Polymerizable liquid crystal hybrid composition, retardation plate, elliptical polarizing plate and organic EL display device

Abstract

The purpose of this invention is to provide a polymerizable liquid crystal mixture composition with excellent solvent solubility and film-forming properties, preferably a polymerizable liquid crystal mixture composition suitable for manufacturing a phase retardation plate exhibiting reverse wavelength dispersion and high optical properties. The polymerizable liquid crystal mixture of the present invention comprises at least three molecules with different molecular structures and derived from formula (I): The polymeric liquid crystal compound represented, and As the aforementioned polymerizable liquid crystal compound, it includes E in formula (I). a and E b. Identical polymerizable liquid crystal compounds, in which E a and E The polymerizable liquid crystal compound with the smallest number of carbon atoms in the alkyl diene group represented by b is defined by formula (I-1): When referring to the polymerizable liquid crystal compound (I-1), it includes the polymerizable liquid crystal compound (I-1) and at least one compound of formula (I-2) defined based on the structure of the polymerizable liquid crystal compound (I-1): The polymerizable liquid crystal compound (I-2) is represented, and at least one compound defined by formula (I-3) based on the structure of the polymerizable liquid crystal compound (I-1) described above is also represented. The polymeric liquid crystal compound represented is (I-3).

Description

Technical Field

[0001] The present invention relates to a polymerizable liquid crystal hybrid composition, a phase difference plate including a liquid crystal cured film as a cured product of the polymerizable liquid crystal hybrid composition, and an elliptically polarizing plate and an organic EL (electroluminescence) display device including the phase difference plate. Prior Art

[0002] Optical films such as phase difference plates used in flat panel displays (FPDs) include, for example, those obtained by dissolving a polymerizable liquid crystal compound in a solvent, applying the resulting coating solution to a supporting substrate, and then polymerizing the resulting film. Previously, polymerizable liquid crystal compounds such as nematic liquid crystal compounds with a rod-like structure consisting of two to four six-membered rings are known. On the other hand, phase difference plates are required to be capable of polarization conversion in the entire wavelength range as one of their characteristics. For example, it is known that, in theory, the same polarization conversion can be performed in the wavelength range that exhibits reverse wavelength dispersion of [Re(450) / Re(550)] <1. Polymerizable compounds that can constitute such phase difference plates are disclosed in, for example, Patent Document 1. [Prior Art Literature] [Patent Document]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-207765 Summary of the Invention

[0004] [Problems to be solved by the invention] Optical films such as retardation plates can be obtained by dissolving a polymerizable liquid crystal compound, as disclosed in Patent Document 1, in a solvent, applying the resulting coating solution to a supporting substrate to form a coating film, then converting the polymerizable liquid crystal compound contained in the coating film into a liquid crystal phase such as a nematic phase, drying the coating film, and distilling off the solvent. However, depending on the type of polymerizable liquid crystal compound, its molecular structure may result in low solubility in solvents. Such polymerizable liquid crystal compounds with low solubility are known to be prone to alignment defects in the resulting optical film. Such compounds may also precipitate in the coating solution, resulting in not only reduced film formability but also alignment defects in the resulting optical film. Polymerizable liquid crystal compounds containing aromatic rings are particularly well-known to be preferred materials for obtaining retardation plates with reverse wavelength dispersion and excellent optical properties. However, compounds with a highly symmetrical molecular structure have a problem in that their solubility is further reduced due to their molecular structure.

[0005] The object of the present invention is to provide a polymerizable liquid crystal hybrid composition having excellent solvent solubility and film-forming properties, preferably to provide a polymerizable liquid crystal hybrid composition suitable for manufacturing a phase difference plate exhibiting reverse wavelength dispersion and having high optical properties. [Technical means to solve the problem]

