalignable group X. Since the photoalignable constituent unit of the copolymer (B) of the present disclosure does not have a straight-chain alkylene group between the photoalignable group and the monomer unit, it is likely to be non-liquid crystal, as described above, and the compatibility with the side chain type liquid crystal polymer (A) is reduced, making it easy to phase separate from the side chain type liquid crystal polymer (A), and the rigidity is increased, and the distance between the photoalignable groups is likely to be small, and it is presumed that excellent photoalignment can be obtained.

[0108] The above L 11 When is a single bond, the photo-alignable group X is a monomer unit Z 1 Specific examples of the divalent linking group include -O-, -S-, -COO-, -COS-, -CO-, -OCO-, -C6H4-, -C6H4O-, -OCOC6H4O-, -COOC6H4O-, -OC6H4O-, and the like, where -C6H4- is a phenylene group.

[0109] On the other hand, the photoalignable group is a functional group that exhibits anisotropy by undergoing a photoreaction upon irradiation with light, and is preferably a functional group that undergoes a photodimerization reaction or a photoisomerization reaction.

[0110] Examples of photo-alignable groups that cause photodimerization include cinnamoyl groups, chalcone groups, coumarin groups, anthracene groups, quinoline groups, azobenzene groups, and stilbene groups. The benzene rings in these functional groups may have a substituent. The substituent may be any group that does not interfere with the photodimerization reaction, and examples of the substituent include alkyl groups, aryl groups, cycloalkyl groups, alkoxy groups, aryloxy groups, hydroxy groups, halogen atoms, trifluoromethyl groups, and cyano groups.

[0111] The photo-alignable group that causes a photoisomerization reaction is preferably one that causes a cis-trans isomerization reaction, and examples thereof include a cinnamoyl group, a chalcone group, an azobenzene group, and a stilbene group. The benzene ring in these functional groups may have a substituent. The substituent may be any group that does not interfere with the photoisomerization reaction, and examples thereof include an alkoxy group, an alkyl group, a halogen atom, a trifluoromethyl group, and a cyano group.

[0112] Among them, the photoalignable group is preferably a cinnamoyl group. Specifically, the cinnamoyl group is preferably at least one selected from the group consisting of groups represented by the following formulae (x-1) and (x-2).

[0113] [ka]

[0114] In the above formula (x-1), R 31 R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, or a cycloalkyl group having 1 to 18 carbon atoms. However, the alkyl group, aryl group, and cycloalkyl group may be bonded via an ether bond, an ester bond, an amide bond, or a urea bond, and may have a substituent. 32 ~R35 R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a cyano group. However, the alkyl group, aryl group, and cycloalkyl group may be bonded via an ether bond, an ester bond, an amide bond, or a urea bond, and may have a substituent. 36 and R 37 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. In addition, in the above formula (x-2), R 41 ~R 45 R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a cyano group. However, the alkyl group, aryl group, and cycloalkyl group may be bonded via an ether bond, an ester bond, an amide bond, or a urea bond, and may have a substituent. 46 and R 47 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.

[0115] In addition, when the photoalignment group is a cinnamoyl group represented by the above formula (x-1), the benzene ring of the styrene skeleton (formula (1-2)) contained in the monomer unit may be the benzene ring of the cinnamoyl group.

[0116] Moreover, the cinnamoyl group represented by the above formula (x-1) is more preferably a group represented by the following formula (x-3).

[0117] [ka]

[0118] In the above formula (x-3), R 32 ~R 37is the same as the above formula (x-1). 38 represents a hydrogen atom, an alkoxy group having 1 to 18 carbon atoms, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. However, the alkyl group, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via an ether bond, an ester bond, an amide bond, or a urea bond. n represents an integer of 1 to 5, and R 38 may be bonded to any of the ortho, meta, and para positions. When n is 2 to 5, R 38 may be the same or different. Among them, n is 1 and R 38 is preferably attached at the para position.

[0119] The photoalignable constitutional unit contained in the copolymer may be of one type or of two or more types. In the synthesis of the copolymer, a monomer having a photo-alignable group that induces the above-mentioned photo-alignable structural unit can be used. The monomer having a photo-alignable group can be used alone or in combination of two or more kinds.

[0120] The content ratio of the photo-alignable structural unit in the copolymer can be set within the range of 10 mol% to 90 mol%, preferably within the range of 20 mol% to 80 mol%, when the amount of the structural units contained in the entire copolymer is taken as 100 mol%. If the content ratio of the photo-alignable structural unit is low, the sensitivity decreases, and it may be difficult to impart good liquid crystal alignment ability. On the other hand, if the content ratio of the photo-alignable structural unit is high, the content ratio of the thermal crosslinkable structural unit becomes relatively low, and sufficient thermosetting property cannot be obtained, and it may be difficult to maintain good liquid crystal alignment ability.

[0121] (2) Thermally crosslinkable structural unit The thermally crosslinkable constituent unit in the present disclosure is a site that bonds with a thermal crosslinking agent upon heating. The thermally crosslinkable structural unit may be a structural unit having a thermally crosslinkable group. The thermally crosslinkable group may be a group that crosslinks by heating at, for example, 30°C to 250°C, and may be, for example, a hydroxyl group, a carboxyl group, a phenolic hydroxyl group, a mercapto group, a glycidyl group, an amino group, an amide group, etc. Among them, from the viewpoint of reactivity, an aliphatic hydroxyl group is preferable, and a primary hydroxyl group is more preferable. The primary hydroxyl group refers to a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a primary carbon atom. The thermally crosslinkable group may be a self-crosslinkable group capable of crosslinking with the same crosslinkable group, such as a hydroxymethyl group, an alkoxymethyl group, a trialkoxysilyl group, or a blocked isocyanate group. When the thermally crosslinkable structural unit has a self-crosslinking group, the thermally crosslinkable structural unit can also function as a thermal crosslinking agent, which is preferable in that the photoalignment performance and solvent resistance are easily improved. When the thermally crosslinkable structural unit has a self-crosslinking group, it is considered that the self-crosslinking group easily reacts with the thermally crosslinkable structural unit in the molecule. Among them, it is preferable that the thermally crosslinkable constituent unit contains at least one type selected from the group consisting of a hydroxy group, a carboxy group, and a mercapto group, from the viewpoints of photoalignment performance and solvent resistance. As the thermally crosslinkable constituent unit, it is preferable to contain a constituent unit having at least one type of thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, and a mercapto group, and a constituent unit having at least one type of self-crosslinking group selected from the group consisting of a hydroxymethyl group, an alkoxymethyl group, a trialkoxysilyl group, and a blocked isocyanate group, since this makes it easier to improve the photoalignment performance and solvent resistance. The alkoxymethyl group of the self-crosslinking group is preferably one having 1 to 6 carbon atoms in the alkoxy group, and specific examples thereof include a methoxymethyl group, an ethoxymethyl group, various propoxymethyl groups, various butoxymethyl groups, various pentoxymethyl groups, etc. Among them, the alkoxymethyl group is more preferably one having 1 to 4 carbon atoms in the alkoxy group, and even more preferably one having 1 to 2 carbon atoms, and a methoxymethyl group or an ethoxymethyl group is preferred from the viewpoint of good crosslinking properties.

[0122] Examples of monomer units constituting the thermally crosslinkable structural unit include acrylic esters, methacrylic esters, styrene, acrylamide, methacrylamide, maleimide, vinyl ethers, and vinyl esters. The thermally crosslinkable constituent unit may be a constituent unit derived from acrylic acid or methacrylic acid when the thermally crosslinkable group is a carboxy group, and may be a constituent unit derived from vinyl alcohol when the thermally crosslinkable group is a hydroxy group.

[0123] An example of the thermally crosslinkable constitutional unit is a constitutional unit represented by the following formula (2).

[0124] [ka] (In the above formula (2), Z 2 represents at least one monomer unit selected from the group consisting of the following formulas (2-1) to (2-6), and R 50 represents a linear alkylene group having 1 to 11 carbon atoms which may have -O- in the carbon chain, and Y represents a thermally crosslinkable group.

[0125] [ka] (In the above formulas (2-1) to (2-6), R 51 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 52 represents a hydrogen atom or a methyl group, and R 53 is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 54represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 12 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-; L 12 If it is a single bond, R 50 is directly bonded to the styrene backbone.)

[0126] In addition, Z 2 is at least one selected from the group consisting of formula (2-2), -L 12 -Y may be bonded to any of the ortho, meta, and para positions, but -L 12 It is preferable that -Y is bonded to the para position because this provides excellent reactivity in thermal crosslinking.

[0127] As the monomer unit constituting the thermally crosslinkable structural unit, from the viewpoint of easiness of procurement of raw materials, at least one selected from the group consisting of formulas (2-1) and (2-2) is preferable. Furthermore, at least one selected from the group consisting of formula (2-2) is more preferable because the copolymer (B) is more likely to be non-liquid crystal, and is more likely to be phase separated from the side chain type liquid crystal polymer (A), thereby improving the vertical alignment of the side chain type liquid crystal polymer (A).

[0128] In the above formula (2), the thermally crosslinkable group for Y may be the same as above, or may be a self-crosslinkable group. In the above formula (2), the thermally crosslinkable group of Y may be at least one type of thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, an amide group, a hydroxymethyl group, an alkoxymethyl group, a trialkoxysilyl group, a blocked isocyanate group, and an alkoxy group substituted with a methyl group, and may be at least one type of thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group. The hydroxymethyl group and the alkoxymethyl group, which are self-crosslinking groups, may be at least one type of thermally crosslinkable group selected from the group consisting of a methyl group (R 50 The methylene group in the formula (I) may be substituted with a hydroxy group or an alkoxy group to form a hydroxymethyl group or an alkoxymethyl group. From the viewpoint of reactivity, the thermally crosslinkable group of Y preferably contains an aliphatic hydroxy group, and more preferably contains a primary hydroxy group.

[0129] In the above formula (2), L 12 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-. 12 When is a single bond, the thermal crosslinking group Y is a monomer unit Z 2 is directly bonded to R 50 is a linear alkylene group having 1 to 11 carbon atoms which may have -O- in the carbon chain, and -(CH2) j -or-(C2H4O) k It is preferable that j is -C2H4- (j is 1 to 11, k is 1 to 4), it is preferable that j is 2 to 11, k is 1 to 4, it is preferable that j is 4 to 11, k is 2 to 4. If j and k are too small, the distance between the thermally crosslinkable group and the main skeleton of the copolymer in the thermally crosslinkable constituent unit is short, so that the thermal crosslinking agent is difficult to bond to the thermally crosslinkable group, and the reactivity between the thermally crosslinkable constituent unit and the thermal crosslinking agent may decrease. On the other hand, if j and k are too large, the chain length of the linking group in the thermally crosslinkable constituent unit is long, so that the thermally crosslinkable group at the terminal is difficult to come out to the surface, it is difficult for the thermal crosslinking agent to bond to the thermally crosslinkable group, and the reactivity between the thermally crosslinkable constituent unit and the thermal crosslinking agent may decrease.

[0130] The thermally crosslinkable constituent unit contained in the copolymer may be of one type or of two or more types. In the synthesis of the copolymer, a monomer having a thermal crosslinkable group that induces the above-mentioned thermal crosslinkable structural unit can be used. The monomer having a thermal crosslinkable group can be used alone or in combination of two or more kinds.

[0131] Examples of the monomer having a thermal crosslinkable group include, but are not limited to, the following: Examples of the acrylic acid ester compound and the methacrylic acid ester compound include monomers having a hydroxy group and an acrylic group or a methacrylic group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, tetraethylene glycol monoacrylate, dipropylene glycol monoacrylate, tripropylene glycol monoacrylate, and tetrapropylene glycol monoacrylate. Examples of the styrene compound include monomers having a hydroxy group and a styrene group, such as an ester of 4-vinylbenzoic acid and a diol, an ester of 4-vinylbenzoic acid and diethylene glycol, an ether of hydroxystyrene and a diol, and an ether of hydroxystyrene and diethylene glycol. Other examples of monomers that can be used to form thermally crosslinkable structural units include those described in paragraphs 0075 to 0079 of Japanese Patent No. 5626493. The above-listed hydroxyl groups may be substituted with carboxyl groups or glycidyl groups.

[0132] Among the monomers having a thermal crosslinkable group, examples of monomers having a self-crosslinking group include acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide; monomers having a trialkoxysilyl group, such as 3-trimethoxysilylpropylacrylate, 3-triethoxysilylpropylacrylate, 3-trimethoxysilylpropylmethacrylate, and 3-triethoxysilylpropylmethacrylate; and monomers having a blocked isocyanate group, such as 2-(0-(1'-methylpropylideneamino)carboxyamino)ethylmethacrylate and 2-(3,5-dimethylpyrazolyl)carbonylaminoethylmethacrylate.

[0133] The content ratio of the thermally crosslinkable structural unit in the copolymer can be set within the range of 5 mol% to 90 mol%, preferably within the range of 20 mol% to 80 mol%, when the amount of the structural units contained in the entire copolymer is taken as 100 mol%. If the content ratio of the thermally crosslinkable structural unit is low, sufficient thermosetting property cannot be obtained, and it may be difficult to maintain good liquid crystal alignment ability. In addition, if the content ratio of the thermally crosslinkable structural unit is high, the content ratio of the photoalignment structural unit is relatively low, the sensitivity is reduced, and it may be difficult to impart good liquid crystal alignment ability.

[0134] (3) Other building blocks In the present disclosure, the copolymer may have a structural unit having neither a photoalignable group nor a thermally crosslinkable group, in addition to the photoalignable structural unit and the thermally crosslinkable structural unit. By including other structural units in the copolymer, for example, the solvent solubility, heat resistance, reactivity, etc. can be improved.

[0135] Examples of monomer units constituting a structural unit having no photoalignable group and no thermally crosslinkable group include acrylic acid esters, methacrylic acid esters, maleimides, acrylamides, acrylonitrile, maleic anhydride, styrene, vinyl, etc. Among these, acrylic acid esters, methacrylic acid esters, and styrene are preferred, as with the thermally crosslinkable structural unit.

[0136] Examples of monomers that form structural units that do not have such a photoalignable group and a thermally crosslinkable group include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds. Specifically, for example, among the monomers described in paragraphs 0036 to 0040 of WO 2010 / 150748, a monomer having neither the photoalignable group nor the thermally crosslinkable group can be used.

[0137] As other structural units, for example, structural units derived from a monomer having a fluorinated alkyl group may be included. In this case, the copolymer (B) is more likely to be localized on the coating film surface, and the photoalignable group is more likely to be oriented on the coating film surface. In order to make the copolymer (B) more likely to be localized on the coating film surface, the fluorinated alkyl group of the monomer having a fluorinated alkyl group may be a fluorinated alkyl group having 2 to 8 carbon atoms to which a fluorine atom is directly bonded.

[0138] The constituent unit having neither a photoalignable group nor a thermally crosslinkable group in the copolymer may be of one type or of two or more types.

[0139] The content ratio of the structural unit not having the photo-alignable group and the thermal crosslinkable group in the copolymer is preferably within the range of 0 mol% to 50 mol%, more preferably within the range of 0 mol% to 30 mol%, when the amount of the structural units contained in the entire copolymer is taken as 100 mol%. If the content ratio of the structural units is high, the content ratio of the photo-alignable structural unit and the thermal crosslinkable structural unit is relatively low, the sensitivity is reduced, it becomes difficult to impart good liquid crystal alignment ability, and sufficient thermosetting property is not obtained, and it may become difficult to maintain good liquid crystal alignment ability.

[0140] (4) Copolymer (B) The mass average molecular weight of the copolymer (B) is not particularly limited, and can be, for example, about 3,000 to 200,000, preferably within the range of 4,000 to 100,000. If the mass average molecular weight is too large, the solubility in the solvent may be reduced or the viscosity may be increased, which may reduce the handling property and make it difficult to form a uniform film. If the mass average molecular weight is too small, the curing may be insufficient during heat curing, which may reduce the solvent resistance and heat resistance. The mass average molecular weight can be measured by gel permeation chromatography (GPC).

[0141] The copolymer (B) can be synthesized by copolymerizing a monomer having a photoalignable group with a monomer having a thermally crosslinkable group by a conventionally known production method. The copolymer (B) may be used in the form of a solution obtained when the copolymer is synthesized, or in the form of a powder, or in the form of a solution obtained by redissolving a purified powder in a solvent described below.

[0142] The copolymer (B) may be used alone or in combination of two or more. In the present embodiment, in order to exert an alignment ability on the liquid crystal material to be directly laminated, the content of the copolymer (B) is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of the solid content of the liquid crystal composition.

[0143] 3. Thermal crosslinking agent The thermosetting liquid crystal composition having photoalignment property of the present disclosure contains a thermal crosslinking agent that bonds with the thermal crosslinking group of the thermal crosslinking structural unit. The thermal crosslinking agent can enhance heat resistance and solvent resistance by bonding with at least the thermal crosslinking group of the copolymer. The thermal crosslinking agent also bonds with the side chain type liquid crystal polymer (A) having a thermal crosslinking group in the side chain, which may be optionally contained, and with a compound having a thermal crosslinking group, thereby improving the durability of the cured film and contributing to the improvement of each function.

[0144] As the thermal crosslinking agent, a compound that bonds with the thermal crosslinkable group of the thermal crosslinkable constitutional unit is selected and used. Examples of such a thermal crosslinking agent include a compound having a crosslinking group capable of reacting with the thermal crosslinking group. Examples of the crosslinking group possessed by the thermal crosslinking agent include an epoxy group, a methylol group, an isocyanate group, a blocked isocyanate group, a carboxyl group, a protected carboxyl group, and a maleimide group. The number of crosslinking groups possessed by the thermal crosslinking agent is preferably 2 or more, and more preferably 2 to 6. Examples of the thermal crosslinking agent include an epoxy compound, a methylol compound, an isocyanate compound, and the like, and among these, a methylol compound is preferred. Specific examples of the methylol compound include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine. Specific examples of alkoxymethylated glycolurils include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds (product names: Cymel 1170, Powder Link 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resin (product name: UFR65), butylated urea resin (product names: UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (high condensation type, product names: Beckamin J-300S, Beckamin P-955, Beckamin N) manufactured by Dainippon Ink and Chemicals, Inc. Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (product name: Cymel 1123), and those manufactured by Sanwa Chemical Co., Ltd. (product names: Nikalac BX-4000, Nikalac BX-37, Nikalac BL-60, and Nikalac BX-55H). Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine, etc. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel 300, Cymel 301, Cymel 303, Cymel 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade names: Mycoat 506, Mycoat 508), methoxymethyl type melamine compounds (trade names: Nikalac MW-30, Nikalac MW-22, Nikalac MW-11, Nikalac MS-001, Nikalac MX-002, Nikalac MX-730, Nikalac MX-750, Nikalac MX-035) manufactured by Sanwa Chemical Co., Ltd., butoxymethyl type melamine compounds (trade names: Nikalac MX-45, Nikalac MX-410, Nikalac MX-302), etc.

[0145] Also, it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound described in U.S. Patent No. 6,323,310 may be mentioned. A commercially available product of the melamine compound may be Cymel 303 (manufactured by Mitsui Cytec Co., Ltd.), and a commercially available product of the benzoguanamine compound may be Cymel 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0146] Furthermore, as the thermal crosslinking agent, a polymer produced using an acrylamide compound or methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group can also be used. Specifically, for example, the thermal crosslinking agents described in paragraphs 0049 to 0050 of WO 2010 / 150748 can be used.

[0147] Thermal crosslinking agents containing multiple benzene rings in the molecule can also be used. Examples of thermal crosslinking agents containing multiple benzene rings in the molecule include phenol derivatives having a total of two or more hydroxymethyl groups or alkoxymethyl groups and a molecular weight of 1200 or less, and melamine-formaldehyde derivatives and alkoxymethyl glycoluril derivatives having at least two free N-alkoxymethyl groups. Phenol derivatives containing hydroxymethyl groups can be obtained by reacting a corresponding phenol compound not containing a hydroxymethyl group with formaldehyde in the presence of a base catalyst.

[0148] Specific examples of epoxy compounds include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxysilane diglycidyl ether, Cyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexyl di(3,4-epoxycyclohexylmethyl)-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, beta-methyl-delta-valerolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, di-2-ethylhexyl epoxycyclohexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ethers;Examples of such polyglycidyl ethers include polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol, or alkylene oxides; glycidyl esters of higher fatty acids; epoxidized soybean oil; epoxy butyl stearate; epoxy octyl stearate; epoxidized linseed oil; and epoxidized polybutadiene. Commercially available epoxy compounds include, for example, UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 (all manufactured by Union Carbide), Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Epolead GT-300, Epolead GT-301, Epolead GT-302, and Epolead GT-400. , Epolead 401, Epolead 403 (all manufactured by Daicel Chemical Industries), KRM-2100, KRM-2110, KRM-2199, KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2200, KRM-2720, KRM-2750 (all manufactured by Asahi Denka Kogyo Co., Ltd.), CER-4221, CER-4221-E, CER-4221-H (all manufactured by Darian Tricho Chemical Co., Ltd.), Rapi-cure Examples include DVE-3, CHVE, PEPC (all manufactured by ISP), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (all manufactured by Japan Epoxy Resins), XDO (manufactured by Toagosei), VECOMER 2010, 2020, 4010, 4020 (all manufactured by Allied Signal), etc.

[0149] These thermal crosslinking agents can be used alone or in combination of two or more kinds. In the present disclosure, from the viewpoint of improving the durability of the cured film, the content of the thermal crosslinking agent is preferably 0.1 parts by mass to 30 parts by mass, more preferably 0.5 parts by mass to 25 parts by mass, and even more preferably 1 part by mass to 20 parts by mass, relative to 100 parts by mass of the solid content of the thermosetting liquid crystal composition having photoalignment properties. In addition, the content of the thermal crosslinking agent in the photoalignable thermosetting liquid crystal composition of the present disclosure is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 3 to 25 parts by mass, per 100 parts by mass of the side chain type liquid crystal polymer (A) and copolymer (B) in total. If the content of the thermal crosslinking agent is too low, the heat resistance and solvent resistance of the cured film formed from the photo-alignable thermosetting liquid crystal composition may decrease, and the vertical alignment property and liquid crystal alignment ability may decrease. On the other hand, if the content is too high, the vertical alignment property, liquid crystal alignment ability, and storage stability may decrease.

[0150] 4. Acid or acid generator The thermosetting liquid crystal composition having photoalignment properties of the present disclosure may contain an acid or an acid generator. The acid or the acid generator can promote the thermosetting reaction of the thermosetting liquid crystal composition having photoalignment properties of the present disclosure.

