Thermosetting liquid crystal compositions with optical orientation, alignment films that also serve as retardation films, methods for manufacturing the same, retardation plates and methods for manufacturing the same, optical components and methods for manufacturing the same, and display devices.

Abstract

The present application provides a thermosetting liquid crystal composition having photo-orientation, which contains: a side chain type liquid crystal polymer (A) having a liquid crystal structural unit having a liquid crystal portion in a side chain and a non-liquid crystal structural unit having an alkylene group in a side chain; a copolymer (B) having a photo-orientation structural unit having a photo-orientation group in a side chain and a thermal crosslinking structural unit having a thermal crosslinking group in a side chain, and the photo-orientation structural unit not having a linear alkylene group between the photo-orientation group and a monomer unit; and a thermal crosslinking agent (C) bonded to the thermal crosslinking group of the thermal crosslinking structural unit.

Description

Technical Field

[0001] The present invention relates to a thermosetting liquid crystal composition with photo-orientation that can form an alignment layer and a retardation layer having the functions of both an alignment layer and a retardation layer, an alignment film and a retardation film and a method thereof for manufacturing the same, a retardation plate and a method thereof for manufacturing the same, an optical component and a method thereof for manufacturing the same, and a display device. Background Technology

[0002] As optical films suitable for image display devices, there are retardation plates that impart a desired phase difference to incident light through a retardation layer. For example, in organic electroluminescent (organic EL) display devices, a quarter-wavelength retardation plate is used as a circular polarizer in combination with a linear polarizer, functioning as an anti-reflective film. Furthermore, in conventional liquid crystal display devices such as IPS displays, to improve contrast for viewing angles from oblique directions, a retardation plate composed of a positive A plate (with positive A-axis characteristics) and a positive C plate (with positive C-axis characteristics) is used as part of a polarizer compensation film (e.g., Patent Document 1).

[0003] In the past, the A-plate and C-plate were bonded together using adhesive layers.

[0004] With the trend towards thinner display devices, there is a growing demand for retardation plates, such as wideband 1 / 4 wavelength retardation plates, which are designed to address the aforementioned issues. These plates require a structure that maintains performance while also being thinner, and for more efficient manufacturing processes.

[0005] With the aim of thinning the phase retardation plate, Patent Document 2 discloses an optical film laminate, characterized in that it is formed by laminating a positive C plate and a positive A plate, wherein the orientation of a vertically aligned layer formed of a first liquid crystal material having photosensitive groups is fixed in the positive C plate, and the orientation of a horizontally aligned layer formed of a polymerizable second liquid crystal material is fixed in the positive A plate, wherein the positive A plate is directly laminated on the positive C plate, and the photosensitive groups in the positive C plate undergo photoreaction anisotropically.

[0006] On the other hand, the inventors disclosed in Patent Document 3 a photo-oriented thermosetting composition, which is a thermosetting composition containing a copolymer having both photo-oriented and thermally crosslinked sites. The purpose of this thermosetting composition, which aims to have highly sensitive photo-oriented properties and an orientation layer using it, is to contain a copolymer of a styrene monomer having photo-oriented groups and a monomer having thermally crosslinked groups, and a crosslinking agent. However, Patent Document 3 makes no mention of using this thermosetting composition to form a phase retardation layer.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent No. 4592005

[0010] Patent Document 2: Japanese Patent Application Publication No. 2016-004142

[0011] Patent Document 3: Japanese Patent No. 5626493 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] In Patent Document 2, the aforementioned positive A plate is directly stacked onto the aforementioned positive C plate for the purpose of thinning the phase retardation plate. However, the positive C plate described in Patent Document 2 is formed using a first liquid crystal material, which has a structure in which photo-orientation groups, which are photosensitive groups, are bonded to the ends of the liquid crystal components with vertical orientation. Therefore, the vertical orientation of the positive C plate itself is poor, and consequently, the ability of the liquid crystal material of the directly stacked positive A plate to orient itself (liquid crystal orientation energy) is also poor. In addition, the durability of the positive C plate in Patent Document 2 is insufficient, and there is also the following problem: due to heating and solvent penetration when the liquid crystal material of the positive A plate is stacked on the positive C plate, the vertical orientation of the positive C plate is prone to change.

[0014] Furthermore, the retardation plate, in which a positive A plate is directly laminated onto a positive C plate, which is a cured product of a photocurable resin composition containing a polymerizable liquid crystal compound, has the following problems: insufficient adhesion between the positive C plate and the positive A plate, and poor bending resistance. This is because if the positive C plate, as a cured product of the photocurable resin composition, is fully cured to achieve good vertical orientation, it becomes hard and brittle. Insufficient adhesion results in the positive C plate not being transferred along with the positive A plate during transfer printing, leaving residue on the substrate. Additionally, poor bending resistance makes this retardation plate unsuitable for use in flexible displays.

[0015] The present invention was made in view of the above-mentioned problems, and its first object is to provide a thermosetting liquid crystal composition with photo-orientation properties that can form an alignment layer and a retardation layer with excellent vertical orientation and excellent ability to orient directly stacked liquid crystal materials, an alignment film and a retardation film and a method for manufacturing the same, a retardation plate containing the above-mentioned alignment layer and retardation layer and a method for manufacturing the same, an optical component and a method for manufacturing the same, and a display device.

[0016] Furthermore, the present invention was made in view of the above-mentioned problems, and its second object is to provide a thermosetting liquid crystal composition with optical orientation that can form an alignment layer and retardation layer exhibiting good vertical orientation and the ability to orient directly stacked liquid crystal materials and has durability, an alignment film and retardation film and a method for manufacturing the same, a retardation plate containing the above-mentioned alignment layer and retardation layer and a method for manufacturing the same, an optical component and a method for manufacturing the same, and a display device.

[0017] Furthermore, the present invention was made in view of the above-mentioned problems, and its third objective is to provide a phase retardation plate having a positive C-type phase retardation layer and a positive A-type phase retardation layer directly laminated with good adhesion and good bending resistance, as well as a method for manufacturing the same, an optical component and a method for manufacturing the same, and a display device.

[0018] Technical means to solve the problem

[0019] To achieve the first objective mentioned above, the present invention provides a first photo-oriented thermosetting liquid crystal composition comprising:

[0020] A side-chain type liquid crystal polymer (A) having liquid crystal structural units containing liquid crystal moieties in the side chains and non-liquid crystal structural units containing alkylene groups in the side chains.

[0021] A copolymer (B) having a photooriented structural unit having a structural unit represented by the following formula (1) and a thermally crosslinked structural unit having thermally crosslinked groups in the side chain, and

[0022] A thermal crosslinking agent (C) bonded to the thermal crosslinking groups of the above-mentioned thermal crosslinking structural units.

[0023] [Chemical Formula 1]

[0024] Equation (1)

[0025]

[0026] (In the above formula (1), Z) 1 The expression represents at least one monomer unit selected from formulas (1-1) to (1-6) below, where X represents a photooriented group, and L represents a photooriented group. 11 (This refers to a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, or combinations thereof with aryl groups)

[0027] [Chemical Formula 2]

[0028]

[0029] (In the above equations (1-1) to (1-6), R) 21 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 22 R represents a hydrogen atom or a methyl group.23 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 24 (This refers to a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[0030] In the first photo-oriented thermosetting liquid crystal composition of the present invention, the photo-oriented group of the copolymer (B) is at least one selected from cinnamyl, chalcone, coumarin, anthracene, quinolinyl, azophenyl, and styrene.

[0031] Furthermore, in the first photo-oriented thermosetting liquid crystal composition of the present invention, the aforementioned thermal crosslinking group may contain at least one selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups.

[0032] Furthermore, in the first photo-oriented thermosetting liquid crystal composition of the present invention, in terms of improving the vertical orientation of the phase difference layer, it is preferable that the liquid crystal structural unit of the side chain type liquid crystal polymer (A) has the structural unit represented by the following formula (I).

[0033] [Chemical Formula 3]

[0034] Formula (I)

[0035]

[0036] (In general formula (I), R) 1 R represents a hydrogen atom or a methyl group. 2 It represents -(CH2) m -or-(C2H4O) m' - represents the group; L 1 Ar represents a single bond, or a linking group represented by -O-, -OCO-, or -COO-. 1 This indicates an optional arylene group with 6 to 10 carbon atoms having substituents, and multiple L... 1 and Ar 1 They can be the same or different; R 3 This indicates -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2. -R 5 or -OR 5 R 4 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 5 This indicates an alkyl group having 1 to 6 carbon atoms; a is an integer from 2 to 4, and m and m' are each independently an integer from 2 to 10.

[0037] To achieve the second objective mentioned above, the present invention provides a second photo-oriented thermosetting liquid crystal composition comprising:

[0038] A side-chain type liquid crystal polymer (A) having liquid crystal structural units containing liquid crystal moieties in the side chains and non-liquid crystal structural units containing alkylene groups in the side chains.

[0039] A copolymer (B) having photooriented structural units containing photooriented groups in the side chains and thermally crosslinked structural units having structural units represented by the following formula (2), and

[0040] The thermal crosslinking agent (C) bonded to the thermal crosslinking groups of the above-mentioned thermal crosslinking structural unit, and

[0041] The above-mentioned side-chain liquid crystal polymer (A) satisfies any one of (i) to (vi) below.

[0042] In order to achieve the second objective, the composition of the second photo-oriented thermosetting liquid crystal composition can be applied to the first photo-oriented thermosetting liquid crystal composition described above.

[0043] (i) The aforementioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing a thermally crosslinking group and an alkylene group in the side chain. The non-liquid crystal and thermally crosslinked structural unit of the aforementioned side-chain liquid crystal polymer (A) has a structure in which the aforementioned thermally crosslinking group is bonded to a primary carbon of an alkylene group optionally having -O- in the carbon chain. The total number of carbons and oxygens of the alkylene group is smaller than that of the linear alkylene group of the thermally crosslinked structural unit of the aforementioned copolymer (B), which optionally has 4 to 11 carbons having -O- in the carbon chain.

[0044] (ii) The above-mentioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing a thermally crosslinking group and an alkylene group in the side chain, and the non-liquid crystal and thermally crosslinked structural unit of the above-mentioned side-chain liquid crystal polymer (A) has a structure in which the thermally crosslinking group is bonded to a secondary or tertiary carbon of the alkylene group.

[0045] (iii) The above-mentioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing at least one thermally crosslinking group selected from hydroxyl, mercapto, and amino, an alkylene group, and an arylene group in its side chain, and the non-liquid crystal and thermally crosslinked structural unit of the above-mentioned side-chain liquid crystal polymer (A) has a structure in which the above-mentioned thermally crosslinking group is bonded to the arylene group.

[0046] (iv) The aforementioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing at least one thermally crosslinking group selected from carboxyl, glycidyl, and amide groups, an alkylene group, and an arylene group in its side chain. The non-liquid crystal and thermally crosslinked structural unit of the aforementioned side-chain liquid crystal polymer (A) has a structure in which the aforementioned thermally crosslinking group is bonded to an arylene group, and has a structure in which the arylene group is bonded to a carbon atom or oxygen atom of an alkylene group optionally having a -O- at the end of the carbon chain. The total number of carbon atoms and oxygen atoms of the alkylene group is at least 3 fewer than the number of carbon atoms (4 to 11) of the linear alkylene group optionally having a -O- at the end of the carbon chain in the thermally crosslinked structural unit of the aforementioned copolymer (B).

[0047] (v) The above-mentioned side-chain liquid crystal polymer (A) has a thermally crosslinked structural unit in which the side chain does not contain alkylene groups and contains thermally crosslinked groups.

[0048] (vi) The above-mentioned side-chain type liquid crystal polymer (A) does not have non-liquid crystal properties and thermally crosslinked structural units containing thermally crosslinked groups and alkylene groups in the side chains, nor does it have thermally crosslinked structural units containing thermally crosslinked groups in the side chains.

[0049] [Chemical Formula 4] (2)

[0051]

[0052] (In the above formula (2), Z) 2 R represents at least one monomer unit selected from the following formulas (2-1) to (2-6). 50 The alkylene group is a straight-chain alkylene group with 4 to 11 carbon atoms, optionally having an -O- group in the carbon chain. Y represents at least one thermally crosslinking group selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups.

[0053] [Chemical Formula 5]

[0054]

[0055] (In the above equations (2-1) to (2-6), R) 51 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 52 R represents a hydrogen atom or a methyl group. 53 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 54 L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 12 Indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-, in L 12 In the case of a single bond, R 50 It bonds directly to the styrene skeleton.

[0056] Regarding the second photo-oriented thermosetting liquid crystal composition of the present invention, in terms of ease of raw material supply, it is preferable that the non-liquid crystal and thermally crosslinkable structural unit of the above-mentioned side-chain type liquid crystal polymer (A) has the structural unit represented by the following formula (III).

[0057] In the first photo-oriented thermosetting liquid crystal composition described above, the structural unit represented by the following formula (III) of the second photo-oriented thermosetting liquid crystal composition can be applied.

[0058] [Chemical Formula 6]

[0059] Equation (III)

[0060]

[0061] (In equation (III) above, Z) a R represents at least one monomer unit selected from the following formulas (a-1) to (a-6). 16 -L 2a -R 13' - The group represented (here, L) 2a R represents a straight-chain or branched alkylene group having 1 to 10 carbon atoms in its carbon chain, optionally containing an -O- group. 13 'Indicates a residue from which a hydrogen atom is removed from an optional methyl group, a residue from which a hydrogen atom is removed from an aryl group, or -OR 15′ R 15′ This indicates a residue from which a hydrogen atom has been removed from an aryl group. a (This indicates at least one thermally crosslinkable group selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups.)

[0062] [Chemical Formula 7]

[0063]

[0064] (In the above formulas (a-1) to (a-6), R) 11 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 17 R represents a hydrogen atom or a methyl group. 18 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 19 L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a Indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-, in L a In the case of a single bond, R 16 It bonds directly to the styrene skeleton.

[0065] In addition, the present invention provides a first or second alignment film that also serves as a retardation film, which contains an alignment layer that also serves as a retardation layer, and the alignment layer that also serves as a retardation layer is a cured film of the first or second photo-oriented thermosetting liquid crystal composition of the present invention.

[0066] Furthermore, the present invention provides a method for manufacturing a first or second orientation film that also serves as a retardation film, comprising:

[0067] The process of forming a film of the first or second photo-oriented thermosetting liquid crystal composition of the present invention.

[0068] The process of forming a cured film with a phase difference by heating the thermosetting liquid crystal composition formed above, and...

[0069] The process of imparting liquid crystal alignment energy to the aforementioned cured film by irradiating it with polarized ultraviolet light with a phase difference.

[0070] Additionally, the present invention provides a first or second phase difference plate, comprising:

[0071] As the first phase difference layer of the cured film of the first or second photo-oriented thermosetting liquid crystal composition of the present invention, and

[0072] A second phase retardation layer comprising a cured material containing a polymeric liquid crystal composition is disposed directly adjacent to the first phase retardation layer.

[0073] In the first or second phase retardation plate of the present invention, a phase retardation plate that improves viewing angle characteristics can be efficiently manufactured. In terms of effectively exerting the effects of the present invention, it is preferred that the first phase retardation layer is a positive C-type phase retardation layer and the second phase retardation layer is a positive A-type phase retardation layer.

[0074] In addition, the present invention provides a method for manufacturing a first or second phase retardation plate, comprising:

[0075] The process of forming a film of the first or second photo-oriented thermosetting liquid crystal composition of the present invention;

[0076] A process of forming a cured film with a phase difference by heating the thermosetting liquid crystal composition formed above;

[0077] The process of irradiating the aforementioned cured film with phase difference with polarized ultraviolet light to impart liquid crystal alignment energy to the cured film, thereby forming an alignment film that also serves as a first phase difference layer.

[0078] A process in which a polymerizable liquid crystal composition is coated onto the alignment film and first retardation layer to form a coating of the polymerizable liquid crystal composition, and the coating is heated to the phase transition temperature of the polymerizable liquid crystal composition, thereby aligning liquid crystal molecules using the alignment film and retardation layer; and

[0079] The process of curing a coating of a polymeric liquid crystal composition in which the above-mentioned liquid crystal molecules have been oriented by light to form a second phase retardation layer.

[0080] In addition, to achieve the third objective mentioned above, the present invention provides a third phase difference plate, which comprises:

[0081] As a positive C-type phase retardation layer of a cured thermosetting resin composition containing photooriented components and a thermal crosslinking agent, and

[0082] A positive A-type phase retardation layer containing a polymeric liquid crystal composition is disposed directly adjacent to the aforementioned positive C-type phase retardation layer.

[0083] In the third phase retardation plate of the present invention, the thickness direction phase difference Rth at a wavelength of 550nm is -35nm to 35nm, the in-plane phase difference Re at a wavelength of 550nm is more than 100nm, and the total thickness of the positive C-type phase retardation layer and the positive A-type phase retardation layer can be 0.2μm to 6μm.

[0084] In the third phase retardation plate of the present invention, the composite elastic modulus of the above-mentioned positive C-type phase retardation layer can be 4.5 GPa or more and 9.0 GPa or less.

[0085] The third phase retardation plate of the present invention may contain a substrate disposed directly adjacent to the above-mentioned positive C-type phase retardation layer.

[0086] In the third retardation plate of the present invention, the aforementioned positive C-type retardation layer may include a region infiltrated by a specific component contained in the aforementioned positive A-type retardation layer. Furthermore, the aforementioned specific component may contain a polymeric liquid crystal compound or a cured form thereof.

[0087] In addition, the present invention provides a method for manufacturing a third phase difference plate, which includes:

[0088] The process of forming a film of a photo-oriented thermosetting liquid crystal composition, wherein the photo-oriented thermosetting liquid crystal composition comprises: a side-chain type liquid crystal polymer having a liquid crystal structural unit having a liquid crystal portion in the side chain, a copolymer having a photo-oriented structural unit and a thermally crosslinking structural unit having a thermally crosslinking group in the side chain, and a thermally crosslinking agent bonded to the thermally crosslinking group of the aforementioned thermally crosslinking structural unit.

[0089] A process of forming a cured film with a phase difference by heating the thermosetting liquid crystal composition formed above;

[0090] The process of forming a positive C-type phase difference layer that imparts liquid crystal alignment energy is achieved by irradiating the above-mentioned cured film with phase difference with polarized ultraviolet light.

[0091] A process involving coating a polymerizable liquid crystal composition onto the aforementioned positive C-type retardation layer to form a coating film of the polymerizable liquid crystal composition, heating the coating film to the phase transition temperature of the polymerizable liquid crystal composition, thereby aligning liquid crystal molecules using the aforementioned positive C-type retardation layer; and

[0092] The process involves curing a coating of a polymeric liquid crystal composition in which the above-mentioned liquid crystal molecules have been oriented by light to form a positive A-type phase retardation layer.

[0093] In addition, the present invention provides an optical component comprising a first, second, or third phase difference plate and a polarizing plate.

[0094] In addition, the present invention provides a method for manufacturing an optical component, which comprises:

[0095] The process of preparing polarizing plates;

[0096] The process of preparing the first, second, or third phase difference plates; and

[0097] The process of stacking phase difference plates and polarizing plates.

[0098] In addition, the present invention provides a display device having a first, second or third phase retardation plate, or an optical component containing the phase retardation plate and a polarizing plate.

[0099] Invention Effects

[0100] In the first invention, the following effects are achieved: a thermosetting liquid crystal composition with photo-orientation properties that can form an alignment layer and retardation layer with excellent vertical orientation and excellent ability to orient directly stacked liquid crystal materials, an alignment film and retardation film and a method for manufacturing the same, a retardation plate containing the above-mentioned alignment layer and retardation layer and a method for manufacturing the same, an optical component and a method for manufacturing the same, and a display device.

[0101] In the second invention, the following effects are achieved: a thermosetting liquid crystal composition with photo-orientation that can form a durable alignment layer and retardation layer with good vertical orientation and the ability to orient directly stacked liquid crystal materials is provided; an alignment film and retardation film and a method for manufacturing the same thereof; a retardation plate containing the above-mentioned alignment layer and retardation layer and a method for manufacturing the same thereof; an optical component and a method for manufacturing the same thereof; and a display device are provided.

[0102] Furthermore, in the third invention, the following effects are achieved: a phase retardation plate having a positive C-type phase retardation layer and a positive A-type phase retardation layer directly laminated with good adhesion and good bending resistance, and a method for manufacturing the same, as well as an optical component using the phase retardation plate and a method for manufacturing the same, and a display device. Attached Figure Description

[0103] Figure 1This is a schematic cross-sectional view showing an example of the orientation film and phase difference film of the present invention.

[0104] Figure 2 This is a schematic cross-sectional view showing an example of the orientation film and phase difference film of the present invention.

[0105] Figure 3 This is a schematic cross-sectional view showing an example of the orientation film and phase difference film of the present invention.

[0106] Figure 4 This is a schematic cross-sectional view showing an example of the phase difference plate of the present invention.

[0107] Figure 5 This is a schematic cross-sectional view showing an example of the phase difference plate of the present invention.

[0108] Figure 6 This is a schematic cross-sectional view showing an example of the optical component of the present invention.

[0109] Figure 7 (A) to (C) are diagrams used to illustrate the method of dynamic bending test. Detailed Implementation

[0110] Hereinafter, embodiments and examples of the present invention will be described with reference to the accompanying drawings. However, the present invention can be implemented in many different ways and is not limited to the embodiments and examples described below. Furthermore, regarding the drawings, for the purpose of clarity, there are instances where the width, thickness, shape, etc., of each part are schematically shown compared to the actual embodiment; these are merely examples and do not limit the interpretation of the present invention. Additionally, in this specification and the drawings, sometimes the same symbols are used for the same elements described above as in previously shown figures, and detailed descriptions are appropriately omitted. Furthermore, for ease of explanation, phrases such as "above" or "below" are sometimes used, but the vertical direction can be reversed.

[0111] "In this specification, when a component or region is described as being located 'above (or below)' other components or regions, unless otherwise specified, it includes not only being located immediately above (or immediately below) other components, but also being located above (or below) other components, that is, it also includes the case where other components are located between the above (or below) other components."

[0112] In this invention, the so-called orientation confinement force refers to the effect of aligning the liquid crystal compounds in the phase difference layer along a specific direction.

[0113] In this invention, the term (meth)acryloyl group refers to either acryloyl group or methacryloyl group, and the term (meth)acrylate refers to either acrylate or methacrylate.

[0114] Furthermore, in this specification, the terms "plate," "sheet," and "membrane" are not distinguished from each other solely based on different names. The term "membrane surface (plate surface, sheet surface)" refers to the surface that is aligned with the plane of the membrane-like (plate-like, sheet-like) component when viewed as a whole and globally.

[0115] Furthermore, in this invention, the term "~" indicating a numerical range is used to mean that the numerical values ​​before and after it are included as the lower limit and the upper limit.

[0116] It should be noted that, in this invention, the term "orientation layer and retardation layer" refers to a layer that is itself a retardation layer and has the ability to orient directly stacked liquid crystal materials; it can be replaced with "retardation layer that imparts orientation energy to liquid crystals." Furthermore, in this invention, "orientation layer and retardation layer" refers to a retardation layer that functions as an orientation layer; it can also be replaced with "retardation layer that functions as an orientation layer."

[0117] In this invention, "alignment film and phase reversal film" can also be replaced with "phase reversal film that functions as an alignment film" or "phase reversal film that imparts alignment energy to liquid crystal".

[0118] Furthermore, in this invention, "optionally having -O- in the carbon chain...alkylene" means "optionally having -O- in the carbon chain, i.e., alkylene other than at the end, where both ends of the alkylene are carbon atoms," and "optionally having -O- in the carbon chain or at the end" means "not only in the carbon chain, but also at the end, where -O- can be present in the alkylene, where both ends of the alkylene are carbon atoms or oxygen atoms."

[0119] Hereinafter, the photo-oriented thermosetting liquid crystal composition, the alignment film and retardation film using the same, and the manufacturing method thereof, as well as the retardation plate and the manufacturing method thereof, of the present invention will be described in detail.

[0120] I. The First Invention

[0121] A. A thermosetting liquid crystal composition with photo-orientation properties

[0122] The photo-oriented thermosetting liquid crystal composition of the present invention is characterized by containing:

[0123] A side-chain type liquid crystal polymer (A) having liquid crystal structural units containing liquid crystal portions in the side chains and non-liquid crystal structural units containing alkylene groups in the side chains; a copolymer (B) having photo-oriented structural units having structural units represented by the following formula (1) and thermally crosslinked structural units containing thermally crosslinked groups in the side chains; and

[0124] A thermal crosslinking agent (C) bonded to the thermal crosslinking groups of the above-mentioned thermal crosslinking structural units.

[0125] [Chemical Formula 8]

[0126] Equation (1)

[0127]

[0128] (In the above formula (1), Z) 1 The expression represents at least one monomer unit selected from formulas (1-1) to (1-6) below, where X represents a photooriented group, and L represents a photooriented group. 11 (This indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, or combinations thereof with aryl groups.)

[0129] [Chemical Formula 9]

[0130]

[0131] (In the above equations (1-1) to (1-6), R) 21 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 22 R represents a hydrogen atom or a methyl group. 23 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 24 (This refers to a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[0132] The photo-oriented thermosetting liquid crystal composition of the present invention contains the above-mentioned side-chain type liquid crystal polymer (A), a copolymer (B) of photo-oriented structural units and thermally crosslinked structural units that have the ability to orient directly stacked liquid crystal materials, and a thermally crosslinking agent (C) bonded to the thermally crosslinked groups of the above-mentioned thermally crosslinked structural units. Therefore, by forming a cured film of the composition, an orientation layer and a phase retardation layer that functions as both an orientation layer and a phase retardation layer can be formed, which has excellent vertical orientation and excellent ability to orient directly stacked liquid crystal materials.

[0133] In the photo-oriented thermosetting liquid crystal composition of the present invention, the copolymer (B) having photo-oriented structural units has the following structure: no alkylene chains are present between the photo-oriented groups and the main chain of the copolymer. It is presumed that the copolymer (B) becomes more non-liquid crystal-like due to the absence of alkylene chains in its photo-oriented structural units, thus reducing its compatibility with the aforementioned side-chain type liquid crystal polymer (A) and making it easier to separate from the aforementioned side-chain type liquid crystal polymer (A). Furthermore, it is presumed that the copolymer (B) has increased rigidity due to the absence of alkylene chains in its photo-oriented structural units, making it easier to reduce the distance between the photo-oriented groups and improve photo-orientation (liquid crystal orientation energy). In addition, unlike low-molecular-weight polymerizable liquid crystal compounds, the aforementioned side-chain type liquid crystal polymer (A) is easily disposed on the substrate side even when mixed with the copolymer (B), and its vertical orientation is easily improved. As a result, the copolymer (B) is also easily disposed on the air interface side, and its photo-orientation is easily improved. Considering these synergistic effects, in the photo-oriented thermosetting liquid crystal composition of the present invention, the aforementioned side-chain type liquid crystal polymer (A) exhibiting phase difference due to vertical orientation and the copolymer (B) having photo-oriented structural units exhibiting orientation of directly stacked liquid crystal materials are less likely to impair each other's properties. By forming a cured film of this composition, it is possible to achieve an orientation layer and phase difference layer with excellent vertical orientation and excellent ability to orient directly stacked liquid crystal materials in a single layer.

[0134] Furthermore, the photo-oriented thermosetting liquid crystal composition according to the present invention contains a copolymer having both photo-oriented structural units and thermally crosslinked structural units, and a thermally crosslinking agent. Therefore, if thermal curing is performed, the film has good heat resistance and solvent resistance due to its crosslinked structure, and a highly durable orientation layer and phase retardation layer can be obtained.

[0135] Furthermore, the orientation layer and retardation layer of the cured product of the photo-oriented thermosetting liquid crystal composition of the present invention are cross-linked with each other by a thermal cross-linking agent. Therefore, compared with the case of the cured product of the photocurable resin composition containing polymeric liquid crystal compound, it is less prone to hardening and has flexibility, and the adhesion to the directly laminated liquid crystal material is also good. Therefore, according to the orientation layer and retardation layer of the cured product of the photo-oriented thermosetting liquid crystal composition of the present invention, a thin retardation plate with good bending resistance, in which the first retardation layer and the second retardation layer are directly laminated with good adhesion, can be obtained as described in the third invention below.

[0136] The components of the photo-oriented thermosetting liquid crystal composition of the present invention will be described below.

[0137] 1. Side-chain type liquid crystal polymer (A)

[0138] The side-chain type liquid crystal polymer (A) used in this invention has liquid crystal structural units containing liquid crystal portions in the side chains and non-liquid crystal structural units containing alkylene groups in the side chains.

[0139] The structural units of the side-chain liquid crystal polymer (A) will be described below.

[0140] (1) Liquid crystal structure unit

[0141] In embodiments of the present invention, the liquid crystal structural unit has side chains containing liquid crystal portions, i.e., portions exhibiting liquid crystal properties. The liquid crystal structural unit is preferably a structural unit in which liquid crystal moieties exhibiting liquid crystal properties are present in the side chains. The liquid crystal structural unit is preferably a structural unit derived from a liquid crystal-sensitive compound whose polymeric groups are bonded to the liquid crystal moieties via spacer groups. In the present invention, a liquid crystal moieties refer to a portion with high rigidity exhibiting liquid crystal properties; examples include portions having two or more ring structures, preferably three or more ring structures, where the ring structures are connected to each other by direct bonding or by one to three atoms. By having such liquid crystal-sensitive portions in the side chains, the liquid crystal structural unit becomes easier to align vertically.

[0142] The aforementioned ring structure can be an aromatic ring such as benzene, naphthalene, or anthracene, or a cyclic aliphatic hydrocarbon such as cyclopentyl or cyclohexyl.

[0143] Furthermore, when the ring structure is connected by one to three atoms, the structures that serve as the connecting part can be: -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)-O-, -NR-C(=O)-NR-, -OC(=O)-NR-, -NR-C(=O)-O-, -NR-C(=O)-NR-, -O-NR-, or -NR-O- (where R is a hydrogen atom or a hydrocarbon group), etc.

[0144] Among them, as liquid crystal units, it is preferable to form rod-shaped liquid crystal units with the above-mentioned ring structure in the form of rods, which are connected at the para position in the case of benzene and at the 2 and 6 positions in the case of naphthalene.

[0145] Furthermore, when the liquid crystal structural unit is a structural unit containing liquid crystal elements that display liquid crystal properties in its side chains, in terms of vertical orientation, it is preferable that the end of the side chain of this structural unit is a polar group or has an alkyl group. 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 -OR” (R' is a hydrogen atom or a hydrocarbon group, and R” is an alkyl group), etc.