[0006] The present invention provides the following preferred aspects. [1] A polymerizable liquid crystal hybrid composition comprising at least three different molecular structures represented by formula (I): [In formula (I), M1 represents a divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocycle, B1 and B2 each independently represent a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -Ra1ORa2-, -Ra3COORa4-, -Ra5OCORa6-, -Ra7OC=OORa8-, -ORbO-, -C(=O)-NRc-, -N=N-, -CRc=CRd-, or -C≡C-, wherein Ra1 to Ra8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, Rb represents an alkylene group having 1 to 4 carbon atoms, and Rc and Rd represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. G1 and G2 each independently represent a divalent alicyclic hydrocarbon group or an aromatic group. The hydrogen atoms contained in the divalent alicyclic hydrocarbon group or aromatic group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atoms constituting the divalent alicyclic hydrocarbon group or aromatic group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. When n1 and / or n2 is 2, the two G1s and / or two G2s may be the same or different. L1 and L2 each independently represent a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -Ra1ORa2-, -Ra3COORa4-, -Ra5OCORa6-, -Ra7OC=OORa8-, -ORbO-, -C(=O)-NRc-, -N=N-, -CRc=CRd-, or -C≡C-; wherein Ra1 to Ra8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, Rb represents an alkylene group having 1 to 4 carbon atoms, and Rc and Rd represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. When n1 and / or n2 is 2, the two L1s and / or the two L2s may be the same or different. Ea and Eb each independently represent an alkanediyl group having 1 to 20 carbon atoms, wherein the hydrogen atoms contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms or a halogen atom, and the -CH2- contained in the alkanediyl group may be substituted with -O- or -S- (wherein, when there are multiple -O- and / or -S- groups, they are not adjacent to each other), P is an acryloyloxy group or a methacryloyloxy group, n1 and n2 are each independently 1 or 2] The polymerizable liquid crystal compound represented by The polymerizable liquid crystal compound includes a polymerizable liquid crystal compound in which Ea and Eb in formula (I) are identical to each other. Among the polymerizable liquid crystal compounds, the polymerizable liquid crystal compound having the smallest carbon number in the alkanediyl group represented by Ea and Eb is represented by formula (I-1): [In formula (I-1), M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 are respectively defined similarly to M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 in the above formula (I). E1 is defined in the same manner as Ea and Eb in the above formula (I), and the two E1 are the same.] In the case of the polymerizable liquid crystal compound (I-1) represented by the above, the polymerizable liquid crystal compound (I-1) is included, and at least one compound defined based on the structure of the polymerizable liquid crystal compound (I-1) represented by formula (I-2): [In formula (I-2), M1, B1, B2, G1, G2, L1, L2, E1, P, n1 and n2 are the same as M1, B1, B2, G1, G2, L1, L2, E1, P, n1 and n2 in the above formula (I-1), respectively. E2 represents an alkanediyl group having 1 to 20 carbon atoms, which is different from E1 in the above formula (I-1), wherein the hydrogen atoms contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms or a halogen atom, and the -CH2- contained in the alkanediyl group may be substituted with -O- or -S- (wherein, when multiple -O- and / or -S- groups exist, they are not adjacent to each other) The polymerizable liquid crystal compound (I-2) represented by the formula (I-3) and at least one compound defined based on the structure of the polymerizable liquid crystal compound (I-1): [In formula (I-3), M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 are the same as M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 in the above formula (I-1), respectively. E2 is the same as E2 in the above formula (I-2), and the two E2 in formula (I-3) are the same] The polymerizable liquid crystal compound (I-3) represented. [2] The polymerizable liquid crystal composition as described in [1] above, wherein in formula (I-1), n1 and n2 are the same. [3] A polymerizable liquid crystal compound as described in [1] or [2] above, wherein M1 is a divalent linking group comprising at least one aromatic hydrocarbon ring or aromatic heterocyclic ring having a total number Nπ of π electrons of 16 or more and less than 36. [4] The polymerizable liquid crystal composition according to any one of [1] to [3] above, wherein in formula (I-1), when n1 and n2 are each 1, G1 and G2 are identical to each other; when n1 and n2 are each 2, G1 bonded to B1 and G2 bonded to B2 are identical to each other, and the other G1 and G2 are identical to each other. [5] The polymerizable liquid crystal composition according to any one of [1] to [4], wherein in formula (I-1), when n1 and n2 are each 1, L1 and L2 are identical to each other; when n1 and n2 are each 2, L1 and L2 respectively bonded to E1 are identical to each other, and the other L1 and L2 are identical to each other. [6] The polymerizable liquid crystal hybrid composition as described in any one of [1] to [5] above, wherein each E1 in formula (I-1) and formula (I-2) and each E2 in formula (I-2) and formula (I-3) are all alkanediyl groups having 4 to 20 carbon atoms, and The difference between the number of carbon atoms in the alkanediyl group represented by each E 1 in formula (I-1) and formula (I-2) and the number of carbon atoms in the alkanediyl group represented by each E 2 in formula (I-2) and formula (I-3) is 2 or more. [7] A polymerizable liquid crystal mixed composition as described in any one of [1] to [6] above, wherein among the polymerizable liquid crystal compounds represented by formula (I), the polymerizable liquid crystal compound represented by formula (I-1), the polymerizable liquid crystal compound represented by formula (I-2), and the polymerizable liquid crystal compound represented by formula (I-3) are included in an amount of 10 mol% or more relative to the total molar amount of the polymerizable liquid crystal compounds represented by formula (I) in which M1, B1, B2, G1, G2, L1, L2, P, n1, and n2 are respectively the same. [8] The polymerizable liquid crystal mixed composition described in any one of [1] to [7] above, which contains an organic solvent. [9] A phase difference plate comprising a liquid crystal cured film, wherein the liquid crystal cured film is a cured product of the polymerizable liquid crystal mixed composition described in any one of [1] to [8] above, and is cured in a state where the polymerizable liquid crystal compound in the polymerizable liquid crystal mixed composition is aligned.