[0151] The acid or acid generator is not particularly limited as long as it is a sulfonic acid group-containing compound, hydrochloric acid or its salt, or a compound that undergoes thermal decomposition to generate an acid when the coating film is dried or cured by heating, i.e., a compound that undergoes thermal decomposition to generate an acid at a temperature of 50° C. to 250° C. Specifically, those described in paragraph 0054 of WO 2010 / 150748 can be used.

[0152] The content of the acid or acid generator in the photoalignable thermosetting liquid crystal composition of the present disclosure is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the solid content of the photoalignable thermosetting liquid crystal composition. In addition, the content of the acid or acid generator in the photo-alignable thermosetting liquid crystal composition of the present disclosure is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the side chain liquid crystal polymer (A) and the copolymer (B) in total. By setting the content of the acid or acid generator within the above range, sufficient thermosetting properties and solvent resistance can be imparted, and high sensitivity to light irradiation can also be imparted. On the other hand, if the content is too high, the storage stability of the photo-alignable thermosetting liquid crystal composition may decrease.

[0153] 5. Solvent The thermosetting liquid crystal composition having photo-alignment property of the present disclosure may contain a solvent as necessary from the viewpoint of coating property. The solvent may be appropriately selected from among conventionally known solvents capable of dissolving or dispersing each component contained in the thermosetting liquid crystal composition having photo-alignment property of the present disclosure. Specifically, for example, hydrocarbon-based solvents such as hexane, cyclohexane, toluene, etc., ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc., ether-based solvents such as tetrahydrofuran, 1,3-dioxolane, propylene glycol monoethyl ether (PGME), etc., halogenated alkyl-based solvents such as chloroform, dichloromethane, etc., ester-based solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, etc., amide-based solvents such as N,N-dimethylformamide, N-methylpyrrolidone, etc., sulfoxide-based solvents such as dimethyl sulfoxide, and alcohol-based solvents such as methanol, ethanol, and propanol, etc. In the present embodiment, the solvent may be used alone or in combination as a mixed solvent of two or more kinds.

[0154] In the thermosetting liquid crystal composition having photoalignment properties of the present disclosure, the content of the solvent is not particularly limited as long as each component is uniformly dissolved in the solvent, and in the composition including the solvent, the content is preferably 50% by mass to 99% by mass, more preferably 60% by mass to 95% by mass, and even more preferably 70% by mass to 90% by mass. If the content of the solvent is too high and the ratio of the solid content is too low, it may be difficult to impart retardation, liquid crystal alignment ability, and thermosetting property. Also, if the content of the solvent is too low and the ratio of the solid content is too high, the viscosity of the thermosetting liquid crystal composition having photoalignment property increases, making it difficult to form a uniform film. The solid content refers to all components of the thermosetting liquid crystal composition having photoalignment properties excluding the solvent.

[0155] 6. Other Ingredients The thermosetting liquid crystal composition having photoalignment property of the present disclosure may further contain other components within a range that does not impair the effect. Specifically, as the other components, for example, a polymerizable liquid crystal compound different from the side chain type liquid crystal polymer (A), a polymerizable compound having two or more polymerizable groups in one molecule for improving the hardness and durability of the coating film, a photopolymerization initiator, a compound having a polymerizable group and a thermal crosslinkable group, a compound having a photoalignment group and a thermal crosslinkable group different from the copolymer (B), a sensitizer, a leveling agent, a polymerization inhibitor, an antioxidant, a light stabilizer, etc. may be contained. These may be appropriately selected from conventionally known materials.

[0156] (1) A polymerizable liquid crystal compound different from the side chain type liquid crystal polymer (A) The photoalignable thermosetting liquid crystal composition of the present disclosure may further contain a polymerizable liquid crystal compound different from the side chain liquid crystal polymer (A) as necessary, in order to adjust the retardation and improve durability. In the embodiment of the present disclosure, the polymerizable liquid crystal compound different from the side chain type liquid crystal polymer (A) can be appropriately selected from conventionally known compounds. Examples of the polymerizable liquid crystal compound include so-called low molecular weight polymerizable liquid crystal monomers. In the present embodiment, the polymerizable liquid crystal compound is preferably a polymerizable liquid crystal compound having a polymerizable group at at least one end of a rod-shaped mesogen, since it is easy to achieve vertical alignment in combination with the side chain type liquid crystal polymer (A), and may be a polymerizable liquid crystal compound having a polymerizable group at both ends of a rod-shaped mesogen. The mesogen or rod-like mesogen contained in the polymerizable liquid crystal compound may be the same as the mesogen or rod-like mesogen contained in the liquid crystal constituent unit in the side chain type liquid crystal polymer.

[0157] Examples of the polymerizable group that the polymerizable liquid crystal compound has include cyclic ether-containing groups such as oxirane rings and oxetane rings, and ethylenic double bond-containing groups, among which, ethylenic double bond-containing groups are preferred from the viewpoints of photocurability and excellent handling properties. Examples of the ethylenic double bond-containing group include vinyl groups, allyl groups, and (meth)acryloyl groups, among which, (meth)acryloyl groups are preferred.

[0158] In this embodiment, the polymerizable liquid crystal compound is preferably one or more compounds selected from the compound represented by the following general formula (IV) and the compound represented by the following general formula (V), because they exhibit liquid crystal alignment properties and have excellent heat resistance.

[0159] [ka] (In general formula (IV), R 61 represents a hydrogen atom or a methyl group, R 62 is -(CH2) p - or -(C2H4O) p’ - represents a group represented by L 3 represents a direct bond or a linking group represented by -O-, -OC(=O)-, or -C(=O)-O-, 3 represents an arylene group having 6 to 10 carbon atoms which may have a substituent, 3 and Ar 3 may be the same or different. 63 are -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHC(=O)-R 64 , -C(=O)-OR 64 , -OH, -SH, -CHO, -SO3H, -NR 64 2, -R 65 -OR 65 , R64 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R 65 represents an alkyl group having 1 to 6 carbon atoms, b is an integer of 2 to 4, and p and p' are each independently an integer of 2 to 10.

[0160] [ka] (In general formula (V), R 71 and R 72 each independently represents a hydrogen atom or a methyl group; R 73 is -(CH2) q - or -(C2H4O) q’ - is represented by R 74 is -(CH2) r - or - (OC2H4) r’ - represents a group represented by L 4 represents a direct bond or a linking group represented by -O-, -OC(=O)-, or -C(=O)-O-, 4 represents an arylene group having 6 to 10 carbon atoms which may have a substituent, 4 and Ar 4 may be the same or different. c is an integer of 2 to 4, and q, q', r and r' are each independently an integer of 2 to 10.

[0161] L 3 and L 4 is L in the general formula (I). 2 It can be similar to the above. Also, Ar 3 and Ar 4 is Ar in the general formula (I). 1 It can be similar to the above. The compound represented by general formula (IV) and the compound represented by the following general formula (V) can be, for example, the polymerizable liquid crystal compounds described in paragraphs 0057 to 0064 of International Publication No. 2018 / 003498.

[0162] In the present embodiment, the polymerizable liquid crystal compound different from the side chain type liquid crystal polymer (A) may be used alone or in combination of two or more. When a polymerizable liquid crystal compound other than the side chain type liquid crystal polymer (A) is used in the photoalignable thermosetting liquid crystal composition of the present disclosure, the content thereof is not particularly limited as long as the retardation and durability are appropriately adjusted to improve, but the content is preferably 1 part by mass to 90 parts by mass, more preferably 5 parts by mass to 50 parts by mass, and even more preferably 10 parts by mass to 30 parts by mass relative to 100 parts by mass of the solid content of the photoalignable thermosetting liquid crystal composition. In addition, when a polymerizable liquid crystal compound other than the side chain type liquid crystal polymer (A) is used in the photoalignable thermosetting liquid crystal composition of the present disclosure, the content thereof is preferably 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass to 60 parts by mass, and even more preferably 20 parts by mass to 40 parts by mass, relative to 100 parts by mass of the side chain type liquid crystal polymer (A).

[0163] (2) A polymerizable compound having two or more polymerizable groups in one molecule. The photoalignable thermosetting liquid crystal composition of the present disclosure may further contain a polymerizable compound having two or more polymerizable groups in one molecule, if necessary, in order to improve the hardness and durability of the coating film. As the polymerizable compound having two or more polymerizable groups in one molecule, in addition to the above-mentioned polymerizable liquid crystal compounds, a polymerizable compound having no liquid crystallinity can be used. As the polymerizable compound having two or more polymerizable groups in one molecule, so-called polyfunctional monomers can be used, and examples thereof include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, trimethylolpropane tri(meth)acrylate, dimethy ... Examples of the polyether ether ester include pentaerythritol octa(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, isocyanuric acid tri(meth)acrylate, isocyanuric acid di(meth)acrylate, polyester tri(meth)acrylate, polyester di(meth)acrylate, bisphenol di(meth)acrylate, diglycerin tetra(meth)acrylate, adamantyl di(meth)acrylate, isobornyl di(meth)acrylate, dicyclopentane di(meth)acrylate, tricyclodecane di(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and those modified with PO, EO, etc. Since the crosslinking reaction proceeds and the durability of the coating film is improved, a polymerizable compound having three or more polymerizable groups in one molecule, such as pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPPA), or trimethylolpropane triacrylate (TMPTA), may be used. When a polymerizable compound having two or more polymerizable groups in one molecule that does not have liquid crystallinity is used in the photoalignable thermosetting liquid crystal composition of the present disclosure, the content thereof is not particularly limited as long as it is appropriately adjusted to improve the hardness and durability of the coating film, but is preferably 1 part by mass to 40 parts by mass, more preferably 5 parts by mass to 35 parts by mass, and even more preferably 10 parts by mass to 30 parts by mass, relative to 100 parts by mass of the solid content of the photoalignable thermosetting liquid crystal composition.

[0164] (3) Photopolymerization initiator When the thermosetting liquid crystal composition having photoalignment properties of the present disclosure contains a compound having a polymerizable group such as an ethylenic double bond-containing group, it is preferable that the composition further contains a photopolymerization initiator, since this makes it possible to obtain an alignment layer / retardation layer having better adhesion to the liquid crystal layer to be laminated thereon. As the photopolymerization initiator, a radical-based photopolymerization initiator that generates radical species by irradiation with light is preferably used. The photopolymerization initiator can be appropriately selected from conventionally known ones and used. Specific examples of such photopolymerization initiators include aromatic ketones including thioxanthone, α-aminoalkylphenones, α-hydroxyketones, acylphosphine oxides, oxime esters, aromatic onium salts, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having carbon-halogen bonds, and alkylamine compounds. When the acid or acid generator is contained in the thermosetting liquid crystal composition having photoalignment properties of the present disclosure, the photoinitiator is preferably not a photoinitiator having basicity such as an aminoalkylphenone-based photoinitiator, and is preferably a photoinitiator having no basic group. Among these, at least one selected from the group consisting of acylphosphine oxide-based polymerization initiators, α-hydroxyketone-based polymerization initiators, and oxime ester-based polymerization initiators is preferred, as it hardens to the inside of the coating film and improves durability. Specifically, the photopolymerization initiator that can be used may be, for example, the photopolymerization initiators described in paragraphs 0067 to 0070 of WO 2018 / 003498.

[0165] In the present embodiment, the photopolymerization initiator may be used alone or in combination of two or more. When a photopolymerization initiator is used in the photoalignable thermosetting liquid crystal composition of the present disclosure, the content thereof is not particularly limited as long as it promotes the curing of the compound having the polymerizable group, but the content thereof is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 9 parts by mass, and even more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the solid content of the photoalignable thermosetting liquid crystal composition.

[0166] (4) Compound having a polymerizable group and a thermally crosslinkable group The photo-alignable thermosetting liquid crystal composition of the present disclosure may further contain a compound having a polymerizable group and a thermal crosslinkable group, if necessary, in order to improve the hardness and durability of the coating film and to improve the interlayer adhesion. Here, the polymerizable group may be the same as the polymerizable group described in the above-mentioned polymerizable liquid crystal compound. In addition, the thermal crosslinkable group may be the same as the thermal crosslinkable group described in the above-mentioned copolymer (B). As the compound having a polymerizable group and a thermal crosslinking group, it is preferable to use a compound having at least one of a hydroxy group and a carboxy group and an ethylenically unsaturated double bond group, and more preferably a compound having at least one of a hydroxy group and a carboxy group, an aromatic hydrocarbon group, and an ethylenically unsaturated double bond group.When a compound having at least one of a hydroxy group and a carboxy group, an aromatic hydrocarbon group, and an ethylenically unsaturated double bond group is contained, it is preferable because the liquid crystal alignment ability of the surface is not inhibited and an alignment layer / retardation layer having better adhesion to the liquid crystal layer to be laminated can be obtained. In addition, a hydroxyl group-containing polyfunctional acrylate, which is a compound having a hydroxyl group and two or more ethylenically unsaturated double bond groups, is also preferably used from the viewpoints of improving the hardness and durability of the coating film and improving the interlayer adhesion.

[0167] Specific examples of compounds having a polymerizable group and a thermally crosslinkable group include compounds having a polymerizable group and a thermally crosslinkable group described in paragraphs

[0106] to

[0112] of WO 2014 / 073658, thermally crosslinkable polymerizable compounds containing aromatic hydrocarbon groups described in paragraphs

[0087] to

[0100] of JP 2017-068019, and hydroxyl group-containing polyfunctional acrylates described in JP 2013 / 054784, JP 20125-0126.

[0168] In the present embodiment, the compound having a polymerizable group and a thermally crosslinkable group may be used alone or in combination of two or more kinds. When a compound having a polymerizable group and a thermally crosslinkable group is used in the photoalignable thermosetting liquid crystal composition of the present disclosure, the content thereof is not particularly limited as long as it improves durability and interlayer adhesion, but is preferably 1 part by mass to 50 parts by mass, more preferably 5 parts by mass to 40 parts by mass, and even more preferably 10 parts by mass to 30 parts by mass, relative to 100 parts by mass of the solid content of the photoalignable thermosetting liquid crystal composition.

[0169] (5) A compound having a photoalignment group and a thermal crosslinking group different from the copolymer (B) The thermosetting liquid crystal composition having photoalignment property of the present disclosure may further contain a compound having a photoalignment group and a thermal crosslinking group different from the copolymer (B) as necessary in order to improve the durability and photoalignment property of the coating film. Here, the photoalignment group may be the same as the photoalignment group described in the above-mentioned copolymer (B). In addition, the thermal crosslinking group may be the same as the thermal crosslinking group described in the above-mentioned copolymer (B). Examples of the compound having a photo-aligning group and a thermal crosslinking group different from the copolymer (B) include non-polymer low molecular weight compounds. As the compound having a photo-aligning group and a thermal crosslinking group different from the copolymer (B), it is preferable to use a compound having at least one of a hydroxy group and a carboxy group, and at least one of a cinnamoyl group, a chalcone group, an azobenzene group, and a stilbene group, and more preferably a compound having at least one of a hydroxy group and a carboxy group, and a cinnamoyl group. It is preferable to use a compound having at least one of a hydroxy group and a carboxy group, an aromatic hydrocarbon group, and an ethylenically unsaturated double bond group, since the liquid crystal alignment ability of the surface is not inhibited and an alignment layer / retardation layer having better adhesion to the laminated liquid crystal layer can be obtained.

[0170] Specific examples of compounds having a photoalignment group and a thermal crosslinking group that can be used include compounds having a photoalignment group and a thermal crosslinking group described in paragraphs 0064 to 0074 of WO 2013 / 054784.

[0171] In the present embodiment, the compound having a photoalignable group and a thermally crosslinkable group different from the copolymer (B) can be used alone or in combination of two or more. In the case where a compound having a photoalignable group and a thermally crosslinkable group other than the copolymer (B) is used in the photoalignable thermosetting liquid crystal composition of the present disclosure, the content thereof is not particularly limited as long as it improves the durability and photoalignability of the coating film, but is preferably 1 part by mass to 50 parts by mass, more preferably 10 parts by mass to 40 parts by mass, and even more preferably 15 parts by mass to 30 parts by mass, relative to 100 parts by mass of the solid content of the photoalignable thermosetting liquid crystal composition.

[0172] (6) Sensitizer The thermosetting liquid crystal composition having photoalignment properties according to the present disclosure may contain a sensitizer, which can promote photoreactions such as photodimerization and photoisomerization. Specifically, the sensitizers that can be used include those described in paragraph 0057 of WO 2010 / 150748. Among them, benzophenone derivatives and nitrophenyl compounds are preferable. The sensitizers can be used alone or in combination of two or more compounds.

[0173] When a sensitizer is used in the thermosetting liquid crystal composition having photoalignment properties of the present disclosure, the content thereof is not particularly limited as long as it improves the durability and photoalignment properties of the coating film, but is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.2 parts by mass to 10 parts by mass, and even more preferably 0.5 parts by mass to 10 parts by mass, relative to 100 parts by mass of the solid content of the thermosetting liquid crystal composition having photoalignment properties.

[0174] In addition, in order to achieve the second object, the thermosetting liquid crystal composition having the first photoalignment property may have the composition of a thermosetting liquid crystal composition having the second photoalignment property described below. That is, the first thermosetting liquid crystal composition having photoalignment property comprises a side chain type liquid crystal polymer (A) having a liquid crystal constituent unit having a liquid crystal moiety in a side chain and a non-liquid crystal constituent unit having an alkylene group in a side chain; A copolymer (B) having a photoalignable structural unit containing a photoalignable group in a side chain and a thermally crosslinkable structural unit having a structural unit represented by the following formula (2): and a crosslinking agent (C) that bonds to the thermal crosslinkable group of the thermal crosslinkable structural unit, The side chain liquid crystal polymer (A) may satisfy any one of the following (i) to (vi). (i) The side chain type liquid crystal polymer (A) has a non-liquid crystalline and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and the non-liquid crystalline and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to a primary carbon of an alkylene group which may have -O- in the carbon chain and which has a smaller total carbon number and oxygen number than the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain in the thermally crosslinkable constituent unit of the copolymer (B). (ii) The side chain type liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and the non-liquid crystal and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to a secondary carbon or a tertiary carbon of an alkylene group. (iii) The side chain type liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinkable constituent unit containing at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a mercapto group, and an amino group, an alkylene group, and an arylene group in the side chain, and the non-liquid crystal and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to an arylene group. (iv) The side chain type liquid crystal polymer (A) has a non-liquid crystallinity and thermal crosslinking structural unit containing at least one thermal crosslinking group selected from the group consisting of a carboxyl group, a glycidyl group, and an amide group, and an alkylene group and an arylene group in the side chain, and the non-liquid crystallinity and thermal crosslinking structural unit of the side chain type liquid crystal polymer (A) has a structure in which the thermal crosslinking group is bonded to an arylene group, and the arylene group has a structure bonded to a carbon atom or oxygen atom of an alkylene group which may have -O- in the carbon chain or at the terminal, and the total number of carbon atoms and the number of oxygen atoms is 3 or more smaller than that of the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain in the thermal crosslinking structural unit of the copolymer (B). (v) The side chain type liquid crystal polymer (A) has a thermally crosslinkable constituent unit that does not contain an alkylene group in the side chain but contains a thermally crosslinkable group in the side chain. (vi) The side chain type liquid crystal polymer (A) does not have a non-liquid crystal and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and does not have a thermally crosslinkable constituent unit containing a thermally crosslinkable group in the side chain.

[0175] [ka] (In the above formula (2), Z 2 represents at least one monomer unit selected from the group consisting of the following formulas (2-1) to (2-6), and R 50represents a linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain, and Y represents at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group.

[0176] [ka] (In the above formulas (2-1) to (2-6), R 51 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 52 represents a hydrogen atom or a methyl group, and R 53 is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 54 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 12 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-; L 12 If it is a single bond, R 50 is directly bonded to the styrene backbone.)

[0177] 7. Thermosetting liquid crystal composition having photoalignment properties The method for preparing the thermosetting liquid crystal composition having photoalignment property of the present disclosure is not particularly limited, but in order to prolong the storage stability, a method in which the side chain type liquid crystal polymer (A), the copolymer (B), the thermal crosslinking agent (C), and other components are mixed and the acid or acid generator is added later is preferred. When the acid or acid generator is added from the beginning, it is preferred to use a compound that generates an acid by thermal decomposition during drying and heat curing of the coating film as the acid or acid generator. In preparing the thermosetting liquid crystal composition having photoalignment properties of the present disclosure, the solution of the side-chain liquid crystal polymer (A) or the solution of the copolymer (B) obtained by polymerization reaction in a solvent can be used as is. In this case, the thermal crosslinking agent and other components are added to the solution of the side-chain liquid crystal polymer (A) or the solution of the copolymer (B) as described above to prepare a homogeneous solution, and then an acid or an acid generator is added. At this time, a solvent may be further added for the purpose of adjusting the concentration. At this time, the solvent used in the process of producing the copolymer and the solvent used to adjust the concentration of the thermosetting liquid crystal composition having photoalignment properties may be the same or different. The prepared solution of the thermosetting liquid crystal composition having photoalignment properties is preferably filtered using a filter having a pore size of about 0.2 μm before use.

[0178] The thermosetting liquid crystal composition having photoalignment properties according to the present disclosure is suitable for use in the manufacture of an alignment layer / retardation layer or an alignment film / retardation film, which functions as both an alignment layer and a retardation layer in a single layer, since the side-chain liquid crystal polymer (A) is easily oriented vertically and the copolymer (B) has an excellent ability to align a liquid crystal material directly laminated thereon.

[0179] B. Alignment film and retardation film The alignment film / retardation film of the present disclosure is an alignment film / retardation film containing an alignment layer / retardation layer, characterized in that the alignment layer / retardation layer is a cured film of the thermosetting liquid crystal composition having photoalignment properties of the present disclosure. Hereinafter, each component of the alignment film / retardation film of the present disclosure will be described.

[0180] The layer structure of the alignment film and retardation film will be described with reference to the drawings. Each of FIGS. 1 to 3 shows an embodiment of the alignment film and retardation film of the present disclosure. An embodiment of the alignment film and retardation film 10 shown in the example of FIG. 1 is an alignment film and retardation film consisting of only an alignment layer and retardation layer 1. An embodiment of the alignment film and retardation film 10 shown in the example of FIG. 2 has an alignment layer and retardation layer 1 formed directly on a substrate 2'. The alignment film and retardation film shown in the example of FIG. 2 may have a means for exerting an alignment regulating force on the surface of the substrate 2' on the alignment layer and retardation layer 1 side. Also, an embodiment of the alignment film and retardation film 10 shown in the example of FIG. 3 has an alignment film 3 and an alignment layer and retardation layer 1 laminated in this order on a substrate 2. As described above, the thermosetting liquid crystal composition having alignment property containing the side chain type liquid crystal polymer (A) is likely to be vertically aligned, and therefore the polymerizable liquid crystal compound which may be optionally contained therein is also likely to be vertically aligned, so that the composition can exhibit vertical alignment property even without using an alignment film 3.