[0146] Examples of liquid crystal structural units include those with -R 2 -(L 1 -Ar 1 ) a -R 3 The group represented (here, R) 2 It represents -(CH2) m -or-(C2H4O) m' - represents the group; L 1 Ar represents a single bond, or a linking group represented by -O-, -OCO-, or -COO-. 1 This indicates an optional arylene group with 6 to 10 carbon atoms having substituents, and multiple L... 1 and Ar 1 They can be the same or different; R 3 This indicates -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2. -R 5 or -OR 5 R 4 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 5 ) represents an alkyl group having 1 to 6 carbon atoms; a is an integer from 2 to 4, and m and m' are each an integer from 2 to 10 independently. ) as a structural unit for the side chain.

[0147] R 2 m and m' are each independently an integer from 2 to 10. In terms of vertical orientation, m and m' are preferably 2 to 8, and more preferably 2 to 6.

[0148] As Ar 1 The optional arylene group having 6 to 10 carbon atoms and substituents can be exemplified by: phenylene, naphthylene, etc., with phenylene being more preferred. R may be present as the arylene group. 3Other substituents include alkyl groups having 1 to 5 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms, and other halogen atoms.

[0149] R 3 R in 4 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Additionally, R 3 R in 5 It is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms.

[0150] The liquid crystal structural unit is preferably a structural unit derived from a monomer having a group containing a polymerizable olefinic double bond. Examples of such monomers having a group containing an olefinic double bond include derivatives such as (meth)acrylates, styrene, (meth)acrylamide, maleimide, vinyl ethers, or vinyl esters. Regarding vertical orientation, structural units derived from (meth)acrylate derivatives are preferred as liquid crystal structural units.

[0151] In embodiments of the present invention, as a liquid crystal structural unit, in terms of vertical orientation, it is preferable to include a structural unit represented by the following general formula (I).

[0152] [Chemical Formula 10]

[0153] Formula (I)

[0154]

[0155] (In general formula (I), R) 1 R represents a hydrogen atom or a methyl group. 2 It represents -(CH2) m -or-(C2H4O) m' - represents the group; L 1 Ar represents a single bond, or a linking group represented by -O-, -OCO-, or -COO-. 1 This indicates an optional arylene group with 6 to 10 carbon atoms having substituents, and multiple L... 1 and Ar 1 They can be the same or different; R 3 This indicates -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2. -R 5 or -OR 5 R 4 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 5This indicates an alkyl group having 1 to 6 carbon atoms; a is an integer from 2 to 4, and m and m' are each independently an integer from 2 to 10.

[0156] In the structural unit represented by general formula (I), -R 2 -(L 1 -Ar 1 ) a -R 3 The groups represented can be the same as those described above.

[0157] Preferred examples of liquid crystal structure units represented by general formula (I) include those represented by the following general formulas (I-1), (I-2) and (I-3), but are not limited to these.

[0158] [Chemical Formula 11]

[0159]

[0160] Here, in the structural units represented by the above general formulas (I-1) to (I-3), R 2 and R 3 R, respectively, with general formula (I) 2 and R 3 same.

[0161] In embodiments of the present invention, the liquid crystal structural unit may be used alone or in combination of two or more.

[0162] Monomers such as (meth)acrylate derivatives that derive liquid crystal structural units can be used in the synthesis of copolymers. Monomers such as (meth)acrylate derivatives that derive liquid crystal structural units can be used alone or in combination of two or more.

[0163] Regarding the content ratio of the aforementioned liquid crystal structural units in the copolymer, in order to improve the vertical orientation of the liquid crystal structural units and have sufficient liquid crystal orientation, when the amount of structural units contained in the copolymer as a whole is set to 100 mol%, it is preferably set in the range of 40 mol% to 90 mol%, more preferably in the range of 40 mol% to 80 mol%, even more preferably in the range of 45 mol% to 70 mol%, and particularly preferably in the range of 50 mol% to 65 mol%.

[0164] It should be noted that the content ratio of each structural unit in the copolymer can be determined by... 1 It is calculated from the integrated value of H-NMR measurement.

[0165] (2) Non-liquid crystal structural units containing alkylene groups in the side chain

[0166] The non-liquid-liquid-state structural unit containing alkylene side chains has the following effect: when the side-chain type liquid crystal polymer is in a liquid crystal state, the alkylene-containing side chain promotes the homeotropic alignment of the liquid crystal-displaying portion (liquid crystal moiety) of the side chain of the aforementioned liquid crystal structural unit. By including the non-liquid-liquid-state structural unit containing alkylene side chains, the homeotropic alignment of the side-chain type liquid crystal polymer (A) is improved, and its solvent solubility is also improved.

[0167] Examples of non-liquid crystal structural units containing alkylene groups in their side chains include those with -L 2 -R 13 or -L 2 '-R 14 The group represented (here, L) 2 It represents -(CH2) n -, L 2 'Indicates -(C2H4O)' n' - Represents the linking group, R 13 This indicates a methyl group optionally having a substituent, an aryl group optionally having an alkyl group, or -OR. 15 R 14 and R 15 Each of the following independently represents an alkyl group or an aryl group optionally having a substituent, where n and n' are each an integer from 1 to 18. ) as structural units of the side chain.

[0168] L 2 It represents -(CH2) n -, L 2 'Indicates -(C2H4O)' n' -The linking group represented, wherein -(CH2) is preferred in terms of ease of achieving good vertical orientation. n - Additionally, n is an integer from 1 to 18, preferably an integer from 2 to 18. In R 13 When n is a methyl group with a substituent or an alkyl group with a substituent, it is also preferable to use an integer of 1. In addition, n′ is an integer from 1 to 18, preferably an integer from 1 to 8, and more preferably an integer from 2 to 8.

[0169] As R 14 and R 15 The alkyl group can be straight-chain, branched, or cyclic, with a preference for straight-chain.

[0170] As R 14 and R 15The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, specifically including: straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl; branched-chain alkyl groups such as isopropyl, isobutyl, and tert-butyl; alkenyl groups such as 1-propenyl and 1-butenyl; alkynyl groups such as ethynyl and 2-propynyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norpyrenyl, and adamantyl; and cycloalkenyl groups such as 1-cyclohexenyl. In the case of the above-mentioned cycloalkyl groups, cycloalkyl groups substituted with straight-chain alkyl groups are preferred.

[0171] R 14 and R 15 The alkyl group is not particularly limited, but in terms of the in-plane uniformity of the phase difference, an alkyl group with 1 to 12 carbon atoms is preferred.

[0172] As R 13 R 14 and R 15 The aryl group is preferably an aryl group with 6 to 20 carbon atoms, specifically including phenyl, naphthyl, anthracene, etc., wherein phenyl or naphthyl is preferred, and phenyl is more preferred. In the case of the above-mentioned aryl group, a linear alkyl-substituted aryl group is preferred.

[0173] The non-liquid crystal structural unit containing alkylene in the side chain may optionally have reactive groups that react with other components as substituents, for example, may optionally have the same thermal crosslinking groups as the copolymer (B) described below.

[0174] Examples of non-liquid crystal structural units containing alkylene groups in their side chains include: non-liquid crystal and non-crosslinked structural units, and non-liquid crystal and thermally crosslinked structural units. Non-liquid crystal structural units containing alkylene groups in their side chains may contain only non-liquid crystal and non-crosslinked structural units, or only non-liquid crystal and thermally crosslinked structural units.

[0175] As a non-liquid crystal structural unit containing alkylene in the side chain, it is preferable to contain at least a non-liquid crystal and non-crosslinked structural unit in terms of easy improvement of vertical orientation. More preferably, it contains both a non-liquid crystal and non-crosslinked structural unit and a non-liquid crystal and thermally crosslinked structural unit in terms of easy improvement of vertical orientation and easy improvement of durability.

[0176] In non-liquid crystal and non-crosslinked structural units with alkylene side chains, as R 13 The methyl group may optionally have substituents and R 14 and R 15 The alkyl group may optionally have substituents, including non-crosslinking substituents such as halogen atoms (e.g., fluorine, chlorine, bromine), alkoxy groups, and nitro groups. Halogen atoms (e.g., fluorine, chlorine, bromine) are preferred.

[0177] In non-liquid crystal and non-crosslinked structural units with alkylene side chains, as R 13 R 14 and R 15 The aryl group may contain any substituents, including non-crosslinking substituents such as halogen atoms (e.g., fluorine, chlorine, bromine), alkyl groups, alkoxy groups, and nitro groups. The alkyl group may be 1 to 12 carbon atoms or 1 to 9 carbon atoms, and may be a straight-chain alkyl group or an alkyl group containing branches or ring structures. Preferably, the alkyl group contains halogen atoms (e.g., fluorine, chlorine, bromine) and has 1 to 9 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and cyclohexylpropyl. The hydrogen atoms in the alkyl group may be replaced with halogen atoms.

[0178] In non-liquid crystal and thermally crosslinked structural units with alkylene side chains, as R 13 methyl, R 14 and R 15 Alkyl groups, and R 13 R 14 and R 15 The aryl group may optionally have substituents, preferably thermally crosslinking groups. Examples of such thermally crosslinking groups are those similar to those in copolymer (B) described below, and may include at least one selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, amide, hydroxymethyl, alkoxymethyl, trialkoxysilyl, capped isocyanate, and alkoxy groups substituted on the methyl group. The hydroxymethyl and alkoxymethyl groups, as self-crosslinking groups, may be formed by the hydroxyl and alkoxy groups on the R group. 13 It can be substituted to form hydroxymethyl or alkoxymethyl.

[0179] As a thermally crosslinking group, the hydroxyl group is preferred in terms of reactivity, and more preferably a primary hydroxyl group. It should be noted that a primary hydroxyl group refers to a hydroxyl group to which the carbon atom bonded is a primary carbon atom.

[0180] The non-liquid crystal structural unit is preferably a structural unit derived from a monomer having a group containing a polymerizable olefinic double bond. Examples of such monomers having a group containing an olefinic double bond include derivatives of (meth)acrylate, styrene, (meth)acrylamide, maleimide, vinyl ether, or vinyl ester. In terms of vertical orientation, the non-liquid crystal structural unit is preferably a structural unit derived from a (meth)acrylate derivative or styrene, and more preferably a structural unit derived from a (meth)acrylate derivative.

[0181] In embodiments of the present invention, the above-mentioned non-liquid crystal structural unit preferably has the structural unit represented by the following formula (II).

[0182] [Chemical Formula 12]

[0183] Equation (II)

[0184]

[0185] (In general formula (II), R) 11 R represents a hydrogen atom or a methyl group. 12 Indicates -L 2 -R 13 or -L 2′ -R 14 The group represented, L 2 It represents -(CH2) n -, L 2′ It represents -(C2H4O) n′ - Represents the linking group, R 13 This indicates a methyl group optionally having a substituent, an aryl group optionally having an alkyl group, or -OR. 15 R 14 and R 15 Each of the following groups independently represents an alkyl group optionally having a substituent or an aryl group optionally having a substituent, where n and n′ are each independently integers from 1 to 18.

[0186] In the structural unit represented by equation (II), -L 2 -R 13 or -L 2' -R 14 The groups represented can be the same as those described above.

[0187] In embodiments of the present invention, when the above-mentioned non-liquid crystal structural unit is a non-liquid crystal and non-crosslinked structural unit, the above-mentioned non-crosslinked substituent can be cited as an optional substituent contained in the structural unit represented by the above formula (II).

[0188] Furthermore, in embodiments of the present invention, when the aforementioned non-liquid crystal structural unit is a non-liquid crystal and thermally crosslinked structural unit, the thermally crosslinked group can be cited as an optional substituent contained in the structural unit represented by formula (II). In one non-liquid crystal and thermally crosslinked structural unit, it is preferable to have one thermally crosslinked group, but two or more may also be present.

[0189] In embodiments of the present invention, when the above-mentioned non-liquid crystal structural unit is a non-liquid crystal and thermally crosslinked structural unit, in terms of improved reactivity and improved durability, it is preferable to have a structural unit represented by the following formula (III).

[0190] [Chemical Formula 13]

[0191] Equation (III)

[0192]

[0193] (In equation (III) above, Z) a R represents at least one monomer unit selected from the following formulas (a-1) to (a-6). 16 Y is an optional straight-chain alkylene group having 1 to 11 carbon atoms in its carbon chain and having an -O- group. a This indicates a thermally crosslinking group.

[0194] [Chemical Formula 14]

[0195]

[0196] (In the above formulas (a-1) to (a-6), R) 11 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 17 R represents a hydrogen atom or a methyl group. 18 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 19 L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a Indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-, in L a In the case of a single bond, R 16 It bonds directly to the styrene skeleton.

[0197] R 16 It can be a straight-chain alkylene group having 1 to 11 carbon atoms and having -O- in the carbon chain, preferably -(CH2). n” -or-(C2H4O) m” -C2H4- (n” is 1 to 11, m” is 1 to 4), preferably n” is 2 to 11, m” is 1 to 4, preferably n” is 4 to 11, m” is 2 to 4. If n” and m” are too small, the distance between the thermally crosslinking group and the main skeleton of the copolymer becomes shorter in the thermally crosslinking structural unit. Therefore, it is difficult for the thermal crosslinking agent to bond with the thermally crosslinking group, raising concerns about a decrease in the reactivity between the thermally crosslinking structural unit and the thermal crosslinking agent. On the other hand, if n” and m” are too large, the chain length of the connecting group becomes longer in the thermally crosslinking structural unit. Therefore, it is difficult for the terminal thermally crosslinking group to be exposed on the surface, making it difficult for the thermal crosslinking agent to bond with the thermally crosslinking group, raising concerns about a decrease in the reactivity between the thermally crosslinking structural unit and the thermal crosslinking agent.

[0198] Y aThe thermally crosslinking group can be the same as the aforementioned thermally crosslinking group, and for example, it can be at least one selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, amide, hydroxymethyl, alkoxymethyl, trialkoxysilyl, terminal isocyanate, and alkoxy groups substituted on the methyl group. The hydroxymethyl and alkoxymethyl groups, as self-crosslinking groups, can be formed by the hydroxyl and alkoxy groups on the methyl group (R... 16 It can be substituted on the methylene group to become hydroxymethyl or alkoxymethyl.

[0199] Furthermore, in embodiments of the present invention, when the above-mentioned non-liquid crystal structural unit contains a non-liquid crystal and thermally crosslinked structural unit, the non-liquid crystal and thermally crosslinked structural unit may also be the same as the structural unit represented by the following formula (III) described in the second side-chain type liquid crystal polymer (A) of the present invention.

[0200] The copolymer may have one or more non-liquid crystal structural units.

[0201] Among the structural units represented by general formula (II), the following chemical formulas (II-1) to (II-10) can be cited as non-liquid crystal and non-crosslinked structural units.

[0202] Furthermore, among the structural units represented by general formula (II), examples of non-liquid crystal and thermally crosslinkable structural units include structures in which one hydrogen atom of the hydrocarbon group in the following chemical formulas (II-1) to (II-10) is replaced by the aforementioned thermally crosslinkable group. Moreover, examples of non-liquid crystal and thermally crosslinkable structural units include the following chemical formulas (III-1) to (III-11).

[0203] [Chemical Formula 15]

[0204]

[0205] [Chemical Formula 16]

[0206]

[0207] Alternatively, the structural units represented by the chemical formulas (III-1) to (III-12) of the second invention described in the second side-chain liquid crystal polymer (A) of the second invention can also be used.

[0208] In the synthesis of copolymers, monomers such as (meth)acrylate derivatives derived from the above-mentioned non-liquid crystal structural units can be used. These monomers can be used alone or in combination of two or more.

[0209] Regarding the content ratio of the aforementioned non-liquid crystal structural units in the copolymer, in terms of improving the vertical orientation of the liquid crystal structural units and having sufficient liquid crystal orientation, when the amount of structural units contained in the copolymer as a whole is set to 100 mol%, it is preferably set in the range of 10 mol% to 60 mol%, more preferably in the range of 15 mol% to 50 mol%, even more preferably in the range of 15 mol% to 45 mol%, and particularly preferably in the range of 20 mol% to 40 mol%.

[0210] As the aforementioned non-liquid crystal structural unit in the copolymer, when both non-liquid crystal and non-crosslinked structural units and non-liquid crystal and thermally crosslinked structural units are contained, the proportion of the non-liquid crystal and thermally crosslinked structural units is preferably set in the range of 10 mol% to 70 mol%, and more preferably in the range of 30 mol% to 50 mol%, when the total amount of non-liquid crystal structural units contained in the copolymer is set to 100 mol%.

[0211] It should be noted that the content ratio of each structural unit in the copolymer can be determined by... 1 It is calculated from the integrated value of H-NMR measurement.

[0212] (3) Other structural units

[0213] The side-chain type liquid crystal polymer (A) used in this invention has at least the above-mentioned liquid crystal structural unit and the above-mentioned non-liquid crystal structural unit containing alkylene in the side chain, but may also have other structural units.

[0214] Other structural units include, for example, a thermally crosslinked structural unit having a side chain without alkylene groups and having the aforementioned thermally crosslinked groups, and a photo-oriented structural unit having a side chain containing photo-oriented groups in the copolymer (B) described below.

[0215] Examples of thermally crosslinkable structural units that do not contain alkylene groups in their side chains and have the aforementioned thermally crosslinkable groups include (meth)acrylic acid, 4-hydroxystyrene, and 4-carboxystyrene.

[0216] In terms of improving the durability and reliability of the phase retardation layer, it is preferable that the side-chain type liquid crystal polymer (A) used in the present invention has at least one thermally crosslinked structural unit with thermally crosslinked groups in the side chain, selected from non-liquid crystal and thermally crosslinked structural units containing alkylene groups in the side chain, and thermally crosslinked structural units without alkylene groups in the side chain but having the above-mentioned thermally crosslinked groups.

[0217] As a photo-orientation structural unit, it can be the same as the photo-orientation structural unit with photo-orientation groups in the side chains of the copolymer (B) described below.

[0218] Regarding the content ratio of the other structural units mentioned above in the copolymer, in order to improve the vertical orientation of the liquid crystal structural units and have sufficient liquid crystal orientation, when the amount of structural units contained in the copolymer as a whole is set to 100 mol%, it is preferably set in the range of 30 mol% or less, and more preferably in the range of 20 mol% or less.

[0219] (4) Copolymer of side-chain liquid crystal polymer (A)

[0220] In embodiments of the present invention, the side-chain liquid crystal polymer (A) may be a block copolymer having a block portion comprising liquid crystal structural units and a block portion comprising non-liquid crystal structural units containing alkylene groups in the side chain, or it may be a random copolymer in which the liquid crystal structural units and the non-liquid crystal structural units containing alkylene groups in the side chain are arranged irregularly. In this embodiment, a random copolymer is preferred in terms of improving the vertical orientation and in-plane uniformity of the phase difference value of the side-chain liquid crystal polymer.

[0221] Furthermore, the mass-average molecular weight (Mw) of the side-chain liquid crystal polymer used as the copolymer is not particularly limited, but is preferably in the range of 5,000 to 80,000, more preferably in the range of 8,000 to 50,000, and even more preferably in the range of 10,000 to 36,000. By setting it within the above range, the liquid crystal composition exhibits excellent stability and excellent operability during the formation of the retardation layer.

[0222] It should be noted that the above-mentioned mass-average molecular weight Mw is a value determined by GPC (gel permeation chromatography). The determination was performed as follows: an HLC-8120 GPC manufactured by Tosoh Co., Ltd. was used, the dissolution solvent was N-methylpyrrolidone with 0.01 mol / L lithium bromide added, and the calibration curve was performed using polystyrene standards Mw377400, 210500, 96000, 50400, 206500, 10850, 5460, 2930, 1300, 580 (all of which are Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Co., Ltd.), and the assay column was set as TSK-GEL ALPHA-M×2 (manufactured by Tosoh Co., Ltd.).

[0223] As a method for synthesizing copolymers of side-chain type liquid crystal polymers (A), one example is to copolymerize monomers that derive liquid crystal structural units with monomers that derive non-liquid crystal structural units containing alkylene groups in the side chains by conventional manufacturing methods.

[0224] The side-chain liquid crystal polymer (A) can be used in solution form during copolymer synthesis, or in powder form, or in solution form obtained by redissolving the purified powder in the solvents described below.

[0225] The aforementioned side-chain liquid crystal polymer (A) can be used alone or in combination of two or more. In this embodiment, in terms of achieving vertical orientation, the content ratio of the aforementioned side-chain liquid crystal polymer relative to 100 parts by mass of the solid component of the liquid crystal composition is preferably 20 to 80 parts by mass, more preferably 25 to 70 parts by mass, and even more preferably 30 to 60 parts by mass.

[0226] It should be noted that, in this invention, the term "solid component" refers to all components other than the solvent. For example, even if the polymerizable liquid crystal compound described below is in liquid form, it is still included in the solid component.

[0227] 2. Copolymer (B)

[0228] The copolymer (B) used in this invention has photooriented structural units with photooriented groups in the side chains and thermally crosslinked structural units with thermally crosslinked groups in the side chains, through a specific structure.

[0229] Copolymer (B) is a photooriented copolymer.

[0230] The following describes each structural unit in the copolymer.

[0231] (1) Photooriented structural unit

[0232] The optical orientation structural unit of the present invention has a structural unit represented by the following formula (1).

[0233] [Chemical Formula 17]

[0234] Equation (1)

[0235]

[0236] (In the above formula (1), Z) 1 The expression represents at least one monomer unit selected from formulas (1-1) to (1-6) below, where X represents a photooriented group, and L represents a photooriented group. 11 (This indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, or combinations thereof with aryl groups.)

[0237] [Chemical Formula 18]

[0238]

[0239] (In the above equations (1-1) to (1-6), R) 21 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 22 R represents a hydrogen atom or a methyl group. 23R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 24 (This refers to a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[0240] As a single unit constituting the optical orientation structural unit, at least one selected from formulas (1-1) to (1-6) above can be cited. It should be noted that in Z... 1 In the case where at least one of formulas (1-2) is selected, -L 11 -X can bond to any of the ortho, meta, or para positions. In terms of ease of achieving photoorientation by reducing the distance between photoorientation groups, -L... 11 -X is preferred for bonding at the alignment point.

[0241] As the monomer unit constituting the photo-orientation structural unit, in terms of the ease of raw material supply, it is preferable to select at least one of formulas (1-1) and (1-2). Furthermore, if it is selected from at least one of formulas (1-2), it is more preferable in that the copolymer (B) is more likely to become non-liquid crystal, is easier to separate from the side-chain liquid crystal polymer (A), the vertical orientation of the side-chain liquid crystal polymer (A) is improved, and the rigidity of the photo-orientation structural unit of the copolymer (B) is increased. Therefore, the distance between the photo-orientation groups is easier to reduce, and excellent photo-orientation is easier to obtain.

[0242] Furthermore, if the copolymer has a styrene backbone and contains a large number of π electron systems, it is believed that through the interaction of the π electron systems, the adhesion between the alignment layer and the phase difference layer formed by the photo-oriented thermosetting liquid crystal composition of the present invention and the liquid crystal material directly stacked on the alignment layer and phase difference layer also becomes higher.

[0243] L 11 The terms "-O-", "-S-", "-COO-", "-COS-", "-CO-", "-OCO-", or combinations thereof with aryl groups, refer to the connection of the monomer unit to the photo-orientation group X. In the copolymer (B) of the present invention, the photo-orientation structural unit does not have a straight-chain alkylene group between the photo-orientation group and the monomer unit. Therefore, it is presumed that, as described above, it is prone to becoming non-liquid crystallizable, its compatibility with the aforementioned side-chain liquid crystal polymer (A) decreases, it is easy to separate from the aforementioned side-chain liquid crystal polymer (A), and its rigidity increases. The distance between the photo-orientation groups is easily reduced, resulting in excellent photo-orientation properties.

[0244] In the above L 11 In the case of a single bond, the photooriented group X and the monomer unit Z 1Direct bonding. Specific examples of divalent linking groups include: -O-, -S-, -COO-, -COS-, -CO-, -OCO-, -C6H4-, -C6H4O-, -OCOC6H4O-, -COOC6H4O-, -OC6H4O-, etc., where -C6H4- represents phenylene.

[0245] On the other hand, the photooriented group is a functional group that exhibits anisotropy by generating a photoreaction through light irradiation, and is preferably a functional group that generates a photodimerization reaction or a photoisomerization reaction.

[0246] Examples of photo-orienting groups that generate photodimerization reactions include cinnamyl, chalcone, coumarin, anthracene, quinolinyl, azophenyl, and piracene. The benzene ring in these functional groups may optionally have substituents. Substituents can be any groups that do not hinder the photodimerization reaction; examples include alkyl, aryl, cycloalkyl, alkoxy, aryloxy, hydroxyl, halogen atoms, trifluoromethyl, and cyano groups.

[0247] The photo-orienting group that generates the photoisomerization reaction is preferably one that generates a cis-trans isomerization reaction, such as cinnamyl, chalcone, azophenyl, piracene, etc. The benzene ring in these functional groups may optionally have substituents. Substituents are acceptable as long as they do not hinder the photoisomerization reaction, such as alkoxy, alkyl, halogen atoms, trifluoromethyl, cyano, etc.

[0248] The photo-orientation group is preferably cinnamoyl. Specifically, the cinnamoyl group is preferably at least one selected from the groups represented by the following formulas (x-1) and (x-2).

[0249] [Chemical Formula 19]

[0250] Equation (x-1)

[0251]

[0252] Equation (x-2)

[0253]

[0254] In the above equation (x-1), R 31 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. The alkyl, aryl, and cycloalkyl groups may be bonded via ether bonds, ester bonds, amide bonds, or urea bonds, and optionally contain substituents. R 32 ~R 35Each of these groups 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. The alkyl, aryl, and cycloalkyl groups may be bonded via ether, ester, amide, or urea bonds, and may optionally contain substituents. R 36 and R 37 Each can independently represent 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.

[0255] In addition, in the above equation (x-2), R 41 ~R 45 Each of these groups 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. The alkyl, aryl, and cycloalkyl groups may be bonded via ether, ester, amide, or urea bonds, and may optionally contain substituents. R 46 and R 47 Each can independently represent 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.

[0256] It should be noted that when the photo-orientation group is cinnamoyl and is the group represented by the above formula (x-1), the benzene ring of the styrene skeleton (formula (1-2)) contained in the monomer unit can become the benzene ring of cinnamoyl.

[0257] Furthermore, the cinnamyl group represented by the above formula (x-1) is more preferably the group represented by the following formula (x-3).

[0258] [Chemical Formula 20]

[0259] Equation (x-3)

[0260]

[0261] In the above equation (x-3), R 32 ~R 37 Same as equation (x-1) above. R 38 This represents a hydrogen atom, an alkoxy group (1-18 carbon atoms), a cyano group, an alkyl group (1-18 carbon atoms), a phenyl group, a biphenyl group, or a cyclohexyl group. Alkyl, phenyl, biphenyl, and cyclohexyl groups can be bonded via ether, ester, amide, or urea bonds. n represents 1-5, R... 38 Bonding can occur at adjacent, intermediate, or contralateral sites. When n is 2–5, R 38 They can be the same or different. Preferably, n is 1, and R... 38 Bonding at the alignment.

[0262] The copolymer may have one or more photo-oriented structural units.

[0263] Monomers with photo-orientation groups that derive the aforementioned photo-orientation structural units can be used in the synthesis of copolymers. Monomers with photo-orientation groups can be used alone or in combination of two or more.

[0264] Regarding the proportion of photo-orienting structural units in the copolymer, when the total amount of structural units in the copolymer is set to 100 mol%, it can be set in the range of 10 mol% to 90 mol%, preferably in the range of 20 mol% to 80 mol%. If the proportion of photo-orienting structural units is low, the sensitivity will decrease, making it difficult to impart good liquid crystal alignment energy. On the other hand, if the proportion of photo-orienting structural units is high, the proportion of thermally crosslinking structural units will be relatively low, resulting in insufficient thermosetting properties and difficulty in maintaining good liquid crystal alignment energy.

[0265] (2) Thermally cross-linked structural unit

[0266] The thermally crosslinked structural unit of the present invention is a site that is bonded to a thermally crosslinking agent by heating.

[0267] The thermally crosslinkable structural unit can be any structural unit having a thermally crosslinkable group. As a thermally crosslinkable group, it can be any group that is crosslinked by heating at 30°C to 250°C, and examples include: hydroxyl, carboxyl, phenolic hydroxyl, mercapto, glycidyl, amino, amide, etc. From a reactivity point of view, aliphatic hydroxyl groups are preferred, and primary hydroxyl groups are more preferred. It should be noted that a primary hydroxyl group refers to a hydroxyl group to which the carbon atom bonded is a primary carbon atom.

[0268] In addition, as a thermally crosslinking group, it can be a self-crosslinking group that can crosslink with the same crosslinking group. Examples of self-crosslinking groups include: hydroxymethyl, alkoxymethyl, trialkoxysilyl, and terminal isocyanate groups.

[0269] When the thermally crosslinking structural unit has a self-crosslinking group, the thermally crosslinking structural unit can also act as a thermal crosslinking agent, which is preferred in terms of easily improving photoorientation properties and solvent resistance. When the thermally crosslinking structural unit has a self-crosslinking group, it is considered to readily react with intramolecular thermally crosslinking structural units.

[0270] As a thermally crosslinkable structural unit, it preferably contains at least one selected from hydroxyl, carboxyl, and thiol groups in terms of photoorientation properties and solvent resistance.

[0271] As a thermally crosslinkable structural unit, in terms of more easily improving photoorientation properties and solvent resistance, it is preferable to have a structural unit having at least one thermally crosslinkable group selected from hydroxyl, carboxyl and mercapto groups, and a structural unit having at least one self-crosslinkable group selected from hydroxymethyl, alkoxymethyl, trialkoxysilyl and capped isocyanate groups.

[0272] It should be noted that the alkoxymethyl group of the self-crosslinking group preferably has an alkoxy group with 1 to 6 carbon atoms, specifically including: methoxymethyl, ethoxymethyl, various propoxymethyl, various butoxymethyl, various pentoxymethyl, etc. As an alkoxymethyl group, it is more preferred that the alkoxy group has 1 to 4 carbon atoms, and even more preferred that it has 1 to 2 carbon atoms. In terms of improving crosslinking properties, methoxymethyl and ethoxymethyl are preferred.

[0273] Examples of monomer units constituting thermally crosslinked structural units include: acrylates, methacrylates, styrene, acrylamide, methacrylamide, maleimide, vinyl ether, vinyl ester, etc.