[10] The phase difference plate as described in [9] above, wherein the liquid crystal cured film has the optical properties represented by formulas (1), (2) and (3), Re(450) / Re(550)≦1.00 (1) 1.00≦Re(650) / Re(550) (2) 100 nm ≦ Re (550) ≦ 180 nm (3) [Wherein, Re(λ) represents the in-plane retardation value of the liquid crystal cured film at a wavelength of λ nm, Re = (nx(λ) - ny(λ)) × d (d represents the thickness of the liquid crystal cured film, nx represents the principal refractive index at a wavelength of λ nm in a direction parallel to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film, and ny represents the refractive index at a wavelength of λ nm in a direction parallel to the plane of the liquid crystal cured film and orthogonal to the direction of nx in the refractive index ellipsoid formed by the liquid crystal cured film).

[11] The phase difference plate as described in [9] above, wherein the liquid crystal cured film has the optical properties represented by formulas (4), (5) and (6), Rth(450) / Rth(550)≦1.00 (4) 1.00≦Rth(650) / Rth(550) (5) -100 nm≦Rth(550)≦-40 nm (6) [Wherein, Rth(λ) represents the retardation value of the liquid crystal cured film in the thickness direction at a wavelength of λ nm, Rth = ((nx(λ) + ny(λ)) / 2-nz) × d (d represents the thickness of the liquid crystal cured film, nx represents the refractive index at a wavelength of λ nm in a direction parallel to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film, ny represents the refractive index at a wavelength of λ nm in a direction parallel to the plane of the liquid crystal cured film and perpendicular to the direction of nx in the refractive index ellipsoid formed by the liquid crystal cured film, and nz represents the refractive index at a wavelength of λ nm in a direction perpendicular to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film).

[12] An elliptically polarizing plate comprising a phase difference plate as described in any one of [9] to

[11] above and a polarizing film.

[13] An organic EL display device comprising an elliptically polarizing plate as described in

[12] above.

[14] A method for producing a polymerizable liquid crystal hybrid composition as described in any one of [1] to [8] above, comprising reacting a reactive group R2 of a compound represented by the following formula (III-1), a reactive group R2 of a compound represented by (III-2), and R1 of a compound represented by (III-3), [wherein, R 1 and R 2 independently represent reactive groups, M1, L1, L2, G1, G2, P, n1 and n2 have the same meanings as M1, L1, L2, G1, G2, P, n1 and n2 in formula (I-1). E1 represents the same meaning as E1 in formula (I-1), E2 has the same meaning as E2 in formula (I-2). [Effects of the Invention]

[0007] According to the present invention, a polymerizable liquid crystal hybrid composition having excellent solvent solubility and film-forming properties can be provided, preferably a polymerizable liquid crystal hybrid composition suitable for manufacturing a phase difference plate exhibiting reverse wavelength dispersion and having high optical properties. Implementation Method

[0008] The following describes the embodiments of the present invention in detail. The scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without detracting from the spirit of the present invention.