[0181] 1. Alignment layer / retardation layer The alignment layer / retardation layer 1 of the present disclosure is a cured film of the thermosetting liquid crystal composition having photoalignment property of the present disclosure, and is formed from the thermosetting liquid crystal composition having photoalignment property of the present disclosure. The alignment layer / retardation layer of the present disclosure is a cured film in a state in which the liquid crystal portion of the side chain type liquid crystal polymer (A) is vertically aligned and the photoalignable group present on the surface of the alignment layer / retardation layer has a photodimerization structure or a photoisomerization structure. The alignment layer / retardation layer of the present disclosure contains, in one layer, the above-mentioned side-chain liquid crystal polymer aligned vertically, a copolymer having a photodimerization structure or photoisomerization structure of the photoalignment group of the photoalignment structural unit, and a crosslinked structure formed by bonding a thermal crosslinking group of the thermal crosslinking structural unit with a thermal crosslinking agent. When the side-chain liquid crystal polymer has a thermal crosslinking structural unit containing a thermal crosslinking group in the side chain, the alignment layer / retardation layer may further contain a crosslinked structure formed by bonding a thermal crosslinking group of the thermal crosslinking structural unit of the side-chain liquid crystal polymer with a thermal crosslinking agent.

[0182] Here, the crosslinked structure refers to a three-dimensional network structure. The crosslinked structure includes a crosslinked structure formed by bonding a thermal crosslinkable group of the thermal crosslinkable structural unit of the copolymer with a thermal crosslinking agent, and a crosslinked structure formed by bonding a thermal crosslinkable group of other components with a thermal crosslinking agent as necessary. The crosslinked structure does not include a structure in which photo-alignment groups are crosslinked by a photodimerization reaction, and a structure in which ethylenically unsaturated double bond groups are polymerized together. However, the alignment layer / retardation layer of the present disclosure may further include a structure in which ethylenically unsaturated double bond groups are polymerized together.

[0183] The alignment layer / retardation layer in the alignment film / retardation film of the present disclosure is presumed to exhibit both excellent vertical alignment properties and excellent liquid crystal alignment ability (ability to align a liquid crystal material directly laminated thereon) in a single layer, since the side-chain liquid crystal polymer having the specific structure and exhibiting retardation through vertical alignment, the photodimerization structure or photoisomerization structure of the photoalignment group contained in the photoalignment structural unit having the specific structure, and the copolymer having a crosslinked structure formed by bonding the thermal crosslinkable group of the thermal crosslinking structural unit with a thermal crosslinking agent are unlikely to interfere with each other's performance. In addition, since the alignment layer / retardation layer in the alignment film / retardation film of the present disclosure is a cured film of the thermosetting liquid crystal composition having the photoalignment property of the present disclosure, the crosslinked structure of the film provides it with good heat resistance and solvent resistance, and it has high durability.

[0184] The side-chain liquid crystal polymer that is vertically aligned to exhibit retardation may be the same as the side-chain liquid crystal polymer described in the above "A. Thermosetting liquid crystal composition having photoalignment properties", and therefore the description thereof will be omitted here. The alignment layer / retardation layer of the present disclosure includes a copolymer having a crosslinked structure formed by bonding a photodimerization structure or photoisomerization structure of a photoalignment group of a photoalignment constituent unit and a thermal crosslinking group of a thermal crosslinking constituent unit with a thermal crosslinking agent. The copolymer contained in the alignment layer / retardation layer of the present disclosure can be formed by thermally curing and photo-aligning the copolymer having the photoalignable structural unit and the thermal crosslinkable structural unit described in the above "A. Thermosetting liquid crystal composition having photoalignment". In the present disclosure, a thermal crosslinking agent is used, and the thermal crosslinkable group of the thermal crosslinkable structural unit is bonded to the thermal crosslinking agent. Therefore, the crosslinked structure is a structure in which the thermal crosslinkable group and the thermal crosslinking agent are crosslinked by heating. In addition, when the non-liquid crystal and thermal crosslinkable structural unit of the side chain type liquid crystal polymer has a thermal crosslinking group, the crosslinked structure may include a crosslinked structure formed by bonding the thermal crosslinkable group of the side chain type liquid crystal polymer and the thermal crosslinking agent. In addition, the thermal crosslinking agent may be any of those described in "A. Thermosetting liquid crystal composition having photoalignment properties" above, and the crosslinked structure contains residues of the thermal crosslinking agent after the reaction of the thermal crosslinking agent.

[0185] For example, when the thermal crosslinking agent is hexamethoxymethylmelamine, the crosslinked structure is, for example, as shown below. In the following formula, each symbol is the same as in formula (1) above. The following copolymer is an example, and the monomer unit, residue of the thermal crosslinking group, etc. are not limited to the following.

[0186] [ka]

[0187] Incidentally, each of the structural units of the copolymer has been described in detail in the above section "A. Thermosetting liquid crystal composition having photoalignment properties," so description thereof will be omitted here. The content of the copolymer in the alignment layer can be confirmed by collecting and analyzing a material from the alignment layer. The analysis method can be NMR, IR, GC-MS, XPS, TOF-SIMS, or a combination of these.

[0188] The photodimerized structure in the copolymer is a structure in which the photoalignment groups of the photoalignment structural units represented by the above formula (1) are crosslinked by a photodimerization reaction, and has a cyclobutane skeleton. The photodimerization reaction is as shown below, in which the olefin structure contained in the photo-aligning group forms a cyclobutane skeleton by photoreaction. Xa to Xd and Xa' to Xd' vary depending on the type of the photo-aligning group.

[0189] [ka]

[0190] The photodimerization structure is preferably a photodimerization structure of a cinnamoyl group. Specifically, a structure in which cinnamoyl groups described in the above "A. Thermosetting liquid crystal composition having photoalignment properties" are crosslinked by a photodimerization reaction is preferred. In particular, the alignment layer preferably has a photodimerization structure as represented by the following formulae (x-4) and (x-5). In the following formulae, each symbol is the same as in the above formulae (x-1), (x-2), and (x-3).

[0191] [ka]

[0192] When the alignment layer has a photodimerization structure as represented by the above formula (x-4) or (x-5), many aromatic rings are arranged and it contains many π electrons, which is considered to increase the affinity with the liquid crystal layer formed on the alignment layer, improve the liquid crystal alignment ability, and further increase the adhesion with the liquid crystal layer.

[0193] The photoisomerized structure in the copolymer is a structure in which the photoalignment group of the photoalignment structural unit is isomerized by a photoisomerization reaction. For example, in the case of a cis-trans isomerization reaction, the photoisomerized structure may be either a structure in which a cis form is changed to a trans form or a structure in which a trans form is changed to a cis form. For example, when the photo-alignable group is a cinnamoyl group, the photoisomerization reaction is as shown below, in which the olefin structure contained in the photo-alignable group forms a cis or trans isomer by photoreaction. Xa to Xd vary depending on the type of photo-alignable group.

[0194] [ka]

[0195] The photoisomerization structure is preferably a photoisomerization structure of a cinnamoyl group. Specifically, a structure in which the cinnamoyl group described in the above "A. Thermosetting liquid crystal composition having photoalignment properties" is isomerized by a photoisomerization reaction is preferable. In this case, the photoisomerization structure may be either a structure in which a cis form is changed to a trans form or a structure in which a trans form is changed to a cis form. In particular, the alignment layer preferably has a photoisomerization structure of a cinnamoyl group represented by the above formulas (x-1) and (x-2), as shown in the following formulas (x-6) and (x-7).

[0196] [ka]

[0197] The presence of the photodimerization structure or photoisomerization structure of the alignment layer can be determined by NMR or IR analysis.

[0198] The alignment layer / retardation layer may further contain other components which may be further contained in the thermosetting liquid crystal composition having photoalignment properties. The alignment layer / retardation layer may contain, for example, a structure in which at least one of ethylenically unsaturated double bond groups of a polymerizable liquid crystal compound different from the side chain type liquid crystal polymer (A), a polymerizable compound having two or more polymerizable groups in one molecule, and a compound having a polymerizable group and a thermal crosslinkable group is polymerized. In addition, the alignment layer / retardation layer may contain, for example, a crosslinked structure formed by bonding at least one of a compound having a polymerizable group and a thermal crosslinkable group, and a thermal crosslinking agent, which is a compound having a photoalignment group and a thermal crosslinkable group different from the copolymer (B), and may further contain a photodimerization structure or a photoisomerization structure of a photoalignment group of a compound having a photoalignment group and a thermal crosslinkable group different from the copolymer (B). The alignment layer / retardation layer may further contain an acid or an acid generator, a photopolymerization initiator, a sensitizer, other additives, and decomposition products thereof. These additives are the same as those described in "A. Thermosetting liquid crystal composition having photoalignment properties" above.

[0199] The fact that the alignment layer / retardation layer is formed from the above-mentioned thermosetting liquid crystal composition having photoalignment can be confirmed by collecting and analyzing the material from the alignment layer / retardation layer. NMR, IR, GC-MS, XPS, TOF-SIMS, and combinations thereof can be used as the analysis method.

[0200] In addition, in the alignment layer / retardation layer, the fact that the liquid crystal components contained therein, such as the liquid crystal portion of the side-chain liquid crystal polymer, are vertically aligned can be confirmed by measuring the retardation using an automatic birefringence measuring device (e.g., Oji Scientific Instruments Co., Ltd., product name: KOBRA-WR).

[0201] The phase difference can be measured by an automatic birefringence measuring device (for example, Oji Scientific Instruments, product name: KOBRA-WR). A measuring light is incident on the surface of the phase difference layer perpendicularly or obliquely, and the anisotropy that increases the phase difference of the phase difference layer can be confirmed from a chart of the optical phase difference and the incident angle of the measuring light.

[0202] The thickness of the alignment layer / retardation layer may be appropriately set depending on the application, and is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm.

[0203] 2. Base material In the alignment film / retardation film of the present disclosure, the substrate may be a glass substrate, a metal foil, a resin substrate, or the like. Among them, the substrate is preferably transparent, and may be appropriately selected from conventionally known transparent substrates. Examples of the transparent substrate include glass substrates, as well as transparent resin substrates formed using acetylcellulose-based resins such as triacetylcellulose, polyester-based resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polylactic acid, olefin-based resins such as polypropylene, polyethylene, and polymethylpentene, acrylic resins, polyurethane-based resins, polyethersulfone, polycarbonate, polysulfone, polyether, polyether ketone, acrylonitrile, methacrylonitrile, cycloolefin polymer, and cycloolefin copolymer.

[0204] The transparent substrate preferably has a transmittance of 80% or more, more preferably 90% or more, in the visible light region. The transmittance of the transparent substrate can be measured according to JIS K7361-1 (Test method for total light transmittance of plastic transparent materials).

[0205] In addition, when the retardation layer is formed by a roll-to-roll method, the transparent base material is preferably a flexible material having flexibility that allows it to be wound into a roll. Examples of such flexible materials include cellulose derivatives, norbornene-based polymers, cycloolefin-based polymers, polymethyl methacrylate, polyvinyl alcohol, polyimide, polyarylate, polyethylene terephthalate, polysulfone, polyethersulfone, amorphous polyolefin, modified acrylic polymers, polystyrene, epoxy resins, polycarbonate, and polyesters. Among them, in this embodiment, it is preferable to use cellulose derivatives and polyethylene terephthalate. This is because cellulose derivatives are particularly excellent in optical isotropy and can be made to have excellent optical properties. In addition, polyethylene terephthalate is preferable because it has high transparency and excellent mechanical properties.

[0206] The thickness of the substrate used in this embodiment is not particularly limited as long as it is within a range that can impart the necessary self-supporting properties depending on the application of the alignment film / retardation film, but is usually within a range of about 10 μm to 200 μm. In particular, the thickness of the substrate is preferably in the range of 25 μm to 125 μm, and more preferably in the range of 30 μm to 100 μm. If the thickness is greater than the above range, for example, when a long retardation film is formed and then cut into a sheet of alignment film / retardation film, processing waste may increase or the cutting blade may wear quickly.

[0207] The configuration of the base material used in this embodiment is not limited to a single layer, and may have a laminated configuration of multiple layers. When multiple layers are laminated, layers of the same composition may be laminated, or multiple layers of different compositions may be laminated. For example, when the alignment film used in this embodiment contains an ultraviolet-curable resin, a primer layer may be formed on the substrate to improve the adhesion between the transparent substrate and the ultraviolet-curable resin. This primer layer may be any layer that has adhesion to both the substrate and the ultraviolet-curable resin, is optically transparent in the visible light, and transmits ultraviolet light. For example, a vinyl chloride / vinyl acetate copolymer, a urethane-based layer, or the like may be appropriately selected and used.

[0208] In addition, when the vertical alignment film described later is not provided, an anchor coat layer may be laminated on the substrate. The anchor coat layer can improve the strength of the substrate and ensure good vertical alignment. Metal alkoxides, particularly metal silicon alkoxide sols, can be used as anchor coat materials. Metal alkoxides are usually used as alcohol-based solutions. Since the anchor coat layer needs to be a uniform and flexible film, the thickness of the anchor coat layer is preferably about 0.04 μm to 2 μm, more preferably about 0.05 μm to 0.2 μm. When the substrate has an anchor coat layer, the adhesion between the substrate and the anchor coat layer may be improved by further laminating a binder layer between the substrate and the anchor coat layer, or by making the anchor coat layer contain a material that strengthens the adhesion with the substrate. The binder material used to form the binder layer can be any material that can improve the adhesion between the substrate and the anchor coat layer without any particular limitation. Examples of the binder material include a silane coupling agent, a titanium coupling agent, and a zirconium coupling agent.

[0209] 3.Alignment film As the alignment film 3 used in the embodiment of the alignment film / retardation film of the present disclosure, a vertical alignment film may be used since the liquid crystal composition of the alignment layer / retardation layer 1 is easily vertically aligned. The vertical alignment film is provided as a coating film and has the function of vertically aligning the long axis of the mesogens of the liquid crystal components contained in the alignment layer / retardation layer 1, such as the liquid crystal portion of the side-chain liquid crystal polymer.

[0210] The vertical alignment film is an alignment film having a vertical alignment control force, and can be various vertical alignment films used in the manufacture of C-plates, various vertical alignment films applied to VA liquid crystal display devices, etc., such as polyimide alignment films, alignment films made of LB films, etc. Specifically, as the constituent material of the alignment film, for example, lecithin, silane-based surfactants, titanate-based surfactants, pyridinium salt-based polymer surfactants, silane coupling-based compositions for vertical alignment films such as n-octadecyltriethoxysilane, soluble polyimides having a long-chain alkyl group or an alicyclic structure in the side chain, and polyamic acids having a long-chain alkyl group or an alicyclic structure in the side chain can be used. As the composition for vertical alignment film, commercially available products such as polyimide-based compositions for vertical alignment film "JALS-2021" and "JALS-204" manufactured by JSR Co., Ltd., "RN-1517", "SE-1211", and "EXPOA-018" manufactured by Nissan Chemical Industries, Ltd. may be used. In addition, the vertical alignment film described in JP-A-2015-191143 may be used.

[0211] The method for forming the alignment film 3 is not particularly limited, but for example, the alignment film can be formed by applying the composition for alignment film onto the substrate 2 and imparting an alignment regulating force to the composition. The means for imparting an alignment regulating force to the alignment film can be a conventionally known means.

[0212] The thickness of the alignment film 3 may be appropriately set as long as it can align the liquid crystal component in a certain direction in the alignment layer / retardation layer 1. The thickness of the alignment film is usually within the range of 1 nm to 10 μm, and preferably within the range of 60 nm to 5 μm.

[0213] 4.Applications The alignment film / retardation film of the present disclosure is suitably used as a retardation film containing a positive C-type retardation layer that also functions as an alignment film for aligning a liquid crystalline material directly laminated thereon. Here, the positive C characteristics are characterized in that, when the refractive index in the X-axis direction along the layer surface is Nx, the refractive index in the Y-axis direction along the layer surface and perpendicular to the X-axis is Ny, and the refractive index in the layer thickness direction is Nz, the relationship Nz>Nx≒Ny is satisfied, and the optical axis is in the Nz direction.

[0214] The alignment film / retardation film of the present disclosure is preferably used, for example, as a part of an external light antireflection film or a part of a polarizing plate compensation film, and is preferably used as a retardation plate or optical member for various display devices.

[0215] C. Manufacturing method of alignment film and retardation film The method for producing an alignment film / retardation film of the present disclosure includes the steps of: forming a film of the thermosetting liquid crystal composition having photoalignment properties of the present disclosure; forming a cured film having a retardation by heating the thermosetting liquid crystal composition formed into the film; and irradiating the cured film having retardation with polarized ultraviolet light to impart liquid crystal alignment ability to the cured film.

[0216] (1) A film-forming process of a thermosetting liquid crystal composition having photoalignment properties The thermosetting liquid crystal composition having photoalignment properties according to the present disclosure is uniformly applied onto a support to form a film. The support here may be the substrate, or the alignment film of the substrate provided with the alignment film.

[0217] The coating method may be appropriately selected as long as it can form a film with a desired thickness with good accuracy, for example, gravure coating, reverse coating, knife coating, dip coating, spray coating, air knife coating, spin coating, roll coating, printing, immersion and pulling up, curtain coating, die coating, casting, bar coating, extrusion coating, E-type coating, etc.

[0218] (2) A process for forming a cured film having a phase difference Next, the formed film of the thermosetting liquid crystal composition is heated to form a cured film having a retardation, which has a function as a retardation layer. This process includes a step of heating the thermosetting liquid crystal composition thus formed into a film, thereby aligning at least the liquid crystalline portion of the side chain liquid crystal polymer (A) in the thermosetting liquid crystal composition thus formed into a film. Specifically, the liquid crystal composition is heated at a temperature at which the liquid crystal moiety of the liquid crystal constituent unit of the side chain liquid crystal polymer in the formed film can be vertically aligned. When a polymerizable liquid crystal compound is further included, the heating temperature is adjusted to a temperature at which the polymerizable liquid crystal compound can also be vertically aligned. By this heat treatment, the liquid crystal moiety of the liquid crystal constituent unit of the side chain liquid crystal polymer can be at least vertically aligned and dried, and the liquid crystal composition can be fixed in a state where the alignment state is maintained. The temperature at which vertical alignment can be achieved varies depending on the substances in the liquid crystal composition, and therefore needs to be adjusted appropriately. For example, it is preferably performed within a range of 40° C. to 200° C., and more preferably within a range of 40° C. to 150° C. The photo-alignable thermosetting liquid crystal composition of the present disclosure contains the side-chain liquid crystal polymer, and therefore has a wide temperature range at which vertical alignment can be achieved, and temperature control is easy. As the heating means, for example, a hot plate, an oven, or other known heating and drying means can be appropriately selected and used. The heating time may be appropriately selected, for example, within the range of 10 seconds to 2 hours, preferably 20 seconds to 30 minutes.

[0219] The process also includes a step of heating the thermosetting liquid crystal composition thus formed into a film to cause a reaction between the thermal crosslinkable group of the copolymer (B) in the thermosetting liquid crystal composition thus formed into a film and the thermal crosslinking agent (C) to harden the composition while aligning the liquid crystalline portion. In the case where the heat treatment for at least aligning the liquid crystalline portion of the side chain type liquid crystal polymer (A) in the formed film of the thermosetting liquid crystal composition causes the thermal crosslinkable group of the copolymer (B) in the formed film to react with the thermal crosslinking agent (C) and harden, the heating may be a one-step heating. Alternatively, after heating for at least aligning the liquid crystalline portion of the side chain type liquid crystal polymer (A) in the thermosetting liquid crystal composition thus formed into a film, the film may be further heated at a different heating temperature, whereby the thermal crosslinkable group of the copolymer (B) in the thermosetting liquid crystal composition thus formed into a film may react with the thermal crosslinking agent (C) to harden the film in a state in which the liquid crystalline portion is aligned. The heating temperature for thermal curing can be set, for example, at about 40° C. to 250° C. The heating time can be set, for example, at least 20 seconds and no more than 60 minutes.

[0220] The thickness of the cured film obtained by thermally curing the thermosetting liquid crystal composition having photoalignment properties is appropriately selected depending on the application, etc., and can be, for example, about 0.1 μm to 5 μm, preferably about 0.5 μm to 3 μm. If the thickness of the cured film is too thin, sufficient retardation function and liquid crystal alignment ability may not be obtained.

[0221] (3) A step of imparting liquid crystal alignment ability to the cured film Next, the cured film having the retardation is irradiated with polarized UV light to impart liquid crystal alignment ability to the cured film. That is, in this step, the cured film is irradiated with polarized UV light to form a cured film that also functions as an alignment layer. The obtained cured film can be irradiated with polarized ultraviolet light to cause the photo-alignable group of the copolymer (B) to undergo a photoreaction, thereby exhibiting anisotropy. The wavelength of the polarized ultraviolet light is usually within the range of 150 nm to 450 nm. The irradiation direction of the polarized ultraviolet light can be perpendicular or oblique to the substrate surface. In this manner, a cured film having liquid crystal aligning ability can be formed. In this manner, the cured film has a function as a retardation layer and a function as an alignment layer, and a cured film that functions as both an alignment layer and a retardation layer is obtained.

[0222] (4) Other processes The method for producing an alignment film / retardation film of the present disclosure may further include another step. For example, when the thermosetting liquid crystal composition having photoalignment properties according to the present disclosure contains a compound having a polymerizable group, such as a polymerizable liquid crystal compound, the compound having the polymerizable group may be polymerized by, for example, irradiating the coating film fixed while maintaining the alignment state of the liquid crystal component. As the light irradiation, ultraviolet irradiation is preferably used. For the ultraviolet irradiation, ultraviolet rays emitted from the light beam of an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, or the like can be used. The irradiation amount of the energy ray source may be appropriately selected, and the cumulative exposure amount at an ultraviolet wavelength of 365 nm is, for example, 10 mJ / cm. 2 ~10000mJ / cm 2 It is preferable that the range is within the range of 100 μm. In addition, after a cured film functioning as an alignment layer and retardation layer is obtained, the support can be peeled off to obtain an alignment layer and retardation film consisting of only the alignment layer and retardation layer 1.