[0274] As a thermally crosslinking structural unit, when the thermally crosslinking group is a carboxyl group, it can be a structural unit derived from acrylic acid or methacrylic acid; when the thermally crosslinking group is a hydroxyl group, it can be a structural unit derived from vinyl alcohol.

[0275] As a thermally crosslinked structural unit, the structural unit represented by the following equation (2) can be exemplified.

[0276] [Chemical Formula 21]

[0277] Equation (2)

[0278]

[0279] (In the above formula (2), Z) 2 R represents at least one monomer unit selected from the following formulas (2-1) to (2-6). 50 (Y represents a linear alkylene group, optionally having 1 to 11 carbon atoms with -O- in the carbon chain, and a thermally crosslinking group.)

[0280] [Chemical Formula 22]

[0281]

[0282] (In the above equations (2-1) to (2-6), R) 51 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 52 R represents a hydrogen atom or a methyl group. 53 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 54 L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.12 Indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-, in L 12 In the case of a single bond, R 50 It bonds directly to the styrene skeleton.

[0283] It should be noted that in Z 2 When -L is selected from at least one of equations (2-2), 12 -Y can be bonded at any of the ortho, meta, or para positions, but -L is preferred in terms of its excellent thermal crosslinking reactivity. 12 -Y is bonded at the bisector.

[0284] As the monomer unit constituting the thermally crosslinked structural unit, in terms of the ease of raw material supply, it is preferably selected from at least one of formulas (2-1) and (2-2). Furthermore, if it is selected from at least one of formula (2-2), it is more preferable in that the copolymer (B) is more likely to become non-liquid crystal, is easier to separate from the above-mentioned side-chain liquid crystal polymer (A), and the vertical orientation of the side-chain liquid crystal polymer (A) is improved.

[0285] In the above formula (2), the thermal crosslinking group of Y can be the same as above, or it can be a self-crosslinking group.

[0286] In formula (2) above, the thermally crosslinking group of Y can be at least one thermally crosslinking group selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, amide, hydroxymethyl, alkoxymethyl, trialkoxysilyl, capped isocyanate, and alkoxy groups substituted on the methyl group, or at least one thermally crosslinking group selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups. The hydroxymethyl and alkoxymethyl groups, as self-crosslinking groups, can be formed by the hydroxyl and alkoxy groups on the methyl group (R... 50 It can be substituted on the methylene group to become hydroxymethyl or alkoxymethyl.

[0287] From a reactivity point of view, it is preferable that the thermal crosslinking group of Y contains an aliphatic hydroxyl group, and more preferably a primary hydroxyl group.

[0288] In equation (2) above, L 12 This indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-. It should be noted that in L... 12 In the case of a single bond, the thermally crosslinking group Y and the monomer unit Z 2 Direct bonding.

[0289] R 50 It can be a straight-chain alkylene group having 1 to 11 carbon atoms and having -O- in the carbon chain, preferably -(CH2).j -or-(C2H4O) k -C2H4- (j is 1 to 11, k is 1 to 4), preferably j is 2 to 11, k is 1 to 4, and more preferably j is 4 to 11, k is 2 to 4. If j and k are too small, the distance between the thermally crosslinking group and the main skeleton of the copolymer becomes shorter in the thermally crosslinking structural unit. Therefore, it is difficult for the thermally crosslinking agent to bond with the thermally crosslinking group, raising concerns about a decrease in the reactivity between the thermally crosslinking structural unit and the thermally crosslinking agent. On the other hand, if j and k are too large, the chain length of the connecting group becomes longer in the thermally crosslinking structural unit. Therefore, it is difficult for the terminal thermally crosslinking group to be exposed on the surface, making it difficult for the thermally crosslinking agent to bond with the thermally crosslinking group, raising concerns about a decrease in the reactivity between the thermally crosslinking structural unit and the thermally crosslinking agent.

[0290] The copolymer may have one or more thermally crosslinking structural units.

[0291] Monomers having thermally crosslinkable groups that derive the aforementioned thermally crosslinkable structural units can be used in the synthesis of copolymers. Monomers having thermally crosslinkable groups can be used alone or in combination of two or more.

[0292] Monomers having thermally crosslinking groups include, but are not limited to, the following examples.

[0293] Examples of acrylate and methacrylate compounds include, for example, 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, tetrapropylene glycol monoacrylate, etc., monomers having hydroxyl and acryloyl or methacryloyl groups.

[0294] Examples of styrene compounds include monomers having hydroxyl and styrene groups, such as esters of 4-vinylbenzoic acid and diol, esters of 4-vinylbenzoic acid and diethylene glycol, ethers of hydroxystyrene and diol, and ethers of hydroxystyrene and diethylene glycol.

[0295] In addition, as monomers forming thermally crosslinked structural units, for example, the monomers described in paragraphs 0075-0079 of Japanese Patent No. 5626493 may also be used. Alternatively, monomers in which the hydroxyl groups exemplified above are replaced with carboxyl or glycidyl groups may also be used.

[0296] Among monomers with thermally crosslinking groups, examples of monomers with self-crosslinking groups include: N-hydroxymethylacrylamide, N-hydroxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, and N-butoxymethylacrylamide, which are acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl or alkoxymethyl groups; monomers with trialkoxysilyl groups, such as 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, and 3-triethoxysilylpropyl methacrylate; and monomers with terminal isocyanate groups, such as 2-(O-(1′-methylpropyleneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylaminoethyl methacrylate.

[0297] Regarding the proportion of thermally crosslinkable structural units in the copolymer, when the total amount of structural units in the copolymer is set to 100 mol%, it can be set in the range of 5 mol% to 90 mol%, preferably in the range of 20 mol% to 80 mol%. If the proportion of thermally crosslinkable structural units is low, sufficient thermosetting properties may not be obtained, making it difficult to maintain good liquid crystal alignment energy. Conversely, if the proportion of thermally crosslinkable structural units is high, the proportion of photo-alignment structural units will be relatively low, resulting in decreased sensitivity and difficulty in imparting good liquid crystal alignment energy.

[0298] (3) Other structural units

[0299] In this invention, the copolymer may have structural units that do not possess either photo-oriented or thermally crosslinked structural units, in addition to photo-oriented and thermally crosslinked structural units. By including other structural units in the copolymer, for example, solvent solubility, heat resistance, and reactivity can be improved.

[0300] Examples of monomeric units constituting structural units that do not have photo-oriented or thermally crosslinking groups include: acrylates, methacrylates, maleimide, acrylamide, acrylonitrile, maleic anhydride, styrene, and vinyl groups. Among these, acrylates, methacrylates, and styrene are preferred, similar to the thermally crosslinking structural units described above.

[0301] Examples of monomers that form structural units that do not have photo-oriented or thermally crosslinking groups include: acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, etc.

[0302] Specifically, for example, monomers that do not possess either the aforementioned photo-orientation group or thermal crosslinking group can be used, as described in paragraphs 0036 to 0040 of International Publication No. 2010 / 150748.

[0303] Additionally, other structural units may be included, for example, structural units derived from monomers having fluorinated alkyl groups. In this case, the copolymer (B) readily exists locally on the coating surface, and the photo-orientation groups readily orient on the coating surface. Regarding the ease with which the copolymer (B) readily exists locally on the coating surface, the fluorinated alkyl group of the monomer having fluorinated alkyl groups may be a fluorinated alkyl group with 2 to 8 carbon atoms directly bonded to the fluorine atom.

[0304] The structural units in the copolymer that do not have photo-oriented groups and thermal crosslinking groups can be one type or more types.

[0305] Regarding the content ratio of the structural units in the copolymer that do not have photo-orientation groups and thermal crosslinking groups, when the total amount of structural units in the copolymer is set to 100 mol%, it is preferably in the range of 0 mol% to 50 mol%, and more preferably in the range of 0 mol% to 30 mol%. If the content ratio of the above-mentioned structural units is high, the content ratio of photo-orientation structural units and thermal crosslinking structural units will be relatively low, resulting in the following situation: decreased sensitivity, difficulty in imparting good liquid crystal alignment energy, and inability to obtain sufficient thermosetting properties, making it difficult to maintain good liquid crystal alignment energy.

[0306] (4) Copolymer (B)

[0307] The mass-average molecular weight of copolymer (B) is not particularly limited, but can be, for example, around 3,000 to 200,000, preferably in the range of 4,000 to 100,000. If the mass-average molecular weight is too high, the solubility in solvents will decrease or the viscosity will increase, resulting in reduced workability and difficulty in forming a uniform film. On the other hand, if the mass-average molecular weight is too low, the curing will be insufficient during thermosetting, and the solvent resistance and heat resistance will decrease.

[0308] It should be noted that the mass-average molecular weight can be determined by gel permeation chromatography (GPC).

[0309] As a method for synthesizing copolymer (B), one example is to copolymerize a monomer having photo-orientation groups with a monomer having thermal crosslinking groups by a conventionally known manufacturing method.

[0310] The copolymer (B) can be used in the form of a solution during copolymer synthesis, or in the form of a powder, or in the form of a solution obtained by redissolving the purified powder in the solvents described below.

[0311] The copolymer (B) described above can be used alone or in combination of two or more. In this embodiment, in terms of exerting orientation energy on the directly laminated liquid crystal material, the content ratio of the copolymer (B) relative to 100 parts by mass of the solid component of the liquid crystal composition 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.

[0312] 3. Thermal crosslinking agent

[0313] The photo-oriented thermosetting liquid crystal composition of the present invention contains a thermal crosslinking agent bonded to the thermal crosslinking groups of the aforementioned thermal crosslinking structural units. The thermal crosslinking agent can improve heat resistance and solvent resistance by bonding to at least the aforementioned thermal crosslinking groups of the copolymer. Furthermore, the thermal crosslinking agent can also be bonded to side-chain type liquid crystal polymers (A) containing thermal crosslinking groups on their side chains, or to compounds having thermal crosslinking groups, which may be present in any form, thereby contributing to improved durability of the cured film or enhanced functionality.

[0314] As a thermal crosslinking agent, a compound bonded to the thermal crosslinking groups of the aforementioned thermal crosslinking structural unit is selected.

[0315] Examples of such thermal crosslinking agents include compounds having crosslinking groups that can react with the aforementioned thermal crosslinking groups. Examples of crosslinking groups in the thermal crosslinking agent include epoxy groups, hydroxymethyl groups, isocyanate groups, terminal isocyanate groups, carboxyl groups, protected carboxyl groups, maleimide groups, etc. Preferably, the thermal crosslinking agent has two or more crosslinking groups, more preferably two to six. Examples of thermal crosslinking agents include epoxy compounds, hydroxymethyl compounds, isocyanate compounds, etc., with hydroxymethyl compounds being preferred.

[0316] Specific examples of hydroxymethyl compounds include alkoxymethylated glycourea, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

[0317] Specific examples of alkoxymethylated glycoureas include: 1,3,4,6-tetra(methoxymethyl)glycourea, 1,3,4,6-tetra(butoxymethyl)glycourea, 1,3,4,6-tetra(hydroxymethyl)glycourea, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetra(butoxymethyl)urea, 1,1,3,3-tetra(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, etc. Examples of commercially available products include: glycourea compounds (trade names Cymel 1170, Powderlink 1174) manufactured by MitsuiCytec Co., Ltd.; methylated urea resin (trade name UFR65); butylated urea resin (trade names UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV); and urea / formaldehyde resins (high condensation type, trade names Beckamine J-300S, Beckamine P-955, Beckamine N) manufactured by Dai Nippon Ink Chemical Co., Ltd.

[0318] Specific examples of alkoxymethylated benzoguanidines include tetramethoxymethylbenzoguanidine. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (trade name Cymel1123) and those manufactured by Sanwa Chemical Co., Ltd. (trade names NIKALAC BX-4000, NIKALAC BX-37, NIKALAC BL-60, NIKALAC BX-55H).

[0319] Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine. Examples of commercially available products include: methoxymethyl melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade names Cymel 300, Cymel 301, Cymel 303, Cymel 350), butoxymethyl melamine compounds (trade names Micoat 506, Micoat 508), methoxymethyl melamine compounds manufactured by Sanwa Chemical Co., Ltd. (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), and butoxymethyl melamine compounds (trade names NIKALAC MX-45, NIKALAC MX-410, NIKALAC MX-302), etc.

[0320] Alternatively, the compound can be obtained by condensing melamine compounds, urea compounds, glycourea compounds, and benzoguanidine compounds in which the hydrogen atoms of the amino group are replaced with hydroxymethyl or alkoxymethyl groups. For example, the high molecular weight compound made from melamine compounds and benzoguanidine compounds described in U.S. Patent No. 6,323,310 can be cited. Commercially available products of the aforementioned melamine compounds include Cymel 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the aforementioned benzoguanidine compounds include Cymel 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0321] Furthermore, as a thermal crosslinking agent, a polymer can also be used that is manufactured using an acrylamide compound or a methacrylamide compound substituted with hydroxymethyl or alkoxymethyl.

[0322] Specifically, for example, the thermal crosslinking agent described in paragraphs 0049 to 0050 of International Publication No. 2010 / 150748 may be used.

[0323] Alternatively, thermal crosslinking agents containing multiple benzene rings within the molecule can be used. Examples of thermal crosslinking agents containing multiple benzene rings within the molecule include: phenolic derivatives having a total of two or more hydroxymethyl or alkoxymethyl groups and a molecular weight of 1200 or less; melamine-formaldehyde derivatives having at least two free N-alkoxymethyl groups; and alkoxymethyl glycourea derivatives. Phenolic derivatives containing hydroxymethyl groups can be obtained by reacting the corresponding phenolic compound without hydroxymethyl groups with formaldehyde under an alkaline catalyst.

[0324] In addition, 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 phenolic varnish resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3',4'-epoxycyclohexylcarboxylic acid 3,4-epoxycyclohexylmethyl ester, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4) -Epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl) adipic acid, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipic acid, 3,4-epoxy-6-methylcyclohexane carboxylic acid, ε-caprolactone-modified 3',4'-epoxycyclohexane carboxylic acid, trimethylcaprolactone-modified 3',4'-epoxycyclohexane carboxylic acid, β-methyl-δ-valerolactone-modified 3',4'-epoxycyclohexane 3,4-Epoxycyclohexylmethyl formate, methylene bis(3,4-epoxycyclohexane), ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexane carboxylate), dioctyl epoxycyclohexane phthalate, di-2-ethylhexyl epoxycyclohexane phthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, polypropylene glycol... Diglycidyl alcohol ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more epoxides to aliphatic polyols such as ethylene glycol, propylene glycol, and glycerol; diglycidyl esters of aliphatic long-chain dicarboxylic acids; monoglycidyl ethers of aliphatic higher alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol, or epoxides; glycidyl esters of higher fatty acids; epoxidized soybean oil; epoxidized butyl stearate; epoxidized octyl stearate; epoxidized linseed oil; epoxidized polybutadiene, etc.

[0325] 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, Epolead GT-400, Epolead 401, and Epolead... 403 (manufactured by Daicel Chemical Industry), KRM-2100, KRM-2110, KRM-2199, KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2200, KRM-2720, KRM-2750 (manufactured by Asahi Denko), CER-4221, CER-4221-E, CER-4221-H (manufactured by Dalian Trico Chemical), Rapi-cure DVE-3, CHVE, PEPC (manufactured by ISP), Epikote 828, Epikote 812, Epikote 1031, Epikote 872, Epikote CT508 (manufactured by JapanEpoxy Resin), XDO (manufactured by Toa Gosei), VECOMER 2010, VECOMER 2020, VECOMER 4010, VECOMER 4020 (all manufactured by Allied Signal), etc.

[0326] These thermal crosslinking agents can be used alone or in combination of two or more.

[0327] In this invention, in terms of improving the durability of the cured film, the content of the above-mentioned thermal crosslinking agent is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the solid component of the photo-oriented thermosetting liquid crystal composition, more preferably 0.5 to 25 parts by mass, and even more preferably 1 to 20 parts by mass.

[0328] Furthermore, the proportion of the thermal crosslinking agent in the photo-oriented thermosetting liquid crystal composition of the present invention is preferably 1 to 30 parts by mass relative to the total of 100 parts by mass of the above-mentioned side-chain type liquid crystal polymer (A) and copolymer (B), more preferably 2 to 25 parts by mass, and even more preferably 3 to 25 parts by mass.

[0329] If the content of the thermal crosslinking agent is too low, there are concerns that the heat resistance and solvent resistance of the cured film formed from the photo-oriented thermosetting liquid crystal composition may decrease, as may the vertical alignment and liquid crystal alignment energy decrease. Conversely, if the content is too high, there are concerns that the vertical alignment, liquid crystal alignment energy, and storage stability may decrease.

[0330] 4. Acid or acid-producing agent

[0331] The photo-oriented thermosetting liquid crystal composition of the present invention may contain an acid or an acid-generating agent. The acid or acid-generating agent can promote the thermosetting reaction of the photo-oriented thermosetting liquid crystal composition of the present invention.

[0332] As an acid or acid-producing agent, there are no particular limitations as long as it is a compound containing a sulfonic acid group, hydrochloric acid or its salt, or a compound that thermally decomposes to produce an acid during the drying and curing of the coating, i.e., a compound that thermally decomposes to produce an acid at a temperature of 50°C to 250°C. Specifically, the compounds described in paragraph 0054 of International Publication No. 2010 / 150748 may be used.

[0333] The content of acid or acid-generating agent in the photo-oriented thermosetting liquid crystal composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and even more preferably 0.05 to 5 parts by weight, relative to 100 parts by weight of the solid component of the photo-oriented thermosetting liquid crystal composition.

[0334] Furthermore, the proportion of acid or acid-generating agent in the photo-oriented thermosetting liquid crystal composition of the present invention is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, and even more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the total of the aforementioned side-chain type liquid crystal polymer (A) and copolymer (B). By keeping the content of acid or acid-generating agent within the above range, sufficient thermosetting properties and solvent resistance can be imparted, and high sensitivity to light can also be imparted. On the other hand, if the content is too high, the storage stability of the photo-oriented thermosetting liquid crystal composition may decrease.

[0335] 5. Solvent

[0336] The photo-oriented thermosetting liquid crystal composition of the present invention may contain a solvent as needed, in terms of its coatability. As the solvent, it is acceptable to select a suitable solvent from conventionally known solvents that can dissolve or disperse the components contained in the photo-oriented thermosetting liquid crystal composition of the present invention. Specifically, examples include: hydrocarbon solvents such as hexane, cyclohexane, and toluene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ether solvents such as tetrahydrofuran, 1,3-dioxane, and propylene glycol monoethyl ether (PGME); haloalkane solvents such as chloroform and dichloromethane; ester solvents such as ethyl acetate and propylene glycol monomethyl ether acetate; amide solvents such as N,N-dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and alcohol solvents such as methanol, ethanol, and propanol. In this embodiment, one solvent may be used alone or in combination of two or more as a mixed solvent.

[0337] In the photo-oriented thermosetting liquid crystal composition of the present invention, the solvent content is not particularly limited as long as the components are uniformly dissolved in the solvent. In the composition containing solvent, it is preferably 50% to 99% by mass, more preferably 60% to 95% by mass, and even more preferably 70% to 90% by mass.

[0338] If the solvent content is too high and the solid content is too low, it will be difficult to impart phase difference, liquid crystal alignment energy, and thermosetting properties. In addition, if the solvent content is too low and the solid content is too high, the viscosity of the photo-aligned thermosetting liquid crystal composition will increase, making it difficult to form a uniform film.

[0339] It should be noted that the so-called solid component refers to the component obtained by removing the solvent from all components of a photo-oriented thermosetting liquid crystal composition.

[0340] 6. Other ingredients

[0341] The photo-oriented thermosetting liquid crystal composition of the present invention may contain other components without compromising its effectiveness. Specifically, these other components may include, for example: a polymerizable liquid crystal compound different from the aforementioned side-chain type liquid crystal polymer (A); a polymerizable compound having two or more polymerizable groups per molecule to improve the hardness and durability of the coating; a photopolymerization initiator; a compound having both polymerizable and thermally crosslinking groups; a compound having both photo-oriented and thermally crosslinking groups different from the aforementioned copolymer (B); a sensitizer; a leveling agent; a polymerization inhibitor; an antioxidant; a light stabilizer; etc. These can be made by appropriately selecting conventionally known materials.

[0342] (1) Polymerizable liquid crystal compounds that are different from the above-mentioned side-chain type liquid crystal polymer (A)

[0343] In terms of adjusting phase difference and improving durability, the photo-oriented thermosetting liquid crystal composition of the present invention may contain polymeric liquid crystal compounds different from the above-mentioned side-chain type liquid crystal polymer (A) as needed.

[0344] In embodiments of the present invention, a polymeric liquid crystal compound different from the aforementioned side-chain type liquid crystal polymer (A) may be appropriately selected from those already known. Examples of such polymeric liquid crystal compounds include low-molecular-weight polymeric liquid crystal monomers. In this embodiment, regarding ease of vertical orientation in combination with the aforementioned side-chain type liquid crystal polymer (A), a polymeric liquid crystal compound having polymeric groups at at least one end of the rod-shaped liquid crystal unit is preferred; alternatively, a polymeric liquid crystal compound having polymeric groups at both ends of the rod-shaped liquid crystal unit may also be used.

[0345] The liquid crystal units or rod-shaped liquid crystal units in the polymeric liquid crystal compound may be the same as those in the liquid crystal structural units of the aforementioned side-chain liquid crystal polymer.

[0346] Examples of polymerizable groups in polymerizable liquid crystal compounds include groups containing cyclic ethers such as ethylene oxide rings and oxobutane rings, and groups containing olefinic double bonds. Among these, groups containing olefinic double bonds are preferred for their superior photocurability and workability. Examples of groups containing olefinic double bonds include vinyl, allyl, and (meth)acryloyl groups, with (meth)acryloyl groups being the most preferred.

[0347] In this embodiment, the polymerizable liquid crystal compound is preferably selected from one or more compounds represented by the following general formula (IV) and the following general formula (V) in terms of exhibiting excellent liquid crystal orientation and heat resistance.

[0348] [Chemical Formula 23]

[0349] General Formula (IV)

[0350]

[0351] (In general formula (IV), R) 61 R represents a hydrogen atom or a methyl group. 62 It represents -(CH2) p -or-(C2H4O) p′ - represents the group; L 3 Ar represents a direct bond, or a linking group represented by -O-, -OC(=O)-, or -C(=O)-O-. 3 This indicates an optional arylene group with 6 to 10 carbon atoms having substituents, and multiple L... 3 and Ar 3They can be the same or different; R 63 This indicates -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 -OR 65 R 64 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 65 This indicates an alkyl group having 1 to 6 carbon atoms; b is an integer from 2 to 4, and p and p' are each independently an integer from 2 to 10.

[0352] [Chemical Formula 24]

[0353] General formula (V)

[0354]

[0355] (In general formula (V), R) 71 and R 72 Each can independently represent a hydrogen atom or a methyl group, R 73 It represents -(CH2) q -or-(C2H4O) q' - The group represented, R 74 It represents -(CH2) r -or-(OC2H4) r '- represents the group; L 4 Ar represents a direct bond, or a linking group represented by -O-, -OC(=O)-, or -C(=O)-O-. 4 This indicates an optional arylene group with 6 to 10 carbon atoms having substituents, and multiple L... 4 and Ar 4 Each can be the same or different; c is an integer from 2 to 4, and q, q', r, and r' are each an independent integer from 2 to 10.

[0356] L 3 and L 4 It can be used with L in the above general formula (I) 2 same.

[0357] Additionally, Ar 3 and Ar 4 Ar can be used in the above general formula (I) 1 same.

[0358] The compounds represented by general formula (IV) and the compounds represented by general formula (V) below, specifically, for example, may be polymerizable liquid crystal compounds described in paragraphs 0057 to 0064 of International Publication No. 2018 / 003498.

[0359] In this embodiment, a polymeric liquid crystal compound different from the aforementioned side-chain type liquid crystal polymer (A) may be used alone or in combination of two or more.

[0360] When a polymerizable liquid crystal compound different from the above-mentioned side-chain type liquid crystal polymer (A) is used in the photo-oriented thermosetting liquid crystal composition of the present invention, its content is not particularly limited as long as the phase difference and durability can be appropriately adjusted. It is preferably 1 part to 90 parts by mass relative to 100 parts by mass of the solid content of the photo-oriented thermosetting liquid crystal composition, more preferably 5 parts to 50 parts by mass, and even more preferably 10 parts to 30 parts by mass.

[0361] Furthermore, when a polymeric liquid crystal compound different from the aforementioned side-chain liquid crystal polymer (A) is used in the photo-oriented thermosetting liquid crystal composition of the present invention, its content relative to 100 parts by mass of the aforementioned side-chain liquid crystal polymer (A) is preferably 5 to 100 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 40 parts by mass.

[0362] (2) Polymer compounds having two or more polymeric groups in one molecule

[0363] In terms of improving the hardness and durability of the coating, the photo-oriented thermosetting liquid crystal composition of the present invention may, as needed, further contain a polymeric compound having two or more polymeric groups per molecule. In addition to the polymeric liquid crystal compound described above, a non-liquid crystal polymeric compound may also be used as the polymeric compound having two or more polymeric groups per molecule.

[0364] As polymeric compounds having two or more polymerizable groups in one molecule, so-called multifunctional monomers can also be used, such as: 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, di-trimethylolpropane tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. These include pentaerythritol octa(meth)acrylate, pentaerythritol deca(meth)acrylate, isocyanurate tri(meth)acrylate, isocyanurate di(meth)acrylate, polyester tri(meth)acrylate, polyester di(meth)acrylate, bisphenol di(meth)acrylate, diglycerol tetra(meth)acrylate, adamantane di(meth)acrylate, isoprene di(meth)acrylate, dicyclopentane di(meth)acrylate, tricyclodecane di(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, and those modified with PO, EO, etc. For improving coating durability through crosslinking reactions, polymeric compounds with three or more polymeric groups per molecule, such as pentaerythritol triacrylate (PETA), pentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA), pentaerythritol pentaacrylate (DPPA), and trimethylolpropane triacrylate (TMPTA), are available.

[0365] In the case of using a polymeric compound having two or more polymeric groups in one molecule that does not have liquid crystal properties in the photo-oriented thermosetting liquid crystal composition of the present invention, its content is not particularly limited as long as it can be appropriately adjusted to improve the hardness and durability of the coating film. It is preferably 1 to 40 parts by mass relative to 100 parts by mass of the solid component of the photo-oriented thermosetting liquid crystal composition, more preferably 5 to 35 parts by mass, and even more preferably 10 to 30 parts by mass.

[0366] (3) Photopolymerization initiator

[0367] In the case that the photo-oriented thermosetting liquid crystal composition of the present invention contains a compound having polymerizable groups such as groups containing olefinic double bonds, it is preferable to further contain a photopolymerization initiator in order to obtain an alignment layer and phase retardation layer with better adhesion to the stacked liquid crystal layer.

[0368] As photopolymerization initiators, radical-based photopolymerization initiators that generate free radicals through light irradiation can be suitably used. Photopolymerization initiators can be appropriately selected from those already known. Specific examples of such photopolymerization initiators include, for instance, aromatic ketones containing thioxanthone, α-aminoalkylphenyl ketones, α-hydroxy ketones, acylphosphine oxides, oxime esters, aromatic onium salts, organic peroxides, sulfur-containing compounds, hexaaryl biimidazole compounds, ketoxime ester compounds, borate compounds, azadinium compounds, metallocene compounds, active ester compounds, compounds having carbon-halogen bonds, and alkylamine compounds. In the case where the photo-oriented thermosetting liquid crystal composition of the present invention contains the above-mentioned acid or acid-generating agent, a basic photoinitiator that is not an aminoalkylphenyl ketone-based photoinitiator is preferred, for example, and a photoinitiator without basic groups is preferred. In terms of improving durability by curing into the interior of the coating, it is preferable to select at least one selected from acylphosphine oxide polymerization initiator, α-hydroxy ketone polymerization initiator, and oxime ester polymerization initiator.

[0369] Specifically, the photopolymerization initiator may be, for example, the photopolymerization initiator described in paragraphs 0067 to 0070 of International Publication No. 2018 / 003498.

[0370] In this embodiment, the photopolymerization initiator can be used alone or in combination of two or more.

[0371] When a photopolymerization initiator is used in the photo-oriented thermosetting liquid crystal composition of the present invention, its content is not particularly limited as long as it can promote the curing of the above-mentioned compound with polymerizable groups. It is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the solid content of the photo-oriented thermosetting liquid crystal composition, more preferably 0.5 to 9 parts by mass, and even more preferably 1 to 8 parts by mass.

[0372] (4) Compounds with polymerizable groups and thermally crosslinking groups

[0373] In terms of improving the hardness, durability, and interlayer adhesion of the coating, the photo-oriented thermosetting liquid crystal composition of the present invention may, as needed, further contain a compound having polymerizable groups and thermally crosslinking groups. Here, the polymerizable groups may be the same as those described in the polymerizable liquid crystal compound above. Furthermore, the thermally crosslinking groups may be the same as those described in the copolymer (B) above.

[0374] The compound having polymerizable and thermally crosslinkable groups is preferably a compound having at least one of a hydroxyl and a carboxyl group and an olefinic unsaturated double bond. More preferably, it is a compound having at least one of a hydroxyl and a carboxyl group, an aromatic hydrocarbon group, and an olefinic unsaturated double bond. If the compound contains at least one of a hydroxyl and a carboxyl group, an aromatic hydrocarbon group, and an olefinic unsaturated double bond, it is preferable to obtain an alignment layer / phase retardation layer that does not hinder the liquid crystal alignment energy of the surface and has better adhesion to the stacked liquid crystal layer.

[0375] In addition, in terms of improving the hardness, durability, and interlayer adhesion of the coating, hydroxyl-containing polyfunctional acrylates, which are compounds having hydroxyl groups and two or more olefinic unsaturated double bonds, can also be appropriately used.

[0376] Specifically, compounds having polymerizable and thermally crosslinkable groups can be used, for example: compounds having polymerizable and thermally crosslinkable groups as described in paragraphs 0106 to 0112 of International Publication No. 2014 / 073658; thermally crosslinkable polymeric compounds containing aromatic hydrocarbon groups as described in paragraphs 0087 to 0100 of Japanese Patent Application Publication No. 2017-068019; and hydroxyl-containing polyfunctional acrylates as described in Japanese Patent Application Publication No. 0125 to 0126 of International Publication No. 2013 / 054784.

[0377] In this embodiment, compounds having polymerizable groups and thermally crosslinking groups can be used alone or in combination of two or more.