[0223] D. Retardation plate The retardation plate of the present disclosure includes a first retardation layer which is a cured film of the thermosetting liquid crystal composition having photoalignment property of the present disclosure; and a second retardation layer that is located directly adjacent to the first retardation layer and contains a cured product of a polymerizable liquid crystal composition.

[0224] Fig. 4 is a schematic cross-sectional view showing an example of a retardation plate according to the present disclosure. In the retardation plate 20 shown in Fig. 4, a first retardation layer 11, which is an alignment layer and a retardation layer, is formed on a substrate 13, and a second retardation layer 12 is formed on the first retardation layer 11.

[0225] The retardation plate of the present disclosure has excellent vertical alignment properties and excellent ability to align a liquid crystal material directly laminated thereon, since the first retardation layer is a cured film of the thermosetting liquid crystal composition having photoalignment properties of the present disclosure. Therefore, the retardation plate 20 of the present disclosure has a second retardation layer formed by directly laminating a liquid crystal material on the first retardation layer 11 without providing a separate alignment film, and has a second retardation layer 12 located directly adjacent to the first retardation layer 11. In the retardation plate of the present disclosure, the first retardation layer is a cured film of the thermosetting liquid crystal composition having photoalignment property of the present disclosure, and therefore has excellent solvent resistance as described above. Therefore, even when the second retardation layer is laminated, deterioration of the retardation of the first retardation layer is suppressed, and a retardation plate with good optical properties can be obtained. In addition, the retardation plate of the present disclosure has a first retardation layer which is a cured film of the thermosetting liquid crystal composition having the photoalignment property of the present disclosure, and therefore, as described above, is less likely to become hard and has flexibility compared to the cured product of the photocurable resin composition containing a polymerizable liquid crystal compound, and has good adhesion to the liquid crystal material directly laminated thereon. Therefore, the retardation plate of the present disclosure has a first retardation layer and a second retardation layer directly laminated thereon with good adhesion, and can be a thin retardation plate with good bending resistance, similar to the third retardation plate of the present disclosure described later.

[0226] A method for producing a retardation plate according to the present disclosure includes the steps of: forming a film of the thermosetting liquid crystal composition having photoalignment properties according to the present disclosure; forming a cured film having a retardation by heating the thermosetting liquid crystal composition formed into the film; A step of irradiating the cured film having a retardation with polarized ultraviolet light to impart liquid crystal alignment ability to the cured film, thereby forming an alignment film and a first retardation layer; a step of applying a polymerizable liquid crystal composition onto the alignment film / first retardation layer to form a coating film of the polymerizable liquid crystal composition, and heating the coating film to a phase transition temperature of the polymerizable liquid crystal composition to align liquid crystal molecules by the alignment film / retardation layer; a step of forming a second retardation layer by irradiating the coating film of the polymerizable liquid crystal composition in which the liquid crystal molecules are aligned with light and curing the coating film; It may have the following structure.

[0227] The substrate may be the same as that described above in "B. Alignment film and retardation film," and therefore a description thereof will be omitted here.

[0228] 1. First retardation layer Since the first retardation layer is a cured film of the thermosetting liquid crystal composition having photoalignment properties of the present disclosure, the first retardation layer functions as an alignment layer and a retardation layer as described above. The first retardation layer may be the same as the alignment layer / retardation layer described in "B. Alignment film / retardation film" above, and therefore a description thereof will be omitted here. When the first retardation layer contains a compound that reacts with a compound having a polymerizable group or a thermal crosslinking group contained in the second retardation layer, the interface side of the first retardation layer and the second retardation layer may contain a reaction product between the compounds contained in each layer. For example, the interface between the first retardation layer and the second retardation layer may contain a structure in which the polymerizable group of the compound having a polymerizable group contained in the first retardation layer and the polymerizable group of the polymerizable liquid crystal compound contained in the second retardation layer are polymerized. When such a reaction product is contained on the interface side of the second retardation layer of the first retardation layer, it is preferable from the viewpoint of improving the adhesion between the first retardation layer and the second retardation layer. In addition, the first retardation layer of the thermosetting resin composition containing the thermal crosslinking agent of the present disclosure is more likely to have a moderate penetration area at the interface with the directly laminated second retardation layer, so that the vertical alignment of the first retardation layer is not hindered, compared to the case of a cured product of a photocurable resin composition containing a polymerizable liquid crystal compound, and therefore adhesion is more likely to be improved. Since the first retardation layer of the thermosetting resin composition containing the thermal crosslinking agent of the present disclosure is crosslinked by the thermal crosslinking agent, it is estimated that the solvent penetration is likely to occur slightly only on the surface when the second retardation layer is directly laminated, but the solvent penetration to the extent that the vertical alignment is reduced is unlikely to occur.

[0229] The first retardation layer is a cured film of the thermosetting liquid crystal composition having photoalignment properties according to the present disclosure, and is preferably used as a positive C-type retardation layer because the side-chain liquid crystal polymer contained therein is easily vertically aligned.

[0230] 2. Second retardation layer The second retardation layer in the retardation plate of the present disclosure is located directly adjacent to the first retardation layer, and contains a cured product of a polymerizable liquid crystal composition. As the polymerizable liquid crystal composition, a composition containing a polymerizable liquid crystal compound having a polymerizable group can be used, and a composition generally used for a retardation layer can be used. Examples of the polymerizable group contained in the polymerizable liquid crystal compound include an acryloyl group and a methacryloyl group.

[0231] The polymerizable liquid crystal composition may have, for example, horizontal alignment, cholesteric alignment, vertical alignment, hybrid alignment, or the like, and may be appropriately selected depending on the desired retardation and the like.

[0232] The polymerizable liquid crystal composition in the second retardation layer is preferably a polymerizable liquid crystal composition having horizontal alignment properties in terms of the liquid crystal alignment ability of the first retardation layer.

[0233] The polymerizable liquid crystal composition in the second retardation layer preferably contains a polymerizable liquid crystal compound (rod-shaped compound) that exhibits liquid crystallinity and has a polymerizable group in the molecule. As the polymerizable liquid crystal compound, a conventionally known polymerizable liquid crystal compound having horizontal alignment property can be appropriately selected and used. The polymerizable liquid crystal composition may be composed of one liquid crystal compound or a mixture of two or more liquid crystal compounds.

[0234] The polymerizable liquid crystal composition in the second retardation layer can be suitably the same as the polymerizable liquid crystal compound described in the above "A. Thermosetting liquid crystal composition having photoalignment property" as the polymerizable liquid crystal compound different from the side chain type liquid crystal polymer (A). In the polymerizable liquid crystal composition in the second retardation layer, the polymerizable liquid crystal compound exhibits liquid crystal alignment properties and has excellent heat resistance, and is preferably one or more compounds selected from the compounds represented by the general formula (IV) and the compounds represented by the general formula (V). Specifically, the compound represented by the general formula (IV) and the compound represented by the following general formula (V) can be, for example, the polymerizable liquid crystal compounds described in paragraphs 0057 to 0064 of International Publication No. 2018 / 003498. In the polymerizable liquid crystal composition in the second retardation layer, other examples of the polymerizable liquid crystal compound include those described in Japanese Patent No. 6473537, Japanese Patent No. 5463666, Japanese Patent No. 4186981, Japanese Patent No. 5962760, and Japanese Patent No. 5826759, Japanese Patent No. 6568103, Japanese Patent No. 6427340, JP-A-2016-166344, and Recueil des Travaux Chimiques des Pays-Bas (1996), 115 (6), 321-328. In addition, examples of the polymerizable liquid crystal composition in the second retardation layer include compositions described in paragraphs 0133 to 0143 of JP-A No. 2014-174468 and compositions described in paragraphs 0083 to 0092 of Japanese Patent No. 6,739,621.

[0235] The polymerizable liquid crystal composition in the second retardation layer may further contain a photopolymerization initiator or a solvent in addition to the liquid crystal compound, and may further contain other components as described in "A. Thermosetting liquid crystal composition having photoalignment properties."

[0236] The second retardation layer is formed by applying a polymerizable liquid crystal composition onto the first retardation layer, which also functions as an alignment layer, and heating the composition to a phase transition temperature of the polymerizable liquid crystal composition to align the liquid crystal component by the liquid crystal alignment ability of the first retardation layer; and forming a retardation layer by irradiating a coating film of the polymerizable liquid crystal composition in which the liquid crystalline component is aligned with light.

[0237] In the step of orienting the liquid crystal component, the method of forming a coating film of the polymerizable liquid crystal composition and the method of heating to a phase transition temperature may be any conventionally known method, and are not particularly limited. The coating method and heating method may be the same as the coating method and heating method in the above-mentioned method for producing the alignment layer / retardation layer.

[0238] The coating film of the polymerizable liquid crystal composition in which the liquid crystal component is aligned is irradiated with light to cause a polymerization reaction, and polymerizable groups of the polymerizable liquid crystal compound contained in the second retardation layer are polymerized with each other, and further, when the first retardation layer contains a compound containing a polymerizable group, the polymerizable group of the compound containing a polymerizable group in the first retardation layer is polymerized with the polymerizable group of the polymerizable liquid crystal compound contained in the second retardation layer. The light irradiation method may be a conventionally known method, and may be the same as the method described in "C. Alignment film and retardation film".

[0239] In the retardation plate of the present disclosure, the first retardation layer functions as an alignment layer and a retardation film, and therefore the second retardation layer is directly laminated on the first retardation layer, and does not include a substrate for the second retardation layer, an alignment film, an adhesive layer, etc., and can be made thin. In the retardation plate of the present disclosure, the total thickness of the laminate of the first retardation layer and the second retardation layer excluding the substrate can be 0.2 μm to 6 μm, and more preferably 1 μm to 4 μm.

[0240] In the retardation plate of the present disclosure, it is preferable that the first retardation layer is a positive C-type retardation layer, and the second retardation layer is a positive A-type retardation layer. Here, the positive A characteristic is characterized in that, when the refractive index in the X-axis direction along the layer surface is Nx, the refractive index in the Y-axis direction perpendicular to the X-axis in the direction along the layer surface is Ny, and the refractive index in the layer thickness direction is Nz, the relationship of Nx>Ny≒Nz is satisfied, and the optical axis is in the Nx direction. A retardation plate in which a positive C-type retardation layer and a positive A-type retardation layer are laminated is preferably used as a circular polarizing plate in a form in which a λ / 4 retardation plate and a linear polarizing plate are combined in an organic electroluminescence display device, for example, and is preferably used as an external light antireflection film, and is also preferably used as a part of a polarizing plate compensation film in a liquid crystal display device.

[0241] In the retardation plate of the present disclosure, the thickness direction retardation Rth at a wavelength of 550 nm may be −35 nm to 35 nm, and may further be −30 nm to 30 nm. The in-plane retardation Re at a wavelength of 550 nm may be 120 nm or more, and may further be 135 nm or more.

[0242] The retardation plate of the present disclosure may further include another retardation layer. The retardation plate of the present disclosure further contains a third retardation layer different from the first retardation layer, and the third retardation layer, the first retardation layer, and the second retardation layer are located directly adjacent to each other in this order, The third retardation layer may be a positive C-type retardation layer, the first retardation layer may be a positive C-type retardation layer, and the second retardation layer may be a positive A-type retardation layer. When the third retardation layer is a positive C-type retardation layer, it is preferable to form it using a side-chain type liquid crystal polymer like the first retardation layer. For example, it can be formed using a thermosetting resin composition obtained by removing the copolymer (B) from the thermosetting resin composition having photoalignment property used for forming the first retardation layer.

[0243] 4.Applications In the retardation plate of the present disclosure, the second retardation layer can be directly laminated on the first retardation layer, and the retardation plate does not include a base material, an alignment film, an adhesive layer, or the like for the second retardation layer, and can be made thin. The retardation plate of the present disclosure can be suitably used as an optical member for various image display devices that aim to be made thinner.

[0244] II. Second Disclosure A. Photo-alignable thermosetting liquid crystal composition The thermosetting liquid crystal composition having photoalignment properties of the present disclosure comprises a side chain type liquid crystal polymer (A) having a liquid crystal constituent unit having a liquid crystal moiety in a side chain and a non-liquid crystal constituent unit having an alkylene group in a side chain; A copolymer (B) having a photoalignable structural unit containing a photoalignable group in a side chain and a thermally crosslinkable structural unit having a structural unit represented by the following formula (2): and a thermal crosslinking agent (C) that bonds to the thermal crosslinkable group of the thermal crosslinkable structural unit, The side chain type liquid crystal polymer (A) is a thermosetting liquid crystal composition having photoalignment properties, which satisfies any one of the following (i) to (vi). (i) The side chain type liquid crystal polymer (A) has a non-liquid crystalline and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and the non-liquid crystalline and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to a primary carbon of an alkylene group which may have -O- in the carbon chain and which has a smaller total carbon number and oxygen number than the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain in the thermally crosslinkable constituent unit of the copolymer (B). (ii) The side chain type liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and the non-liquid crystal and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to a secondary carbon or a tertiary carbon of an alkylene group. (iii) The side chain type liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinkable constituent unit containing at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a mercapto group, and an amino group, an alkylene group, and an arylene group in the side chain, and the non-liquid crystal and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to an arylene group. (iv) The side chain type liquid crystal polymer (A) has a non-liquid crystallinity and thermal crosslinking structural unit containing at least one thermal crosslinking group selected from the group consisting of a carboxyl group, a glycidyl group, and an amide group, and an alkylene group and an arylene group in the side chain, and the non-liquid crystallinity and thermal crosslinking structural unit of the side chain type liquid crystal polymer (A) has a structure in which the thermal crosslinking group is bonded to an arylene group, and the arylene group has a structure bonded to a carbon atom or oxygen atom of an alkylene group which may have -O- in the carbon chain or at the terminal, and the total number of carbon atoms and the number of oxygen atoms is 3 or more smaller than that of the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain in the thermal crosslinking structural unit of the copolymer (B). (v) The side chain type liquid crystal polymer (A) has a thermally crosslinkable constituent unit that does not contain an alkylene group in the side chain but contains a thermally crosslinkable group in the side chain. (vi) The side chain type liquid crystal polymer (A) does not have a non-liquid crystal and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and does not have a thermally crosslinkable constituent unit containing a thermally crosslinkable group in the side chain.

[0245] [ka] (In the above formula (2), Z 2 represents at least one monomer unit selected from the group consisting of the following formulas (2-1) to (2-6), and R 50 represents a linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain, and Y represents at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group.

[0246] [ka] (In the above formulas (2-1) to (2-6), R 51 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 52 represents a hydrogen atom or a methyl group, and R 53 is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 54 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 12 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-; L 12 If it is a single bond, R 50 is directly bonded to the styrene backbone.)

[0247] The thermosetting liquid crystal composition having photoalignment properties of the present disclosure combines the side-chain liquid crystal polymer (A) with the copolymer (B) having a photoalignment structural unit and a thermally crosslinkable structural unit that exhibit the ability to align a liquid crystal material directly laminated thereon, in a manner that satisfies the specific conditions described above, and further contains a thermal crosslinking agent (C) that bonds to the thermally crosslinkable group of the thermally crosslinkable structural unit. Therefore, by forming a cured film of the composition, it is possible to form an alignment layer / retardation layer that has the functions of both an alignment layer and a retardation layer in one layer, while exhibiting good vertical alignment properties and good liquid crystal alignment ability (the ability to align a liquid crystal material directly laminated thereon), and that is durable. The present inventors have conducted extensive research to form an integrated functional layer of a durable alignment layer and retardation layer from a composition containing a side-chain liquid crystal polymer (A) having vertical alignment properties and a photoalignment film material (copolymer (B) having a photoalignment unit and a thermal crosslinking unit that exerts the ability to align a directly laminated liquid crystal material). As a result, it was found that the photoalignment function of copolymer (B), which is a photoalignment film material, improves as the heat curing proceeds, but the vertical alignment property of side-chain liquid crystal polymer (A) having vertical alignment properties decreases as the heat curing proceeds. Therefore, it was considered necessary to promote the heat curing of copolymer (B), which is a photoalignment film material in the composition, while suppressing the heat curing of side-chain liquid crystal polymer (A) having vertical alignment properties. In the thermosetting liquid crystal composition having photoalignment property of the present disclosure, the thermally crosslinkable constituent unit of the copolymer (B) which is a photoalignment film material has a structure in which a thermally crosslinkable group is bonded to a monomer unit via a linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain, so that the copolymer (B) which is a photoalignment film material is easily thermally crosslinked and easily thermoset. On the other hand, the side chain type liquid crystal polymer (A) having vertical alignment property in the composition satisfies any one of the above (i) to (vi), so that the thermal crosslinking reaction is relatively difficult to proceed and the polymer is difficult to thermoset or is not thermoset, compared to the copolymer (B). The thermosetting liquid crystal composition having photoalignment properties of the present disclosure relatively reduces the thermal crosslinking property of the side-chain-type liquid crystal polymer (A) having vertical alignment properties, and facilitates the thermal curing of the copolymer (B), which is a photoalignment film material. This makes it possible to form an alignment layer / retardation layer that has the functions of both an alignment layer and a retardation layer in a single layer, while exhibiting good vertical alignment properties and good liquid crystal alignment ability (the ability to align a liquid crystal material that is directly laminated thereon), and that is also durable.

[0248] In addition, in the thermosetting liquid crystal composition having photoalignment property of the present disclosure, it is presumed that the thermosetting of the copolymer (B) proceeds well, so that a three-dimensional crosslinking structure is formed in the film, and as a result, the vertical alignment of the aligned vertical alignment polymer (A) becomes less likely to fluctuate. This suppresses fluctuation in the vertical alignment property caused by heating the alignment layer / retardation layer, and furthermore, it is easy to suppress fluctuation in the vertical alignment property caused by solvent penetration of the liquid crystal material directly applied on the alignment layer / retardation layer, and the reproducibility and durability of the vertical alignment property are good.

[0249] Hereinafter, each component in the thermosetting liquid crystal composition having photoalignment properties according to the present disclosure will be described. 1. Side-chain liquid crystal polymer (A) The side chain liquid crystal polymer (A) used in the present disclosure has a liquid crystal constituent unit containing a liquid crystal moiety in the side chain, and a non-liquid crystal constituent unit containing an alkylene group in the side chain. Each of the structural units in the side chain type liquid crystal polymer (A) will be described below.

[0250] The side chain liquid crystal polymer (A) used in the present disclosure satisfies any one of the above (i) to (vi) in relation to the copolymer (B) described below. When the above (i) is satisfied, in the non-liquid crystal and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain of the side chain of the side chain of the side chain liquid crystal polymer (A), the alkylene group which may have -O- in the carbon chain and which connects the thermally crosslinkable group and the monomer unit has a smaller total number of carbon atoms and oxygen atoms than the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain and which connects the thermally crosslinkable group and the monomer unit in the thermally crosslinkable constituent unit of the copolymer (B). In the side chain liquid crystal polymer (A), the length of the portion connecting the thermally crosslinkable group and the monomer unit is relatively short, so that the thermal crosslinking agent is less likely to bond to the thermally crosslinkable group, the reactivity of the thermally crosslinkable constituent unit and the thermal crosslinking agent is reduced, and the thermal crosslinking reaction of the side chain liquid crystal polymer (A) proceeds relatively more slowly than that of the copolymer (B). If there is a difference in curing speed between the side chain type liquid crystal polymer (A) and the copolymer (B), it is possible to create conditions in which the copolymer (B) cures first by adjusting the amount of the thermal crosslinking agent or the amount of the acid catalyst described below. The alkylene group in which the thermal crosslinkable group is bonded to a primary carbon which may have -O- in the carbon chain in the non-liquid crystal and thermal crosslinkable constituent unit of the side chain type liquid crystal polymer (A) is preferably smaller in total number of carbon atoms and oxygen atoms by 2 or more, more preferably by 3 or more, than the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain in the thermal crosslinkable constituent unit of the copolymer (B). In the side chain type liquid crystal polymer (A), the length of the linking group between the thermal crosslinkable group and the monomer unit is different as described above, so that the thermal crosslinking reaction of the side chain type liquid crystal polymer (A) is relatively more difficult to proceed, and the difference in the curing speed between the side chain type liquid crystal polymer (A) and the copolymer (B) is easily generated, which makes it easy to create a situation in which the copolymer (B) is thermally cured first in the coating film, and makes it easy to improve vertical alignment and photoalignment.

[0251] When the above (ii) is satisfied, the non-liquid crystal and thermally crosslinkable constitutional unit containing the thermally crosslinkable group and the alkylene group in the side chain of ... In addition, a primary carbon is a primary carbon atom that is bonded to one other carbon atom, a secondary carbon is a secondary carbon atom that is bonded to two other carbon atoms, and a tertiary carbon is a tertiary carbon atom that is bonded to three other carbon atoms.

[0252] When the above (iii) is satisfied, the non-liquid crystal and thermally crosslinkable structural unit of the side chain type liquid crystal polymer (A) has a structure in which at least one type of thermally crosslinkable group selected from the group consisting of a hydroxyl group, a mercapto group, and an amino group is bonded to an aryl group, and therefore the thermal crosslinking reaction proceeds relatively more slowly than the thermally crosslinkable group of the copolymer (B) having a structure in which the thermally crosslinkable group is bonded to the end of a linear alkylene group and thereby bonded to a primary carbon. As a result, a difference in the curing speed between the side chain type liquid crystal polymer (A) and the copolymer (B) is likely to occur, making it easier to create a situation in which the copolymer (B) is thermally cured first in the coating film, and making it easier to improve vertical alignment and photoalignment.

[0253] When the above (iv) is satisfied, the non-liquid crystal and thermally crosslinkable structural unit has at least one thermally crosslinkable group selected from the group consisting of a carboxy group, a glycidyl group, and an amide group, and an alkylene group and an arylene group in the side chain, and the non-liquid crystal and thermally crosslinkable structural unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to an arylene group, and the arylene group has a structure bonded to a carbon atom or oxygen atom of an alkylene group that may have -O- in the carbon chain or at the end, the total number of carbon atoms and the number of oxygen being 3 or more smaller than the linear alkylene group having 4 to 11 carbon atoms that may have -O- in the carbon chain in the thermally crosslinkable structural unit of the copolymer (B). Therefore, it becomes difficult for a thermal crosslinking agent to bond to the thermally crosslinkable group of the side chain type liquid crystal polymer (A), the reactivity between the thermally crosslinkable structural unit and the thermal crosslinking agent decreases, and the thermal crosslinking reaction of the side chain type liquid crystal polymer (A) proceeds relatively more slowly than that of the copolymer (B). As a result, a difference in the curing speed between the side-chain liquid crystal polymer (A) and the copolymer (B) is likely to occur, making it easier to create a situation in which the copolymer (B) thermally cures first in the coating film, which makes it easier to achieve good vertical alignment and photoalignment properties.

[0254] When the condition (v) is satisfied, the side chain type liquid crystal polymer (A) has a thermal crosslinking structural unit that does not contain an alkylene group in the side chain and contains a thermal crosslinking group in the side chain in addition to the non-liquid crystal structural unit that contains an alkylene group in the side chain. In this case, the thermal crosslinking reaction of the thermal crosslinking group of the side chain type liquid crystal polymer (A) is relatively difficult to proceed compared to the thermal crosslinking group of the copolymer (B) having a structure in which the thermal crosslinking group is bonded to the terminal of a linear alkylene group and bonded to a primary carbon. As a result, the difference in the curing speed between the side chain type liquid crystal polymer (A) and the copolymer (B) is easily generated, so that it is easy to create a situation in which the copolymer (B) is thermally cured first in the coating film, and it is easy to improve the vertical alignment and photoalignment properties.

[0255] When the condition (vi) is satisfied, the side chain type liquid crystal polymer (A) does not have a non-liquid crystal and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and a thermally crosslinkable constituent unit containing a thermally crosslinkable group in the side chain. In other words, since the side chain type liquid crystal polymer (A) does not contain a thermally crosslinkable group, it is easy to create a situation in which only the copolymer (B) is thermally cured in the coating film, and it is easy to achieve good vertical alignment and photoalignment.

[0256] In addition, when the side chain type liquid crystal polymer (A) contains two or more types of non-liquid crystal and thermally crosslinkable structural units, all of the two or more types of non-liquid crystal and thermally crosslinkable structural units satisfy any one of the above (i) to (iv). In addition, when the side chain type liquid crystal polymer (A) has two or more thermally crosslinkable groups in one non-liquid crystal and thermally crosslinkable constituent unit, all of the two or more thermally crosslinkable groups need only satisfy any one of the above (i) to (iv).

[0257] (1) Liquid crystal structural unit In an embodiment of the present disclosure, the liquid crystal constitutional unit has a side chain including a liquid crystal portion, i.e., a portion exhibiting liquid crystallinity. The liquid crystal constitutional unit is preferably a constitutional unit including a mesogen exhibiting liquid crystallinity in a side chain. The liquid crystal constitutional unit is preferably a constitutional unit derived from a compound exhibiting liquid crystallinity in which a polymerizable group is bonded to a mesogen group via a spacer. In the present disclosure, the mesogen refers to a highly rigid portion exhibiting liquid crystallinity, for example, a partial structure having two or more ring structures, preferably three or more ring structures, in which the ring structures are connected to each other by direct bonds, or the ring structures are connected via one to three atoms. By having such a portion exhibiting liquid crystallinity in the side chain, the liquid crystal constitutional unit is easily aligned vertically. The ring structure may be an aromatic ring such as benzene, naphthalene, or anthracene, or may be a cyclic aliphatic hydrocarbon such as cyclopentyl or cyclohexyl. Furthermore, when the ring structure is linked via 1 to 3 atoms, examples of the structure of the linking portion include -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)-O-, -NR-C(=O)-, -C(=O)-NR-, -OC(=O)-NR-, -NR-C(=O)-O-, -NR-C(=O)-NR-, -O-NR-, -NR-O- (R is a hydrogen atom or a hydrocarbon group), and the like. Among them, the mesogen is preferably a rod-shaped mesogen in which the ring structures are connected in a rod shape at the para position in the case of benzene, or at the 2,6 position in the case of naphthalene.

[0258] In addition, when the liquid crystal structural unit is a structural unit containing a mesogen exhibiting liquid crystallinity in the side chain, it is preferable that the terminal of the side chain of the structural unit is a polar group or has an alkyl group from the viewpoint of vertical alignment. Specific examples of such polar groups include -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHC(=O)-R', -C(=O)-OR', -OH, -SH, -CHO, -SO3H, -NR'2, -R ” -OR ” (R' is a hydrogen atom or a hydrocarbon group, R ” is an alkyl group).

[0259] The liquid crystal structural unit has a side chain of -R 2 -(L 1 -Ar 1 ) a -R 3 (wherein R 2 is -(CH2) m - or -(C2H4O) m’ - represents a group represented by L 1 represents a single bond or a linking group represented by -O-, -OCO-, or -COO-, 1 represents an arylene group having 6 to 10 carbon atoms which may have a substituent, 1 and Ar 1 may be the same or different. 3are -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 , -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2, -R 5 -OR 5 , R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R 5 represents an alkyl group having 1 to 6 carbon atoms. a is an integer of 2 to 4, and m and m' are each independently an integer of 2 to 10.) are examples of structural units having these structures.

[0260] R 2 In the formula, m and m' are each independently an integer of 2 to 10. In terms of vertical alignment, m and m' are preferably 2 to 8, and more preferably 2 to 6.

[0261] Ar 1 In the formula (I), examples of the arylene group having 6 to 10 carbon atoms, which may have a substituent, include a phenylene group and a naphthylene group, and among these, a phenylene group is more preferable. 3 Examples of the substituent other than the above include an alkyl group having 1 to 5 carbon atoms, and halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom.

[0262] R 3 In R 4 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 3 In R 5 is an alkyl group having 1 to 6 carbon atoms, and among these, an alkyl group having 1 to 5 carbon atoms is preferable.

[0263] The liquid crystal structural unit is preferably a structural unit derived from a monomer having a polymerizable ethylenic double bond-containing group. Examples of such a monomer having an ethylenic double bond-containing group include derivatives such as (meth)acrylic acid ester, styrene, (meth)acrylamide, maleimide, vinyl ether, or vinyl ester. In terms of vertical alignment, the liquid crystal structural unit is preferably a structural unit derived from a (meth)acrylic acid ester derivative.

[0264] In the embodiment of the present disclosure, the liquid crystal constitutional unit preferably contains a constitutional unit represented by the following general formula (I) in terms of vertical alignment properties.

[0265] [ka] (In general formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 is -(CH2) m - or -(C2H4O) m’ - represents a group represented by L 1 represents a single bond or a linking group represented by -O-, -OCO-, or -COO-, 1 represents an arylene group having 6 to 10 carbon atoms which may have a substituent, 1 and Ar 1 may be the same or different. 3 are -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 , -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2, -R 5 -OR 5 , R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R 5 represents an alkyl group having 1 to 6 carbon atoms; a is an integer of 2 to 4, and m and m' are each independently an integer of 2 to 10.

[0266] In the structural unit represented by formula (I), -R 2 -(L 1 -Ar 1 ) a -R 3 The group represented by the formula (I) may be the same as above.

[0267] Suitable specific examples of the structural unit represented by general formula (I) include, but are not limited to, those represented by the following general formulae (I-1), (I-2) and (I-3).

[0268] [ka]

[0269] In the constitutional units represented by the above general formulas (I-1) to (I-3), R 2 , and R 3 are R in general formula (I), 2 , and R 3 is the same as:

[0270] In the embodiments of the present disclosure, the liquid crystal structural units may be used alone or in combination of two or more.

[0271] In the synthesis of the copolymer, a monomer such as a (meth)acrylic acid ester derivative that induces a liquid crystal constitutional unit can be used. The monomer such as a (meth)acrylic acid ester derivative that induces a liquid crystal constitutional unit can be used alone or in combination of two or more kinds.

[0272] In order to improve the vertical alignment of the liquid crystalline constituent units and to provide sufficient liquid crystal alignment, the content of the liquid crystalline constituent units in the copolymer is preferably set within the range of 40 mol% to 90 mol%, more preferably within the range of 40 mol% to 80 mol%, even more preferably within the range of 45 mol% to 70 mol%, and particularly preferably within the range of 50 mol% to 65 mol%, when the amount of the constituent units contained in the entire copolymer is taken as 100 mol%. The content ratio of each structural unit in the copolymer is as follows: 1 It can be calculated from the integral value obtained by H-NMR measurement.

[0273] (2) Non-liquid crystal structural unit containing an alkylene group in the side chain A non-liquid crystal structural unit having an alkylene group in a side chain has the effect of promoting vertical alignment (homeotropic alignment) of the portion (mesogen) exhibiting liquid crystallinity in the side chain of the liquid crystal structural unit when the side chain-type liquid crystal polymer becomes liquid crystal. The non-liquid crystal structural unit having an alkylene group in the side chain has -L 2 -R 13 , or -L 2’ -R 14 (wherein L 2 represents a linear or branched alkylene group having 1 to 18 carbon atoms which may have a substituent; L 2’ Ha-(C2H4O) n’ - represents a linking group represented by R 13 represents a methyl group which may have a substituent, an aryl group which may have an alkyl group, or -OR 15 R 14 and R 15 each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and n′ is an integer of 1 to 18.

[0274] L 2 represents a linear or branched alkylene group having 1 to 18 carbon atoms which may have a substituent; L 2’ Ha-(C2H4O) n’ - represents a linking group represented by the formula: L 2Examples of the linear or branched alkylene group having 1 to 18 carbon atoms in the formula (I) include linear alkylene groups such as a methylene group, a dimethylene group (ethylene group), a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, a dodecamethylene group, a tridecamethylene group, a pentadecamethylene group, a hexadecamethylene group, a heptadecamethylene group, and an octadecamethylene group; and branched alkylene groups such as a methylmethylene group, a methylethylene group, a 1,1-dimethylethylene group, a 1-methylpentylene group, and a 1,4-dimethylbutylene group.

[0275] R 14 and R 15 The alkyl group in may be linear, branched or cyclic. R 14 , and R 15 The alkyl group in is preferably an alkyl group having 1 to 20 carbon atoms, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl groups, branched alkyl groups such as i-propyl, i-butyl, and t-butyl groups, alkenyl groups such as 1-propenyl and 1-butenyl groups, alkynyl groups such as ethynyl and 2-propynyl groups, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl, and adamantyl groups, and cycloalkenyl groups such as 1-cyclohexenyl groups. In the case of the cycloalkyl group, it is preferable that the linear alkyl group is substituted with a cycloalkyl group.

[0276] R 14 and R 15 The alkyl group in is not particularly limited, but is preferably an alkyl group having 1 to 12 carbon atoms in terms of the in-plane uniformity of retardation.

[0277] R 13 , R 14 , and R 15The aryl group in is preferably an aryl group having 6 to 20 carbon atoms, specifically, a phenyl group, a naphthyl group, an anthracenyl group, etc., among which a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. In the case of the above aryl group, it is preferable that the aryl group is substituted with a linear alkyl group.

[0278] The non-liquid crystal structural unit having an alkylene group in a side chain may have, as a substituent, a reactive group that reacts with other components, and may have, for example, a thermally crosslinkable group similar to that of the copolymer (B) described later. The non-liquid crystal structural unit having an alkylene group in the side chain may include a non-liquid crystal and non-thermally crosslinkable structural unit and a non-liquid crystal and thermally crosslinkable structural unit. The non-liquid crystal structural unit having an alkylene group in the side chain may include only a non-liquid crystal and non-crosslinkable structural unit or may include only a non-liquid crystal and thermally crosslinkable structural unit. The non-liquid crystalline structural unit having an alkylene group in a side chain preferably contains at least a non-liquid crystalline and non-thermally crosslinkable structural unit, since this tends to result in good vertical alignment, and more preferably contains a non-liquid crystalline and non-thermally crosslinkable structural unit and a non-liquid crystalline and thermally crosslinkable structural unit, since this tends to result in good vertical alignment and improved durability.

[0279] In the non-liquid crystalline and non-thermally crosslinkable constitutional unit containing an alkylene group in the side chain, R 13 The substituent that the methyl group in the formula (I) may have includes a non-thermally crosslinkable substituent, for example, a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. In the non-liquid crystalline and non-thermally crosslinkable constitutional unit containing an alkylene group in the side chain, L 2 A linear or branched alkylene group in R 14 and R 15 Examples of the substituent that the alkyl group in the formula (I) may have include non-thermally crosslinkable substituents, such as halogen atoms, e.g., fluorine atoms, chlorine atoms, bromine atoms, etc., alkoxy groups, nitro groups, etc. Among these, halogen atoms, e.g., fluorine atoms, chlorine atoms, bromine atoms, etc., are preferred.

[0280] In the non-liquid crystalline and non-thermally crosslinkable constitutional unit containing an alkylene group in the side chain, R 13 , R 14 , and R 15 The substituent that the aryl group in the formula (I) may have includes a non-thermally crosslinkable substituent, for example, a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, an alkyl group, an alkoxy group, or a nitro group. The alkyl group may be an alkyl group having 1 to 12 carbon atoms, such as an alkyl group having 1 to 9 carbon atoms, and may be a linear alkyl group or an alkyl group having a branched or ring structure. Among them, a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, or an alkyl group having 1 to 9 carbon atoms is preferred. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, and a cyclohexylpropyl group. The hydrogen atom of the alkyl group may be substituted with a halogen atom.

[0281] In the non-liquid crystalline and thermally crosslinkable constitutional unit containing an alkylene group in the side chain, R 13 The methyl group in L 2 A linear or branched alkylene group in R 14 and R 15 The alkyl group in R 13 , R 14 , and R 15 The substituent that the aryl group in may have is preferably a thermal crosslinkable group, and may be the same as the thermal crosslinkable group of the copolymer (B) described later, and may be at least one selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group. Among them, a hydroxy group is preferred from the viewpoint of reactivity. Although it is preferable that one non-liquid crystal and thermally crosslinkable constituent unit has one thermally crosslinkable group, it may have two or more thermally crosslinkable groups.

[0282] In the case of a non-liquid crystallinity and non-thermally crosslinkable constitutional unit containing an alkylene group in the side chain, the vertical alignment property is easily improved. 2 is -(CH2) n - (where n is an integer of 1 to 18) is preferable. Furthermore, n is preferably an integer of 3 to 17, and more preferably an integer of 5 to 17. Furthermore, n' is an integer of 1 to 18, and is preferably an integer of 3 to 17, and more preferably an integer of 5 to 17. On the other hand, in the case of a non-liquid crystal and thermally crosslinkable structural unit having an alkylene group in the side chain, L 2 is preferably a branched alkyl group or has a small number of carbon atoms, preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. In addition, in the non-liquid crystal and non-thermally crosslinkable constitutional unit containing an alkylene group in the side chain, R 14 and R 15 In the case of the alkyl group, a straight chain is preferable because the vertical alignment is easily improved. On the other hand, in the non-liquid crystal and thermally crosslinkable constituent unit containing an alkylene group in the side chain, a straight chain, branched or cyclic alkyl group may be appropriately selected and used to slow down the progress of the thermal crosslinking reaction.

[0283] The non-liquid crystal structural unit is preferably a structural unit derived from a monomer having a polymerizable ethylenic double bond-containing group. Examples of such a monomer having an ethylenic double bond-containing group include derivatives such as (meth)acrylic acid ester, styrene, (meth)acrylamide, maleimide, vinyl ether, or vinyl ester. From the viewpoint of vertical alignment, the non-liquid crystal structural unit is preferably a structural unit derived from a (meth)acrylic acid ester derivative or styrene, and more preferably a structural unit derived from a (meth)acrylic acid ester derivative.

[0284] In the embodiment of the present disclosure, of the non-liquid crystal structural units, the non-liquid crystal and non-thermally crosslinkable structural unit preferably has a structural unit represented by the following formula (II).

[0285] [ka] (In general formula (II), R 11 represents a hydrogen atom or a methyl group, R 12 -L 2” -R 13 , or -L 2’ -R 14 L represents a group represented by 2” Ha-(CH2) n - represents L 2’ Ha-(C2H4O) n’ - represents a linking group represented by R 13 represents a methyl group which may have a substituent, an aryl group which may have an alkyl group, or -OR 15 R 14 and R 15 each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and n and n' each independently represent an integer of 1 to 18.

[0286] In the constitutional unit represented by formula (II), -L 2” -R 13 , or -L 2’ -R 14 The group represented by the formula (I) may be the same as above. When the non-liquid crystalline and non-thermally crosslinkable structural unit is a structural unit represented by formula (II), examples of the substituent that may be contained in the structural unit represented by formula (II) include the non-thermally crosslinkable substituents described above.

[0287] In an embodiment of the present disclosure, when the non-liquid crystalline constituent unit contains a non-liquid crystalline and thermally crosslinkable constituent unit, it is preferable that the non-liquid crystalline and thermally crosslinkable constituent unit has a constituent unit represented by the following formula (III) from the viewpoints of improving reactivity and improving durability.

[0288] [ka] (In the above formula (III), Z arepresents at least one monomer unit selected from the group consisting of the following formulas (a-1) to (a-6), and R 16 -L 2a -R 13’ - (wherein L 2a represents a linear or branched alkylene group having 1 to 10 carbon atoms which may have -O- in the carbon chain, R 13’ represents a residue obtained by removing a hydrogen atom from a methyl group which may have a substituent, a residue obtained by removing a hydrogen atom from an aryl group, or -OR 15’ R 15’ represents a residue obtained by removing a hydrogen atom from an aryl group. a represents at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group.

[0289] [ka] (In the above formulas (a-1) to (a-6), R 11 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 17 represents a hydrogen atom or a methyl group, and R 18 is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 19 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L a represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-; L a If it is a single bond, R 16 is directly bonded to the styrene backbone.)

[0290] R 16 -L 2a -R 13’ - (wherein L 2a represents a linear or branched alkylene group having 1 to 10 carbon atoms which may have -O- in the carbon chain, R 13’ represents a residue obtained by removing a hydrogen atom from a methyl group which may have a substituent, a residue obtained by removing a hydrogen atom from an aryl group, or -OR 15’ R 15’represents a residue obtained by removing a hydrogen atom from an aryl group. R 13’ , and R 15’ The methyl group and aryl group which may have a substituent before removing the hydrogen atom are each represented by R 13 and R 15 It may be the same as: L 2a may be a linear or branched alkylene group having 1 to 6 carbon atoms which may have -O- in the carbon chain, may be a linear or branched alkylene group having 1 to 4 carbon atoms which may have -O- in the carbon chain, may be a linear or branched alkylene group having 1 to 3 carbon atoms which may have -O- in the carbon chain, may be a linear alkylene group having 1 to 2 carbon atoms which may have -O- in the carbon chain, or may be a methylene group. L 2a If the number of carbon atoms is small, the distance between the thermally crosslinkable group and the main skeleton of the copolymer in the thermally crosslinkable constituent unit becomes short, making it difficult for the thermally crosslinking agent to bond to the thermally crosslinkable group, and reducing the reactivity between the thermally crosslinkable constituent unit and the thermal crosslinking agent. L 2a is a branched alkylene group which may have -O- in the carbon chain, the thermal crosslinking group Y a An example of such an alkylene group is one in which the carbon atom to which R is bonded is a secondary or tertiary carbon. 16 When is a branched alkylene group which may have -O- in the carbon chain, examples of the branched alkylene group include a methylmethylene group, a methylethylene group, a 1,1-dimethylethylene group, a 1-methylpropylene group, and an ethylethylene group.

[0291] Also, R 16 In the above, examples of the substituent that may be possessed by the linear or branched alkylene group having 1 to 11 carbon atoms and which may have -O- in the carbon chain include non-thermally crosslinkable substituents, such as halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, alkoxy groups, nitro groups, aryl groups which may have a substituent, and aryloxy groups which may have a substituent. Examples of the substituent in the aryl group which may have a substituent and the aryloxy group which may have a substituent include the above-mentioned R 13 , R14 , and R 15 The substituents are the same as those which the aryl group in the above may have.

[0292] The non-liquid crystal structural unit having an alkylene group in the side chain contained in the copolymer may be of one type or of two or more types. Examples of non-liquid crystallinity and non-thermally crosslinkable structural units containing an alkylene group in a side chain include, but are not limited to, the following chemical formulas (II-1) to (II-10): Furthermore, examples of non-liquid crystallinity and non-thermally crosslinkable structural units containing an alkylene group in a side chain include, but are not limited to, the following chemical formulas (III-1) to (III-12):

[0293] [ka]

[0294] [ka]

[0295] In the synthesis of the copolymer, a monomer such as a (meth)acrylic acid ester derivative that derives the non-liquid crystal structural unit can be used. The monomer such as a (meth)acrylic acid ester derivative that derives the non-liquid crystal structural unit can be used alone or in combination of two or more.

[0296] In order to improve the vertical alignment of the liquid crystalline structural units and to provide sufficient liquid crystal alignment, the content of the non-liquid crystal structural units in the copolymer is preferably set within the range of 10 mol % to 60 mol %, more preferably within the range of 15 mol % to 50 mol %, further preferably within the range of 15 mol % to 45 mol %, and particularly preferably within the range of 20 mol % to 40 mol %, when the amount of the structural units contained in the entire copolymer is taken as 100 mol %.

[0297] When the copolymer contains both a non-liquid crystalline and non-thermally crosslinkable constituent unit and a non-liquid crystalline and thermally crosslinkable constituent unit as the non-liquid crystalline constituent unit, the content of the non-liquid crystalline and thermally crosslinkable constituent unit is preferably set in the range of 5 mol % to 70 mol %, and more preferably set in the range of 20 mol % to 50 mol %, when the total amount of the non-liquid crystalline constituent units contained in the entire copolymer is taken as 100 mol %. The content ratio of each structural unit in the copolymer is as follows: 1 It can be calculated from the integral value obtained by H-NMR measurement.

[0298] (3) Other constituent units The side chain liquid crystal polymer (A) used in the present disclosure has at least the liquid crystal constituent unit and the non-liquid crystal constituent unit containing an alkylene group in the side chain, and may further have other constituent units. Examples of other structural units include a thermally crosslinkable structural unit that does not contain an alkylene group in the side chain but contains the thermally crosslinkable group in the side chain, and a photoalignable structural unit that contains a photoalignable group in the side chain of the copolymer (B) described later. Examples of the thermally crosslinkable constituent unit that does not contain an alkylene group in the side chain but contains the thermally crosslinkable group in the side chain include (meth)acrylic acid, 4-hydroxyphenyl (meth)acrylate, 4-hydroxystyrene, and 4-carboxystyrene. The side chain type liquid crystal polymer (A) used in the present disclosure preferably has at least one type of thermally crosslinkable structural unit having a thermally crosslinkable group in a side chain selected from the group consisting of a non-liquid crystal and thermally crosslinkable structural unit having an alkylene group in a side chain, and a thermally crosslinkable structural unit having no alkylene group in a side chain and the thermally crosslinkable group, from the viewpoint of improving the durability and reliability of the retardation layer. The photoalignable constituent unit may be the same as the photoalignable constituent unit containing a photoalignable group in the side chain contained in the copolymer (B) described below.