[0378] When a compound having polymerizable and thermally crosslinking groups is used in the photo-oriented thermosetting liquid crystal composition of the present invention, its content is not particularly limited as long as it can improve durability and interlayer adhesion. It is preferably 1 to 50 parts by mass relative to 100 parts by mass of the solid component of the photo-oriented thermosetting liquid crystal composition, more preferably 5 to 40 parts by mass, and even more preferably 10 to 30 parts by mass.

[0379] (5) Compounds having photooriented groups and thermally crosslinking groups, different from the copolymer (B) mentioned above.

[0380] Regarding improving the durability and photoalignment of the coating, the photoalignment-oriented thermosetting liquid crystal composition of the present invention may, as needed, further contain compounds having photoalignment groups and thermal crosslinking groups different from those in the copolymer (B) described above. Here, the photoalignment groups may be the same as those described in the copolymer (B). Similarly, the thermal crosslinking groups may be the same as those described in the copolymer (B).

[0381] Examples of compounds having photo-alignment and thermal crosslinking groups, different from the copolymer (B) described above, include low-molecular-weight, non-polymeric compounds. Among these compounds, those having photo-alignment and thermal crosslinking groups, different from the copolymer (B) described above, are preferably compounds having at least one of a hydroxyl and a carboxyl group, and at least one of a cinnamoyl, chalcone, azophenyl, and piracene group; even more preferably, compounds having at least one of a hydroxyl and a carboxyl group, and a cinnamoyl group. Compounds containing at least one of a hydroxyl and a carboxyl group, an aromatic hydrocarbon group, and an olefinic unsaturated double bond group are preferred for obtaining an alignment layer / phase retardation layer that does not hinder the liquid crystal alignment energy of the surface and has better adhesion to the stacked liquid crystal layer.

[0382] Specifically, as a compound having photo-orientation groups and thermal crosslinking groups, for example, a compound having photo-orientation groups and thermal crosslinking groups as described in paragraphs 0064 to 0074 of International Publication No. 2013 / 054784 may be used.

[0383] In this embodiment, compounds having photooriented groups and thermal crosslinking groups, different from the copolymer (B) described above, may be used alone or in combination of two or more.

[0384] When a compound with photo-oriented and thermally crosslinking groups, different from the copolymer (B) mentioned above, is used in the photo-oriented thermosetting liquid crystal composition of the present invention, its content is not particularly limited as long as it can improve the durability and photo-orientedness of the coating film. It is preferably 1 to 50 parts by mass relative to 100 parts by mass of the solid content of the photo-oriented thermosetting liquid crystal composition, more preferably 10 to 40 parts by mass, and even more preferably 15 to 30 parts by mass.

[0385] (6) Sensitizers

[0386] The photo-oriented thermosetting liquid crystal composition of the present invention may contain a sensitizer. The sensitizer can promote photoreactions such as photodimerization and photoisomerization.

[0387] As a sensitizer, specifically, the one described in paragraph 0057 of International Publication No. 2010 / 150748 may be used.

[0388] Among them, benzophenone derivatives and nitrobenzene compounds are preferred. Sensitizers can be used alone or in combination of two or more compounds.

[0389] When a sensitizer is used in the photo-oriented thermosetting liquid crystal composition of the present invention, its content is not particularly limited as long as it can improve the durability and photo-orientation of the coating film. It is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the solid component of the photo-oriented thermosetting liquid crystal composition, more preferably 0.2 to 10 parts by mass, and even more preferably 0.5 to 10 parts by mass.

[0390] It should be noted that, in the first photo-oriented thermosetting liquid crystal composition, the composition of the second photo-oriented thermosetting liquid crystal composition described below can be used to achieve the second objective.

[0391] That is, the first photo-oriented thermosetting liquid crystal composition may be one containing:

[0392] A side-chain type liquid crystal polymer (A) having liquid crystal structural units containing liquid crystal moieties in the side chains and non-liquid crystal structural units containing alkylene groups in the side chains.

[0393] A copolymer (B) having photooriented structural units containing photooriented groups in the side chains and thermally crosslinked structural units having structural units represented by the following formula (2), and

[0394] The crosslinking agent (C) bonded to the thermally crosslinking groups of the above-mentioned thermally crosslinking structural units,

[0395] The above-mentioned side-chain liquid crystal polymer (A) satisfies any one of (i) to (vi) below.

[0396] (i) The aforementioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing a thermally crosslinking group and an alkylene group in the side chain. The non-liquid crystal and thermally crosslinked structural unit of the aforementioned side-chain liquid crystal polymer (A) has a structure in which the aforementioned thermally crosslinking group is bonded to a primary carbon of an alkylene group optionally having -O- in the carbon chain. The total number of carbons and oxygens of the alkylene group is smaller than that of the linear alkylene group of the thermally crosslinked structural unit of the aforementioned copolymer (B), which optionally has 4 to 11 carbons having -O- in the carbon chain.

[0397] (ii) The above-mentioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing a thermally crosslinking group and an alkylene group in the side chain, and the non-liquid crystal and thermally crosslinked structural unit of the above-mentioned side-chain liquid crystal polymer (A) has a structure in which the thermally crosslinking group is bonded to a secondary or tertiary carbon of the alkylene group.

[0398] (iii) The above-mentioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing at least one thermally crosslinking group selected from hydroxyl, mercapto, and amino, an alkylene group, and an arylene group in its side chain, and the non-liquid crystal and thermally crosslinked structural unit of the above-mentioned side-chain liquid crystal polymer (A) has a structure in which the above-mentioned thermally crosslinking group is bonded to the arylene group.

[0399] (iv) The aforementioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing at least one thermally crosslinking group selected from carboxyl, glycidyl, and amide groups, an alkylene group, and an arylene group in its side chain. The non-liquid crystal and thermally crosslinked structural unit of the aforementioned side-chain liquid crystal polymer (A) has a structure in which the aforementioned thermally crosslinking group is bonded to an arylene group, and has a structure in which the arylene group is bonded to a carbon atom or oxygen atom of an alkylene group optionally having a -O- at the end of the carbon chain. The total number of carbon atoms and oxygen atoms of the alkylene group is at least 3 fewer than the number of carbon atoms (4 to 11) of the linear alkylene group optionally having a -O- at the end of the carbon chain in the thermally crosslinked structural unit of the aforementioned copolymer (B).

[0400] (v) The above-mentioned side-chain liquid crystal polymer (A) has a thermally crosslinked structural unit in which the side chain does not contain alkylene groups and contains thermally crosslinked groups.

[0401] (vi) The above-mentioned side-chain type liquid crystal polymer (A) does not have non-liquid crystal properties and thermally crosslinked structural units containing thermally crosslinked groups and alkylene groups in the side chains, nor does it have thermally crosslinked structural units containing thermally crosslinked groups in the side chains.

[0402] [Chemical Formula 25]

[0403] Equation (2)

[0404]

[0405] (In the above formula (2), Z) 2 R represents at least one monomer unit selected from the following formulas (2-1) to (2-6). 50 The alkylene group is a straight-chain alkylene group with 4 to 11 carbon atoms, optionally having an -O- group in the carbon chain. Y represents at least one thermally crosslinking group selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups.

[0406] [Chemical Formula 26]

[0407]

[0408] (In the above equations (2-1) to (2-6), R) 51 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 52 R represents a hydrogen atom or a methyl group. 53 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom.54 L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 12 Indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-, in L 12 In the case of a single bond, R 50 It bonds directly to the styrene skeleton.

[0409] 7. A thermosetting liquid crystal composition with photo-orientation properties

[0410] The method for preparing the photo-oriented thermosetting liquid crystal composition of the present invention is not particularly limited. However, in terms of extending shelf life, it is preferable to mix the side-chain liquid crystal polymer (A), copolymer (B), thermal crosslinking agent (C), and other components, and then add an acid or an acid-generating agent. It should be noted that when the acid or acid-generating agent is added at the beginning, compounds that thermally decompose to produce acid during the drying and heat curing of the coating are preferred.

[0411] In the preparation of the photo-oriented thermosetting liquid crystal composition of the present invention, a solution of a side-chain liquid crystal polymer (A) and a solution of a copolymer (B) obtained by polymerization in a solvent can be used directly. In this case, a thermal crosslinking agent and other components are added to the solution of the side-chain liquid crystal polymer (A) and the solution of the copolymer (B) as described above to form a homogeneous solution, and then an acid or acid-generating agent is added. At this time, a solvent can be further added to adjust the concentration. At this time, the solvent used in the copolymer formation process can be the same as or different from the solvent used for adjusting the concentration of the photo-oriented thermosetting liquid crystal composition.

[0412] Furthermore, the solution of the prepared photo-oriented thermosetting liquid crystal composition is preferably used after being filtered using a filter with a pore size of about 0.2 μm.

[0413] As an application of the photo-oriented thermosetting liquid crystal composition of the present invention, since the above-mentioned side-chain type liquid crystal polymer (A) is easy to be vertically oriented and the copolymer (B) has excellent ability to orient liquid crystal materials directly stacked thereon, it is suitable for manufacturing an orientation layer that functions as both an orientation layer and a retardation layer, or an orientation film that functions as both an orientation layer and a retardation film, in a single layer.

[0414] B. Orientation film and phase difference film

[0415] The orientation film and phase retardation film of the present invention are characterized in that: it contains an orientation layer and a phase retardation layer, and the orientation layer and phase retardation layer is a cured film of the thermosetting liquid crystal composition with photoorientation of the present invention.

[0416] The following describes the various configurations of the orientation film and phase difference film of the present invention.

[0417] The layer composition of the alignment film and phase retardation film is explained with reference to the attached diagram. Figures 1-3 This invention illustrates one embodiment of the orientation film and phase difference film of the present invention. Figure 1 One embodiment of the alignment film and phase retardation film 10 shown in the example is an alignment film and phase retardation film that only includes the alignment layer and phase retardation layer 1. Figure 2 In one embodiment of the alignment layer and phase retardation layer 10 shown in the example, the alignment layer and phase retardation layer 1 are directly formed on the substrate 2'. Figure 2 The example shown, an alignment layer that also serves as a retardation layer, can be equipped with a mechanism that causes the side surface of the alignment layer / retardation layer 1 of the substrate 2' to exhibit an alignment constraint force. Furthermore, Figure 3 In one embodiment of the alignment film and phase retardation film 10 shown in the example, an alignment film 3 and an alignment film and phase retardation film 1 are sequentially stacked on a substrate 2.

[0418] It should be noted that, as described above, the thermosetting liquid crystal composition containing the aforementioned side-chain liquid crystal polymer (A) is oriented. The aforementioned side-chain liquid crystal polymer is easily oriented vertically, and consequently, the aforementioned polymeric liquid crystal compound, which may be arbitrarily contained, is also easily oriented vertically. Therefore, even without the use of the orientation film 3, it can exhibit vertical orientation.

[0419] 1. Orientation layer and phase difference layer

[0420] The alignment layer and retardation layer 1 of the present invention is a cured film of the photo-oriented thermosetting liquid crystal composition of the present invention, and is formed from the photo-oriented thermosetting liquid crystal composition of the present invention. The alignment layer and retardation layer of the present invention is a film cured in the following state: the liquid crystal portion of the side-chain type liquid crystal polymer (A) is vertically aligned, and the photo-oriented groups present on the surface of the alignment layer and retardation layer become a photodimerization structure or a photoisomerization structure.

[0421] The orientation layer and retardation layer of the present invention comprises, in one layer: the aforementioned side-chain liquid crystal polymer with vertical orientation; and a copolymer having a photodimerization or photoisomerization structure having photo-oriented groups in the photo-oriented structural unit, and a crosslinked structure formed by bonding the thermally crosslinked groups in the thermally crosslinked structural unit to a thermally crosslinking agent. When the aforementioned side-chain liquid crystal polymer has a thermally crosslinked structural unit with thermally crosslinked groups in its side chains, the orientation layer and retardation layer may further comprise a crosslinked structure formed by bonding the thermally crosslinked groups in the thermally crosslinked structural unit of the aforementioned side-chain liquid crystal polymer to a thermally crosslinking agent.

[0422] Here, the term "crosslinked structure" refers to a three-dimensional network structure. Crosslinked structures include: crosslinked structures formed by the bonding of thermally crosslinked groups of the thermally crosslinked structural units of the above-mentioned copolymer with a thermally crosslinking agent, and crosslinked structures formed by the bonding of thermally crosslinked groups of other components with a thermally crosslinking agent, as needed. Crosslinked structures do not include: structures formed by the crosslinking of photo-orientation groups through photodimerization, and structures formed by the polymerization of olefinic unsaturated double bonds. However, the orientation layer and phase retardation layer of the present invention may further include structures formed by the polymerization of olefinic unsaturated double bonds.

[0423] It is speculated that in the alignment layer and phase difference layer of the alignment film and phase difference film of the present invention, the side chain type liquid crystal polymer having the above-mentioned specific structure and exhibiting phase difference through vertical orientation, and the copolymer of the photodimer structure or photoisomerization structure having the photo-oriented structural unit having the above-mentioned specific structure and the thermocrosslinking structural unit having the thermocrosslinking group and the thermocrosslinking agent bonded together, are unlikely to damage each other's properties. Therefore, a single layer can exhibit both excellent vertical orientation and excellent liquid crystal orientation ability (the ability to orient directly stacked liquid crystal materials).

[0424] Furthermore, the orientation layer and phase retardation layer in the orientation film and phase retardation film of the present invention is a cured film of the thermosetting liquid crystal composition with photoorientation of the present invention. Therefore, due to its cross-linked structure, the film has good heat resistance, solvent resistance and high durability.

[0425] The side-chain type liquid crystal polymer exhibiting phase difference through vertical orientation can be the same as the side-chain type liquid crystal polymer described in "A. Thermosetting liquid crystal composition with photoorientation" above, so the description here is omitted.

[0426] The orientation layer and phase difference layer of the present invention contains: a photodimer structure or photoisomerization structure having photooriented groups of photooriented structural units, and a crosslinked structure copolymer having thermal crosslinked groups of thermal crosslinked structural units bonded to a thermal crosslinking agent.

[0427] The copolymer contained in the orientation layer and phase difference layer of the present invention can be formed by thermally curing and photo-oriented copolymers having photo-oriented structural units and thermally crosslinked structural units as described in "A. A Thermosetting Liquid Crystal Composition with Photo-Orientation". In the present invention, a thermally crosslinking agent is used, and the thermally crosslinked groups of the thermally crosslinked structural units are bonded to the thermally crosslinking agent. Therefore, the crosslinked structure is a structure obtained by crosslinking the thermally crosslinked groups and the thermally crosslinking agent through heating. It should be noted that, in the case where the side-chain liquid crystal polymer is non-liquid crystal and the thermally crosslinked structural unit has thermally crosslinked groups, the crosslinked structure may contain a crosslinked structure formed by bonding the thermally crosslinked groups of the side-chain liquid crystal polymer to the thermally crosslinking agent.

[0428] It should be noted that the thermal crosslinking agent can be the thermal crosslinking agent described in "A. Thermosetting liquid crystal composition with photoorientation" above, and the crosslinking structure contains residues of the thermal crosslinking agent after the thermal crosslinking agent reaction.

[0429] For example, when the thermal crosslinking agent is hexamethoxymethyl melamine, the crosslinking structure becomes, for example, the structure shown below. It should be noted that in the following formulas, each symbol is the same as in formula (1) above. The following copolymers are examples, and the monomer units, residues of thermal crosslinking groups, etc., are not limited to those described below.

[0430] [Chemical Formula 27]

[0431]

[0432] It should be noted that the structural units of the copolymer are described in detail in "A. Thermosetting liquid crystal composition with photoorientation" above, so the description is omitted here.

[0433] The presence of the aforementioned copolymer in the orientation layer can be confirmed by analyzing material taken from the orientation layer. Analytical methods include NMR, IR, GC-MS, XPS, TOF-SIMS, and combinations thereof.

[0434] The photodimer structure in the copolymer is the structure obtained by cross-linking the photo-oriented groups of the photo-oriented structural unit represented by the above formula (1) through a photodimerization reaction, and it is a structure with a cyclobutane skeleton.

[0435] Photodimerization is a reaction shown below, in which the olefin structure contained in the photo-oriented group forms a cyclobutane skeleton through a photoreaction. The types of photo-oriented groups differ, Xa~Xd and Xa'~Xd'.

[0436] [Chemical Formula 28]

[0437]

[0438] The photodimer structure is preferably a cinnamic yl photodimer structure. Specifically, it is preferably the structure obtained by cross-linking cinnamic yl groups through a photodimerization reaction as described in "A. A thermosetting liquid crystal composition with photoorientation" above. The orientation layer preferably has a photodimer structure represented by the following formulas (x-4) and (x-5). It should be noted that the symbols in the following formulas are the same as those in formulas (x-1), (x-2), and (x-3) above.

[0439] [Chemical Formula 29]

[0440]

[0441] When the alignment layer has a photodimer structure as represented by equations (x-4) and (x-5) above, it contains more aromatic rings and more π electrons. It is believed that this increases the affinity with the liquid crystal layer formed on the alignment layer, improves the liquid crystal alignment energy, and further enhances the adhesion to the liquid crystal layer.

[0442] Furthermore, the photoisomerized structure in the copolymer is the structure obtained by isomerizing the photooriented groups of the photooriented structural unit through a photoisomerization reaction. For example, in the case of cis-trans isomerization reaction, the photoisomerized structure can be either a structure that changes from cis to trans or a structure that changes from trans to cis.

[0443] For example, when the photo-orientation group is cinnamoyl, the photoisomerization reaction is as follows: the olefin structure contained in the photo-orientation group forms either the cis or trans isomer through a photoreaction. Xa to Xd vary depending on the type of photo-orientation group.

[0444] [Chemical Formula 30]

[0445]

[0446] The photoisomerization structure is preferably a cinnamic yl photoisomerization structure. Specifically, it is preferably the structure obtained by isomerization of the cinnamic yl group through a photoisomerization reaction as described in "A. A thermosetting liquid crystal composition with photoorientation" above. In this case, the photoisomerization structure can be either a structure that changes from a cis to a trans or a structure that changes from a trans to a cis. The alignment layer preferably has the cinnamic yl photoisomerization structure represented by formulas (x-1) and (x-2) as shown in formulas (x-6) and (x-7) below.

[0447] [Chemical Formula 31]

[0448]

[0449] It should be noted that the orientation layer can be analyzed by NMR or IR to show that it has the above-mentioned photodimerization structure or photoisomerization structure.

[0450] The alignment layer and phase retardation layer may also contain other components that are also present in the above-mentioned thermosetting liquid crystal composition with photo-alignment properties.

[0451] The orientation layer and phase difference layer may, for example, contain polymeric liquid crystal compounds different from the aforementioned side-chain type liquid crystal polymer (A), polymeric compounds having two or more polymeric groups in one molecule, and structures formed by the polymerization of at least one of the following: olefinic unsaturated double bond groups.

[0452] In addition, the orientation layer and phase difference layer may contain, for example, a cross-linked structure formed by bonding at least one of the following: a compound having polymerizable groups and thermal cross-linking groups, a compound having photo-oriented groups and thermal cross-linking groups different from the above copolymer (B) with a thermal cross-linking agent; and may also contain a photodimerization structure or a photoisomerization structure of the photo-oriented groups of the compound having photo-oriented groups and thermal cross-linking groups different from the above copolymer (B).

[0453] The alignment layer and phase retardation layer may also contain acids or acid-generating agents, photopolymerization initiators, sensitizers, other additives, and their decomposition products. It should be noted that these additives are the same as those described in "A. Thermosetting Liquid Crystal Composition with Photoalignment" above.

[0454] It should be noted that the alignment layer and retardation layer can be confirmed to be formed from the aforementioned photo-aligned thermosetting liquid crystal composition by analyzing materials taken from the alignment layer and retardation layer. As analytical methods, NMR, IR, GC-MS, XPS, TOF-SIMS, and combinations thereof can be used.

[0455] Alternatively, the vertical orientation of liquid crystal components, such as the liquid crystal portion of the side-chain liquid crystal polymer in the alignment layer and phase difference layer, can be confirmed by measuring the phase difference using an automatic birefringence measuring device (e.g., manufactured by Oji Mecha Machine Co., Ltd., trade name: KOBRA-WR).

[0456] The phase difference can be measured using an automatic birefringence measuring device (e.g., manufactured by Oji Measurement Machine Co., Ltd., trade name: KOBRA-WR). By incident the measuring light perpendicularly or obliquely to the surface of the phase difference layer, the anisotropy of the increased phase difference of the phase difference layer can be confirmed by plotting the optical phase difference against the incident angle of the measuring light.

[0457] The thickness of the orientation layer and phase retardation layer can be appropriately set according to the application. Preferably, it is 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm.

[0458] 2. Substrate

[0459] In the orientation film and phase retardation film of the present invention, the substrate may include glass substrate, metal foil, resin substrate, etc. Preferably, the substrate is transparent, and can be appropriately selected from conventionally known transparent substrates. Besides glass substrates, transparent resin substrates formed using acetylcellulose resins such as triacetylcellulose, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polylactic acid, olefin resins such as polypropylene, polyethylene, and polymethylpentene, acrylic resins, polyurethane resins, polyethersulfone, polycarbonate, polysulfone, polyether, polyetherketone, acrylonitrile, methacrylonitrile, cyclic olefin polymers, and cyclic olefin copolymers are also examples of transparent resin substrates.

[0460] The transmittance of the aforementioned transparent substrate in the visible light region is preferably 80% or more, more preferably 90% or more. Here, the transmittance of the transparent substrate can be determined by JIS K7361-1 (Test method for total light transmittance of plastic-transparent materials).

[0461] In addition, when the phase difference layer is formed in a roll-to-roll manner, the transparent substrate is preferably a flexible material that can be rolled into a roll.

[0462] Examples of such flexible materials include: cellulose derivatives, norpyrenes-based polymers, cycloolefin polymers, polymethyl methacrylate, polyvinyl alcohol, polyimide, polyacrylate, polyethylene terephthalate, polysulfone, polyethersulfone, amorphous polyolefins, modified acrylic polymers, polystyrene, epoxy resins, polycarbonate, and polyesters. In this embodiment, cellulose derivatives and polyethylene terephthalate are preferred. This is because cellulose derivatives exhibit particularly excellent optical isotropy, resulting in superior optical properties. Furthermore, polyethylene terephthalate is preferred due to its high transparency and excellent mechanical properties.

[0463] The thickness of the substrate used in this embodiment is not particularly limited as long as it is set within the range that can impart the required self-supporting properties, depending on the application of the alignment film and phase difference film. It is usually in the range of about 10μm to 200μm.

[0464] 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. This is because if the thickness is greater than the above range, for example, when forming a strip-shaped retardation film and then cutting it to make a single-piece alignment film / retardation film, there will be an increase in processing debris or faster wear of the cutting blade.

[0465] The composition of the substrate used in this embodiment is not limited to a single-layer composition; it may also have a composition consisting of multiple layers. In the case of a composition consisting of multiple layers, layers of the same composition may be stacked, or multiple layers with different compositions may be stacked.

[0466] For example, when the orientation film used in this embodiment contains a UV-curable resin, a primer coating can be formed on the substrate to improve the adhesion between the transparent substrate and the UV-curable resin. This primer coating only needs to be adhesive to both the substrate and the UV-curable resin, be optically transparent, and allow UV light to pass through; for example, a vinyl chloride / vinyl acetate copolymer or a urethane primer coating can be appropriately selected.

[0467] Alternatively, in the absence of the vertically oriented film described above, an anchoring layer can be laminated onto the substrate. This anchoring layer improves the strength of the substrate and ensures good vertical orientation. Metal alkoxides, particularly metal silane oxide sols, can be used as the anchoring layer material. Metal alkoxides are typically used in the form of alcohol-based solutions. The anchoring layer needs to be a uniform and flexible film; therefore, its thickness is preferably about 0.04 μm to 2 μm, more preferably about 0.05 μm to 0.2 μm.

[0468] When the substrate has an anchoring layer, the adhesion between the substrate and the anchoring layer can be improved by further laminating an adhesive layer between the substrate and the anchoring layer, or by including a material in the anchoring layer that enhances the adhesion to the substrate. Regarding the adhesive material used in forming the adhesive layer, any material that improves the adhesion between the substrate and the anchoring layer can be used without particular limitation. Examples of adhesive materials include silane coupling agents, titanium coupling agents, and zirconium coupling agents.

[0469] 3. Orientation film

[0470] As the alignment film 3 used in the embodiment of the present invention that is both an alignment film and a phase retardation film, a vertical alignment film can be used in terms of the ease with which the liquid crystal composition of the above-mentioned alignment layer and phase retardation layer 1 can be vertically aligned.

[0471] The vertical alignment film is an alignment film that is provided as a coating film, thereby having the function of vertically aligning the long axis of the liquid crystal units of the liquid crystal components contained in the liquid crystal layer and the phase difference layer 1 of the side chain type liquid crystal polymer liquid crystal polymer liquid crystal functional group.

[0472] Vertical alignment films are alignment films with vertical orientation restraint forces. They can be used in various vertical alignment films for the manufacture of C-plates, VA liquid crystal display devices, etc., such as polyimide alignment films and LB-based alignment films. Specifically, as constituent materials of the alignment film, for example, the following can be used: lecithin; silane-based surfactants; titanate-based surfactants; pyridinium salt-based polymeric surfactants; silane coupling compositions for vertical alignment films such as n-octadecyltriethoxysilane; soluble polyimides with long-chain alkyl or alicyclic structures in the side chains; and polyimide-based vertical alignment film compositions such as polyamides with long-chain alkyl or alicyclic structures in the side chains.

[0473] It should be noted that, as compositions for vertically oriented films, commercially available products such as "JALS-2021" and "JALS-204" (polyimide-based vertically oriented films manufactured by JSR Corporation), and "RN-1517," "SE-1211," and "EXPOA-018" (manufactured by Nissan Chemical Industries, Ltd.) can be used. Alternatively, the vertically oriented film described in Japanese Patent Application Publication No. 2015-191143 can also be used.

[0474] The method for forming the alignment film 3 is not particularly limited. For example, the alignment film composition described above can be coated onto the substrate 2 to impart an alignment restraining force, thereby forming the alignment film. The method for imparting an alignment restraining force to the alignment film can be any method known in the prior art.

[0475] The thickness of the alignment film 3 only needs to ensure that the liquid crystal components in the alignment layer and retardation layer 1 are aligned in a certain direction, and can be appropriately set. The thickness of the alignment film is usually in the range of 1 nm to 10 μm, preferably in the range of 60 nm to 5 μm.

[0476] 4. Uses

[0477] The alignment film and retardation film of the present invention can be suitably used as an alignment film containing a positive C-type retardation layer, and also function as an alignment film for orienting directly stacked liquid crystal materials.

[0478] Here, the so-called positive C characteristic refers to the following features: when the refractive index along the X-axis of the layer is set as Nx, the refractive index along the Y-axis (orthogonal to the X-axis) along the layer is set as Ny, and the refractive index along the layer thickness is set as Nz, the relationship becomes Nz > Nx ≒ Ny, and the optical axis becomes the Nz direction.

[0479] The alignment film and phase retardation film of the present invention can be suitably used as part of an anti-reflection film, part of a polarizer compensation film, and can be suitably used in phase retardation plates and optical components for various display devices.

[0480] C. Manufacturing method of alignment film and phase retardation film

[0481] The method for manufacturing the alignment film and retardation film of the present invention comprises:

[0482] The process of forming a film of the photo-oriented thermosetting liquid crystal composition of the present invention,

[0483] The process of forming a cured film with a phase difference by heating the thermosetting liquid crystal composition formed above, and...

[0484] The process of imparting liquid crystal alignment energy to the aforementioned cured film by irradiating it with polarized ultraviolet light with a phase difference.

[0485] (1) Film-forming process of thermosetting liquid crystal composition with photo-orientation properties

[0486] The photo-oriented thermosetting liquid crystal composition of the present invention is uniformly coated on a support to form a film.

[0487] The support here can be the aforementioned substrate or the alignment film of a substrate having the aforementioned alignment film.

[0488] The coating method can be any method that can form a film with good thickness accuracy as desired, and can be selected appropriately. Examples include: gravure coating, reverse coating, doctor blade coating, dip coating, spraying, air knife coating, spin coating, roller coating, printing, dip-coating, curtain coating, mold coating, casting, bar coating, extrusion coating, and E-type coating.

[0489] (2) Process of forming a cured film with phase difference

[0490] Then, a cured film with a phase difference is formed by heating the thermosetting liquid crystal composition formed above. This cured film functions as a phase difference layer.

[0491] The process includes the following steps: heating the thermosetting liquid crystal composition formed above to orient at least the liquid crystal portion of the side chain type liquid crystal polymer (A) in the thermosetting liquid crystal composition formed above.

[0492] Specifically, the liquid crystal portion of the liquid crystal structural unit of the side-chain liquid crystal polymer in the liquid crystal composition for film formation is heated to a temperature at which it can be vertically oriented. If a polymerizable liquid crystal compound is also optionally present, the heating temperature is adjusted to a temperature at which the polymerizable liquid crystal compound can also be vertically oriented. Through this heat treatment, at least the liquid crystal portion of the liquid crystal structural unit of the side-chain liquid crystal polymer can be vertically oriented and dried, thereby immobilizing it while maintaining the aforementioned orientation state.

[0493] The temperature at which vertical orientation is possible varies depending on the substances in the liquid crystal composition, and therefore needs to be adjusted appropriately. For example, it is preferable to perform the operation in the range of 40°C to 200°C, and more preferably in the range of 40°C to 150°C. The photo-oriented thermosetting liquid crystal composition of the present invention contains the aforementioned side-chain type liquid crystal polymer, thus having a wide range of temperatures suitable for vertical orientation and facilitating temperature management.

[0494] As a heating mechanism, well-known heating and drying mechanisms such as heating plates and ovens can be appropriately selected.

[0495] In addition, the heating time can be selected appropriately, for example, within the range of more than 10 seconds and less than 2 hours, preferably within the range of more than 20 seconds and less than 30 minutes.

[0496] In addition, this process includes the following steps: heating the thermosetting liquid crystal composition formed above, and in a state in which the liquid crystal portion is oriented, causing the thermal crosslinking groups of the copolymer (B) in the thermosetting liquid crystal composition formed above to react with the thermal crosslinking agent (C) to cure it.

[0497] In the case where the thermosetting liquid crystal composition is cured by heating the side-chain type liquid crystal polymer (A) in the above-mentioned thermosetting liquid crystal composition, which is used to orient the liquid crystal portion, and the thermosetting group (B) in the above-mentioned thermosetting liquid crystal composition reacts with the thermosetting agent (C) to form a film, the heating can be a one-stage heating.