[0299] The content ratio of the above-mentioned other structural units in the copolymer is preferably set within the range of 30 mol % or less, and more preferably within the range of 20 mol % or less, when the amount of structural units contained in the entire copolymer is taken as 100 mol %, in order to improve the vertical alignment property of the liquid crystalline structural units and to have sufficient liquid crystal alignment property.

[0300] (4) Copolymer of side-chain liquid crystal polymer (A) In an embodiment of the present disclosure, the side chain type liquid crystal polymer (A) may be a block copolymer having a block portion consisting of a liquid crystal constitutional unit and a block portion consisting of a non-liquid crystal constitutional unit containing an alkylene group in the side chain, or may be a random copolymer in which the liquid crystal constitutional unit and the non-liquid crystal constitutional unit containing an alkylene group in the side chain are irregularly arranged. In this embodiment, it is preferable that the side chain type liquid crystal polymer is a random copolymer from the viewpoint of improving the vertical alignment property and the in-plane uniformity of the retardation value.

[0301] The mass average molecular weight Mw of the side chain type liquid crystal polymer, which is a copolymer, is not particularly limited, but is preferably within a range of 5000 to 80000, more preferably within a range of 8000 to 50000, and further preferably within a range of 10000 to 36000. By being within the above range, the stability of the liquid crystal composition is excellent, and the handling during the formation of the retardation layer is excellent.

[0302] The mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). The measurement was performed using HLC-8120GPC manufactured by Tosoh Corporation, N-methylpyrrolidone containing 0.01 mol / L lithium bromide as an elution solvent, polystyrene standards for calibration curve Mw 377400, 210500, 96000, 50400, 206500, 10850, 5460, 2930, 1300, 580 (all manufactured by Polymer Laboratories, Easi PS-2 series) and Mw 1090000 (manufactured by Tosoh Corporation), and two TSK-GEL ALPHA-M columns (manufactured by Tosoh Corporation).

[0303] As a method for synthesizing a copolymer of the side chain type liquid crystal polymer (A), a method of copolymerizing a monomer that derives a liquid crystal constituent unit and a monomer that derives a non-liquid crystal constituent unit containing an alkylene group in the side chain by a conventionally known production method can be mentioned. The side chain type liquid crystal polymer (A) may be used in the form of a solution obtained when the copolymer is synthesized, or in the form of a powder, or in the form of a solution obtained by redissolving the purified powder in a solvent described below.

[0304] The side chain type liquid crystal polymer (A) may be used alone or in combination of two or more. In the present embodiment, in order to exhibit vertical alignment properties, the content of the side chain type liquid crystal polymer (A) may be 60 parts by mass to 99 parts by mass, preferably 70 parts by mass to 95 parts by mass, and more preferably 80 parts by mass to 90 parts by mass, based on 100 parts by mass of the solid content of the liquid crystal composition. In the present disclosure, the solid content refers to all components excluding the solvent. For example, even if a polymerizable liquid crystal compound described below is in a liquid state, it is included in the solid content.

[0305] 2.Copolymer (B) The copolymer (B) used in the present disclosure has a photoalignable constituent unit containing a photoalignable group in the side chain, and a thermally crosslinkable constituent unit containing a thermally crosslinkable group in the side chain with a specific structure. Each of the structural units in the copolymer (B) will be described below.

[0306] (1) Photo-orientable building block The photo-alignable structural unit in the present invention is a site that exhibits anisotropy by generating a photoreaction upon irradiation with light. The photoreaction is preferably a photodimerization reaction or a photoisomerization reaction. That is, the photo-alignable structural unit is preferably a photodimerization structural unit that exhibits anisotropy by generating a photodimerization reaction upon irradiation with light, or a photoisomerization structural unit that exhibits anisotropy by generating a photoisomerization reaction upon irradiation with light.

[0307] The photo-alignable structural unit has a photo-alignable group. As described above, the photo-alignable group is a functional group that exhibits anisotropy by causing a photoreaction upon irradiation with light, and is preferably a functional group that causes a photodimerization reaction or a photoisomerization reaction.

[0308] Examples of photo-alignment groups that cause photodimerization include cinnamoyl, chalcone, coumarin, anthracene, quinoline, azobenzene, and stilbene groups. The benzene rings in these functional groups may have a substituent. The substituent may be any group that does not interfere with the photodimerization reaction, such as an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a hydroxy group, a halogen atom, a trifluoromethyl group, and a cyano group.

[0309] The photo-alignable group that causes a photoisomerization reaction is preferably one that causes a cis-trans isomerization reaction, and examples thereof include a cinnamoyl group, a chalcone group, an azobenzene group, and a stilbene group. The benzene ring in these functional groups may have a substituent. The substituent may be any group that does not interfere with the photoisomerization reaction, and examples thereof include an alkoxy group, an alkyl group, a halogen atom, a trifluoromethyl group, and a cyano group.

[0310] Among them, the photoalignable group is preferably a cinnamoyl group. Specifically, the cinnamoyl group is preferably at least one selected from the group consisting of groups represented by the following formulae (x-1) and (x-2).

[0311] [ka]

[0312] In the above formula (x-1), R 31R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, or a cycloalkyl group having 1 to 18 carbon atoms. However, the alkyl group, aryl group, and cycloalkyl group may be bonded via an ether bond, an ester bond, an amide bond, or a urea bond, and may have a substituent. 32 ~R 35 R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a cyano group. However, the alkyl group, aryl group, and cycloalkyl group may be bonded via an ether bond, an ester bond, an amide bond, or a urea bond, and may have a substituent. 36 and R 37 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. In addition, in the above formula (x-2), R 41 ~R 45 R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a cyano group. However, the alkyl group, aryl group, and cycloalkyl group may be bonded via an ether bond, an ester bond, an amide bond, or a urea bond, and may have a substituent. 46 and R 47 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.

[0313] In addition, when the photoalignment group is a cinnamoyl group represented by the above formula (x-1), the benzene ring of the styrene skeleton (formula (1-2)) contained in the monomer unit may be the benzene ring of the cinnamoyl group.

[0314] Moreover, the cinnamoyl group represented by the above formula (x-1) is more preferably a group represented by the following formula (x-3).

[0315] [ka]

[0316] In the above formula (x-3), R 32 ~R 37 is the same as the above formula (x-1). 38 represents a hydrogen atom, an alkoxy group having 1 to 18 carbon atoms, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. However, the alkyl group, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via an ether bond, an ester bond, an amide bond, or a urea bond. n represents an integer of 1 to 5, and R 38 may be bonded to any of the ortho, meta, and para positions. When n is 2 to 5, R 38 may be the same or different. Among them, n is 1 and R 38 is preferably attached at the para position.

[0317] When the photo-alignment group is at least one group selected from the group consisting of the groups represented by the above formulas (x-3) and (x-2), an aromatic ring is arranged near the end of the photo-alignment structural unit, and the unit contains many π electrons. Therefore, it is considered that the affinity with the liquid crystal layer formed on the alignment layer is increased, the liquid crystal alignment ability is improved, and the adhesion with the liquid crystal layer is increased.

[0318] Examples of monomer units constituting the photoalignment structural unit include acrylic acid esters, methacrylic acid esters, styrene, acrylamide, methacrylamide, maleimide, vinyl ethers, vinyl esters, etc. Among these, acrylic acid esters, methacrylic acid esters, and styrene are preferred from the viewpoint of ease of procurement of raw materials.

[0319] An example of the photoalignable constitutional unit of the present disclosure is a constitutional unit represented by the following formula (1).

[0320] [ka] (In the above formula (1), Z 1 represents at least one monomer unit selected from the group consisting of the following formulas (1-1) to (1-6), X represents a photoalignment group, L 11 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, an alkylene group, an arylene group, a cycloalkylene group, or a combination thereof.

[0321] [ka] (In the above formulas (1-1) to (1-6), R 21 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 22 represents a hydrogen atom or a methyl group, and R 23 is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 24 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0322] The monomer unit constituting the photoalignment structural unit may be at least one selected from the group consisting of the above formulas (1-1) to (1-6). 1 is at least one selected from the group consisting of formula (1-2), -L 11 -X may be bonded to any of the ortho, meta, and para positions, but -L 11 It is preferable that -X is bonded to the para position, since the distance between the photoalignable groups tends to be small and photoalignment is easily obtained.

[0323] As the monomer unit constituting the photo-alignable structural unit, at least one selected from the group consisting of formulas (1-1) and (1-2) is preferred from the viewpoint of easiness of procurement of raw materials. Furthermore, at least one selected from the group consisting of formula (1-2) is more preferred because the rigidity of the photo-alignable structural unit of the copolymer (B) is increased, so that the distance between the photo-alignable groups is likely to be small, and excellent photo-alignment is likely to be obtained. In addition, when the copolymer has a styrene skeleton and contains a large amount of π electron systems, it is considered that the alignment layer / retardation layer formed from the thermosetting liquid crystal composition having photo-alignment property of the present disclosure also has high adhesion to the liquid crystal material directly laminated on the alignment layer / retardation layer due to the interaction of the π electron systems.

[0324] In the above formula (1), X represents a photo-alignable group, which may be the same as above, and may be at least one selected from the group consisting of a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, a quinoline group, an azobenzene group, and a stilbene group. The benzene ring in these functional groups may have a substituent. The substituent may be any group that does not interfere with the photodimerization reaction or the photoisomerization reaction, and may be, for example, an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a trifluoromethyl group, a cyano group, etc. Among them, the photoalignable group is preferably a cinnamoyl group, specifically, a group represented by the above formula (x-1) or (x-2).

[0325] L 11 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, an alkylene group, an arylene group, a cycloalkylene group, or a combination thereof, and connects the monomer unit and the photoalignable group X.

[0326] The above L 11 When is a single bond, the photo-alignable group X is a monomer unit Z 1 Specific examples of the divalent linking group include -O-, -S-, -COO-, -COS-, -CO-, -OCO-, -(CH2) n -, -(CH2CH2O) m-, -C6H4-, -C6H 10 -, -(CH2) n O-, -(CH2CH2O) m O-, -C6H4O-, -C6H 10 O-, -O(CH2) n O-, -O(CH2CH2O) m O-, -OC6H4O-, -OC6H 10 O-, -OCO(CH2) n COO-, -OCO(CH2CH2O) m COO-, -OCOC6H4O-, -OCOC6H 10 O-, -COO(CH2) n O-, -COO(CH2CH2O) m -, -COOC6H4O-, -COOC6H 10 O-, etc., where -C6H4- is a phenylene group, -C6H 10 - represents a cyclohexylene group. n is 1 to 20, and m is 1 to 10.

[0327] From the viewpoint of photoalignment, it is preferable that the alkylene chain between the monomer unit and the photoalignment group X is short. In the photoalignment constitutional unit, the structure having a short alkylene chain increases rigidity, and the distance between the photoalignment groups is likely to be small, which is presumed to improve the photoalignment (liquid crystal alignment ability). From the viewpoint of photoalignment, the smaller the n and m, the more preferable. n is preferably 1 to 6, and more preferably 1 to 4; m is preferably 1 to 3, and more preferably 1 to 2. From the viewpoint of photoalignment, it is more preferable that the photoalignment structural unit has a structure that does not have an alkylene chain between the photoalignment group and the main chain of the copolymer (B). 11 is more preferably a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, or a combination of these with an arylene group.

[0328] The photoalignable structural unit contained in the copolymer (B) may be of one type or of two or more types. A monomer having a photo-alignable group that induces the above-mentioned photo-alignable structural unit can be used to synthesize the copolymer (B). The monomer having a photo-alignable group can be used alone or in combination of two or more kinds.

[0329] The content of the photoalignable structural unit in the copolymer (B) can be set within the range of 10 mol% to 90 mol%, preferably within the range of 20 mol% to 80 mol%, when the amount of the structural units contained in the entire copolymer (B) is taken as 100 mol%. If the content of the photoalignable structural unit is low, the sensitivity decreases, and it may be difficult to impart good liquid crystal alignment ability. On the other hand, if the content of the photoalignable structural unit is high, the content of the thermally crosslinkable structural unit becomes relatively low, and sufficient thermosetting property cannot be obtained, and it may be difficult to maintain good liquid crystal alignment ability.

[0330] (2) Thermally crosslinkable structural unit The thermally crosslinkable constituent unit in the copolymer (B) of the present disclosure is a site that bonds with a thermal crosslinking agent described below upon heating, and has a constituent unit represented by the following formula (2).

[0331] [ka] (In the above formula (2), Z 2 represents at least one monomer unit selected from the group consisting of the following formulas (2-1) to (2-6), and R 50 represents a linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain, and Y represents at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group.

[0332] [ka] (In the above formulas (2-1) to (2-6), R 51 represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group, and R 52 represents a hydrogen atom or a methyl group, and R 53is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 54 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 12 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-; L 12 If it is a single bond, R 50 is directly bonded to the styrene backbone.)

[0333] In the general formula (2), the thermally crosslinkable group Y is a linear alkylene group R having 4 to 11 carbon atoms which may have -O- in the carbon chain. 50 Since the carbon atom to which the thermal crosslinkable group is bonded is a primary carbon, the reactivity is high. Among them, a hydroxy group is preferable as the thermal crosslinkable group from the viewpoint of reactivity.

[0334] In the above formula (2), L 12 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-. 12 When is a single bond, the thermal crosslinking group Y is a monomer unit Z 2 is directly bonded to R 50 is a straight-chain alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain, the distance between the thermally crosslinkable group in the thermally crosslinkable constituent unit and the main skeleton of the copolymer becomes appropriately long, so that the thermally crosslinkable agent is easily bonded to the thermally crosslinkable group, the reactivity between the thermally crosslinkable constituent unit and the thermally crosslinking agent becomes high, and the curing speed of copolymer (B) becomes high. Among them, R 50 is -(CH2) j - or - (C2H4O) kIt is preferably -C2H4- (j is 4 to 11, k is 1 to 4). The above j is more preferably 6 to 11, and k is more preferably 2 to 4. If j and k are too small, the distance between the thermally crosslinkable group and the main skeleton of the copolymer in the thermally crosslinkable constituent unit becomes short, so that the thermal crosslinking agent is difficult to bond to the thermally crosslinkable group, and the reactivity between the thermally crosslinkable constituent unit and the thermal crosslinking agent may decrease. On the other hand, if j and k are too large, the chain length of the linking group in the thermally crosslinkable constituent unit becomes long, so that the thermally crosslinkable group at the terminal is difficult to come out to the surface, so that the thermal crosslinking agent is difficult to bond to the thermally crosslinkable group, and the reactivity between the thermally crosslinkable constituent unit and the thermal crosslinking agent may decrease.

[0335] Z 2 is at least one selected from the group consisting of formula (2-2), -L 12 -R 50 -Y may be bonded to any of the ortho, meta, and para positions, but -L 12 -R 50 It is preferable that -Y is bonded to the para position because this provides excellent reactivity in thermal crosslinking.

[0336] As the monomer unit constituting the thermally crosslinkable constitutional unit, from the viewpoint of ease of procurement of raw materials, at least one selected from the group consisting of the formulae (2-1) and (2-2) is preferable.

[0337] The thermally crosslinkable constituent unit contained in the copolymer (B) may be of one type or of two or more types. In addition, when the copolymer (B) contains two or more types of thermally crosslinkable structural units having a structural unit represented by formula (2), the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain having the largest carbon number among them should satisfy any one of the above (i) to (iv) in comparison with all the non-liquid crystal and thermally crosslinkable structural units of the side chain type liquid crystal polymer (A). In the synthesis of the copolymer (B), a monomer having a thermal crosslinkable group that induces the above-mentioned thermal crosslinkable structural unit can be used. The monomer having a thermal crosslinkable group can be used alone or in combination of two or more kinds.

[0338] The content ratio of the thermally crosslinkable structural unit in the copolymer (B) can be set within the range of 10 mol% to 90 mol%, preferably within the range of 20 mol% to 80 mol%, when the amount of the structural units contained in the entire copolymer (B) is taken as 100 mol%. If the content ratio of the thermally crosslinkable structural unit is low, sufficient thermosetting property cannot be obtained, and it may be difficult to maintain good liquid crystal alignment ability. In addition, if the content ratio of the thermally crosslinkable structural unit is high, the content ratio of the photoalignment structural unit is relatively low, the sensitivity is reduced, and it may be difficult to impart good liquid crystal alignment ability.

[0339] (3) Other building blocks In the present disclosure, the copolymer (B) may have other structural units in addition to the photo-alignable structural units and the thermally crosslinkable structural units. By including other structural units in the copolymer (B), for example, the solvent solubility, heat resistance, reactivity, etc. can be improved.

[0340] The other structural units may include self-crosslinking structural units having self-crosslinking groups capable of crosslinking with each other of the same crosslinking group. Examples of the self-crosslinking group include a hydroxymethyl group, an alkoxymethyl group, a trialkoxysilyl group, and a blocked isocyanate group. When the copolymer (B) further has a self-crosslinking structural unit in addition to the thermally crosslinkable structural unit, the self-crosslinking structural unit can also function as a thermal crosslinking agent, which is preferable since it is easy to improve the photoalignment performance and solvent resistance. When the copolymer (B) further has a self-crosslinking structural unit, it is likely to react with the thermally crosslinkable structural unit in the molecule, and therefore the thermal crosslinking of the copolymer (B) is likely to proceed, while the thermal crosslinking of the side chain type liquid crystal polymer (A) is unlikely to proceed. This is effective in promoting the curing of the copolymer (B), which is the photoalignment film material in the composition, while at the same time suppressing the curing of the side chain type liquid crystal polymer (A) having vertical alignment properties.

[0341] Examples of monomers having a self-crosslinking group include acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide; monomers having a trialkoxysilyl group, such as 3-trimethoxysilylpropylacrylate, 3-triethoxysilylpropylacrylate, 3-trimethoxysilylpropylmethacrylate, and 3-triethoxysilylpropylmethacrylate; and monomers having a blocked isocyanate group, such as 2-(0-(1'-methylpropylideneamino)carboxyamino)ethylmethacrylate and 2-(3,5-dimethylpyrazolyl)carbonylaminoethylmethacrylate.

[0342] Examples of monomer units constituting a structural unit having no photoalignable group and no thermally crosslinkable group include acrylic acid esters, methacrylic acid esters, maleimides, acrylamides, acrylonitrile, maleic anhydride, styrene, vinyl, etc. Among these, acrylic acid esters, methacrylic acid esters, and styrene are preferred, as with the thermally crosslinkable structural unit.

[0343] Examples of monomers forming a structural unit having neither a photoalignment group nor a thermal crosslinking group include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, etc. Specifically, for example, among the monomers described in paragraphs 0036 to 0040 of International Publication No. 2010 / 150748, a monomer having neither a photoalignment group nor a thermal crosslinking group can be used.

[0344] In addition, as other structural units, for example, structural units derived from a monomer having a fluorinated alkyl group may be included. In this case, the copolymer (B) is more likely to be localized on the coating film surface, and the photoalignable group is more likely to be oriented on the coating film surface. In order to make it easier to localize the copolymer (B) on the coating film surface, the fluorinated alkyl group of the monomer having a fluorinated alkyl group may be a fluorinated alkyl group having 2 to 8 carbon atoms to which a fluorine atom is directly bonded.

[0345] The other structural units in the copolymer (B) may be of one type or of two or more types.

[0346] The content ratio of the other structural units in the copolymer (B) is preferably within the range of 0 mol% to 50 mol%, and more preferably within the range of 0 mol% to 30 mol%, when the amount of structural units contained in the entire copolymer (B) is taken as 100 mol%. If the content ratio of the above structural units is high, the content ratios of the photoalignable structural units and the thermally crosslinkable structural units will be relatively low, the sensitivity will decrease, it will be difficult to impart good liquid crystal alignment ability, and sufficient thermosetting property will not be obtained, making it difficult to maintain good liquid crystal alignment ability.

[0347] (4) Copolymer (B) The mass average molecular weight of the copolymer (B) is not particularly limited, and can be, for example, about 3,000 to 200,000, preferably within the range of 4,000 to 100,000. If the mass average molecular weight is too large, the solubility in the solvent may be reduced or the viscosity may be increased, which may reduce the handling property and make it difficult to form a uniform film. If the mass average molecular weight is too small, the curing may be insufficient during heat curing, which may reduce the solvent resistance and heat resistance. The mass average molecular weight can be measured by gel permeation chromatography (GPC).

[0348] The copolymer (B) can be synthesized by copolymerizing a monomer having a photoalignable group with a monomer having a thermally crosslinkable group by a conventionally known production method. The copolymer (B) may be used in the form of a solution obtained when the copolymer is synthesized, or in the form of a powder, or in the form of a solution obtained by redissolving a purified powder in a solvent described below.

[0349] The copolymer (B) may be used alone or in combination of two or more. In the present embodiment, in order to exert an alignment ability on the liquid crystal material to be directly laminated, the content of the copolymer (B) is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 25 parts by mass, per 100 parts by mass of the solid content of the liquid crystal composition.

[0350] 3. Thermal crosslinking agent The thermosetting liquid crystal composition having photoalignment properties according to the present disclosure contains a thermal crosslinking agent that bonds with the thermal crosslinkable group of the thermal crosslinkable constituent unit. In the thermosetting liquid crystal composition having the second photoalignment property of the present disclosure, the thermal crosslinker (C) may be the same as the thermal crosslinker (C) in the thermosetting liquid crystal composition having the first photoalignment property, and therefore, the explanation thereof will be omitted here. In the thermosetting liquid crystal composition having the second photoalignment property of the present disclosure, the decrease in vertical alignment property can be suppressed by appropriately adjusting the content of the thermal crosslinking agent (C) in accordance with the structure of the thermal crosslinkable constituent unit of the side chain type liquid crystal polymer (A). In addition, in the thermosetting liquid crystal composition having the second photoalignment property of the present disclosure, the acid or acid generator, solvent, and other components may be similar to the acid or acid generator, solvent, and other components in the thermosetting liquid crystal composition having the first photoalignment property, and therefore the description thereof will be omitted here. In addition, in the thermosetting liquid crystal composition having the second photoalignment property of the present disclosure, the production method and uses may be similar to the production method and uses of the thermosetting liquid crystal composition having the first photoalignment property, so the explanation thereof will be omitted here.

[0351] B. Alignment film and retardation film The second alignment film / retardation film of the present disclosure is an alignment film / retardation film containing an alignment layer / retardation layer, characterized in that the alignment layer / retardation layer is a cured film of the thermosetting liquid crystal composition having the second photoalignment property of the present disclosure. The second alignment film / retardation film of the present disclosure may be similar to the first alignment film / retardation film of the present disclosure, except for the thermosetting liquid crystal composition having photoalignment properties used, and therefore a description thereof will be omitted here.

[0352] C. Manufacturing method of alignment film and retardation film The second method for producing an alignment film / retardation film of the present disclosure includes forming a film of the thermosetting liquid crystal composition having the second photoalignment property of the present disclosure; forming a cured film having a retardation by heating the thermosetting liquid crystal composition formed into the film; and irradiating the cured film having retardation with polarized ultraviolet light to impart liquid crystal alignment ability to the cured film. The manufacturing method of the second alignment film / retardation film of the present disclosure may be similar to the manufacturing method of the first alignment film / retardation film of the present disclosure, except that the thermosetting liquid crystal composition having photoalignment properties used is different, and therefore the description thereof will be omitted here.

[0353] D. Retardation plate The second retardation plate of the present disclosure includes a first retardation layer which is a cured film of the thermosetting liquid crystal composition having the second photoalignment property of the present disclosure; and a second retardation layer located adjacent to the first retardation layer and containing a cured product of a polymerizable liquid crystal composition. The second retardation plate and the manufacturing method thereof according to the present disclosure may be similar to the first retardation plate and the manufacturing method thereof according to the present disclosure, except that the thermosetting liquid crystal composition having photoalignment properties used is different, and therefore the description thereof will be omitted here.

[0354] III. Third Disclosure The present disclosure relates to a positive C-type retardation layer which is a cured product of a thermosetting resin composition containing a photoalignment component and a thermal crosslinking agent; a positive A-type retardation layer containing a cured product of a polymerizable liquid crystal composition, the positive A-type retardation layer being located directly adjacent to the positive C-type retardation layer; A third retardation plate is provided, comprising:

[0355] Fig. 5 is a schematic cross-sectional view showing an example of the third retardation plate of the present disclosure. In the retardation plate 30 shown in Fig. 5, a positive C-type retardation layer 21 is formed on a substrate 23, and the positive C-type retardation layer 21 and a positive A-type retardation layer 22 are directly laminated.

[0356] In the third retardation plate 30 of the present disclosure, the positive C-type retardation layer 21 is a cured product of a thermosetting resin composition containing a photo-alignable component and a thermal crosslinking agent, and is directly laminated with the positive A-type retardation layer 22, so that the positive C-type retardation layer 21 also has liquid crystal alignment ability. The positive C-type retardation layer 21 is a cured product of a thermosetting resin composition containing a thermal crosslinking agent. Therefore, the positive C-type retardation layer 21 is less likely to harden and has flexibility, and also has good adhesion with the positive A-type retardation layer directly laminated thereto, compared to the case where it is a cured product of a photocurable resin composition containing a polymerizable liquid crystal compound. The positive C-type retardation layer of the thermosetting resin composition containing a thermal crosslinking agent of the present disclosure is more likely to have a moderate permeation region at the interface with the directly laminated positive A-type retardation layer, so that the vertical alignment of the positive C-type retardation layer is not inhibited, and adhesion is more likely to be improved. The third retardation plate of the present disclosure has a positive C-type retardation layer and a positive A-type retardation layer laminated directly with good adhesion, and does not require a conventional adhesive layer for bonding, so that the thickness can be reduced. The third retardation plate of the present disclosure has a positive C-type retardation layer and a positive A-type retardation layer laminated directly with good adhesion, so that the thickness can be reduced, and the positive C-type retardation layer has flexibility, so that the retardation plate has good bending resistance.

[0357] In one embodiment of the third retardation plate 30 shown in the example of Fig. 5, the substrate 23 and the positive C-type retardation layer 21 are directly laminated. In the third retardation plate shown in the example of Fig. 5, a means for exerting an alignment regulating force may be provided on the surface of the substrate 23 on the side of the positive C-type retardation layer 21. In one embodiment of the third retardation plate, the substrate, the alignment film, and the positive C-type retardation layer may be laminated in this order. The substrate and the alignment film may be the same as those described in "B. Alignment film and retardation film" above, and therefore a description thereof will be omitted here.

[0358] In the third retardation plate of the present disclosure, from the viewpoint of improving productivity, it is preferable that no alignment film is contained between the substrate and the positive C-type retardation layer, and it is preferable that the substrate is located directly adjacent to the positive C-type retardation layer.

[0359] Furthermore, in the third retardation plate of the present disclosure, the thickness after production can be reduced, so that the substrate may be peeled off after production, thereby eliminating the need to include the substrate.

[0360] 1. Positive C-type retardation layer The photo-alignment component used in the positive C-type retardation layer, which is a cured product of a thermosetting resin composition containing a photo-alignment component and a thermal crosslinking agent, may be a compound or polymer containing a photo-alignment group. The photo-alignment component may be a copolymer having a photo-alignment structural unit containing a photo-alignment group in a side chain and a thermal crosslinking structural unit containing a thermal crosslinking group in a side chain, or a compound having a photo-alignment group and a thermal crosslinking group different from the copolymer. The photo-alignment structural unit containing a photo-alignment group in a side chain in the copolymer may be the same as the photo-alignment structural unit of the copolymer (B) in the thermosetting liquid crystal composition having the first or second photo-alignment property. In addition, the thermal crosslinking structural unit containing a thermal crosslinking group in a side chain in the copolymer may be the same as the thermal crosslinking structural unit of the copolymer (B). In addition, other configurations and properties of the copolymer may be the same as those of the copolymer (B). In addition, the compound having a photoalignable group and a thermally crosslinkable group different from those of the copolymer may be the same as the compound having a photoalignable group and a thermally crosslinkable group different from those of the copolymer (B) in the thermosetting liquid crystal composition having the first or second photoalignment property. As the photo-alignment component used in the positive C-type retardation layer, which is a cured product of a thermosetting resin composition containing a photo-alignment component and a thermal crosslinking agent, it is preferable to use a copolymer having a photo-alignment structural unit containing a photo-alignment group in a side chain and a thermal crosslinking structural unit containing a thermal crosslinking group in a side chain, in order to exhibit good vertical alignment properties and liquid crystal alignment ability, and the copolymer (B) in the thermosetting liquid crystal composition having the first or second photo-alignment property may be used.

[0361] The thermal crosslinking agent used in the positive C-type retardation layer, which is a cured product of a thermosetting resin composition containing a photoalignment component and a thermal crosslinking agent, may be the same as the thermal crosslinking agent (C) in the thermosetting liquid crystal composition having the first or second photoalignment property.

[0362] The structures derived from the photo-alignment component and the thermal crosslinker contained in the positive C-type retardation layer can be analyzed by applying NMR, IR, GC-MS, XPS, TOF-SIMS, or a combination of these methods. For example, materials can be collected from the positive C-type retardation layer, and the chemical structures of the photo-alignment component and the thermal crosslinker component can be analyzed by nuclear magnetic resonance spectroscopy (NMR). In addition, fragments derived from the photo-alignment group can be detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS). Furthermore, peaks of bonds and functional groups derived from the thermal crosslinker and the photo-alignment component can be confirmed by X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), and Raman spectroscopy. The structure of the components contained in the positive C-type retardation layer can be analyzed by a composite judgment of these analysis results.

[0363] The thermosetting resin composition used in the positive C-type retardation layer contains a liquid crystal component for expressing retardation. As the liquid crystal component, a side-chain liquid crystal polymer having a liquid crystal constituent unit containing a liquid crystal moiety in the side chain is preferably used, since it is easy to obtain good vertical alignment even when mixed with a photo-alignable component and is easy to impart flexibility. The liquid crystal constituent unit containing a liquid crystal moiety in the side chain in the side-chain liquid crystal polymer may be the same as the liquid crystal constituent unit of the side-chain liquid crystal polymer (A) in the thermosetting liquid crystal composition having the first or second photo-alignable property. The side chain liquid crystal polymer may or may not have a non-liquid crystal structural unit containing an alkylene group in the side chain. The non-liquid crystal structural unit that may be contained in the side chain liquid crystal polymer may be the same as the non-liquid crystal structural unit or other structural unit of the side chain liquid crystal polymer (A) in the thermosetting liquid crystal composition having the first or second photoalignment property. In addition, other configurations and properties of the side chain liquid crystal polymer may be the same as those of the side chain liquid crystal polymer (A).

[0364] The thermosetting resin composition used in the positive C-type retardation layer may contain an acid or an acid generator, a solvent, and other components. The acid or the acid generator, the solvent, and other components may be the same as the acid or the acid generator, the solvent, and other components in the thermosetting liquid crystal composition having the first photoalignment property.

[0365] The positive C-type retardation layer may be a structure containing the vertically aligned side-chain liquid crystal polymer in one layer, the photodimerization structure or photoisomerization structure of the photoalignment group, and the crosslinking structure formed by bonding the thermal crosslinking group and the thermal crosslinking agent. The positive C-type retardation layer may be a structure containing the vertically aligned side-chain liquid crystal polymer in one layer, and a copolymer having a crosslinking structure formed by bonding the photodimerization structure or photoisomerization structure of the photoalignment group of the photoalignment structural unit, and the thermal crosslinking group of the thermal crosslinking structural unit and the thermal crosslinking agent. The photodimerization structure or photoisomerization structure of the photoalignment group contained in the positive C-type retardation layer, and the crosslinked structure formed by bonding the thermal crosslinking group and the thermal crosslinking agent may be the same as the alignment layer and retardation layer described in "B. Alignment film and retardation film".

[0366] In the third retardation plate of the present disclosure, it is preferable to adjust the composite elastic modulus of the positive C-type retardation layer in order to obtain a retardation plate with good bending resistance. The composite elastic modulus of the positive C-type retardation layer may be 4.5 GPa or more and 9.0 GPa or less, 5.0 GPa or more and 8.5 GPa or less, or 5.0 GPa or more and 8.0 GPa or less. Since the positive C-type retardation layer is a cured product of a thermosetting resin composition, the composite elastic modulus can be easily adjusted. The composite elastic modulus of the positive C-type retardation layer is calculated by measuring the indentation hardness (H IT ) is measured using the contact projection area A p The "indentation hardness" is a value obtained from a load-displacement curve from loading to unloading of the indenter obtained by hardness measurement using the nanoindentation method. The composite elastic modulus of the positive C-type retardation layer is an elastic modulus including the elastic deformation of the positive C-type retardation layer and the elastic deformation of the indenter. The composite elastic modulus of the positive C type retardation layer is measured on the surface opposite to the interface between the positive C type retardation layer and the positive A type retardation layer. The composite elastic modulus of the positive C type retardation layer can be determined by the method for determining the composite elastic modulus described in the examples.

[0367]

number

[0368] In the third retardation plate of the present disclosure, the positive C-type retardation layer may include a region in which a specific component contained in the positive A-type retardation layer described later is permeated. The specific component may include a polymerizable liquid crystal compound or a cured product thereof. The presence of a permeated region as well as specific components can be analyzed by the following procedure. First, the surface of the positive A-type retardation layer of the third retardation plate of the present disclosure is etched in the film thickness direction with a gas cluster ion beam (Ar-GCIB) gun, and measured with a time-of-flight secondary ion mass spectrometer (TOF-SIMS). Then, the distribution in the film thickness direction is analyzed for fragment ions derived from the components of the polymerizable liquid crystal compound contained in the positive A-type retardation layer described later and fragment ions derived from the photo-alignment component contained in the positive C-type retardation layer. The permeation region can be measured as the portion where both fragment ions derived from the components of the polymerizable liquid crystal compound and fragment ions derived from the photo-alignment component are detected. In addition, the thickness of the permeated region can be roughly estimated from the proportion of the permeated region in the film thickness direction distribution of each fragment ion measured by TOF-SIMS, in light of the film thickness measured using a scanning transmission electron microscope (STEM).

[0369] The thickness of the positive C-type retardation layer may be appropriately set depending on the application, and is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm.

[0370] 2. Positive A-type retardation layer In the third retardation plate of the present disclosure, the positive A-type retardation layer contains a cured product of a polymerizable liquid crystal composition. In the third retardation plate of the present disclosure, the positive A-type retardation layer may be the same as the second retardation layer in the first or second retardation plate.

[0371] 3. Retardation plate In the third retardation plate of the present disclosure, the thickness direction retardation Rth at a wavelength of 550 nm may be −35 nm to 35 nm, the in-plane retardation Re at a wavelength of 550 nm may be 100 nm or more, and the total thickness of the positive C-type retardation layer and the positive A-type retardation layer may be 0.2 μm to 6 μm. The thickness direction retardation Rth at a wavelength of 550 nm may be −30 nm to 30 nm, and may further be −25 nm to 25 nm. The in-plane retardation Re at a wavelength of 550 nm may be 120 nm or more, and may further be 135 nm or more. The thickness direction retardation Rth and the in-plane retardation Re at a wavelength of 550 nm can be determined specifically by the method described in the Examples. The total thickness of the positive C-type retardation layer and the positive A-type retardation layer may be 0.8 μm to 5 μm, and further may be 1 μm to 4 μm. The total thickness of the positive C-type retardation layer and the positive A-type retardation layer can be determined by using a scanning transmission electron microscope (STEM) described in the Examples.

[0372] 4. Manufacturing method of retardation plate The method for producing the third retardation plate is not particularly limited as long as the third retardation plate can be provided. The third method for producing a retardation plate includes, for example, a step of forming a film of a thermosetting liquid crystal composition having photoalignment properties, the thermosetting liquid crystal composition including a side chain type liquid crystal polymer having a liquid crystal constituent unit having a liquid crystal moiety in a side chain, a copolymer having a photoalignment constituent unit and a thermal crosslinking constituent unit having a thermal crosslinking group in a side chain, and a thermal crosslinking agent that bonds with the thermal crosslinking group of the thermal crosslinking constituent unit; forming a cured film having a retardation by heating the thermosetting liquid crystal composition formed into the film; A step of forming a positive C-type retardation layer having a liquid crystal alignment ability by irradiating the cured film having a retardation with polarized ultraviolet light; A step of applying a polymerizable liquid crystal composition onto the positive C-type retardation layer to form a coating film of the polymerizable liquid crystal composition, and heating the coating film to a phase transition temperature of the polymerizable liquid crystal composition to align liquid crystal molecules by the positive C-type retardation layer; a step of forming a positive A-type retardation layer by irradiating the coating film of the polymerizable liquid crystal composition in which the liquid crystal molecules are aligned with light and curing the coating film; may have Each component of the thermosetting liquid crystal composition having photoalignment properties may be the same as those explained in the third retardation plate. The third method for producing a retardation plate can be performed in the same manner as each step in the first or second method for producing a retardation plate.

[0373] Next, an optical member and a method for producing the same, and a display device using the retardation plate according to the first, second, or third embodiment of the present disclosure will be described.

[0374] E. Optical components The present disclosure provides an optical member including a first, second, or third retardation plate and a polarizing plate.

[0375] The optical member of this embodiment will be described with reference to the drawings, in which: Figure 6 is a schematic cross-sectional view showing one embodiment of the optical member. The example of the optical member 50 in Fig. 6 includes the retardation plate 30 of the present disclosure and a polarizing plate 40 adjacent to the retardation plate. An adhesive layer (bonding layer) may be included between the retardation plate 30 and the polarizing plate 40 as necessary (not shown). The retardation plate 30 of the present disclosure may be a first, second, or third retardation plate. 6, a polarizing plate 40 is disposed on a retardation plate 30 on which the first retardation layer 31 and the second retardation layer 32 of the present disclosure are directly laminated. The first retardation layer 31 and the second retardation layer 32 may be the positive C-type retardation layer and the positive A-type retardation layer, respectively. In this embodiment, the first, second, or third retardation plate of the present disclosure may be the same as that described above, and therefore the description thereof will be omitted here.

[0376] In the present embodiment, the polarizing plate is a plate-like plate that transmits only light that vibrates in a specific direction, and may be appropriately selected from conventionally known polarizing plates. In the present embodiment, the polarizing plate may be a linear polarizing plate. The linear polarizing plate may include a plate containing a polarizer and a polarizer protective layer provided on at least one surface of the polarizer. Examples of the polarizer include a stretched film or layer adsorbed with a dye having anisotropic absorption, and a film coated with and cured with a dye having anisotropic absorption. Examples of the dye having anisotropic absorption include dichroic dyes. Specifically, iodine and dichroic organic dyes are used as the dichroic dyes. Examples of stretched films having adsorbed dyes having absorption anisotropy include polyvinyl alcohol films, polyvinyl formal films, polyvinyl acetal films, and saponified ethylene-vinyl acetate copolymer films that are dyed with iodine or a dye and stretched. A linear polarizing plate can be used, for example, by referring to paragraphs 0025 to 0059 of JP 2021-51287 A. The thickness of the polarizing plate is, for example, from 2 μm to 100 μm, and preferably from 10 μm to 60 μm.

[0377] In the present embodiment, the adhesive or adhesive for the adhesive layer (bonding layer) may be appropriately selected from conventionally known adhesives, and any adhesive form may be suitably used, such as a pressure-sensitive adhesive (adhesive), a two-component curing adhesive, an ultraviolet curing adhesive, a heat curing adhesive, a hot melt adhesive, etc. The adhesive for the adhesive layer may be an adhesive composition having a (meth)acrylic resin as a base polymer, preferably from the viewpoints of transparency, weather resistance, heat resistance, etc. The thickness of the adhesive layer (bonding layer) is determined depending on the adhesive strength and the like, and may be, for example, 1 μm to 50 μm, preferably 2 μm to 45 μm, more preferably 3 μm to 40 μm, and further preferably 5 μm to 35 μm.

[0378] The optical member of the present embodiment may further include other layers that are included in known optical members in addition to the polarizing plate. Examples of the other layers include, but are not limited to, a retardation layer different from the retardation layer of the present embodiment, an antireflection layer, a diffusion layer, an antiglare layer, an antistatic layer, a protective film, and the like.

[0379] The optical member of the present embodiment can be suitably used, for example, as a circular polarizing plate.The optical member of the present embodiment can be suitably used, for example, as an optical member for suppressing external light reflection in a light-emitting display device.

[0380] F. Manufacturing method of optical components The present disclosure also provides a method for producing a polarizing plate, comprising: providing a first, second, or third retarder; and laminating a retardation plate and a polarizing plate. In the method for producing an optical member according to the present disclosure, the steps may be performed in any order. For example, a step of preparing a polarizing plate may be performed, and a first, second, or third retardation plate may be formed on the polarizing plate to prepare the first, second, or third retardation plate. In this case, the step of laminating the retardation plate and the polarizing plate is performed simultaneously with the step of preparing the retardation plate.

[0381] 1. Preparation of polarizing plates As a process for preparing a polarizing plate, for example, a stretched film adsorbed with a dye having absorption anisotropy is used as a polarizer. The stretched film adsorbed with a dye having absorption anisotropy can usually be manufactured through a process of uniaxially stretching a polyvinyl alcohol-based resin film, a process of dyeing the polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye, a process of treating the polyvinyl alcohol-based resin film adsorbed with the dichroic dye with an aqueous boric acid solution, and a process of washing with water after the treatment with the aqueous boric acid solution. A polarizer protective layer is attached to one or both sides of the obtained polarizer to prepare a polarizing plate. The polarizing plate can be prepared, for example, by referring to paragraphs 0025 to 0059 of JP 2021-51287 A.

[0382] 2. Preparation of the retardation plate The step of preparing the first, second, or third retardation plate is not particularly limited as long as the step can prepare the first, second, or third retardation plate. The step of preparing the first, second or third retardation plate can be performed, for example, in the same manner as the above-mentioned method for producing the first, second or third retardation plate. When preparing the retardation plate, it is preferable to form the first retardation layer and the second retardation layer on a substrate which can be peeled off later. The releasable substrate can be appropriately selected so as to be releasable. The substrate may be surface-treated, may be release-treated, or may have a release layer formed thereon.

[0383] 3. Step of laminating the retardation plate and the polarizing plate In the step of laminating the retardation plate and the polarizing plate, the retardation plate and the polarizing plate may be bonded to each other with an adhesive layer (adhesive layer). Alternatively, the retardation plate may be directly formed on the polarizing plate as described above, so that the retardation plate and the polarizing plate are laminated at the same time as the retardation plate is prepared. As the adhesive layer (bonding layer), the same layer as described above can be used.

[0384] When the retardation plate and the polarizing plate are laminated, the angle formed by the slow axis of the positive A-type retardation layer in the retardation layer and the absorption axis of the polarizing plate is preferably 45°±5°.

[0385] In the step of laminating the retardation plate and the polarizing plate, when the retardation plate and the polarizing plate are bonded with an adhesive layer (adhesive layer), it is preferable to peel off the base material of the retardation plate after bonding. By peeling off the base material of the retardation plate later, an optical member including only the polarizing plate and the first and second retardation layers of the retardation plate of the present disclosure can be obtained.

[0386] G.Display device The present disclosure provides a display device including a first, second, or third retardation plate, or an optical member including the retardation plate and a polarizing plate. The display device of the present disclosure is characterized by including a first, second, or third retardation plate, or an optical member including the retardation plate and a polarizing plate. Examples of the display device include, but are not limited to, a light-emitting display device and a liquid crystal display device. The display device may be a touch panel equipped with a touch sensor. The display device may also be a flexible display device.

[0387] The display device of the present disclosure is preferably a light-emitting display device. Since the retardation plate or the optical member of the present disclosure is provided, particularly in a light-emitting display device such as an organic light-emitting display device having a transparent electrode layer, a light-emitting layer, and an electrode layer in this order, the viewing angle is improved while external light reflection is suppressed.

[0388] In addition, the display device of the present disclosure is preferably a flexible display device. Since the retardation plate or the optical member according to the present disclosure, which can be thinned and has good adhesion and bending resistance, is provided, the flexible display device has an effect of improving bending resistance. The flexible display device may be a foldable display device. In the display device of the present disclosure, configurations other than the retardation plate or the optical member may be appropriately selected publicly known configurations.

[0389] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any embodiment that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included in the technical scope of the present disclosure. EXAMPLES

[0390] The present disclosure will be described in further detail below with reference to examples and comparative examples. Example I Series: First Present Disclosure (Synthesis Example 1: Synthesis of Liquid Crystal Monomer 1) With reference to paragraphs 0121 to 0124 of WO 2018 / 003498, 4'-cyano-4-{4-[2-(acryloyloxy)ethoxy]benzoate} (chemical formula (i-1) below) was obtained.

[0391] (Synthesis Example 2: Synthesis of Liquid Crystal Monomer 2) A liquid crystal monomer 2 represented by the following chemical formula (i-2) was obtained in the same manner as in Synthesis Example 1, except that 6-chloro-1-n-hexanol was used instead of 2-bromoethanol in Synthesis Example 1.