[0498] Alternatively, the heating temperature can be further changed after heating the liquid crystal portion of the side-chain type liquid crystal polymer (A) in the thermosetting liquid crystal composition used to at least form a film, and the thermal crosslinking groups of the copolymer (B) in the thermosetting liquid crystal composition formed in the state of liquid crystal portion orientation are reacted with the thermal crosslinking agent (C) to cure the film.

[0499] The heating temperature for thermosetting can be set to approximately 40℃ to 250℃. The heating time can be set to approximately 20 seconds to 60 minutes.

[0500] The thickness of the cured film obtained by thermally curing a photo-oriented thermosetting liquid crystal composition can be appropriately selected according to the application, for example, it can be about 0.1 μm to 5 μm, preferably about 0.5 μm to 3 μm. It should be noted that if the thickness of the cured film is too thin, there may be a situation where sufficient phase difference function and liquid crystal alignment energy cannot be obtained.

[0501] (3) Process of imparting liquid crystal alignment energy to the cured film

[0502] Then, the cured film with the phase difference is irradiated with polarized ultraviolet light to impart liquid crystal alignment energy to the cured film. That is, in this process, a cured film that also functions as an alignment layer is formed by irradiating the cured film with polarized ultraviolet light.

[0503] By irradiating the obtained cured film with polarized ultraviolet light, the photo-orientation groups of the copolymer (B) can undergo a photoreaction, thereby exhibiting anisotropy. The wavelength of the polarized ultraviolet light is typically in the range of 150 nm to 450 nm. In addition, the irradiation direction of the polarized ultraviolet light can be perpendicular or oblique to the substrate surface.

[0504] In this way, a cured film can be formed that imparts alignment energy to the liquid crystal.

[0505] As described above, the cured film becomes functional as a phase retardation layer and as an orientation layer, thereby obtaining a cured film that functions as both an orientation layer and a phase retardation layer.

[0506] (4) Other processes

[0507] In the manufacturing method of the orientation film and phase difference film of the present invention, other steps may also be included.

[0508] For example, when the photo-oriented thermosetting liquid crystal composition of the present invention contains a compound having polymerizable groups, such as a polymerizable liquid crystal compound, the coating film fixed in a state that maintains the orientation of the liquid crystal components can be further subjected to, for example, light irradiation to polymerize the compound having polymerizable groups.

[0509] Ultraviolet (UV) irradiation can be appropriately used for illumination. UV irradiation can utilize UV ​​light emitted from ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, xenon arc lamps, metal halide lamps, etc. The irradiation dose from the energy source can be appropriately selected, preferably based on the cumulative exposure at a UV wavelength of 365 nm, for example, 10 mJ / cm². 2 ~10000mJ / cm 2 Within the range.

[0510] In addition, after obtaining a cured film that functions as both an orientation layer and a phase retardation layer, the support is peeled off, thereby obtaining an orientation film and phase retardation film containing only the orientation layer and phase retardation layer 1.

[0511] D. Phase Difference Plate

[0512] The phase difference plate of the present invention is characterized in that it contains:

[0513] As the first phase difference layer of the curing film of the photo-oriented thermosetting liquid crystal composition of the present invention, and

[0514] A second phase retardation layer comprising a cured material containing a polymeric liquid crystal composition is disposed directly adjacent to the first phase retardation layer.

[0515] Figure 4 This is a schematic cross-sectional view illustrating an example of the phase retardation plate of the present invention. Figure 4 In the phase retardation plate 20 illustrated, a first phase retardation layer 11, which serves as both an orientation layer and a phase retardation layer, is formed on a substrate 13, and a second phase retardation layer 12 is formed on the first phase retardation layer 11.

[0516] In the retardation plate of the present invention, the first retardation layer is a cured film of the photo-oriented thermosetting liquid crystal composition of the present invention, thus exhibiting excellent vertical orientation and excellent ability to orient directly stacked liquid crystal materials. Therefore, the retardation plate 20 of the present invention forms a second retardation layer by directly stacking liquid crystal materials on the first retardation layer 11 without additionally providing an alignment film, and has a second retardation layer 12 disposed directly adjacent to the first retardation layer 11.

[0517] In the phase retardation plate of the present invention, the first phase retardation layer is a cured film of the thermosetting liquid crystal composition with photo-orientation of the present invention. Therefore, as described above, it has excellent solvent resistance. Thus, when the second phase retardation layer is stacked, the deterioration of the phase difference of the first phase retardation layer can also be suppressed, and a phase retardation plate with good optical properties can be obtained.

[0518] Furthermore, in the retardation plate of the present invention, the first retardation layer is a cured film of the photo-oriented thermosetting liquid crystal composition of the present invention described above. Therefore, as described above, compared with the cured product of the photocurable resin composition containing a polymeric liquid crystal compound, it is less prone to hardening and has flexibility, and its adhesion to the directly laminated liquid crystal material is also good. Therefore, the retardation plate of the present invention, like the retardation plate of the third present invention described below, can be made into a thin retardation plate with good adhesion where the first retardation layer and the second retardation layer are directly laminated.

[0519] Furthermore, the manufacturing method of the phase difference plate of the present invention may include the following steps:

[0520] The process of forming a film of the photo-oriented thermosetting liquid crystal composition of the present invention described above;

[0521] A process of forming a cured film with a phase difference by heating the thermosetting liquid crystal composition formed above;

[0522] The process of irradiating the aforementioned cured film with phase difference with polarized ultraviolet light to impart liquid crystal alignment energy to the cured film, thereby forming an alignment film that also serves as a first phase difference layer.

[0523] A process in which a polymerizable liquid crystal composition is coated onto the alignment film and first retardation layer to form a coating of the polymerizable liquid crystal composition, and the coating is heated to the phase transition temperature of the polymerizable liquid crystal composition, thereby aligning liquid crystal molecules using the alignment film and retardation layer; and

[0524] The process of curing a coating of a polymeric liquid crystal composition in which the above-mentioned liquid crystal molecules have been oriented by light to form a second phase retardation layer.

[0525] It should be noted that the substrate can be the same as that described in "B. Orientation film and phase difference film" above, so the description here is omitted.

[0526] 1. First phase difference layer

[0527] The first phase retardation layer is a cured film of the photo-oriented thermosetting liquid crystal composition of the present invention, and thus the first phase retardation layer functions as both an orientation layer and a phase retardation layer as described above.

[0528] The first phase difference layer can be the same as the orientation layer and phase difference layer described in "B. Orientation film and phase difference film" above, so the description here is omitted.

[0529] When the first phase difference layer contains a compound that reacts with a compound containing polymerizable groups and thermally crosslinkable groups contained in the second phase difference layer, the reaction products of the compounds contained in each layer may be present at the interface between the first and second phase difference layers. For example, a structure formed by the polymerization of polymerizable groups of the compound containing polymerizable groups in the first phase difference layer and polymerizable liquid crystal compounds contained in the second phase difference layer may be present at the interface between the first and second phase difference layers. The presence of such reaction products at the interface between the first and second phase difference layers is preferable in terms of improving the adhesion between the first and second phase difference layers.

[0530] It should be noted that, compared to the cured product of a photocurable resin composition containing a polymeric liquid crystal compound, the first phase difference layer of the thermosetting resin composition containing a thermal crosslinking agent of the present invention readily forms a moderately permeable region at the interface with the directly laminated second phase difference layer, to a degree that does not impede the vertical orientation of the first phase difference layer, thereby easily improving adhesion. Since the first phase difference layer of the thermosetting resin composition containing a thermal crosslinking agent of the present invention is crosslinked by the thermal crosslinking agent, when the second phase difference layer is directly laminated, only slight solvent permeation is likely to occur at the surface, but it is presumably unlikely that solvent permeation to the extent that would reduce vertical orientation will occur.

[0531] The first retardation layer is a cured film of the photo-oriented thermosetting liquid crystal composition of the present invention described above. In terms of the ease with which the contained side-chain liquid crystal polymer can be vertically oriented, it can be suitably used as a positive C-type retardation layer.

[0532] 2. Second phase difference layer

[0533] The second phase retardation layer in the phase retardation plate of the present invention is disposed directly adjacent to the first phase retardation layer and contains a cured product of a polymeric liquid crystal composition.

[0534] As a polymeric liquid crystal composition, polymeric liquid crystal compounds containing polymeric groups can be used, and those commonly used in phase retardation layers can be used.

[0535] Examples of polymerizable groups found in polymerizable liquid crystal compounds include acryloyl and methacryloyl groups.

[0536] Polymerizable liquid crystal compositions may include, for example, those with orientations such as horizontal orientation, cholesteric orientation, vertical orientation, and mixed orientation, which are appropriately selected according to the desired phase difference, etc.

[0537] Regarding the liquid crystal alignment energy of the first phase retardation layer, the polymeric liquid crystal composition in the second phase retardation layer is preferably a polymeric liquid crystal composition having horizontal alignment properties.

[0538] The polymeric liquid crystal composition in the second phase retardation layer preferably contains a polymeric liquid crystal compound (rod-shaped compound) that exhibits liquid crystal properties and has polymeric groups within its molecule. As this polymeric liquid crystal compound, conventionally known polymeric liquid crystal compounds with horizontal orientation can be appropriately selected.

[0539] The polymerizable liquid crystal composition may contain only one liquid crystal compound or may be a mixture of two or more liquid crystal compounds.

[0540] The polymeric liquid crystal composition in the second phase difference layer may suitably use the same polymeric liquid crystal compound as described in "A. A thermosetting liquid crystal composition with photoorientation" above, which is a polymeric liquid crystal compound different from the side-chain type liquid crystal polymer (A) described above.

[0541] In the polymeric liquid crystal composition in the second retardation layer, the polymeric liquid crystal compound is preferably selected from one or more compounds represented by general formula (IV) and general formula (V) above, which exhibit excellent liquid crystal orientation and heat resistance. Specifically, the polymeric liquid crystal compounds described in paragraphs 0057 to 0064 of International Publication No. 2018 / 003498 can be used, for example.

[0542] In the polymeric liquid crystal composition in the second phase difference layer, in addition to the polymeric liquid crystal compound, specifically, for example, the polymeric liquid crystal compounds described in Japanese Patent Nos. 6473537, 5463666, 4186981, 5962760, 5826759, 6568103, 6427340, Japanese Patent Application Laid-Open No. 2016-166344, and Recueil des Travaux Chimiques des Pays-Bas (1996), 115(6), 321-328 can be used.

[0543] In addition, examples of polymerizable liquid crystal compositions in the second phase difference layer include the compositions described in paragraphs 0133 to 0143 of Japanese Patent Application Publication No. 2014-174468 and the compositions described in paragraphs 0083 to 0092 of Japanese Patent No. 6739621.

[0544] In addition to liquid crystal compounds, the polymerizable liquid crystal composition in the second phase retardation layer may also contain photopolymerization initiators, solvents, and other components as described in "A. A thermosetting liquid crystal composition with photoorientation".

[0545] The second phase retardation layer can be formed by the following steps: coating a polymerizable liquid crystal composition onto the first phase retardation layer, which also functions as an alignment layer; heating to the phase transition temperature of the polymerizable liquid crystal composition; and aligning the liquid crystal components by means of the liquid crystal alignment energy of the first phase retardation layer; and

[0546] The process of forming a phase retardation layer by irradiating a coating of the polymeric liquid crystal composition with the above-mentioned liquid crystal components oriented with light.

[0547] In the process of aligning the liquid crystal components, the method for forming the coating film of the polymeric liquid crystal composition and the method for heating to the phase transition temperature are not particularly limited, as long as conventionally known methods are used. Regarding the coating method and heating method, the same methods as those used in the above-described method for manufacturing the alignment layer and phase retardation layer can be used.

[0548] By irradiating the coating of the polymeric liquid crystal composition with the above-mentioned liquid crystal components aligned with light, a polymerization reaction occurs, causing the polymeric groups of the polymeric liquid crystal compound contained in the second retardation layer to polymerize with each other. Furthermore, if the first retardation layer contains a compound containing polymeric groups, the polymeric groups of the compound containing polymeric groups in the first retardation layer are polymerized with the polymeric groups of the polymeric liquid crystal compound contained in the second retardation layer. The irradiation method can be any conventionally known method, and can be the same as the method described in "C. Alignment Film and Retardation Film" above.

[0549] In the retardation plate of the present invention, since the first retardation layer functions as both an alignment layer and a retardation film, the second retardation layer is directly stacked on the first retardation layer, without including the substrate, alignment film, adhesive layer, etc., used for the second retardation layer, thus achieving a thinner profile. In the retardation plate of the present invention, the total thickness of the stack of the first retardation layer and the second retardation layer, excluding the substrate, can be set to 0.2 μm to 6 μm, more preferably 1 μm to 4 μm.

[0550] In the retardation plate of the present invention, the first retardation layer is preferably a positive C-type retardation layer, and the second retardation layer is preferably a positive A-type retardation layer. Here, the characteristic of positive A refers to having the following features: when the refractive index along the X-axis direction of the layer is set as Nx, the refractive index along the Y-axis direction (orthogonal to the X-axis) along the layer direction is set as Ny, and the refractive index in the layer thickness direction is set as Nz, the relationship is Nx > Ny ≒ Nz, and the optical axis is in the Nx direction.

[0551] A phase retardation plate, formed by stacking a positive C-type phase retardation layer and a positive A-type phase retardation layer, is used as a circular polarizer in an organic electroluminescent display device, in the form of a combination of a λ / 4 phase retardation plate and a linear polarizer. It is preferred to use it as an anti-reflective film for external light, and it is also preferred to use it as part of a polarizer compensation film in a liquid crystal display device.

[0552] In the phase difference plate of the present invention, the phase difference Rth in the thickness direction at a wavelength of 550nm can be -35nm to 35nm, and further can be -30nm to 30nm.

[0553] In addition, the in-plane phase difference Re at a wavelength of 550nm can be above 120nm, and further above 135nm.

[0554] In addition, the phase retardation plate of the present invention may also have other phase retardation layers.

[0555] The phase retardation plate of the present invention further includes a third phase retardation layer, which is different from the first phase retardation layer described above. The third phase retardation layer, the first phase retardation layer, and the second phase retardation layer are arranged sequentially and directly adjacent to each other.

[0556] The third phase difference layer can be a positive C-type phase difference layer, the first phase difference layer can be a positive C-type phase difference layer, and the second phase difference layer can be a positive A-type phase difference layer.

[0557] When the third phase retardation layer is a positive C-type phase retardation layer, it is preferable to use a side-chain type liquid crystal polymer in the same way as the first phase retardation layer. For example, it can be formed by removing the copolymer (B) from a thermosetting resin composition with photo-oriented properties used to form the first phase retardation layer.

[0558] 4. Uses

[0559] In the phase retardation plate of the present invention, the second phase retardation layer can be directly stacked on the first phase retardation layer, and the plate can be made thinner without including the substrate, alignment film, adhesive layer, etc. used for the second phase retardation layer.

[0560] The phase difference plate of the present invention can be suitably used as an optical component in various image display devices aimed at achieving thinness.

[0561] II. The Second Invention

[0562] A. A thermosetting liquid crystal composition with photo-orientation properties

[0563] The photo-oriented thermosetting liquid crystal composition of the present invention contains:

[0564] A side-chain type liquid crystal polymer (A) having liquid crystal structural units containing liquid crystal moieties in the side chains and non-liquid crystal structural units containing alkylene groups in the side chains.

[0565] A copolymer (B) having photooriented structural units containing photooriented groups in the side chains and thermally crosslinked structural units having structural units represented by the following formula (2), and

[0566] The thermal crosslinking agent (C) bonded to the thermal crosslinking groups of the above-mentioned thermal crosslinking structural unit, and

[0567] The aforementioned side-chain type liquid crystal polymer (A) is a photo-oriented thermosetting liquid crystal composition that satisfies any of the following (i) to (vi).

[0568] (i) The aforementioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing a thermally crosslinking group and an alkylene group in the side chain. The non-liquid crystal and thermally crosslinked structural unit of the aforementioned side-chain liquid crystal polymer (A) has a structure in which the aforementioned thermally crosslinking group is bonded to a primary carbon of an alkylene group optionally having -O- in the carbon chain. The total number of carbons and oxygens of the alkylene group is smaller than that of the linear alkylene group of the thermally crosslinked structural unit of the aforementioned copolymer (B), which optionally has 4 to 11 carbons having -O- in the carbon chain.

[0569] (ii) The above-mentioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing a thermally crosslinking group and an alkylene group in the side chain, and the non-liquid crystal and thermally crosslinked structural unit of the above-mentioned side-chain liquid crystal polymer (A) has a structure in which the thermally crosslinking group is bonded to a secondary or tertiary carbon of the alkylene group.

[0570] (iii) The above-mentioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing at least one thermally crosslinking group selected from hydroxyl, mercapto, and amino, an alkylene group, and an arylene group in its side chain, and the non-liquid crystal and thermally crosslinked structural unit of the above-mentioned side-chain liquid crystal polymer (A) has a structure in which the above-mentioned thermally crosslinking group is bonded to the arylene group.

[0571] (iv) The aforementioned side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing at least one thermally crosslinking group selected from carboxyl, glycidyl, and amide groups, an alkylene group, and an arylene group in its side chain. The non-liquid crystal and thermally crosslinked structural unit of the aforementioned side-chain liquid crystal polymer (A) has a structure in which the aforementioned thermally crosslinking group is bonded to an arylene group, and has a structure in which the arylene group is bonded to a carbon atom or oxygen atom of an alkylene group optionally having a -O- at the end of the carbon chain. The total number of carbon atoms and oxygen atoms of the alkylene group is at least 3 fewer than the number of carbon atoms (4 to 11) of the linear alkylene group optionally having a -O- at the end of the carbon chain in the thermally crosslinked structural unit of the aforementioned copolymer (B).

[0572] (v) The above-mentioned side-chain liquid crystal polymer (A) has a thermally crosslinked structural unit in which the side chain does not contain alkylene groups and contains thermally crosslinked groups.

[0573] (vi) The above-mentioned side-chain type liquid crystal polymer (A) does not have non-liquid crystal properties and thermally crosslinked structural units containing thermally crosslinked groups and alkylene groups in the side chains, nor does it have thermally crosslinked structural units containing thermally crosslinked groups in the side chains.

[0574] [Chemical Formula 32]

[0575] Equation (2)

[0576]

[0577] (In the above formula (2), Z) 2 R represents at least one monomer unit selected from the following formulas (2-1) to (2-6). 50 The alkylene group is a straight-chain alkylene group with 4 to 11 carbon atoms, optionally having an -O- group in the carbon chain. Y represents at least one thermally crosslinking group selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups.

[0578] [Chemical Formula 33]

[0579]

[0580] (In the above equations (2-1) to (2-6), R) 51 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 52 R represents a hydrogen atom or a methyl group. 53 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 54 L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 12 Indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-, in L 12 In the case of a single bond, R 50 It bonds directly to the styrene skeleton.

[0581] The photo-oriented thermosetting liquid crystal composition of the present invention combines the aforementioned side-chain type liquid crystal polymer (A) and the aforementioned copolymer (B) which has the ability to orient directly stacked liquid crystal materials in a manner that satisfies the specific conditions described above. It also contains a thermal crosslinking agent (C) bonded to the thermal crosslinking groups of the aforementioned thermal crosslinking structural units. Therefore, by forming a cured film of the composition, an orientation layer and a phase retardation layer that functions as both an orientation layer and a phase retardation layer can be formed, exhibiting good vertical orientation and good liquid crystal orientation ability (the ability to orient directly stacked liquid crystal materials), and has durability.

[0582] The inventors conducted in-depth research to form a durable integrated functional layer that serves as both an orientation layer and a phase retardation layer from a composition containing a vertically oriented side-chain liquid crystal polymer (A) and a photo-alignment film material (a copolymer (B) of photo-oriented structural units and thermally crosslinked structural units capable of orienting directly stacked liquid crystal materials). The results showed that the photo-alignment function improved with thermal curing of the copolymer (B) as the photo-alignment film material, but the vertically oriented side-chain liquid crystal polymer (A) decreased with thermal curing. Therefore, it was deemed necessary to promote the thermal curing of the copolymer (B) as the photo-alignment film material in the composition while simultaneously inhibiting the thermal curing of the vertically oriented side-chain liquid crystal polymer (A).

[0583] Regarding the photo-oriented thermosetting liquid crystal composition of the present invention, the thermocrosslinking structural unit of the copolymer (B), which serves as the photo-oriented film material, has the following structure: the thermocrosslinking group is bonded to the monomer unit via a linear alkylene group having 4 to 11 carbon atoms optionally having -O- in the carbon chain. Therefore, the copolymer (B), as the photo-oriented film material, readily undergoes a thermocrosslinking reaction and is readily thermo-cured. On the other hand, the vertically oriented side-chain liquid crystal polymer (A) in the composition satisfies any of the above (i) to (vi). Therefore, compared with the copolymer (B), the thermocrosslinking reaction is relatively difficult to carry out, and it is difficult to thermo-cur or does not thermo-cur.

[0584] The photo-oriented thermosetting liquid crystal composition of the present invention, by relatively reducing the thermal crosslinking of the vertically oriented side-chain liquid crystal polymer (A) and making the copolymer (B) as a photo-oriented film material easy to be thermally cured, can form a single layer that functions as both an orientation layer and a phase reversal layer, exhibiting good vertical orientation and good liquid crystal orientation ability (the ability to orient directly stacked liquid crystal materials), and has durability as both an orientation layer and a phase reversal layer.

[0585] Furthermore, regarding the photo-oriented thermosetting liquid crystal composition of the present invention, it is speculated that by effectively thermosetting the copolymer (B), a three-dimensional cross-linked structure is formed in the film. As a result, the vertical orientation of the oriented vertically oriented polymer (A) is less prone to fluctuation. Consequently, changes in vertical orientation caused by heating of the orientation layer / phase retarding layer are suppressed. Furthermore, changes in vertical orientation caused by solvent penetration of the liquid crystal material directly coated on the orientation layer / phase retarding layer are also easily suppressed, resulting in good reproducibility and durability of vertical orientation.

[0586] The components of the photo-oriented thermosetting liquid crystal composition of the present invention will be described below.

[0587] 1. Side-chain type liquid crystal polymer (A)

[0588] The side-chain type liquid crystal polymer (A) used in this invention has liquid crystal structural units containing liquid crystal portions in the side chains and non-liquid crystal structural units containing alkylene groups in the side chains.

[0589] The structural units of the side-chain liquid crystal polymer (A) will be described below.

[0590] The side-chain liquid crystal polymer (A) used in this invention satisfies any one of (i) to (vi) above in relation to the copolymer (B) described below.

[0591] Under the condition of (i) above, in the non-liquid-liquid and thermally crosslinked structural units of the side-chain liquid crystal polymer (A) containing thermally crosslinking groups and alkylene groups in the side chains, the total number of carbons and oxygens of the optional alkylene groups having -O- in the carbon chain connecting the thermally crosslinking groups and monomer units is less than that of the linear alkylene groups having 4 to 11 carbons having -O- in the carbon chain connecting the thermally crosslinking groups and monomer units in the thermally crosslinked structural units of the copolymer (B). In the side-chain liquid crystal polymer (A), by making the length of the portion connecting the thermally crosslinking groups and monomer units relatively short, the thermal crosslinking agent becomes difficult to bond with the thermally crosslinking groups, the reactivity of the thermally crosslinked structural units and the thermal crosslinking agent decreases, and the thermal crosslinking reaction of the side-chain liquid crystal polymer (A) is relatively difficult to carry out compared with that of the copolymer (B). If there is a difference in curing speed between the side-chain liquid crystal polymer (A) and the copolymer (B), conditions for preferential curing of the copolymer (B) can be created by adjusting the following thermal crosslinking dosage and acid catalyst dosage.

[0592] In the non-liquid crystal and thermally crosslinkable structural units of the aforementioned side-chain liquid crystal polymer (A), the sum of the number of carbon atoms and oxygen atoms of the alkylene groups selectively having -O- in the carbon chain and bonded to the aforementioned thermally crosslinkable groups on the primary carbon is preferably 2 or more less than the sum of the number of carbon atoms of the linear alkylene groups selectively having -O- in the carbon chain and having 4 to 11 carbon atoms in the thermally crosslinkable structural units of the copolymer (B). More preferably, it is 3 or more less than the sum of the number of carbon atoms of the linear alkylene groups selectively having -O- in the carbon chain in the aforementioned side-chain liquid crystal polymer (A). In the aforementioned side-chain liquid crystal polymer (A), by making the lengths of the aforementioned thermally crosslinkable groups and the linking groups of the monomer units different as described above, the thermal crosslinking reaction of the side-chain liquid crystal polymer (A) is relatively more difficult to carry out, and it is easier to form a difference in the curing speed between the side-chain liquid crystal polymer (A) and the copolymer (B). Therefore, it is easier to create a situation where the copolymer (B) preferentially cures in the coating film, and it is easier to make the vertical orientation and photoorientation good.

[0593] Under the condition described in (ii) above, the structure of the side-chain liquid crystal polymer (A) having a non-liquid crystal structure containing thermally crosslinking groups and alkylene groups in the side chains, and having the thermally crosslinking structural units having secondary or tertiary carbons of alkylene groups bonded to the aforementioned thermally crosslinking groups, is relatively difficult to carry out thermally crosslinking reactions compared to copolymers (B) having a structure in which the aforementioned thermally crosslinking groups are bonded to the primary carbons by bonding the ends of the straight-chain alkylene groups. As a result, a difference in curing speed between the side-chain liquid crystal polymer (A) and copolymer (B) is easily formed, thus making it easier to create a situation where copolymer (B) preferentially cures in the coating film, and making it easier to achieve good vertical orientation and photoorientation.

[0594] It should be noted that primary carbon refers to a primary carbon atom, which is a carbon atom bonded to one other carbon atom; secondary carbon refers to a secondary carbon atom, which is a carbon atom bonded to two other carbon atoms; and tertiary carbon refers to a tertiary carbon atom, which is a carbon atom bonded to three other carbon atoms.

[0595] When condition (iii) above is met, the non-liquid crystal and thermally crosslinking structural unit of the aforementioned side-chain liquid crystal polymer (A) has a structure in which at least one thermally crosslinking group selected from hydroxyl, mercapto, and amino is bonded to an aryl group. Therefore, compared with the thermally crosslinking groups of copolymer (B) having a structure in which the aforementioned thermally crosslinking group is bonded to the end of a linear alkylene group and then to a primary carbon, the thermal crosslinking reaction is relatively difficult to carry out. As a result, a difference in curing speed between the side-chain liquid crystal polymer (A) and copolymer (B) is easily formed, thus making it easier to create a situation where copolymer (B) preferentially thermally cures in the coating film, and making it easier to achieve good vertical orientation and photoorientation.

[0596] When condition (iv) is satisfied, the non-liquid crystal and thermally crosslinked structural unit of the side-chain liquid crystal polymer (A) has at least one thermally crosslinking group selected from carboxyl, glycidyl, and amide groups, an alkylene group, and an arylene group in its side chain. The non-liquid crystal and thermally crosslinked structural unit of the side-chain liquid crystal polymer (A) has a structure in which the thermally crosslinking group is bonded to the arylene group, and the arylene group is bonded to a carbon atom or oxygen atom of an alkylene group optionally having an -O- at the end of the carbon chain. The total number of carbon atoms and oxygen atoms of the alkylene group is at least 3 fewer than the number of linear alkylene groups optionally having an -O- at 4 to 11 carbon atoms in the carbon chain of the thermally crosslinked structural unit of the copolymer (B). Therefore, the thermally crosslinking group of the side-chain liquid crystal polymer (A) is difficult to bond with the thermally crosslinking agent, the reactivity of the thermally crosslinked structural unit with the thermally crosslinking agent decreases, and the thermal crosslinking reaction of the side-chain liquid crystal polymer (A) is relatively difficult to carry out compared to that of the copolymer (B). As a result, it is easy to form a difference in curing speed between the side-chain liquid crystal polymer (A) and the copolymer (B), thus making it easy to create a situation where the copolymer (B) preferentially cures in the coating, and making it easy to achieve good vertical orientation and photoorientation.

[0597] Under condition (v) above, the aforementioned side-chain liquid crystal polymer (A) has, in addition to non-liquid crystal structural units containing alkylene groups in its side chains, also thermally crosslinking structural units that do not contain alkylene groups in their side chains and contain thermally crosslinking groups in their side chains. In this case, compared to the thermally crosslinking groups of the copolymer (B) having a structure bonded to primary carbons by being bonded to the ends of straight-chain alkylene groups, the thermal crosslinking reaction of the aforementioned thermally crosslinking groups of the aforementioned side-chain liquid crystal polymer (A) is relatively difficult to carry out. As a result, a difference in curing speed between the side-chain liquid crystal polymer (A) and the copolymer (B) is easily formed, thus making it easier to create a situation where the copolymer (B) preferentially cures in the coating film, and making it easier to achieve good vertical orientation and photoorientation.

[0598] Under the condition of satisfying (vi) above, the above-mentioned side-chain liquid crystal polymer (A) does not have non-liquid crystal and thermally crosslinked structural units containing thermally crosslinked groups and alkylene groups in the side chain, that is, the above-mentioned side-chain liquid crystal polymer (A) does not contain thermally crosslinked groups, so it is easy to create a situation in which only copolymer (B) is thermally cured in the coating film, and it is easy to make the vertical orientation and photoorientation good.

[0599] It should be noted that when the above-mentioned side-chain liquid crystal polymer (A) contains two or more non-liquid crystal and thermally crosslinkable structural units, all of the two or more non-liquid crystal and thermally crosslinkable structural units satisfy any one of (i) to (iv) above.

[0600] In addition, if the above-mentioned side-chain liquid crystal polymer (A) has two or more thermally crosslinked groups in a non-liquid crystal and thermally crosslinked structural unit, all of the two or more thermally crosslinked groups may satisfy any one of (i) to (iv) above.

[0601] (1) Liquid crystal structure unit

[0602] In embodiments of the present invention, the liquid crystal structural unit has side chains containing liquid crystal portions, i.e., portions exhibiting liquid crystal properties. The liquid crystal structural unit is preferably a structural unit in which liquid crystal moieties exhibiting liquid crystal properties are present in the side chains. The liquid crystal structural unit is preferably a structural unit derived from a liquid crystal-sensitive compound whose polymeric groups are bonded to the liquid crystal moieties via spacer groups. In the present invention, a liquid crystal moieties refer to a portion with high rigidity exhibiting liquid crystal properties; examples include portions having two or more ring structures, preferably three or more ring structures, where the ring structures are connected to each other by direct bonding or by one to three atoms. By having such liquid crystal-sensitive portions in the side chains, the liquid crystal structural unit becomes easier to align vertically.