[0392] (Synthesis Example 3: Synthesis of Liquid Crystal Monomer 3) With reference to paragraphs 0127 to 0130 of International Publication No. 2018 / 003498, 4-[(4-propoxycarbonylphenyloxycarbonyl)phenyl-4-[6-(acryloyloxy)hexyloxy]benzoate (chemical formula (i-3) below) was obtained.

[0393] [Table 1]

[0394] Stearyl acrylate (chemical formula (ii-1) below, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as non-liquid crystal monomer 1, hexyl acrylate (chemical formula (ii-2) below, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as non-liquid crystal monomer 2, and nonylphenoxy polyethylene glycol acrylate (chemical formula (ii-3) below) manufactured by Hitachi Chemical Industry Co., Ltd. was used as non-liquid crystal monomer 3. Non-liquid crystal monomer 3 is a mixture of n' in the chemical formula (ii-3) below, in which n' is 1 to 12, and contains at least a monomer in which n' is 8 and a monomer in which n' is 12, and the average of n' is 8.

[0395] In addition, 2-hydroxyethyl methacrylate (chemical formula (ii-4) below, manufactured by Kyoeisha Chemical Co., Ltd.) was used as the non-liquid crystal monomer 4tc having a thermal crosslinkable group, 4-hydroxybutyl acrylate (chemical formula (ii-5) below, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the non-liquid crystal monomer 5tc having a thermal crosslinkable group, and N-(methoxymethyl)methacrylamide (chemical formula (ii-8) below, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the non-liquid crystal monomer 8tc having a thermal crosslinkable group.

[0396] (Synthesis Example 4: Synthesis of non-liquid crystal monomer 6 having a thermal crosslinking group) A non-liquid crystal monomer 6tc having a thermal crosslinkable group represented by the following chemical formula (ii-6) was synthesized in the same manner as in the thermal crosslinkable monomer B8 of Synthesis Example 6 of Japanese Patent No. 5668881.

[0397] (Synthesis Example 5: Synthesis of non-liquid crystal monomer 7 having a thermal crosslinking group) A non-liquid crystal monomer 7tc having a thermal crosslinkable group represented by the following chemical formula (ii-7) was synthesized in the same manner as in the thermal crosslinkable monomer B9 of Synthesis Example 7 of Japanese Patent No. 5668881.

[0398] [Table 2]

[0399] (Synthesis Example 6: Synthesis of Photo-Alignable Monomer 1) Photoalignment monomer 1 represented by the following chemical formula (iii-1) was synthesized in the same manner as in photoalignment monomer 3 of Synthesis Example 3 of Japanese Patent No. 5626492.

[0400] (Synthesis Example 7: Synthesis of photoalignable monomer 2) Photoalignment monomer 2 represented by the following chemical formula (iii-2) was synthesized in the same manner as in photoalignment monomer 1 of Synthesis Example 1 of Japanese Patent No. 5626492.

[0401] (Synthesis Example 8: Synthesis of Photo-Alignable Monomer 3) Photoalignment monomer 3 represented by the following chemical formula (iii-3) was synthesized in the same manner as in photoalignment monomer 8 of Synthesis Example 8 of Japanese Patent No. 5626492.

[0402] (Synthesis Example 9: Synthesis of Photo-Alignable Monomer 4) Photoalignment monomer 4 represented by the following chemical formula (iii-4) was synthesized in the same manner as in photoalignment monomer 9 of Synthesis Example 9 of Japanese Patent No. 5626492.

[0403] (Synthesis Example 10: Synthesis of Photo-Alignable Monomer 5) Photoalignment monomer 5 represented by the following chemical formula (iii-5) was synthesized in the same manner as in photoalignment monomer 4 in Synthesis Example 4 of Japanese Patent No. 5626492.

[0404] (Synthesis Example 11: Synthesis of Photo-Alignable Monomer 6) A suspension of 4'-hydroxychalcone (Tokyo Chemical Industry Co., Ltd.) (20 g, 90 mmol), acryloyl chloride (7.4 g, 82 mmol), dimethylaniline (DMA) (9.9 g, 82 mmol) in tetrahydrofuran (400 mL) was stirred for 12 hours. After the reaction was completed, water and ethyl acetate were added and the mixture was separated. The solvent was distilled off, the residue was purified by silica gel chromatography, and the solvent was distilled off to synthesize the photoalignable monomer 6 represented by the following chemical formula (iii-6) with a yield of 89% (22 g, 80 mmol).

[0405] (Synthesis Example 12: Synthesis of Photo-Alignable Monomer 7) In the synthesis example a of Japanese Patent No. 5626492, instead of using 4-vinylbenzoic acid, an equimolar amount of 4-methoxycinnamic acid was used, and instead of using ethylene glycol, an equimolar amount of 4-hydroxyphenyl methacrylate (manufactured by Seiko Chemical Co., Ltd.) was used and condensed in the same manner to synthesize photoalignable monomer 7 represented by the following chemical formula (iii-7).

[0406] (Synthesis Example 13: Synthesis of Comparative Photoalignable Monomer 1) Comparative photoalignable monomer 1 represented by the following chemical formula (iii-c1) was synthesized in the same manner as in Synthesis Example 2 of Japanese Patent No. 5668881, except that an equimolar amount of trans-4-hydroxycinnamate was used instead of methyl ferulate, and an equimolar amount of 6-chloro-1-hexanol was used instead of 4-chloro-1-butanol.

[0407] As comparative photoalignable monomer 2 represented by the following chemical formula (iii-c2), 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid methyl ester was prepared.

[0408] (Synthesis Example 15: Synthesis of Comparative Photoalignable Monomer 3) Comparative photoalignable monomer 3 represented by the following chemical formula (iii-c3) was synthesized in the same manner as in reference photoalignable monomer 2 of reference synthesis example 1 of Japanese Patent No. 5626492.

[0409] [Table 3]

[0410] In addition, as the thermal crosslinkable monomer 1, 2-hydroxyethyl methacrylate (represented by the following chemical formula (iv-1): As the thermal crosslinking monomer 2, 4-hydroxybutyl acrylate (chemical formula (iv-2) below, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

[0411] (Synthesis Example 16: Synthesis of thermal crosslinkable monomer 3) Thermally crosslinkable monomer 3 represented by the following chemical formula (iv-3) was synthesized in the same manner as in the thermally crosslinkable monomer B3 in Synthesis Example 4 of Japanese Patent No. 5668881.

[0412] (Synthesis Example 17: Synthesis of thermal crosslinkable monomer 4) Thermally crosslinkable monomer 4 represented by the following chemical formula (iv-4) was synthesized in the same manner as thermally crosslinkable monomer 5 in Synthesis Example e of Japanese Patent No. 5626492.

[0413] (Synthesis Example 18: Synthesis of thermal crosslinkable monomer 5) Thermally crosslinkable monomer 5 represented by the following chemical formula (iv-5) was synthesized in the same manner as thermally crosslinkable monomer 6 in Synthesis Example f of Japanese Patent No. 5626492.

[0414] (Synthesis Example 19: Synthesis of thermal crosslinkable monomer 6) A thermally crosslinkable monomer 6 represented by the following chemical formula (iv-6) was synthesized in the same manner as in compound 46 of Example 9 of JP-A No. 2016-538400.

[0415] (Synthesis Example 20: Synthesis of Thermally Crosslinkable Monomer 7) In the same manner as described in paragraph 124 of JP2018-525444, a thermally crosslinkable monomer 7 represented by the following chemical formula (iv-7) was synthesized.

[0416] In addition, as the third component monomer, N-(methoxymethyl)methacrylamide (chemical formula (iv-8) below, manufactured by Tokyo Chemical Industry Co., Ltd.), which is a thermally crosslinkable monomer 8 having a self-crosslinking group, and Viscoat 13F (chemical formula (v-1) below, manufactured by Osaka Organic Chemical Industry Co., Ltd.), which is a monomer 1 having a fluorinated alkyl group, were used.

[0417] [Table 4]

[0418] (Production Examples A1 to A14: Production of Side Chain Liquid Crystal Polymers A1 to A14) The liquid crystal monomers 1 to 3, the non-liquid crystal monomers 1 to 3 and 4tc to 8tc, and the photoalignable monomer 1 were combined according to Table 5 to synthesize a side chain type liquid crystal polymer. A synthesis example of the side chain type liquid crystal polymer A2 will be specifically described. Non-liquid crystal monomer 1 and non-liquid crystal monomer 2 were combined in a molar ratio of 50:50, and the sum of these non-liquid crystal monomers and liquid crystal monomer 1 were combined and mixed in a molar ratio of 40:60. N,N-dimethylacetamide (DMAc) was added and stirred at 40°C to dissolve. After dissolution, the mixture was cooled to 24°C, and azobisisobutyronitrile (AIBN) was added and dissolved at the same temperature. The above reaction solution was dropped into DMAc heated to 80°C over 30 minutes, and after the dropwise addition, the mixture was stirred at 80°C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and then dropped into another container in which methanol was stirred and stirred for 20 minutes. After removing the supernatant, the slurry was filtered, and the obtained crude product was again stirred in methanol for 20 minutes, and the supernatant was removed and filtered. The obtained crystals were dried to obtain side-chain liquid crystal polymer A2 with a yield of 76.5%. The side-chain liquid crystal polymers thus obtained were subjected to mass average molecular weight measurement and structural analysis, and were confirmed by Py-GC-MS and MALDI-TOFMS to contain constitutional units derived from one, two or three kinds of non-liquid crystal monomers used.

[0419] [Table 5]

[0420] (Production Examples B1 to B15: Production of Copolymers B1 to B15) The photoalignable monomers 1 to 7, the thermally crosslinkable monomers 1 to 7, and the third component monomer were combined according to Table 6 to synthesize a copolymer (B). A synthesis example of copolymer B1 will be specifically described. 3.08 g of photo-alignable monomer 1 and 3.08 g of thermal cross-linkable monomer 1 (hydroxybutyl methacrylate) 1.30g of the copolymer and 50mg of α,α'-azobisisobutyronitrile (AIBN) as a polymerization catalyst were dissolved in 25ml of dioxane and reacted at 90°C for 6 hours. After the reaction was completed, the copolymer was purified by a reprecipitation method to obtain copolymer B1. The mass average molecular weight of the obtained copolymer B1 was 18,000. The mass average molecular weight (hereinafter referred to as Mw) of each synthesized copolymer was calculated by gel permeation chromatography (GPC) using HLC-8220 GPC manufactured by Tosoh Corporation, polystyrene as a standard substance, and NMP as an eluent.

[0421] [Comparative Preparation Examples B'1 to B'3] Synthesis of Comparative Copolymers B'1 to B'3 The comparative photoalignable monomers 1 to 3 and the thermally crosslinkable monomer 1 were combined according to Table 6, and comparative copolymers B'1 to B'3 were synthesized in the same manner as in the copolymer B1.

[0422] [Table 6]

[0423] [Comparative Manufacturing Example C1] Synthesis of Comparative Copolymer C1 In the same manner as in the polymer 1 described in paragraphs 0073 to 0076 and 0079 of JP2016-004142A, a monomer 1 represented by the following chemical formula (vi-1) and a monomer 2 represented by the following chemical formula (vi-2) were copolymerized in a molar ratio of 3:7 to obtain a comparative copolymer C1.

[0424] [ka]

[0425] [Examples 1 to 32] (Preparation of Thermosetting Liquid Crystal Compositions 1 to 32 Having Photoalignment Properties) The side chain type liquid crystal polymer (A) and the copolymer (B) shown in Table 7 were mixed in the mass ratio shown in Table 7 to obtain a composition. A thermosetting liquid crystal composition having photoalignment properties and having the composition shown below was prepared. Composition shown in Table 7: 0.1 parts by weight Thermal crosslinking agent (hexamethoxymethylmelamine, HMM): 0.01 parts by weight p-Toluenesulfonic acid monohydrate (PTSA): 0.001 parts by weight Propylene glycol monomethyl ether (PGME): 0.17 parts by weight Cyclohexanone: 0.4 parts by weight

[0426] [Example 33] (Preparation of Thermosetting Liquid Crystal Composition 33 Having Photoalignment Properties) A thermosetting liquid crystal composition having photoalignment properties and having the composition shown below was prepared. Side-chain liquid crystal polymer A-3: 0.09 parts by weight ·Copolymer B-1: 0.01 part by mass Polymerizable liquid crystal compound (product name LC242, manufactured by BASF): 0.01 part by mass Photopolymerization initiator (product name Omnirad 907, manufactured by IGM Resins): 0.004 parts by mass Thermal crosslinking agent (hexamethoxymethylmelamine, HMM): 0.01 parts by weight p-Toluenesulfonic acid monohydrate (PTSA): 0.001 parts by weight Propylene glycol monomethyl ether (PGME): 0.17 parts by weight Cyclohexanone: 0.4 parts by weight

[0427] [Example 34] (Preparation of thermosetting liquid crystal composition 34 having photoalignment properties) A thermosetting liquid crystal composition having photoalignment properties and having the composition shown below was prepared. Side-chain liquid crystal polymer A-3: 0.09 parts by weight ·Copolymer B-1: 0.01 part by mass Polyfunctional monomer (pentaerythritol triacrylate, PETA): 0.01 parts by weight Photopolymerization initiator (product name Omnirad 907, manufactured by IGM Resins): 0.004 parts by mass Thermal crosslinking agent (hexamethoxymethylmelamine, HMM): 0.01 parts by weight p-Toluenesulfonic acid monohydrate (PTSA): 0.001 parts by weight Propylene glycol monomethyl ether (PGME): 0.17 parts by...

Claims

1. A side-chain liquid crystal polymer (A) having a liquid crystal constituent unit containing a liquid crystal moiety in a side chain and a non-liquid crystal constituent unit containing an alkylene group in a side chain; A copolymer (B) having a photoalignable structural unit containing a photoalignable group in a side chain and a thermally crosslinkable structural unit having a structural unit represented by the following formula (2): and a crosslinking agent (C) that bonds to the thermal crosslinkable group of the thermal crosslinkable structural unit, The side chain type liquid crystal polymer (A) satisfies any one of the following (i) to (vi): (i) The side chain type liquid crystal polymer (A) has a non-liquid crystalline and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and the non-liquid crystalline and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to a primary carbon of an alkylene group which may have -O- in the carbon chain and which has a smaller total carbon number and oxygen number than the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain in the thermally crosslinkable constituent unit of the copolymer (B). (ii) The side chain type liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and the non-liquid crystal and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to a secondary carbon or a tertiary carbon of an alkylene group. (iii) The side chain type liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinkable constituent unit containing at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a mercapto group, and an amino group, and an alkylene group and an arylene group in the side chain, and the non-liquid crystal and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to an arylene group. (iv) The side chain type liquid crystal polymer (A) has a non-liquid crystalline and thermally crosslinkable constituent unit containing at least one type of thermally crosslinkable group selected from the group consisting of a carboxy group, a glycidyl group, and an amide group, and an alkylene group and an arylene group in the side chain, and the non-liquid crystalline and thermally crosslinkable constituent unit of the side chain type liquid crystal polymer (A) has a structure in which the thermally crosslinkable group is bonded to an arylene group, and the arylene group has a structure bonded to a carbon atom or oxygen atom of an alkylene group which may have -O- in the carbon chain or at the terminal, and the total number of carbon atoms and the number of oxygen atoms is 3 or more smaller than that of the linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain in the thermally crosslinkable constituent unit of the copolymer (B). (v) The side chain type liquid crystal polymer (A) has a thermally crosslinkable constituent unit that does not contain an alkylene group in the side chain and contains a thermally crosslinkable group in the side chain. (vi) The side chain type liquid crystal polymer (A) does not have a non-liquid crystal and thermally crosslinkable constituent unit containing a thermally crosslinkable group and an alkylene group in the side chain, and does not have a thermally crosslinkable constituent unit containing a thermally crosslinkable group in the side chain. 【Chemistry 1】 (In the above formula (2), Z ２ represents at least one monomer unit selected from the group consisting of the following formulas (2-1) to (2-6), R ５０ represents a linear alkylene group having 4 to 11 carbon atoms which may have -O- in the carbon chain, and Y represents at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group. 【Chemistry 2】 (In the above formulas (2-1) to (2-6), R ５１ represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group; R ５２ represents a hydrogen atom or a methyl group, R ５３ is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R ５４ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; L １２ represents a single bond, —O—, —S—, —COO—, —COS—, —CO—, or —OCO—; L １２ is a single bond, R ５０ is directly bonded to the styrene backbone.)

2. 2. The thermosetting liquid crystal composition having photoalignment properties according to claim 1, wherein the photoalignable group of the copolymer (B) is at least one selected from the group consisting of a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, a quinoline group, an azobenzene group, and a stilbene group.

3. 3. The photoalignable thermosetting liquid crystal composition according to claim 1, wherein the non-liquid crystalline and thermally crosslinkable structural unit of the side chain liquid crystal polymer (A) has a structural unit represented by the following formula (III): 【Chemistry 3】 (In the above formula (III), Z ａ represents at least one monomer unit selected from the group consisting of the following formulas (a-1) to (a-6), and R １６ Is, -L ２ａ -R １３’ A group represented by - (wherein L ２ａ represents a linear or branched alkylene group having 1 to 10 carbon atoms which may have -O- in the carbon chain, R １３’ represents a residue obtained by removing a hydrogen atom from a methyl group which may have a substituent, a residue obtained by removing a hydrogen atom from an aryl group, or -OR １５’ represents R １５’ represents a residue obtained by removing a hydrogen atom from an aryl group; ａ represents at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, a mercapto group, a glycidyl group, an amino group, and an amide group. 【Chemistry 4】 (In the above formulas (a-1) to (a-6), R １１ represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group; R １７ represents a hydrogen atom or a methyl group, R １８ is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R １９ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; L ａ represents a single bond, —O—, —S—, —COO—, —COS—, —CO—, or —OCO—; L ａ is a single bond, R １６ is directly bonded to the styrene backbone.)

4. The thermosetting liquid crystal composition having photoalignment property according to any one of claims 1 to 3, wherein the liquid crystalline constitutional unit of the side chain type liquid crystal polymer (A) has a constitutional unit represented by the following formula (I): 【Chemistry 5】 (In general formula (I), R １ represents a hydrogen atom or a methyl group, R ２ is -(CH ２ ) ｍ - or - (C ２ H ４ O) ｍ’ represents a group represented by -. １ represents a single bond, or a linking group represented by -O-, -OCO-, or -COO-, １ represents an arylene group having 6 to 10 carbon atoms which may have a substituent, １ and Ar １ may be the same or different. ３ is -F, -Cl, -CN, -OCF ３ , -OCF ２ H, -NCO, -NCS, -NO ２ , -NHCO-R ４ , -CO-OR ４ , -OH, -SH, -CHO, -SO ３ H, -NR ４ ２ , -R ５ , or -OR ５ , R ４ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ５ represents an alkyl group having 1 to 6 carbon atoms; a is an integer of 2 to 4, and m and m' are each independently an integer of 2 to 10.

5. The thermosetting liquid crystal composition having photoalignability according to any one of claims 1 to 4, wherein, among the non-liquid crystal structural units of the side chain type liquid crystal polymer (A), a non-liquid crystal and non-thermally crosslinkable structural unit has a structural unit represented by the following formula (II): 【Chemistry 6】 (In general formula (II), R １１ represents a hydrogen atom or a methyl group, R １２ Is, -L ２ -R １３ , or -L ２’ -R １４ L represents a group represented by the formula: ２ Ha-(CH ２ ) ｎ - represents L ２’ Ha-(C ２ H ４ O) ｎ’ represents a linking group represented by -; R １３ represents a methyl group which may have a substituent, an aryl group which may have an alkyl group, or -OR １５ represents R １４ and R １５ each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and n and n' each independently represent an integer of 1 to 18.

6. The thermosetting liquid crystal composition having photoalignment properties according to any one of claims 1 to 5, wherein the photoalignment structural unit of the copolymer (B) has a structural unit represented by the following formula (1): 【Chemistry 7】 (In the above formula (1), Z １ represents at least one monomer unit selected from the group consisting of the following formulas (1-1) to (1-6), X represents a photoalignment group, L １１ represents an alkylene group, a cycloalkylene group, or a combination thereof. 【Chemistry 8】 (In the above formulas (1-1) to (1-6), R ２１ represents a hydrogen atom, a methyl group, a chlorine atom, or a phenyl group; R ２２ represents a hydrogen atom or a methyl group, R ２３ is a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R ２４ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

7. An alignment film and retardation film having an alignment layer and retardation layer, 7. An alignment film serving as a retardation film, wherein the alignment layer serving as a retardation layer is a cured film of the thermosetting liquid crystal composition having photoalignment properties according to claim 1.

8. A step of forming a film of the thermosetting liquid crystal composition having photoalignment properties according to any one of claims 1 to 6; forming a cured film having a retardation layer function by heating the thermosetting liquid crystal composition formed into a film; and irradiating the cured film with polarized ultraviolet light to form a cured film having an alignment layer function.

9. A first retardation layer which is a cured film of the thermosetting liquid crystal composition having photoalignment property according to any one of claims 1 to 6; a second retardation layer containing a cured product of a polymerizable liquid crystal composition located adjacent to the first retardation layer; A retardation plate having

10. 10. The retardation plate according to claim 9, wherein the first retardation layer is a positive C-type retardation layer, and the second retardation layer is a positive A-type retardation layer.

11. A step of forming a film of the thermosetting liquid crystal composition having photoalignment properties according to any one of claims 1 to 6; forming a cured film having a retardation by heating the thermosetting liquid crystal composition formed into the film; A step of irradiating the cured film having a retardation with polarized ultraviolet light to impart liquid crystal alignment ability to the cured film, thereby forming an alignment film and a first retardation layer; a step of applying a polymerizable liquid crystal composition onto the alignment film / first retardation layer to form a coating film of the polymerizable liquid crystal composition, and heating the coating film to a phase transition temperature of the polymerizable liquid crystal composition to align liquid crystal molecules by the alignment film / first retardation layer; a step of forming a second retardation layer by irradiating the coating film of the polymerizable liquid crystal composition in which the liquid crystal molecules are aligned with light and curing the coating film; The method for producing a retardation plate comprising the steps of:

12. An optical member comprising the retardation plate according to claim 9 or 10 and a polarizing plate.

13. Preparing a polarizing plate; A step of preparing a retardation plate according to claim 9 or 10; and laminating a retardation plate and a polarizing plate.

14. A display device comprising the retardation plate according to claim 9 or 10, or an optical member containing the retardation plate and a polarizing plate.

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