[0603] The aforementioned ring structure can be an aromatic ring such as benzene, naphthalene, or anthracene, or a cyclic aliphatic hydrocarbon such as cyclopentyl or cyclohexyl.

[0604] Furthermore, when the ring structure is connected by one to three atoms, the structures that serve as the connecting part can be: -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)-O-, -NR-C(=O)-NR-, -OC(=O)-NR-, -NR-C(=O)-O-, -NR-C(=O)-NR-, -O-NR-, or -NR-O- (where R is a hydrogen atom or a hydrocarbon group), etc.

[0605] Among them, the preferred liquid crystal unit is a rod-shaped liquid crystal unit with the above-mentioned ring structure connected in a rod-like manner, which is connected at the para position in the case of benzene and at the 2 and 6 positions in the case of naphthalene.

[0606] Furthermore, when the liquid crystal structural unit is a structural unit containing liquid crystal elements that display liquid crystal properties in its side chains, in terms of vertical orientation, it is preferable that the end of the side chain of this structural unit is a polar group or has an alkyl group. 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 -OR” (R′ is a hydrogen atom or a hydrocarbon group, and R” is an alkyl group), etc.

[0607] Examples of liquid crystal structural units include those with -R 2 -(L 1 -Ar 1 ) a -R 3 The group represented (here, R) 2 It represents -(CH2) m -or-(C2H4O) m′ - represents the group; L 1 Ar represents a single bond, or a linking group represented by -O-, -OCO-, or -COO-. 1 This indicates an optional arylene group with 6 to 10 carbon atoms having substituents, and multiple L... 1 and Ar 1 They can be the same or different; R 3 This indicates -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2. -R5 or -OR 5 R 4 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 5 ) represents an alkyl group having 1 to 6 carbon atoms; a is an integer from 2 to 4, and m and m' are each an integer from 2 to 10 independently. ) as a structural unit for the side chain.

[0608] R 2 m and m' are each independently an integer from 2 to 10. In terms of vertical orientation, m and m' are preferably 2 to 8, and more preferably 2 to 6.

[0609] As Ar 1 The optional arylene group having 6 to 10 carbon atoms and substituents can be exemplified by: phenylene, naphthylene, etc., with phenylene being more preferred. The R group optionally present in this arylene group... 3 Other substituents include alkyl groups having 1 to 5 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms, and other halogen atoms.

[0610] R 3 R in 4 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Additionally, R 3 R in 5 It is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms.

[0611] The liquid crystal structural unit is preferably a structural unit derived from a monomer having a polymerizable group containing an olefinic double bond. Examples of such monomers containing an olefinic double bond include derivatives of (meth)acrylate, styrene, (meth)acrylamide, maleimide, vinyl ether, or vinyl ester. Regarding vertical orientation, structural units derived from (meth)acrylate derivatives are preferred as liquid crystal structural units.

[0612] In embodiments of the present invention, as a liquid crystal structural unit, in terms of vertical orientation, it is preferable to include a structural unit represented by the following general formula (I).

[0613] [Chemical Formula 34]

[0614] Formula (I)

[0615]

[0616] (In general formula (I), R) 1 R represents a hydrogen atom or a methyl group. 2 It represents -(CH2) m -or-(C2H4O) m′ - represents the group; L1 Ar represents a single bond, or a linking group represented by -O-, -OCO-, or -COO-. 1 This indicates an optional arylene group with 6 to 10 carbon atoms having substituents, and multiple L... 1 and Ar 1 They can be the same or different; R 3 This indicates -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2. -R 5 or -OR 5 R 4 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 5 This indicates an alkyl group having 1 to 6 carbon atoms; a is an integer from 2 to 4, and m and m′ are each independently an integer from 2 to 10.

[0617] In the structural unit represented by general formula (I), -R 2 -(L 1 -Ar 1 ) a -R 3 The groups represented can be the same as those described above.

[0618] Preferred examples of liquid crystal structure units represented by general formula (I) include those represented by the following general formulas (I-1), (I-2) and (I-3), but are not limited to these.

[0619] [Chemical Formula 35]

[0620]

[0621] Here, in the structural units represented by the above general formulas (I-1) to (I-3), R 2 and R 3 R, respectively, with general formula (I) 2 and R 3 same.

[0622] In embodiments of the present invention, the liquid crystal structural unit may be used alone or in combination of two or more.

[0623] Monomers such as (meth)acrylate derivatives that derive liquid crystal structural units can be used in the synthesis of copolymers. Monomers such as (meth)acrylate derivatives that derive liquid crystal structural units can be used alone or in combination of two or more.

[0624] Regarding the content ratio of the aforementioned liquid crystal structural units in the copolymer, in order to improve the vertical orientation of the liquid crystal structural units and have sufficient liquid crystal orientation, when the amount of structural units contained in the copolymer as a whole is set to 100 mol%, it is preferably set in the range of 40 mol% to 90 mol%, more preferably in the range of 40 mol% to 80 mol%, even more preferably in the range of 45 mol% to 70 mol%, and particularly preferably in the range of 50 mol% to 65 mol%.

[0625] It should be noted that the content ratio of each structural unit in the copolymer can be determined by... 1 It is calculated from the integrated value of H-NMR measurement.

[0626] (2) Non-liquid crystal structural units containing alkylene groups in the side chain

[0627] The non-liquid crystal structural unit containing alkylene in its side chain has the following function: when the side-chain type liquid crystal polymer is in a liquid crystal state, the alkylene-containing side chain promotes the homeotropic alignment of the liquid crystal display portion (liquid crystal moiety) of the side chain of the liquid crystal structural unit.

[0628] Examples of non-liquid crystal structural units containing alkylene groups in their side chains include those with -L 2 -R 13 or -L 2 '-R 14 The group represented (here, L) 2 L represents a straight-chain or branched alkylene group having 1 to 18 carbon atoms, optionally with a substituent. 2 'Indicates -(C2H4O)' n′ - Represents the linking group, R 13 This indicates a methyl group optionally having a substituent, an aryl group optionally having an alkyl group, or -OR. 15 R 14 and R 15 Each of the following independently represents an alkyl group or an aryl group optionally having a substituent, where n' is an integer from 1 to 18. ) as a structural unit for the side chain.

[0629] L 2 L represents a straight-chain or branched alkylene group having 1 to 18 carbon atoms, optionally with a substituent. 2 It represents -(C2H4O) n' - The linking group indicated.

[0630] As L 2Alkyl groups with 1 to 18 carbon atoms, either straight-chain or branched, include, for example: methylene, dimethylene (ethylene), trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, dodecylene, tridecamethylene, pentadecylene, hexadecylene, heptadecylene, heptadecylene, octadecylene, etc., as well as methylmethylene, methylethylene, 1,1-dimethylethylene, 1-methylpentane, 1,4-dimethylbutylene, etc., branched alkyl groups, etc.

[0631] As R 14 and R 15 The alkyl group can be straight-chain, branched, or cyclic.

[0632] As R 14 and R 15 The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, specifically including: straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl; branched-chain alkyl groups such as isopropyl, isobutyl, and tert-butyl; alkenyl groups such as 1-propenyl and 1-butenyl; alkynyl groups such as ethynyl and 2-propynyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norpyrenyl, and adamantyl; and cycloalkenyl groups such as 1-cyclohexenyl. In the case of the above-mentioned cycloalkyl groups, straight-chain alkyl-substituted cycloalkyl groups are preferred.

[0633] R 14 and R 15 The alkyl group is not particularly limited, but in terms of the in-plane uniformity of the phase difference, an alkyl group with 1 to 12 carbon atoms is preferred.

[0634] As R 13 R 14 and R 15 The aryl group is preferably an aryl group with 6 to 20 carbon atoms, specifically including phenyl, naphthyl, anthracene, etc., wherein phenyl or naphthyl is preferred, and phenyl is more preferred. In the case of the above-mentioned aryl group, a straight-chain alkyl-substituted aryl group is preferred.

[0635] The non-liquid crystal structural unit containing alkylene in the side chain may optionally have reactive groups that react with other components as substituents, for example, may optionally have the same thermal crosslinking groups as the copolymer (B) described below.

[0636] Examples of non-liquid crystal structural units containing alkylene groups in their side chains include: non-liquid crystal and non-crosslinked structural units, and non-liquid crystal and thermally crosslinked structural units. Non-liquid crystal structural units containing alkylene groups in their side chains may contain only non-liquid crystal and non-crosslinked structural units, or only non-liquid crystal and thermally crosslinked structural units.

[0637] As a non-liquid crystal structural unit containing alkylene in the side chain, it is preferable to contain at least a non-liquid crystal and non-crosslinked structural unit in terms of easy improvement of vertical orientation. More preferably, it contains both a non-liquid crystal and non-crosslinked structural unit and a non-liquid crystal and thermally crosslinked structural unit in terms of easy improvement of vertical orientation and easy improvement of durability.

[0638] In non-liquid crystal and non-crosslinked structural units with alkylene side chains, as R 13 The methyl group may have any substituents, such as non-thermally crosslinkable substituents, for example, halogen atoms such as fluorine, chlorine, and bromine atoms.

[0639] In non-liquid crystal and non-thermally crosslinked structural units with alkylene side chains, as L 2 Straight-chain or branched alkylene groups, or R 14 and R 15 The alkyl group may optionally have substituents, including non-thermally crosslinkable substituents such as halogen atoms (fluorine, chlorine, bromine, etc.), alkoxy groups, and nitro groups. Halogen atoms (fluorine, chlorine, bromine, etc.) are preferred.

[0640] In non-liquid crystal and non-crosslinked structural units with alkylene side chains, as R 13 R 14 and R 15 The aryl group may contain any substituents, including non-crosslinking substituents such as halogen atoms (e.g., fluorine, chlorine, bromine), alkyl groups, alkoxy groups, and nitro groups. The alkyl group may be 1 to 12 carbon atoms or 1 to 9 carbon atoms, and may be a straight-chain alkyl group or an alkyl group containing branches or ring structures. Preferably, the alkyl group contains halogen atoms (e.g., fluorine, chlorine, bromine) and has 1 to 9 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and cyclohexylpropyl. The hydrogen atoms in the alkyl group may be replaced with halogen atoms.

[0641] In non-liquid crystal and thermally crosslinked structural units with alkylene side chains, as R 13 methyl, L 2 Straight-chain or branched alkylene groups, R 14 and R 15 Alkyl groups, and R 13 R 14 and R 15The aryl group may optionally have substituents, preferably thermally crosslinkable groups. Examples of such thermally crosslinkable groups are those similar to those in copolymer (B) described below, such as at least one selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups. Of these, hydroxyl groups are preferred in terms of reactivity.

[0642] Preferably, one thermally crosslinked group is present in one non-liquid crystal and thermally crosslinked structural unit, but two or more are also permitted.

[0643] In non-liquid crystal and non-thermally crosslinked structural units containing alkylene side chains, L is particularly advantageous in terms of facilitating good vertical orientation. 2 Preferably -(CH2) n -(Here, n is an integer from 1 to 18.) Furthermore, n is preferably an integer from 3 to 17, more preferably an integer from 5 to 17. Additionally, n' is an integer from 1 to 18, preferably an integer from 3 to 17, more preferably an integer from 5 to 17.

[0644] On the other hand, in non-liquid crystal and thermally crosslinkable structural units with alkylene side chains, L is preferred in order to slow down the thermal crosslinking reaction. 2 It is 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.

[0645] Furthermore, in non-liquid crystal and non-thermally crosslinked structural units containing alkylene groups in the side chains, as R 14 and R 15 In terms of alkyl groups, straight-chain alkyl groups are preferred for their ability to facilitate good vertical orientation. On the other hand, in non-liquid crystal and thermally crosslinkable structural units with alkylene side chains, straight-chain, branched, or cyclic alkyl groups can be appropriately selected to slow down the thermal crosslinking reaction.

[0646] The non-liquid crystal structural unit is preferably a structural unit derived from a monomer having a polymerizable group containing an olefinic double bond. Examples of such monomers containing an olefinic double bond include derivatives of (meth)acrylate, styrene, (meth)acrylamide, maleimide, vinyl ether, or vinyl ester. In terms of vertical orientation, the non-liquid crystal structural unit is preferably a structural unit derived from a (meth)acrylate derivative or styrene, and more preferably a structural unit derived from a (meth)acrylate derivative.

[0647] In embodiments of the present invention, the non-liquid crystal structural unit described above preferably has a structural unit represented by the following formula (II).

[0648] [Chemical Formula 36]

[0649] Formula (1)

[0650]

[0651] (In general formula (II), R) 11 R represents a hydrogen atom or a methyl group. 12 Indicates -L 2” -R 13 or -L 2' -R 14 The group represented, L 2” It represents -(CH2) n -, L 2' It represents -(C2H4O) n' - Represents the linking group, R 13 This indicates a methyl group optionally having a substituent, an aryl group optionally having an alkyl group, or -OR. 15 R 14 and R 15 Each of the two groups independently represents an alkyl group optionally having a substituent or an aryl group optionally having a substituent, where n and n' are each independently integers from 1 to 18.

[0652] In the structural unit represented by equation (II), -L 2” -R 13 or -L 2' -R 14 The groups represented can be the same as those described above.

[0653] When the non-liquid crystal and non-thermally crosslinked structural unit is the structural unit represented by the above formula (II), the above-mentioned non-crosslinked substituent can be cited as an optional substituent contained in the structural unit represented by the above formula (II).

[0654] In embodiments of the present invention, when the above-mentioned non-liquid crystal structural unit contains a non-liquid crystal and thermally crosslinked structural unit, the non-liquid crystal and thermally crosslinked structural unit preferably has the structural unit represented by the following formula (III) in terms of improved reactivity and improved durability.

[0655] [Chemical Formula 37]

[0656] Equation (III)

[0657]

[0658] (In equation (III) above, Z) a R represents at least one monomer unit selected from the following formulas (a-1) to (a-6). 16 -L 2a -R 13′ - The group represented (here, L) 2aR represents a straight-chain or branched alkylene group having 1 to 10 carbon atoms in its carbon chain, optionally containing an -O- group. 13′ This indicates a residue from which a hydrogen atom is removed from an optional methyl group, a residue from which a hydrogen atom is removed from an aryl group, or -OR. 15′ R 15′ This indicates a residue from which a hydrogen atom has been removed from an aryl group. a (This indicates at least one thermally crosslinkable group selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups.)

[0659] [Chemical Formula 38]

[0660]

[0661] (In the above formulas (a-1) to (a-6), R) 11 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 17 R represents a hydrogen atom or a methyl group. 18 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 19 L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a Indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-, in L a In the case of a single bond, R 16 It bonds directly to the styrene skeleton.

[0662] R 16 -L 2a -R 13′ - The group represented (here, L) 2a R represents a straight-chain or branched alkylene group having 1 to 10 carbon atoms in its carbon chain, optionally containing an -O- group. 13′ This indicates a residue from which a hydrogen atom is removed from an optional methyl group, a residue from which a hydrogen atom is removed from an aryl group, or -OR. 15′ R 15′ This indicates a residue from which a hydrogen atom has been removed from an aryl group.

[0663] R 13′ and R 15′ The methyl or aryl groups, which are optionally substituents before the removal of the hydrogen atom, can respectively react with R 13 and R 15 same.

[0664] L 2aIt can be a straight-chain or branched alkylene group having -O- in the carbon chain from 1 to 6, or a straight-chain or branched alkylene group having -O- in the carbon chain from 1 to 4, or a straight-chain or branched alkylene group having -O- in the carbon chain from 1 to 3, or a straight-chain alkylene group having -O- in the carbon chain from 1 to 2, or methylene.

[0665] If L 2a When the carbon number is small, the distance between the thermal crosslinking group and the main skeleton of the copolymer in the thermal crosslinking structural unit becomes shorter. Therefore, it is difficult for the thermal crosslinking agent to bond with the thermal crosslinking group, and the reactivity between the thermal crosslinking structural unit and the thermal crosslinking agent decreases.

[0666] In L 2a In the case of optional branched alkylene groups having -O- in the carbon chain, thermally crosslinkable groups Y can be cited as examples. a The bonded carbon atom is a secondary or tertiary alkylene group. As R 16 The branched alkylene group can be optionally a branched alkylene group having -O- in the carbon chain, for example: methylmethylene, methylethylene, 1,1-dimethylethylene, 1-methylpropylene, ethylethylene, etc.

[0667] Additionally, in R 16 In this context, the substituents optionally present in the straight-chain or branched alkylene group having 1 to 11 carbon atoms in the carbon chain and optionally containing -O- can include non-thermally crosslinkable substituents, such as halogen atoms like fluorine, chlorine, and bromine, alkoxy groups, nitro groups, aryl groups optionally substituented, and aryloxy groups optionally substituented. Examples of substituents in the aryl group optionally substituented or the aryloxy group optionally substituented can be those related to the aforementioned R... 13 R 14 and R 15 The aryl group may be selected from those having the same substituents.

[0668] The copolymer may have one or more non-liquid crystal structural units containing alkylene groups in the side chains.

[0669] Examples of non-liquid crystal and non-thermally crosslinked structural units containing alkylene groups in their side chains include chemical formulas (II-1) to (II-10), but these are not limited to. Examples of non-liquid crystal and thermally crosslinked structural units containing alkylene groups in their side chains include chemical formulas (III-1) to (III-12), but these are not limited to.

[0670] [Chemical Formula 39]

[0671]

[0672] [Chemical Formula 40]

[0673]

[0674] In the synthesis of copolymers, monomers such as (meth)acrylate derivatives derived from the above-mentioned non-liquid crystal structural units can be used. These monomers can be used alone or in combination of two or more.

[0675] Regarding the content ratio of the aforementioned non-liquid crystal structural units in the copolymer, in terms of improving the vertical orientation of the liquid crystal structural units and having sufficient liquid crystal orientation, when the amount of structural units contained in the copolymer as a whole is set to 100 mol%, it is preferably set in the range of 10 mol% to 60 mol%, more preferably in the range of 15 mol% to 50 mol%, even more preferably in the range of 15 mol% to 45 mol%, and particularly preferably in the range of 20 mol% to 40 mol%.

[0676] As the aforementioned non-liquid crystal structural unit in the copolymer, when both non-liquid crystal and non-crosslinked structural units and non-liquid crystal and thermally crosslinked structural units are contained, the proportion of the non-liquid crystal and thermally crosslinked structural units is preferably set in the range of 5 mol% to 70 mol%, and more preferably in the range of 20 mol% to 50 mol%, when the total amount of non-liquid crystal structural units contained in the copolymer is set to 100 mol%.

[0677] It should be noted that the content ratio of each structural unit in the copolymer can be determined by... 1 It is calculated from the integrated value of H-NMR measurement.

[0678] (3) Other structural units

[0679] The side-chain type liquid crystal polymer (A) used in this invention has at least the above-mentioned liquid crystal structural unit and the above-mentioned non-liquid crystal structural unit containing alkylene in the side chain, but may also have other structural units.

[0680] Other structural units include, for example, a thermally crosslinked structural unit that does not contain alkylene groups in its side chains and contains the aforementioned thermally crosslinked groups in its side chains, and a photo-oriented structural unit in which the copolymer (B) contains photo-oriented groups in its side chains.

[0681] Examples of thermally crosslinking structural units that do not contain alkylene groups in their side chains but contain the aforementioned thermally crosslinking groups in their side chains include: (meth)acrylic acid, 4-hydroxyphenyl (meth)acrylic acid, 4-hydroxystyrene, 4-carboxystyrene, etc.

[0682] In terms of improving the durability and reliability of the phase retardation layer, it is preferable that the side-chain type liquid crystal polymer (A) used in the present invention has at least one thermally crosslinked structural unit selected from the following that contains thermally crosslinked groups in the side chain: a non-liquid crystal thermally crosslinked structural unit containing alkylene groups in the side chain, and a thermally crosslinked structural unit that does not contain alkylene groups in the side chain and has the above-mentioned thermally crosslinked groups.

[0683] As a photo-orientation structural unit, it can be the same as the photo-orientation structural unit with photo-orientation groups in the side chains of the copolymer (B) described below.

[0684] Regarding the content ratio of the other structural units mentioned above in the copolymer, in order to improve the vertical orientation of the liquid crystal structural units and have sufficient liquid crystal orientation, when the amount of structural units contained in the copolymer as a whole is set to 100 mol%, it is preferably set in the range of 30 mol% or less, and more preferably in the range of 20 mol% or less.

[0685] (4) Copolymer of side-chain liquid crystal polymer (A)

[0686] In embodiments of the present invention, the side-chain liquid crystal polymer (A) may be a block copolymer having a block portion comprising liquid crystal structural units and a block portion comprising non-liquid crystal structural units containing alkylene groups in the side chain, or it may be a random copolymer in which the liquid crystal structural units and the non-liquid crystal structural units containing alkylene groups in the side chain are arranged irregularly. In this embodiment, a random copolymer is preferred in terms of improving the vertical orientation and in-plane uniformity of the phase difference value of the side-chain liquid crystal polymer.

[0687] Furthermore, the mass-average molecular weight (Mw) of the side-chain liquid crystal polymer used as the copolymer is not particularly limited, but is preferably in the range of 5,000 to 80,000, more preferably in the range of 8,000 to 50,000, and even more preferably in the range of 10,000 to 36,000. By setting it within the above range, the liquid crystal composition exhibits excellent stability and excellent operability during the formation of the retardation layer.

[0688] It should be noted that the above-mentioned mass-average molecular weight Mw is a value determined by GPC (gel permeation chromatography). The determination was performed as follows: an HLC-8120 GPC manufactured by Tosoh Co., Ltd. was used, the dissolution solvent was N-methylpyrrolidone with 0.01 mol / L lithium bromide added, and the calibration curve was performed using polystyrene standards Mw377400, 210500, 96000, 50400, 206500, 10850, 5460, 2930, 1300, 580 (all of which are Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Co., Ltd.), and the assay column was set as TSK-GEL ALPHA-M×2 (manufactured by Tosoh Co., Ltd.).

[0689] As a method for synthesizing copolymers of side-chain type liquid crystal polymers (A), one example is to copolymerize monomers that derive liquid crystal structural units with monomers that derive non-liquid crystal structural units containing alkylene groups in the side chains by conventional manufacturing methods.

[0690] The side-chain liquid crystal polymer (A) can be used in solution form during copolymer synthesis, or in powder form, or in solution form obtained by redissolving the purified powder in the solvents described below.

[0691] The aforementioned side-chain liquid crystal polymer (A) can be used alone or in combination of two or more. In this embodiment, in terms of achieving vertical orientation, the content ratio of the aforementioned side-chain liquid crystal polymer (A) relative to 100 parts by mass of the solid component of the liquid crystal composition can be 60 to 99 parts by mass, more preferably 70 to 95 parts by mass, and even more preferably 30 to 60 parts by mass.

[0692] It should be noted that, in this invention, the term "solid component" refers to all components other than the solvent. For example, even if the polymerizable liquid crystal compound described below is in liquid form, it is still included in the solid component.

[0693] 2. Copolymer (B)

[0694] The copolymer (B) used in this invention has photooriented structural units containing photooriented groups in the side chains and thermally crosslinked structural units containing thermally crosslinked groups in the side chains through a specific structure.

[0695] The following describes each structural unit in the copolymer.

[0696] (1) Photooriented structural unit

[0697] The photo-orientation structural unit of the present invention exhibits anisotropic properties by generating a photoreaction through illumination. Preferably, the photoreaction is a photodimerization reaction or a photoisomerization reaction. That is, the photo-orientation structural unit is a photodimerization structural unit that exhibits anisotropic properties by generating a photodimerization reaction through illumination, or a photoisomerization structural unit that exhibits anisotropic properties by generating a photoisomerization reaction through illumination.

[0698] The photo-orientation structural unit has a photo-orientation group. As described above, the photo-orientation group is a functional group that exhibits anisotropy by generating a photoreaction under light, and is preferably a functional group that generates a photodimerization reaction or a photoisomerization reaction.

[0699] Examples of photo-orienting groups that generate photodimerization reactions include cinnamyl, chalcone, coumarin, anthracene, quinolinyl, azophenyl, and piracene. The benzene ring in these functional groups may optionally have substituents. Substituents can be any groups that do not hinder the photodimerization reaction; examples include alkyl, aryl, cycloalkyl, alkoxy, aryloxy, hydroxyl, halogen atoms, trifluoromethyl, and cyano groups.

[0700] The photo-orienting group that generates the photoisomerization reaction is preferably one that generates a cis-trans isomerization reaction, such as cinnamyl, chalcone, azophenyl, piracene, etc. The benzene ring in these functional groups may optionally have substituents. Substituents are acceptable as long as they do not hinder the photoisomerization reaction, such as alkoxy, alkyl, halogen atoms, trifluoromethyl, cyano, etc.

[0701] The photo-orientation group is preferably cinnamoyl. Specifically, the cinnamoyl group is preferably at least one selected from the groups represented by the following formulas (x-1) and (x-2).

[0702] [Chemical Formula 41]

[0703] Equation (x-1)

[0704]

[0705] Equation (x-2)

[0706]

[0707] In the above equation (x-1), R 31 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. The alkyl, aryl, and cycloalkyl groups may be bonded via ether bonds, ester bonds, amide bonds, or urea bonds, and optionally contain substituents. R 32 ~R 35Each of these groups 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. The alkyl, aryl, and cycloalkyl groups may be bonded via ether, ester, amide, or urea bonds, and may optionally contain substituents. R 36 and R 37 Each can independently represent 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.

[0708] In addition, in the above equation (x-2), R 41 ~R 45 Each of these groups 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. The alkyl, aryl, and cycloalkyl groups may be bonded via ether, ester, amide, or urea bonds, and may optionally contain substituents. R 46 and R 47 Each can independently represent 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.

[0709] It should be noted that when the photo-orientation group is cinnamoyl and is the group represented by the above formula (x-1), the benzene ring of the styrene skeleton (formula (1-2)) contained in the monomer unit can become the benzene ring of cinnamoyl.

[0710] Furthermore, the cinnamyl group represented by the above formula (x-1) is more preferably the group represented by the following formula (x-3).

[0711] [Chemical Formula 42]

[0712] Equation (x-3)

[0713]

[0714] In the above equation (x-3), R 32 ~R 37 Same as equation (x-1) above. R 38 This represents a hydrogen atom, an alkoxy group (1-18 carbon atoms), a cyano group, an alkyl group (1-18 carbon atoms), a phenyl group, a biphenyl group, or a cyclohexyl group. Alkyl, phenyl, biphenyl, and cyclohexyl groups can be bonded via ether, ester, amide, or urea bonds. n represents 1-5, R... 38 Bonding can occur at adjacent, intermediate, or contralateral sites. When n is 2–5, R 38 They can be the same or different. Preferably, n is 1, and R... 38 Bonding at the alignment.

[0715] When the photoorientation group is at least one selected from the groups represented by formulas (x-3) and (x-2) above, the aromatic ring is positioned near the end of the photoorientation structural unit and contains more π electrons. It is believed that this increases the affinity with the liquid crystal layer formed on the alignment layer, improves the liquid crystal alignment energy, and enhances the adhesion to the liquid crystal layer.

[0716] Examples of monomeric units constituting photooriented structural units include: acrylates, methacrylates, styrene, acrylamide, methacrylamide, maleimide, vinyl ether, vinyl ester, etc. Among these, acrylates, methacrylates, and styrene are preferred in terms of ease of raw material supply.

[0717] As the optical orientation structural unit of the present invention, the structural unit represented by the following formula (1) can be exemplified.

[0718] [Chemical Formula 43]

[0719] Equation (1)

[0720]

[0721] (In the above formula (1), Z) 1 The expression represents at least one monomer unit selected from formulas (1-1) to (1-6) below, where X represents a photooriented group, and L represents a photooriented group. 11 This indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, alkylene, arylene, cycloalkylene, or a combination thereof.

[0722] [Chemical Formula 44]

[0723]

[0724] (In the above equations (1-1) to (1-6), R) 21 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 22 R represents a hydrogen atom or a methyl group. 23 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 24 (This refers to a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[0725] As a single unit constituting the optical orientation structural unit, at least one selected from formulas (1-1) to (1-6) above can be cited. It should be noted that in Z... 1 In the case where at least one of formulas (1-2) is selected, -L 11 -X can bond to any of the ortho, meta, or para positions. In terms of ease of achieving photoorientation by reducing the distance between photoorientation groups, -L... 11 -X is preferred for bonding at the alignment point.

[0726] As the monomer unit constituting the photo-orientation structural unit, in terms of the ease of raw material supply, it is preferable to select at least one of formulas (1-1) and (1-2). Furthermore, if it is selected from at least one of formulas (1-2), it is more preferable in that the rigidity of the photo-orientation structural unit of the copolymer (B) is increased, so the distance between the photo-orientation groups is easier to reduce, and excellent photo-orientation is easier to obtain. In addition, if the copolymer has a styrene backbone and contains more π electrons, it is believed that through the interaction of the π electrons, the adhesion between the orientation layer and the retardation layer formed by the photo-orientation thermosetting liquid crystal composition of the present invention and the liquid crystal material directly stacked on the orientation layer and retardation layer is also increased.

[0727] In formula (1) above, X represents a photo-orientation group, which can be the same as described above, and can be selected from at least one of cinnamyl, chalcone, coumarin, anthracene, quinolinyl, azophenyl, and styrene. The benzene ring in these functional groups may optionally have substituents. Substituents can be any groups that do not hinder photodimerization or photoisomerization reactions, such as alkyl, aryl, cycloalkyl, alkoxy, hydroxyl, halogen atoms, trifluoromethyl, cyano, etc.

[0728] The photo-orientation group is preferably cinnamoyl. Specifically, it is preferably the group represented by formulas (x-1) and (x-2) above.

[0729] L 11 The term represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, alkylene, arylene, cycloalkylene, or a combination thereof, connecting the aforementioned monomer unit to the photooriented group X.

[0730] In the above L 11 In the case of a single bond, the photooriented group X and the monomer unit Z 1 Direct bonding. Examples of divalent linking groups include: -O-, -S-, -COO-, -COS-, -CO-, -OCO-, and -(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- represents phenylene, -C6H 10 - indicates subcyclohexyl. n is 1 to 20, m is 1 to 10.

[0731] Regarding photoorientation, it is preferable that the alkylene chain between the aforementioned monomer unit and the photoorientation group X is shorter. It is speculated that by making the alkylene chain shorter in the photoorientation structural unit, rigidity increases, the distance between the photoorientation groups is easier to reduce, and photoorientation (liquid crystal alignment energy) is improved.

[0732] Regarding the orientation of light, it is preferable that n and m are smaller than described above, with n preferably being 1 to 6, more preferably 1 to 4, and m preferably being 1 to 3, more preferably 1 to 2.

[0733] Regarding photoorientation, the photoorientation structural unit is more preferably a structure in which there is no alkylene chain between the photoorientation group and the main chain of the copolymer (B), L 11 More preferably, it is a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, or a combination of these with an aryl group.

[0734] The copolymer (B) may have one or more photo-oriented structural units.

[0735] In the synthesis of copolymer (B), monomers having photo-orientation groups derived from the above-mentioned photo-orientation structural units can be used. Monomers having photo-orientation groups can be used alone or in combination of two or more.

[0736] Regarding the proportion of photo-alignment structural units in copolymer (B), when the amount of structural units contained in the total copolymer (B) is set to 100 mol%, it can be set in the range of 10 mol% to 90 mol%, preferably in the range of 20 mol% to 80 mol%. If the proportion of photo-alignment structural units is low, the sensitivity decreases, making it difficult to impart good liquid crystal alignment energy. On the other hand, if the proportion of photo-alignment structural units is high, the proportion of thermally crosslinking structural units is relatively low, resulting in insufficient thermosetting properties and difficulty in maintaining good liquid crystal alignment energy.

[0737] (2) Thermally cross-linked structural unit

[0738] The thermally crosslinkable structural units in the copolymer (B) of the present invention are sites that are bonded to the thermally crosslinking agent by heating, and have the structural units represented by the following formula (2).

[0739] [Chemical Formula 45]

[0740] Equation (2)

[0741]

[0742] (In the above formula (2), Z) 2 R represents at least one monomer unit selected from the following formulas (2-1) to (2-6). 50 The alkylene group is a straight-chain alkylene group with 4 to 11 carbon atoms, optionally having an -O- group in the carbon chain. Y represents at least one thermally crosslinking group selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups.

[0743] [Chemical Formula 46]

[0744]

[0745] (In the above equations (2-1) to (2-6), R) 51 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 52 R represents a hydrogen atom or a methyl group. 53 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 54 L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 12 Indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-, in L 12 In the case of a single bond, R 50 It bonds directly to the styrene skeleton.

[0746] 在 In the above general formula (2), the thermally crosslinking group Y is bonded to a straight-chain alkylene group R, optionally having 4 to 11 carbon atoms with -O- in the carbon chain. 50 Since the carbon atom bonded to the end of the thermal crosslinking group is a primary carbon, its reactivity is increased. From a reactivity point of view, the hydroxyl group is preferred as the thermal crosslinking group.

[0747] In equation (2) above, L 12 This indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-. It should be noted that in L... 12 In the case of a single bond, the thermally crosslinking group Y and the monomer unit Z 2 Direct bonding.

[0748] R 50The linear alkylene group with 4 to 11 carbon atoms having -O- is selected as the thermal crosslinking structural unit. Therefore, the distance between the thermal crosslinking group and the main skeleton of the copolymer is appropriately increased in the thermal crosslinking structural unit. As a result, the thermal crosslinking agent is more likely to bond with the thermal crosslinking group, the reactivity between the thermal crosslinking structural unit and the thermal crosslinking agent is increased, and the curing speed of the copolymer (B) is faster.

[0749] Among them, R 50 Preferably -(CH2) j -or-(C2H4O) k -C2H4- (j is 4 to 11, k is 1 to 4). More preferably, j is 6 to 11, and k is 2 to 4. If j and k are too small, the distance between the thermally crosslinking group and the main skeleton of the copolymer becomes shorter in the thermally crosslinking structural unit. Therefore, it is difficult for the thermally crosslinking agent to bond with the thermally crosslinking group, raising concerns about decreased reactivity between the thermally crosslinking structural unit and the thermally crosslinking agent. On the other hand, if j and k are too large, the chain length of the connecting group becomes longer in the thermally crosslinking structural unit. Therefore, it is difficult for the terminal thermally crosslinking group to expose the surface, making it difficult for the thermally crosslinking agent to bond with the thermally crosslinking group, raising concerns about decreased reactivity between the thermally crosslinking structural unit and the thermally crosslinking agent.

[0750] In Z 2 In the case where at least one of the formulas (2-2) is selected, -L 12 -R 50 -Y can bond at any of the ortho, meta, or para positions. Regarding its excellent thermal crosslinking reactivity, -L... 12 -R 50 -Y is preferably bonded at the alignment point.

[0751] As a monomer unit constituting a thermally crosslinkable structural unit, it is preferred to be selected from at least one of formulas (2-1) and (2-2) in terms of ease of raw material supply.

[0752] The copolymer (B) may have one or more thermally crosslinking structural units.

[0753] It should be noted that when the copolymer (B) contains two or more thermally crosslinkable structural units having the structural units represented by formula (2), as long as the linear alkylene group with the largest number of carbons, having 4 to 11 carbons and having -O- in the carbon chain, satisfies any one of (i) to (iv) above when compared with all the non-liquid crystal and thermally crosslinkable structural units of the side-chain liquid crystal polymer (A).

[0754] In the synthesis of copolymer (B), monomers having thermally crosslinking groups that derive the aforementioned thermally crosslinking structural units can be used. Monomers having thermally crosslinking groups can be used alone or in combination of two or more.

[0755] Regarding the proportion of thermally crosslinkable structural units in copolymer (B), when the amount of structural units contained in the total copolymer (B) is set to 100 mol%, it can be set in the range of 10 mol% to 90 mol%, preferably in the range of 20 mol% to 80 mol%. If the proportion of thermally crosslinkable structural units is low, sufficient thermosetting properties may not be obtained, making it difficult to maintain good liquid crystal alignment energy. On the other hand, if the proportion of thermally crosslinkable structural units is high, the proportion of photo-alignment structural units will be relatively low, resulting in decreased sensitivity and difficulty in imparting good liquid crystal alignment energy.

[0756] (3) Other structural units

[0757] In this invention, the copolymer (B) may have other structural units in addition to the aforementioned photo-orientation structural units and thermal crosslinking structural units. By including other structural units in the copolymer (B), for example, solvent solubility, heat resistance, reactivity, etc., can be improved.

[0758] Other structural units may include self-crosslinking structural units that have the same crosslinking groups and can crosslink with each other. Examples of self-crosslinking groups include hydroxymethyl, alkoxymethyl, trialkoxysilyl, and terminal isocyanate groups.

[0759] In the case where the copolymer (B) has a self-crosslinking structural unit in addition to the aforementioned thermal crosslinking structural unit, the self-crosslinking structural unit can also act as a thermal crosslinking agent, which is preferred in terms of easily improving photoorientation ability and solvent resistance.

[0760] When the copolymer (B) also has self-crosslinking structural units, it is easy to react with the intramolecular thermal crosslinking structural units, thus making it easy to thermally crosslink the copolymer (B). On the other hand, it is difficult to thermally crosslink the side-chain liquid crystal polymer (A). Therefore, the curing of the copolymer (B) as a photo-aligned film material in the composition can be effectively promoted, while the curing of the side-chain liquid crystal polymer (A) with vertical orientation is inhibited.

[0761] Examples of monomers having self-crosslinking groups include: N-hydroxymethylacrylamide, N-hydroxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide and N-butoxymethylacrylamide, etc., which are acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl or alkoxymethyl groups; monomers having trialkoxysilyl groups such as 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, 3-triethoxysilylpropyl methacrylate; and monomers having end-capped isocyanate groups such as 2-(O-(1'-methylpropyleneamino)carboxyamino)ethyl methacrylate, 2-(3,5-dimethylpyrazolyl)carbonylaminoethyl methacrylate.

[0762] Examples of monomeric units constituting structural units that do not have photo-oriented or thermally crosslinking groups include: acrylates, methacrylates, maleimide, acrylamide, acrylonitrile, maleic anhydride, styrene, and vinyl groups. Among these, acrylates, methacrylates, and styrene are preferred, similar to the thermally crosslinking structural units described above.

[0763] Examples of monomers that form structural units lacking photo-orientation groups and thermal crosslinking groups include: acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds. Specifically, monomers that do not possess either the aforementioned photo-orientation groups or thermal crosslinking groups, as described in paragraphs 0036 to 0040 of International Publication No. 2010 / 150748, can be used.

[0764] Additionally, other structural units may be included, for example, structural units derived from monomers having fluorinated alkyl groups. In this case, the copolymer (B) readily exists locally on the coating surface, and the photo-orientation groups readily orient on the coating surface. Regarding the ease with which the copolymer (B) readily exists locally on the coating surface, the fluorinated alkyl group of the monomer having fluorinated alkyl groups may be a fluorinated alkyl group with 2 to 8 carbon atoms directly bonded to the fluorine atom.

[0765] The other structural units in copolymer (B) may be one or more.

[0766] Regarding the content percentage of the other structural units in copolymer (B), when the amount of structural units contained in the copolymer (B) as a whole is set to 100 mol%, it is preferably in the range of 0 mol% to 50 mol%, and more preferably in the range of 0 mol% to 30 mol%. If the content percentage of the above-mentioned structural units is too high, the content percentage of the above-mentioned photo-orientation structural units and the above-mentioned thermal crosslinking structural units will be relatively low, resulting in the following situation: decreased sensitivity, difficulty in imparting good liquid crystal orientation energy, and inability to obtain sufficient thermosetting properties, making it difficult to maintain good liquid crystal orientation energy.

[0767] (4) Copolymer (B)

[0768] The mass-average molecular weight of copolymer (B) is not particularly limited, but can be, for example, around 3,000 to 200,000, preferably in the range of 4,000 to 100,000. If the mass-average molecular weight is too high, the solubility in solvents will decrease or the viscosity will increase, resulting in reduced workability and difficulty in forming a uniform film. On the other hand, if the mass-average molecular weight is too low, the curing will be insufficient during thermosetting, and the solvent resistance and heat resistance will decrease.

[0769] It should be noted that the mass-average molecular weight can be determined by gel permeation chromatography (GPC).

[0770] As a method for synthesizing copolymer (B), one example is to copolymerize a monomer having photo-orientation groups with a monomer having thermal crosslinking groups by a conventionally known manufacturing method.

[0771] The copolymer (B) can be used in the form of a solution during copolymer synthesis, or in the form of a powder, or in the form of a solution obtained by redissolving the purified powder in the solvents described below.

[0772] The copolymer (B) described above can be used alone or in combination of two or more. In this embodiment, in terms of exerting orientation energy on the directly laminated liquid crystal material, the content ratio of the copolymer (B) relative to 100 parts by mass of the solid component of the liquid crystal composition 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.

[0773] 3. Thermal crosslinking agent

[0774] The photo-oriented thermosetting liquid crystal composition of the present invention contains a thermal crosslinking agent bonded to the thermal crosslinking groups of the above-mentioned thermal crosslinking structural unit.

[0775] In the second photo-oriented thermosetting liquid crystal composition of the present invention, the thermal crosslinking agent (C) may be the same as the thermal crosslinking agent (C) in the first photo-oriented thermosetting liquid crystal composition, and therefore the description is omitted here.

[0776] In the second photo-oriented thermosetting liquid crystal composition of the present invention, the decrease in vertical orientation can be suppressed by appropriately adjusting the content of the thermal crosslinking agent (C) according to the structure of the thermal crosslinking structural unit of the side-chain type liquid crystal polymer (A).

[0777] Furthermore, in the second photo-oriented thermosetting liquid crystal composition of the present invention, the acid or acid-generating agent, solvent, and other components may be the same as those in the first photo-oriented thermosetting liquid crystal composition, and therefore the description here is omitted.

[0778] Furthermore, in the second photo-oriented thermosetting liquid crystal composition of the present invention, the preparation method and application are the same as those in the first photo-oriented thermosetting liquid crystal composition, therefore the description here is omitted.

[0779] B. Orientation film and phase difference film

[0780] The second alignment film and phase retardation film of the present invention is characterized in that it contains an alignment layer and a phase retardation layer, and the alignment layer and phase retardation layer is a cured film of the second photo-oriented thermosetting liquid crystal composition of the present invention.

[0781] The second alignment film and retardation film of the present invention are the same as the first alignment film and retardation film of the present invention, except that the photo-oriented thermosetting liquid crystal composition used is different, so the description here is omitted.

[0782] C. Manufacturing method of alignment film and phase retardation film

[0783] The method for manufacturing the second orientation film and retardation film of the present invention comprises:

[0784] The process of forming a film of the second photo-oriented thermosetting liquid crystal composition of the present invention,

[0785] The process of forming a cured film with a phase difference by heating the thermosetting liquid crystal composition formed above, and...

[0786] The process of imparting liquid crystal alignment energy to the aforementioned cured film by irradiating it with polarized ultraviolet light with a phase difference.

[0787] The manufacturing method of the second alignment film and retardation film of the present invention is the same as that of the first alignment film and retardation film of the present invention, except that the photo-oriented thermosetting liquid crystal composition used is different. Therefore, the description here is omitted.

[0788] D. Phase Difference Plate

[0789] The second phase difference plate of the present invention is characterized in that it comprises:

[0790] The first phase difference layer of the cured film of the second photo-oriented thermosetting liquid crystal composition of the present invention, and

[0791] A second phase retardation layer comprising a cured material containing a polymeric liquid crystal composition is disposed adjacent to the first phase retardation layer described above.

[0792] The second phase retardation plate and its manufacturing method of the present invention are the same as the first phase retardation plate and its manufacturing method described above, except that the photo-oriented thermosetting liquid crystal composition used is different. Therefore, the description here is omitted.

[0793] III. The Third Invention

[0794] This invention provides a third phase difference plate, which comprises:

[0795] As a positive C-type phase retardation layer of a cured thermosetting resin composition containing photooriented components and a thermal crosslinking agent, and

[0796] A positive A-type phase retardation layer containing a polymeric liquid crystal composition is disposed directly adjacent to the aforementioned positive C-type phase retardation layer.

[0797] Figure 5 This is a schematic cross-sectional view illustrating an example of the third phase difference plate of the present invention. Figure 5 In the illustrated phase retardation plate 30, a positive C-type phase retardation layer 21 is formed on the substrate 23, and the positive C-type phase retardation layer 21 is directly stacked with the positive A-type phase retardation layer 22.

[0798] In the third retardation plate 30 of the present invention, the positive C-type retardation layer 21 is a cured product of a thermosetting resin composition containing a photo-alignment component and a thermal crosslinking agent, and is directly laminated with the positive A-type retardation layer 22. Therefore, the positive C-type retardation layer 21 also possesses liquid crystal alignment capabilities. This positive C-type retardation layer 21 is a cured product of a thermosetting resin composition containing a thermal crosslinking agent. Therefore, compared to the case of a cured product of a photocurable resin composition containing a polymeric liquid crystal compound, the positive C-type retardation layer 21 is less prone to hardening and possesses flexibility, and its adhesion to the directly laminated positive A-type retardation layer is also improved. Compared to the case of a cured product of a photocurable resin composition containing a polymeric liquid crystal compound, the positive C-type retardation layer of the present invention, containing a thermosetting resin composition with a thermal crosslinking agent, easily forms a suitable penetration region at the interface with the directly laminated positive A-type retardation layer to a degree that does not hinder the vertical alignment of the positive C-type retardation layer, thereby easily improving adhesion.

[0799] The third retardation plate of the present invention directly laminates a positive C-type retardation layer and a positive A-type retardation layer with good adhesion, eliminating the need for adhesive layers as in conventional bonding, thus allowing for a thinner plate. Furthermore, the positive C-type retardation layer's flexibility enables the fabrication of a retardation plate with excellent bending resistance.

[0800] Figure 5 In one embodiment of the third retardation plate 30 shown in the example, the substrate 23 is directly laminated with the positive C-type retardation layer 21. This allows for... Figure 5 The example shown illustrates a third retardation plate that imparts an orientation-restricting force to the side surface of the positive C-shaped retardation layer 21 of the substrate 23. One embodiment of the third retardation plate may consist of a substrate, an alignment film, and a positive C-shaped retardation layer stacked sequentially.

[0801] It should be noted that the substrate and alignment film are the same as those described in "B. Alignment film and phase difference film" above, so the explanation here is omitted.

[0802] In the third phase retardation plate of the present invention, in terms of improving productivity, it is preferable that there is no alignment film between the substrate and the positive C-type phase retardation layer, and it is preferable that there is a substrate disposed directly adjacent to the positive C-type phase retardation layer.

[0803] Furthermore, in the third phase difference plate of the present invention, in terms of reducing the thickness after manufacturing, the substrate can be removed without a substrate after manufacturing.

[0804] 1. Positive C-type phase difference layer

[0805] As a photo-alignment component used in the positive C-type retardation layer of a cured thermosetting resin composition containing a photo-alignment component and a thermal crosslinking agent, examples include compounds or polymers containing photo-alignment groups. Examples of photo-alignment components include: copolymers having photo-alignment structural units with photo-alignment groups on their side chains and thermal crosslinking structural units with thermal crosslinking groups on their side chains, and compounds having photo-alignment groups and thermal crosslinking groups that are different from the aforementioned copolymers. The photo-alignment structural units with photo-alignment groups on their side chains in the aforementioned copolymers may be the same as the photo-alignment structural units of copolymer (B) in the aforementioned first or second photo-aligned thermosetting liquid crystal compositions. Furthermore, the thermal crosslinking structural units with thermal crosslinking groups on their side chains in the aforementioned copolymers may be the same as the thermal crosslinking structural units of copolymer (B) mentioned above. Additionally, other components and properties of the aforementioned copolymers may also be the same as those of copolymer (B).

[0806] Furthermore, the compound having photo-orientation groups and thermal crosslinking groups, which are different from the copolymers described above, may be the same as the compound having photo-orientation groups and thermal crosslinking groups that are different from the copolymers (B) in the first or second photo-orientation thermosetting liquid crystal compositions described above.

[0807] As for the photo-alignment component used in the positive C-type phase difference layer of the cured thermosetting resin composition containing a photo-alignment component and a thermal crosslinking agent, in terms of exhibiting good vertical alignment and liquid crystal alignment energy, a copolymer having a photo-alignment structural unit having a photo-alignment structural unit having a photo-alignment group in the side chain and a thermal crosslinking structural unit having a thermal crosslinking group in the side chain can be used. The copolymer (B) in the first or second photo-alignment thermosetting liquid crystal composition can be used.

[0808] The thermal crosslinking agent used in the positive C-type phase difference layer of the cured thermosetting resin composition containing photo-oriented components and thermal crosslinking agents can be the same as the thermal crosslinking agent (C) in the first or second photo-oriented thermosetting liquid crystal compositions described above.

[0809] The structures of photoorientation components and thermal crosslinking agents contained in the positive C-type retardation layer can be analyzed using methods such as NMR, IR, GC-MS, XPS, TOF-SIMS, and combinations thereof. For example, material can be taken from the positive C-type retardation layer, and the chemical structures of the photoorientation components and thermal crosslinking agents can be analyzed by nuclear magnetic resonance spectroscopy (NMR). Furthermore, fragments originating from photoorientation groups can be detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS). Moreover, the peaks of bonds and functional groups originating from thermal crosslinking agents and photoorientation components can be identified 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 combining these analytical results.

[0810] The thermosetting resin composition used in the aforementioned positive C-type retardation layer contains a liquid crystal component for expressing the retardation. As the liquid crystal component, a side-chain type liquid crystal polymer is preferred, as it readily achieves good vertical alignment even when mixed with a photo-alignment component and readily imparts flexibility. The liquid crystal structural unit with a liquid crystal portion in the side chain of the aforementioned side-chain type liquid crystal polymer may be the same as the liquid crystal structural unit of the side-chain type liquid crystal polymer (A) in the aforementioned first or second photo-alignment thermosetting liquid crystal composition.

[0811] The aforementioned side-chain liquid crystal polymer may or may not have non-liquid crystal structural units containing alkylene groups in its side chains. The non-liquid crystal structural units that may be present in the aforementioned side-chain liquid crystal polymer may be the same as the non-liquid crystal structural units and other structural units of the side-chain liquid crystal polymer (A) in the aforementioned first or second photo-oriented thermosetting liquid crystal compositions. Furthermore, other components and properties of the aforementioned side-chain liquid crystal polymer may also be the same as those of the aforementioned side-chain liquid crystal polymer (A).

[0812] The thermosetting resin composition used in the aforementioned positive C-type retardation layer may contain an acid or acid-generating agent, a solvent, and other components. The acid or acid-generating agent, solvent, and other components may be the same as those in the first photo-oriented thermosetting liquid crystal composition.

[0813] The aforementioned positive C-type phase retardation layer can be a structure comprising a vertically oriented side-chain liquid crystal polymer in one layer, a photodimerization or photoisomerization structure with photo-oriented groups, and a cross-linked structure formed by bonding thermally cross-linking groups with a thermally cross-linking agent. Alternatively, the aforementioned positive C-type phase retardation layer can be a copolymer comprising a vertically oriented side-chain liquid crystal polymer in one layer, a photodimerization or photoisomerization structure having photo-oriented groups in photo-oriented structural units, and a cross-linked structure formed by bonding thermally cross-linking groups in thermally cross-linked structural units with a thermally cross-linking agent.

[0814] The photodimerization structure or photoisomerization structure of the photo-orientation groups contained in the above-mentioned positive C-type phase difference layer, and the cross-linking structure formed by the bonding of thermal cross-linking groups and thermal cross-linking agents, can be the same as the orientation layer and phase difference layer described in "B. Orientation film and phase difference film".

[0815] In the third retardation plate of the present invention, from the aspect of producing a retardation plate with good bending resistance, it is preferable to adjust the composite elastic modulus of the positive C-shaped retardation layer. The composite elastic modulus of the positive C-shaped retardation layer can be 4.5 GPa or more and 9.0 GPa or less, or 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-shaped retardation layer is a cured product of a thermosetting resin composition, the composite elastic modulus can be easily adjusted.

[0816] The composite elastic modulus of the positive C-type retardation layer is set as follows: the indentation hardness (H) is measured on the surface of the positive C-type retardation layer. IT The contact projected area A obtained when ) pEr is calculated by the following mathematical formula (1). The so-called "indentation hardness" refers to the value obtained from the load-displacement curve from the loading to the unloading of the indenter, which is obtained by hardness measurement using the nanoindentation method. The composite elastic modulus of the positive C-type retardation layer is the elastic modulus that includes the elastic deformation of the positive C-type retardation layer and the elastic deformation of the indenter.

[0817] It should be noted that 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. Specifically, the composite elastic modulus of the positive C-type retardation layer can be obtained using the method for determining the composite elastic modulus described in the embodiments.

[0818] [Mathematical Expression 1]

[0819]

[0820] (In the above mathematical formula (1), Ap is the contact projected area, Er is the composite elastic modulus of the orientation film and phase difference layer, and S is the contact rigidity.)

[0821] In the third retardation plate of the present invention, the aforementioned positive C-type retardation layer may include a region permeated with a specific component contained in the aforementioned positive A-type retardation layer. Furthermore, the aforementioned specific component may contain a polymeric liquid crystal compound or a cured form thereof.

[0822] The existence of the permeation zone and its specific components can be analyzed through the following steps.

[0823] First, while etching the surface of the positive A-type retardation layer of the third retardation plate of the present invention in the film thickness direction using a gas cluster ion beam (Ar-GCIB) gun, measurements are performed using a time-of-flight secondary ion mass spectrometry (TOF-SIMS) apparatus. Furthermore, the distribution of fragment ions originating from the polymerizable liquid crystal compound contained in the positive A-type retardation layer and fragment ions originating from the photo-orientation component contained in the positive C-type retardation layer in the film thickness direction is analyzed. The permeation region can be measured as a portion that detects both fragment ions originating from the polymerizable liquid crystal compound and fragment ions originating from the photo-orientation component.

[0824] In addition, the thickness of the permeation region can be estimated based on the proportion of the permeation region in the film thickness direction of each fragment ion of TOF-SIMS, according to the film thickness measured using a scanning transmission electron microscope (STEM).

[0825] The thickness of the aforementioned positive C-type retardation layer can be appropriately set according to the application. Preferably, it is 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm.

[0826] 2. Positive A-type phase retardation layer

[0827] In the third phase retardation plate of the present invention, the above-mentioned positive A-type phase retardation layer contains a cured polymeric liquid crystal composition.

[0828] In the third phase difference plate of the present invention, the above-mentioned positive A-type phase difference layer may be the same as the second phase difference layer in the first or second phase difference plate.

[0829] 3. Phase difference plate

[0830] In the third phase retardation plate of the present invention, the thickness direction phase difference Rth at a wavelength of 550nm is -35nm to 35nm, the in-plane phase difference Re at a wavelength of 550nm is 100nm or more, and the total thickness of the positive C-type phase retardation layer and the positive A-type phase retardation layer can be 0.2μm to 6μm.

[0831] The phase difference Rth in the thickness direction at a wavelength of 550nm can be -30nm to 30nm, and further can be -25nm to 25nm.

[0832] In addition, the in-plane phase difference Re at a wavelength of 550nm can be above 120nm, and further above 135nm.

[0833] The thickness-direction phase difference Rth and the in-plane phase difference Re at a wavelength of 550nm can be obtained specifically through the methods described in the embodiments.

[0834] The combined thickness of the positive C-type retardation layer and the positive A-type retardation layer can be 0.8 μm to 5 μm, and further can be 1 μm to 4 μm.

[0835] The combined thickness of the positive C-type phasing layer and the positive A-type phasing layer can be obtained by using the scanning transmission electron microscope (STEM) described in the examples.

[0836] 4. Manufacturing method of phase retardation plate

[0837] The method of manufacturing the third phase difference plate is not particularly limited as long as the aforementioned third phase difference plate can be provided.

[0838] The manufacturing method of the third phase difference plate may include, for example:

[0839] The process of forming a film of a photo-oriented thermosetting liquid crystal composition, wherein the photo-oriented thermosetting liquid crystal composition comprises: a side-chain type liquid crystal polymer having a liquid crystal structural unit having a liquid crystal portion in the side chain, a copolymer having a photo-oriented structural unit and a thermally crosslinking structural unit having a thermally crosslinking group in the side chain, and a thermally crosslinking agent bonded to the thermally crosslinking group of the aforementioned thermally crosslinking structural unit.

[0840] A process of forming a cured film with a phase difference by heating the thermosetting liquid crystal composition formed above;

[0841] The process of forming a positive C-type phase difference layer that imparts liquid crystal alignment energy by irradiating the above-mentioned cured film with phase difference with polarized ultraviolet light.

[0842] A process involving coating a polymerizable liquid crystal composition onto the aforementioned positive C-type retardation layer to form a coating film of the polymerizable liquid crystal composition, heating the coating film to the phase transition temperature of the polymerizable liquid crystal composition, thereby aligning liquid crystal molecules using the aforementioned positive C-type retardation layer; and

[0843] The process involves curing a coating of a polymeric liquid crystal composition in which the above-mentioned liquid crystal molecules have been oriented by light to form a positive A-type phase retardation layer.

[0844] The components of the photo-oriented thermosetting liquid crystal composition may be the same as those described in the third phase retardation plate.

[0845] The manufacturing method of the third phase difference plate can refer to the manufacturing method of the first or second phase difference plate, and each process is carried out in the same way.

[0846] Next, an optical component using the phase retardation plate of the first, second, or third invention, a method for manufacturing the same, and a display device will be described.

[0847] E. Optical components

[0848] The present invention provides an optical component comprising a first, second or third phase difference plate and a polarizing plate.

[0849] The optical components of this embodiment are described with reference to the accompanying drawings. Figure 6 This is a schematic cross-sectional view showing one embodiment of the optical component.

[0850] Figure 6 In one example of the optical component 50, the phase retardation plate 30 of the present invention described above and a polarizing plate 40 disposed adjacent to the phase retardation plate are included. An adhesive layer (not shown) may be provided between the phase retardation plate 30 and the polarizing plate 40 as needed. As the phase retardation plate 30 of the present invention, a first, second, or third phase retardation plate may be used.

[0851] Figure 6 In the example of the optical component 50, a polarizing plate 40 is disposed on a phase retardation plate 30 on which the first phase retardation layer 31 and the second phase retardation layer 32 of the present invention are directly stacked. The first phase retardation layer 31 and the second phase retardation layer 32 may be the positive C-type phase retardation layer and the positive A-type phase retardation layer, respectively.

[0852] In this embodiment, the first, second, or third phase difference plate of the present invention may be the same as described above, so the description here is omitted.

[0853] In this embodiment, the polarizing plate is a plate-shaped device that allows only light vibrating in a specific direction to pass through, and can be appropriately selected from conventionally known polarizing plates. In this embodiment, the polarizing plate can be a linear polarizing plate.

[0854] Examples of linear polarizing plates include those containing a polarizer and a polarizer protective layer disposed on at least one side of the polarizer.

[0855] Examples of polarizers include: a stretched film or stretched layer adsorbed with an anisotropic pigment, or a film coated with an anisotropic pigment and then cured. Examples of anisotropic pigments include dichroic pigments. Specifically, iodine or dichroic organic dyes can be used as dichroic pigments.

[0856] As a stretched film that adsorbs pigments with anisotropic absorption properties, examples include polyvinyl alcohol films, polyvinyl alcohol acetal films, polyvinyl alcohol acetal films, and ethylene-vinyl acetate copolymer saponified films that are dyed and stretched by iodine or dyes.

[0857] As a linear polarizing plate, it can be used, for example, by referring to sections 0025 to 0059 of Japanese Patent Application Publication No. 2021-51287.

[0858] The thickness of the polarizing plate is, for example, 2 μm or more and 100 μm or less, preferably 10 μm or more and 60 μm or less.

[0859] Furthermore, in this embodiment, the adhesive or bonding agent used as the adhesive layer can be appropriately selected from those already known, and any bonding type such as pressure-sensitive adhesive, two-component curing adhesive, UV-curing adhesive, thermosetting adhesive, or hot-melt adhesive can be used. In terms of transparency, weather resistance, and heat resistance, the adhesive for the adhesive layer is preferably an adhesive composition based on a (meth)acrylic resin polymer.

[0860] The thickness of the adhesive layer can be determined according to its adhesive strength, etc., for example, it can be 1μm to 50μm, preferably 2μm to 45μm, more preferably 3μm to 40μm, and even more preferably 5μm to 35μm.

[0861] In the optical component of this embodiment, in addition to the polarizing plate, other layers commonly found in known optical components may also be included. Examples of such other layers include anti-reflection layers, diffusion layers, anti-glare layers, antistatic layers, and protective films, in addition to phase retardation layers different from those in this embodiment, but these are not limited to these.

[0862] The optical component of this embodiment can be suitably used, for example, as a circular polarizer. The optical component of this embodiment can also be suitably used, for example, as an optical component for suppressing external light reflection in a light-emitting display device.

[0863] F. Manufacturing methods for optical components

[0864] In addition, the present invention provides a method for manufacturing an optical component, which includes:

[0865] The process of preparing polarizing plates;

[0866] The process of preparing the first, second, or third phase difference plates; and

[0867] The process of stacking phase difference plates and polarizing plates.

[0868] In the manufacturing method of the optical component of the present invention, the order of each process is arbitrary.

[0869] For example, in the process of preparing a polarizing plate, a first, second, or third phase retardation plate is formed on the polarizing plate, thereby preparing the first, second, or third phase retardation plate. In this case, the process of stacking the phase retardation plate and the polarizing plate is performed simultaneously with the process of preparing the phase retardation plate.

[0870] 1. Procedures for preparing polarizing plates

[0871] As a step in preparing a polarizing plate, an example is using a stretched film with an anisotropic absorbent pigment as a polarizer. The stretched film with the anisotropic absorbent pigment is typically manufactured through the following steps: uniaxial stretching of a polyvinyl alcohol (PVA) resin film; adsorption of the dichroic pigment by dyeing the PVA resin film with a dichroic pigment; treatment of the PVA resin film with the adsorbed dichroic pigment using a boric acid aqueous solution; and washing with water after the boric acid aqueous solution treatment. A polarizer protective layer can be attached to one or both sides of the obtained polarizer to serve as a polarizing plate.

[0872] As a polarizing plate, for example, reference can be made to sections 0025 to 0059 of Japanese Patent Application Publication No. 2021-51287.

[0873] 2. Procedure for preparing the phase retardation plate

[0874] As a process for preparing the first, second, or third phase difference plate, there are no particular limitations on whether it is a process for preparing the first, second, or third phase difference plate.

[0875] The process of preparing the first, second, or third phase difference plate can be carried out, for example, in the same manner as the manufacturing method of the first, second, or third phase difference plate described above.

[0876] When preparing the phase retardation plate, it is preferable to form the first phase retardation layer and the second phase retardation layer on a substrate that can be peeled off later.

[0877] The peelable substrate can be appropriately selected in a manner that allows for peeling. The substrate may be surface-treated, have a release treatment, or have a release layer formed on it.

[0878] 3. Process of stacking phase retardation plates and polarizing plates

[0879] In the process of laminating the phase retardation plate and the polarizing plate, the phase retardation plate and the polarizing plate can be bonded together by an adhesive layer. Alternatively, as described above, the phase retardation plate can be formed directly on the polarizing plate, thereby laminating the phase retardation plate and the polarizing plate simultaneously with the preparation of the phase retardation plate.

[0880] As an adhesive layer, the same as described above can be used.

[0881] When the phase retardation plate and the polarizer are stacked, the angle between the slow axis of the positive A-type phase retardation layer and the absorption axis of the polarizer is preferably 45°±5°.

[0882] In the process of laminating a phase retardation plate and a polarizing plate, when the phase retardation plate and the polarizing plate are bonded together by an adhesive layer, it is preferable to peel off the substrate of the phase retardation plate after bonding. By subsequently peeling off the substrate of the phase retardation plate, an optical component having only the polarizing plate and the first phase retardation layer and the second phase retardation layer of the phase retardation plate of the present invention can be obtained.

[0883] G. Display device

[0884] The present invention provides a display device having a first, second or third phase retardation plate, or an optical component containing the phase retardation plate and a polarizing plate.

[0885] The display device of the present invention is characterized in that it has a first, second or third phase retardation plate, or an optical component containing the phase retardation plate and a polarizing plate.

[0886] Examples of display devices include, but are not limited to, light-emitting display devices and liquid crystal display devices. The display device may be a touch panel equipped with a touch sensor. Additionally, the display device may be a flexible display device.

[0887] In the display device of the present invention, a light-emitting display device is preferred.

[0888] Because it is equipped with the phase retardation plate or the optical component of the present invention described above, it has the effect of suppressing external light reflection and improving viewing angle, especially in light-emitting display devices such as organic light-emitting display devices that have a transparent electrode layer, a light-emitting layer and an electrode layer in sequence.

[0889] Furthermore, the display device of the present invention is preferably a flexible display device.

[0890] Because it incorporates the phase retardation plate or optical component of the present invention described above, which allows for thinner thickness and better adhesion and bending resistance, it improves bending resistance in flexible display devices. As a flexible display device, it can be a foldable display device.

[0891] It should be noted that, in the display device of the present invention, other than the phase difference plate or optical components, may be appropriately selected from known configurations.

[0892] This invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any embodiments having a substantially the same structure and achieving the same effect as those described in the scope of the claims of this invention are included within the technical scope of this invention.

[0893] Example

[0894] The following examples and comparative examples further illustrate the present invention in detail.

[0895] Example I series: First invention

[0896] (Synthesis Example 1: Synthesis of Liquid Crystal Monomer 1)

[0897] Referring to paragraphs 0121 to 0124 of International Publication No. 2018 / 003498, 4'-cyano-4-{4-[2-(acryloyloxy)ethoxy]benzoate} (chemical formula (i-1) below) was obtained.

[0898] (Synthesis Example 2: Synthesis of Liquid Crystal Monomer 2)

[0899] In the above-mentioned Synthesis Example 1, except that 6-chloro-1-n-hexanol was used instead of 2-bromoethanol, the liquid crystal monomer 2 represented by the following chemical formula (i-2) was obtained in the same manner as in Synthesis Example 1.

[0900] (Synthesis Example 3: Synthesis of Liquid Crystal Monomer 3)

[0901] Referring to paragraphs 0127 to 0130 of International Publication No. 2018 / 003498, 4-[(4-propoxycarbonylphenoxycarbonyl)phenyl-4-[6-(acryloyloxy)hexyloxy] ester of benzoic acid (hereinafter chemical formula (i-3)) was obtained.

[0902] [Table 1]

[0903] Table 1.

[0904]

[0905] Stearate acrylate (chemical formula (ii-1) below, manufactured by Tokyo Chemical Co., Ltd.) is used as non-liquid crystal monomer 1, hexyl acrylate (chemical formula (ii-2) below, manufactured by Tokyo Chemical Co., Ltd.) is used as non-liquid crystal monomer 2, and nonylphenoxy polyethylene glycol acrylate (chemical formula (ii-3) below), manufactured by Hitachi Chemical Co., Ltd., is used as non-liquid crystal monomer 3. This non-liquid crystal monomer 3 is a mixture of monomers in chemical formula (ii-3) where n' is 1 to 12, and contains at least a monomer with n' of 8 and a monomer with n' of 12, with an average n' of 8.

[0906] 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 with thermal crosslinking 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 with thermal crosslinking 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 with thermal crosslinking group.

[0907] (Synthesis Example 4: Synthesis of non-liquid crystal monomer 6 with thermally crosslinking groups)

[0908] The non-liquid crystal monomer 6tc having thermally crosslinking groups, represented by the following chemical formula (ii-6), was synthesized in the same manner as the thermally crosslinking monomer B8 of Synthesis Example 6 of Japanese Patent No. 5668881.

[0909] (Synthesis Example 5: Synthesis of non-liquid crystal monomer 7 with thermally crosslinking groups)

[0910] The non-liquid crystal monomer 7tc having thermally crosslinking groups, represented by the following chemical formula (ii-7), was synthesized in the same manner as the thermally crosslinking monomer B9 in Synthesis Example 7 of Japanese Patent No. 5668881.

[0911] [Table 2]

[0912] Table 2.

[0913]

[0914] (Synthesis Example 6: Synthesis of Photooriented Monomer 1)

[0915] In the same manner as in the synthesis example 3 of Japanese Patent No. 5626492, the photo-oriented monomer 1 represented by the following chemical formula (iii-1) was synthesized.

[0916] (Synthesis Example 7: Synthesis of Photooriented Monomer 2)

[0917] In the same manner as in the synthesis example 1 of Japanese Patent No. 5626492, the photo-oriented monomer 2 represented by the following chemical formula (iii-2) was synthesized.

[0918] (Synthesis Example 8: Synthesis of photo-oriented monomer 3)

[0919] In the same manner as in the synthesis example 8 of Japanese Patent No. 5626492, the photo-orientation monomer 3 represented by the following chemical formula (iii-3) was synthesized.

[0920] (Synthesis Example 9: Synthesis of photo-oriented monomer 4)

[0921] In the same manner as in the synthesis example 9 of Japanese Patent No. 5626492, the photo-orientation monomer 4 represented by the following chemical formula (iii-4) was synthesized.

[0922] (Synthetic Example 10: Synthesis of Photooriented Monomer 5)

[0923] In the same manner as in the synthesis example 4 of Japanese Patent No. 5626492, the photo-orientation monomer 5 represented by the following chemical formula (iii-5) was synthesized.

[0924] (Synthetic Example 11: Synthesis of Photooriented Monomer 6)

[0925] A suspension of 4′-hydroxychalcone (Tokyo Chemical Industry Co., Ltd.) (20 g, 90 mmol), acryloyl chloride (7.4 g, 82 mmol), and dimethylaniline (DMA) (9.9 g, 82 mmol) in tetrahydrofuran (400 mL) was stirred for 12 hours. After the reaction was complete, water and ethyl acetate were added, and the mixture was separated. The solvent was removed by distillation, and the residue was purified by silica gel chromatography. The solvent was removed by distillation again, thereby synthesizing the photo-orientation monomer 6 represented by the following chemical formula (iii-6) in 89% yield (22 g, 80 mmol).

[0926] (Synthetic Example 12: Synthesis of Photooriented Monomer 7)

[0927] In the synthetic example a of Japanese Patent No. 5626492, 4-methoxycinnamic acid was used in place of 4-vinylbenzoic acid in an equimolar amount, and 4-hydroxyphenyl methacrylate (manufactured by Seiko Chemical Co., Ltd.) was used in place of ethylene glycol in an equimolar amount, and the photo-oriented monomer 7 represented by the following chemical formula (iii-7) was synthesized by condensation in the same manner.

[0928] (Synthetic Example 13: Synthesis of Comparative Photooriented Monomer 1)

[0929] In Synthesis Example 2 of Japanese Patent No. 5668881, the comparative photo-orientation monomer 1 represented by the following chemical formula (iii-c1) was synthesized in the same manner, except that methyl trans-4-hydroxycinnamate was used in place of methyl ferulic acid in an equimolar amount and 6-chloro-1-hexanol was used in place of 4-chloro-1-butanol in an equimolar amount.

[0930] Prepare methyl 4-(6-methacryloyloxyhexyl-1-oxy)cinnamate as the comparative photooriented monomer 2 represented by the following chemical formula (iii-c2).

[0931] (Synthetic Example 15: Synthesis of Comparative Photooriented Monomer 3)

[0932] The comparative photo-orientation monomer 3 represented by the following chemical formula (iii-c3) was synthesized in the same manner as the reference photo-orientation monomer 2 in Reference Synthesis Example 1 of Japanese Patent No. 5626492.

[0933] [Table 3]

[0934] Table 3:

[0935]

[0936] In addition, 2-hydroxyethyl methacrylate (chemical formula (iv-1) below, manufactured by Kyoeisha Chemical Co., Ltd.) is used as thermal crosslinking monomer 1, and 4-hydroxybutyl acrylate (chemical formula (iv-2) below, manufactured by Tokyo Chemical Industry Co., Ltd.) is used as thermal crosslinking monomer 2.

[0937] (Synthesis Example 16: Synthesis of Thermally Crosslinkable Monomer 3)

[0938] The thermally crosslinking monomer 3 represented by the following chemical formula (iv-3) was synthesized in the same manner as the thermally crosslinking monomer B3 in Synthesis Example 4 of Japanese Patent No. 5668881.

[0939] (Synthesis Example 17: Synthesis of Thermally Crosslinkable Monomer 4)

[0940] The thermally crosslinking monomer 4 represented by the following chemical formula (iv-4) was synthesized in the same manner as the thermally crosslinking monomer 5 in the synthesis example e of Japanese Patent No. 5626492.

[0941] (Synthetic Example 18: Synthesis of Thermally Crosslinkable Monomer 5)

[0942] The thermally crosslinking monomer 5 represented by the following chemical formula (iv-5) was synthesized in the same manner as the thermally crosslinking monomer 6 in the synthesis example f of Japanese Patent No. 5626492.

[0943] (Synthesis Example 19: Synthesis of Thermally Crosslinkable Monomer 6)

[0944] The thermally crosslinkable monomer 6 represented by the following chemical formula (iv-6) was synthesized in the same manner as compound 46 in Example 9 of Japanese Patent Publication No. 2016-538400.

[0945] (Synthesis Example 20: Synthesis of Thermally Crosslinkable Monomer 7)

[0946] The thermally crosslinkable monomer 7 represented by the following chemical formula (iv-7) was synthesized in the same manner as in section 124 of Japanese Patent Publication No. 2018-525444.

[0947] In addition, N-(methoxymethyl)methacrylamide (chemical formula (iv-8) below, manufactured by Tokyo Chemical Industry Co., Ltd.) as a thermally crosslinking monomer 8 having a self-crosslinking group, and Viscoat 13F (chemical formula (v-1) below, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a monomer 1 having a fluorinated alkyl group, were used as the third component monomers.

[0948] [Table 4]

[0949] Table 4.

[0950]

[0951] (Manufacturing Examples A1 to A14: Manufacturing of Side-Chain Liquid Crystal Polymers A1 to A14)

[0952] Based on Table 5, the above-mentioned liquid crystal monomers 1-3, non-liquid crystal monomers 1-3 and 4tc-8tc, and photo-orientation monomer 1 are combined to synthesize a side-chain type liquid crystal polymer.

[0953] A specific example of the synthesis of the side-chain type liquid crystal polymer A2 is provided.

[0954] Non-liquid crystal monomer 1 and non-liquid crystal monomer 2 were combined in a molar ratio of 50:50. The total amount of these non-liquid crystal monomers was then combined with liquid crystal monomer 1 in a molar ratio of 40:60 and mixed. N,N-dimethylacetamide (DMAc) was added, and the mixture was 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 reaction solution was added dropwise over 30 minutes to DMAc heated to 80°C. After the addition was complete, the mixture was stirred at 80°C for 6 hours. After the reaction was completed and cooled to room temperature, the solution was added dropwise to another container stirring methanol and stirred for 20 minutes. After removing the supernatant, the slurry was filtered. The obtained crude product was stirred again in methanol for 20 minutes, and the supernatant was removed and filtered. The obtained crystals were dried, thus obtaining a side-chain liquid crystal polymer A2 in a yield of 76.5%.

[0955] The mass-average molecular weight of the obtained side-chain liquid crystal polymers was determined, and their structures were analyzed. Furthermore, Py-GC-MS or MALDI-TOFMS confirmed the presence of structural units derived from one, two, or three non-liquid crystal monomers used.

[0956] [Table 5]

[0957] Table 5. Side-chain type liquid crystal polymers (A) Liquid crystal monomer : non-liquid crystal monomer = 60 : 40 (molar ratio)

[0958]

[0959] (Manufacturing Examples B1-B15: Manufacturing of Copolymers B1-B15)

[0960] According to Table 6, the above-mentioned photo-oriented monomers 1-7, thermal crosslinking monomers 1-7, and the third component monomer are combined to synthesize copolymer (B).

[0961] A specific example of the synthesis of copolymer B1 is provided.

[0962] 13.08 g of photo-oriented monomer, 1.30 g of thermally crosslinking monomer 1 (hydroxybutyl methacrylate), and 50 mg of α,α'-azobisisobutyronitrile (AIBN) as a polymerization catalyst were dissolved in 25 ml of dioxane and reacted at 90 °C for 6 hours. After the reaction was completed, the copolymer was purified by reprecipitation to obtain copolymer B1. The mass-average molecular weight of the obtained copolymer B1 was 18,000.

[0963] It should be noted that the mass-average molecular weight (hereinafter referred to as Mw) of each synthesized copolymer was calculated by gel permeation chromatography (GPC) using HLC-8220GPC manufactured by Tosoh Co., Ltd., with polystyrene as the standard and NMP (N-methyl-2-pyrrolidone) as the eluent.

[0964] [Comparative Manufacturing Examples B'1 to B'3] Synthesis of Comparative Copolymers B'1 to B'3

[0965] Based on Table 6, comparative copolymers B'1 to B'3 were synthesized by combining the above-mentioned photo-oriented monomers 1 to 3 and thermal crosslinking monomer 1 in the same manner as copolymer B1.

[0966] [Table 6]

[0967] Table 6. Copolymer (B)

[0968]

[0969] [Comparative Manufacturing Example C1] Synthesis of Comparative Copolymer C1

[0970] In the same manner as polymer 1 described in paragraphs 0073 to 0076 and 0079 of Japanese Patent Application Publication No. 2016-004142, monomer 1 represented by the following chemical formula (vi-1) and monomer 2 represented by the following chemical formula (vi-2) were copolymerized at a molar ratio of 3:7 to obtain comparative copolymer C1.

[0971] [Chemical Formula 47]

[0972] Chemical formula (vi-1)

[0973]

[0974] Chemical formula (vi-2)

[0975]

[0976] [Examples 1-32]

[0977] (Preparation of photo-oriented thermosetting liquid crystal compositions 1-32)

[0978] The side-chain liquid crystal polymer (A) and copolymer (B) shown in Table 7 were mixed according to the mass ratios shown in Table 7 to obtain the composition.

[0979] A photo-oriented thermosetting liquid crystal composition with the composition shown below was prepared.

[0980] • The composition shown in Table 7: 0.1 parts by weight

[0981] • Thermal crosslinking agent (hexamethoxymethyl melamine, HMM): 0.01 parts by weight

[0982] • p-Toluenesulfonic acid monohydrate (PTSA): 0.001 parts by weight

[0983] • Propylene glycol monomethyl ether (PGME): 0.17 parts by weight

[0984] Cyclohexanone: 0.4 parts by weight

[0985] [Example 33]

[0986] (Preparation of photo-oriented thermosetting liquid crystal composition 33)

[0987] A thermosetting liquid crystal composition with photo-oriented properties as shown below was prepared.

[0988] • Side-chain type liquid crystal polymer A-3: 0.09 parts by weight

[0989] Copolymer B-1: 0.01 parts by weight

[0990] • Polymerizable liquid crystal compound (trade name LC242, manufactured by BASF): 0.01 parts by weight

[0991] • Photopolymerization initiator (trade name Omnirad 907, manufactured by IGM Resins): 0.004 parts by weight

[0992] • Thermal crosslinking agent (hexamethoxymethyl melamine, HMM): 0.01 parts by weight

[0993] • p-Toluenesulfonic acid monohydrate (PTSA): 0.001 parts by weight

[0994] • Propylene glycol monomethyl ether (PGME): 0.17 parts by weight

[0995] Cyclohexanone: 0.4 parts by weight

[0996] [Example 34]

[0997] (Preparation of photo-oriented thermosetting liquid crystal composition 34)

[0998] A thermosetting liquid crystal composition with photo-oriented properties as shown below was prepared.

[0999] • Side-chain type liquid crystal polymer A-3: 0.09 parts by weight

[1000] Copolymer B-1: 0.01 parts by weight

[1001] • Multifunctional monomer (pentaerythritol triacrylate, PETA): 0.01 parts by weight

[1002] • Photopolymerization initiator (trade name Omnirad 907, manufacture...

Claims

1. A photo-oriented thermosetting liquid crystal composition comprising: A side-chain type liquid crystal polymer (A) having liquid crystal structural units containing liquid crystal moieties in the side chains and non-liquid crystal structural units containing alkylene groups in the side chains. A copolymer (B) having a photooriented structural unit having a structural unit represented by the following formula (1) and a thermally crosslinked structural unit having thermally crosslinked groups in the side chain, and A thermal crosslinking agent (C) bonded to the thermal crosslinking groups of the thermal crosslinking structural unit; In the 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 photo-orientation group, L 11 represents a single bond, -O-, -S-, -COO-, -COS-, -CO-, -OCO-, or a combination of these with an arylene group, In the formulae (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 represents a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, R 24 represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4.

2. The photo-oriented thermosetting liquid crystal composition according to claim 1, wherein, The photo-orientation group of the copolymer (B) is at least one selected from cinnamyl, chalcone, coumarin, anthracene, quinolinyl, azophenyl, and zirconia.

3. The photo-oriented thermosetting liquid crystal composition according to claim 1 or 2, wherein, The thermal crosslinking group contains at least one selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups.

4. The photo-oriented thermosetting liquid crystal composition according to claim 1 or 2, wherein, The liquid crystal structural unit of the side-chain type liquid crystal polymer (A) has a structural unit represented by the following formula (I); In General Formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 represents -(CH2) m - or -(C2H4O) m' - represented group; L 1 represents a single bond, or a linking group represented by -O-, -OCO- or -COO-, Ar 1 represents an arylene group having 6 to 10 carbons optionally having a substituent, a plurality of L 1 and Ar 1 may be the same or different; R 3 represents -F, -Cl, -CN, -OCF3, -OCF2H, -NCO, -NCS, -NO2, -NHCO-R 4 , -CO-OR 4 , -OH, -SH, -CHO, -SO3H, -NR 4 2, -R 5 or -OR 5 , R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbons, R 5 represents an alkyl group having 1 to 6 carbons; a is an integer of 2 to 4, and m and m' are each independently an integer of 2 to 10.

5. The photo-oriented thermosetting liquid crystal composition according to claim 1 or 2, wherein, The copolymer (B) has a thermally crosslinked structural unit having the structural unit represented by the following formula (2). The side-chain liquid crystal polymer (A) satisfies any one of the following (i) to (vi): (i) The side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing a thermally crosslinking group and an alkylene group in the side chain. The non-liquid crystal and thermally crosslinked structural unit of the side-chain liquid crystal polymer (A) has the thermally crosslinking group bonded to a primary carbon of an alkylene group optionally having -O- in the carbon chain. The total number of carbons and oxygens of the alkylene group optionally having -O- in the carbon chain is smaller than the number of linear alkylene groups optionally having -O- in the carbon chain of the thermally crosslinked structural unit of the copolymer (B) with 4 to 11 carbons. (ii) The side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing a thermally crosslinking group and an alkylene group in the side chain, and the non-liquid crystal and thermally crosslinked structural unit of the side-chain liquid crystal polymer (A) has a structure in which the thermally crosslinking group is bonded to a secondary or tertiary carbon of the alkylene group. (iii) The side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing at least one thermally crosslinking group selected from hydroxyl, thiol and amino, alkylene and arylene in the side chain, and the non-liquid crystal and thermally crosslinked structural unit of the side-chain liquid crystal polymer (A) has the thermally crosslinking group bonded to the arylene. (iv) The side-chain liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit containing at least one thermally crosslinking group selected from carboxyl, glycidyl and amide groups, an alkylene group and an arylene group in the side chain. The non-liquid crystal and thermally crosslinked structural unit of the side-chain liquid crystal polymer (A) has a structure in which the thermally crosslinking group is bonded to the arylene group and has a structure in which the arylene group is bonded to a carbon atom or oxygen atom of an alkylene group optionally having -O- in the carbon chain or at the end. The total number of carbon atoms and oxygen atoms of the alkylene group optionally having -O- in the carbon chain or at the end is more than 3 times smaller than the number of carbon atoms of the linear alkylene group optionally having -O- in the carbon chain of the thermally crosslinked structural unit of the copolymer (B) of 4 to 11. (v) The side-chain liquid crystal polymer (A) has a thermally crosslinked structural unit in which the side chain does not contain alkylene groups and contains thermally crosslinkable groups; (vi) The side-chain type liquid crystal polymer (A) does not have non-liquid crystal and thermally crosslinked structural units containing thermally crosslinked groups and alkylene groups in the side chains, nor does it have thermally crosslinked structural units containing thermally crosslinked groups in the side chains. In equation (2), Z 2 R represents at least one monomer unit selected from the following formulas (2-1) to (2-6). 50 Y represents a linear alkylene group of 4 to 11 carbon atoms selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups. In equations (2-1) to (2-6), R 51 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 52 R represents a hydrogen atom or a methyl group. 53 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 54 L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 12 Indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-, in L 12 In the case of a single bond, R 50 It bonds directly to the styrene skeleton.

6. The photo-oriented thermosetting liquid crystal composition according to claim 1 or 2, wherein, The side-chain type liquid crystal polymer (A) has a non-liquid crystal and thermally crosslinked structural unit, which has a structural unit represented by the following formula (III); In equation (III), Z a R represents at least one monomer unit selected from the following formulas (a-1) to (a-6). 16 -L 2a -R 13' - represents the group, here, L 2a R represents a straight-chain or branched alkylene group having 1 to 10 carbon atoms in its carbon chain, optionally containing an -O- group. 13' This indicates a residue from which a hydrogen atom is removed from an optional methyl group, a residue from which a hydrogen atom is removed from an aryl group, or -OR. 15' R 15' Y represents the residue from which a hydrogen atom has been removed from the aryl group. a It indicates at least one thermally crosslinkable group selected from hydroxyl, carboxyl, mercapto, glycidyl, amino, and amide groups. In equations (a-1) to (a-6), R 11 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 17 R represents a hydrogen atom or a methyl group. 18 R represents a hydrogen atom, methyl, chlorine atom, or phenyl atom. 19 L represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a Indicates a single bond, -O-, -S-, -COO-, -COS-, -CO-, or -OCO-, in L a In the case of a single bond, R 16 It bonds directly to the styrene skeleton.

7. An alignment film that also serves as a retardation film, comprising an alignment layer that also serves as a retardation layer, and The orientation layer and phase difference layer is a cured film of the thermosetting liquid crystal composition with photoorientation as described in any one of claims 1 to 6.

8. A method for manufacturing an alignment film that also serves as a retardation film, comprising the following steps: The process of forming a film of the photo-oriented thermosetting liquid crystal composition according to any one of claims 1 to 6 The process of forming a cured film with a phase difference by heating the thermosetting liquid crystal composition into a film, and The process of imparting liquid crystal alignment energy to the cured film by irradiating it with polarized ultraviolet light with a phase difference.

9. A phase retardation plate, comprising: As the first phase difference layer of the cured film of the photo-oriented thermosetting liquid crystal composition according to any one of claims 1 to 6, and A second phase retardation layer comprising a cured product containing a polymeric liquid crystal composition is disposed directly adjacent to the first phase retardation layer.

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

11. The phase difference plate according to claim 9, wherein, The thickness-direction phase difference Rth at a wavelength of 550 nm is -35 nm to 35 nm, and the total thickness of the first phase difference layer and the second phase difference layer is 0.2 μm to 6 μm.

12. The phase retardation plate according to claim 9, further comprising a third phase retardation layer different from the first phase retardation layer. The third phase difference layer, the first phase difference layer, and the second phase difference layer are arranged directly adjacent to each other in sequence. The third phase difference layer is a positive C-type phase difference layer, the first phase difference layer is a positive C-type phase difference layer, and the second phase difference layer is a positive A-type phase difference layer.

13. A method for manufacturing a phase retardation plate, comprising the following steps: A process for forming a film of the photo-oriented thermosetting liquid crystal composition according to any one of claims 1 to 6; A process of forming a cured film with a phase difference by heating the thermosetting liquid crystal composition into which the film is formed; The process of irradiating the cured film with phase difference with polarized ultraviolet light to impart liquid crystal alignment energy to the cured film, thereby forming an alignment film that also serves as a first phase difference layer. A process involving coating a polymerizable liquid crystal composition onto the alignment film and first retardation layer to form a coating film of the polymerizable liquid crystal composition, heating the coating film to the phase transition temperature of the polymerizable liquid crystal composition, thereby aligning liquid crystal molecules using the alignment film and first retardation layer; and The process of curing a coating of a polymeric liquid crystal composition in which the liquid crystal molecules are oriented by light to form a second phase retardation layer.

14. A phase retardation plate, comprising: A positive C-type phase reversal layer of a cured thermosetting liquid crystal composition containing a photo-alignment component and a thermal crosslinking agent, and a liquid crystal component different from the photo-alignment component and the thermal crosslinking agent, and A positive A-type phase retardation layer containing a polymeric liquid crystal composition is disposed directly adjacent to the positive C-type phase retardation layer.

15. The phase retardation plate according to claim 14, wherein, The thickness-direction phase difference Rth at a wavelength of 550 nm is -35 nm to 35 nm, the in-plane phase difference Re at a wavelength of 550 nm is greater than 100 nm, and the total thickness of the positive C-type phase difference layer and the positive A-type phase difference layer is 0.2 μm to 6 μm.

16. The phase retardation plate according to claim 14 or 15, wherein, The composite elastic modulus of the positive C-type phase retardation layer is above 4.5 GPa and below 9.0 GPa.

17. The retardation plate according to claim 14 or 15, comprising a substrate disposed directly adjacent to the positive C-shaped retardation layer.

18. The phase retardation plate according to claim 14 or 15, wherein, The positive C-type retardation layer includes regions infiltrated by specific components contained in the positive A-type retardation layer.

19. The phase difference plate according to claim 18, wherein, The specific component contains a polymeric liquid crystal compound or a cured form thereof.

20. A method for manufacturing a phase retardation plate, comprising the following steps: A process for forming a film of a photo-oriented thermosetting liquid crystal composition, wherein the photo-oriented thermosetting liquid crystal composition comprises: a side-chain type liquid crystal polymer having a liquid crystal structural unit having a liquid crystal portion in the side chain, a copolymer having a photo-oriented structural unit and a thermally crosslinked structural unit having a thermally crosslinked group in the side chain, and a thermally crosslinking agent bonded to the thermally crosslinked group of the thermally crosslinked structural unit. A process of forming a cured film with a phase difference by heating the thermosetting liquid crystal composition into which the film is formed; The process of forming a positive C-type phase difference layer that imparts liquid crystal alignment energy by irradiating the cured film with phase difference with polarized ultraviolet light. A process involving coating a polymerizable liquid crystal composition onto the positive C-type retardation layer to form a coating film of the polymerizable liquid crystal composition, heating the coating film to the phase transition temperature of the polymerizable liquid crystal composition, thereby aligning liquid crystal molecules using the positive C-type retardation layer; and The process of curing a coating of a polymeric liquid crystal composition in which the liquid crystal molecules are oriented by light to form a positive A-type phase retardation layer.

21. An optical component comprising a phase difference plate and a polarizing plate as described in any one of claims 9 to 12 and 14 to 19.

22. A method for manufacturing an optical component, comprising the following steps: The process of preparing polarizing plates The process of preparing the phase difference plate according to any one of claims 9-12 and 14-19, and The process of stacking phase difference plates and polarizing plates.

23. A display device comprising a phase retardation plate as described in any one of claims 9 to 12 and 14 to 19, or an optical component comprising the phase retardation plate and a polarizing plate.

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