[0009] <Polymerizable Liquid Crystal Hybrid Composition> The polymerizable liquid crystal mixed composition of the present invention comprises at least three polymerizable liquid crystal compounds having different molecular structures and represented by formula (I). By including at least three similar polymerizable liquid crystal compounds as the molecular structures having different molecular structures and represented by formula (I), high solubility in solvents can be ensured. [In formula (I), M1 represents a divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocycle, B1 and B2 each independently represent a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -Ra1ORa2-, -Ra3COORa4-, -Ra5OCORa6-, -Ra7OC=OORa8-, -ORbO-, -C(=O)-NRc-, -N=N-, -CRc=CRd-, or -C≡C-, wherein Ra1 to Ra8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, Rb represents an alkyl group having 1 to 4 carbon atoms, and Rc and Rd represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. G1 and G2 each independently represent a divalent alicyclic hydrocarbon group or an aromatic group. The hydrogen atoms contained in the divalent alicyclic hydrocarbon group or aromatic group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atoms constituting the divalent alicyclic hydrocarbon group or aromatic group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. When n1 and / or n2 is 2, the two G1s and / or two G2s may be the same or different. L1 and L2 each independently represent a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -Ra1ORa2-, -Ra3COORa4-, -Ra5OCORa6-, -Ra7OC=OORa8-, -ORbO-, -C(=O)-NRc-, -N=N-, -CRc=CRd-, or -C≡C-; wherein Ra1 to Ra8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, Rb represents an alkylene group having 1 to 4 carbon atoms, and Rc and Rd represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. When n1 and / or n2 is 2, the two L1s and / or the two L2s may be the same or different. Ea and Eb each independently represent an alkanediyl group having 1 to 20 carbon atoms, wherein the hydrogen atoms contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms or a halogen atom, and the -CH2- contained in the alkanediyl group may be substituted with -O- or -S- (wherein, when there are multiple -O- and / or -S- groups, they are not adjacent to each other), P is an acryloyloxy group or a methacryloyloxy group, n1 and n2 are each independently 1 or 2].

[0010] The polymerizable liquid crystal mixed composition of the present invention comprises a polymerizable liquid crystal compound in which Ea and Eb are identical as the at least three polymerizable liquid crystal compounds, wherein the polymerizable liquid crystal compound having the smallest carbon number in the alkanediyl group represented by Ea and Eb among the polymerizable liquid crystal compounds is represented by formula (I-1): [In formula (I-1), M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 are respectively defined similarly to M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 in the above formula (I). E1 is defined in the same manner as Ea and Eb in the above formula (I), and the two E1 are the same.] In the case of the polymerizable liquid crystal compound (I-1) represented by (hereinafter also referred to as "polymerizable liquid crystal compound (I-1)"), the polymerizable liquid crystal compound (I-1) is included, and at least one compound defined based on the structure of the polymerizable liquid crystal compound (I-1) represented by formula (I-2): [In formula (I-2), M1, B1, B2, G1, G2, L1, L2, E1, P, n1 and n2 are the same as M1, B1, B2, G1, G2, L1, L2, E1, P, n1 and n2 in the above formula (I-1), respectively. E2 represents an alkanediyl group having 1 to 20 carbon atoms, which is different from E1 in the above formula (I-1), wherein the hydrogen atoms contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms or a halogen atom, and the -CH2- contained in the alkanediyl group may be substituted with -O- or -S- (wherein, when multiple -O- and / or -S- groups exist, they are not adjacent to each other) The polymerizable liquid crystal compound represented by (hereinafter also referred to as "polymerizable liquid crystal compound (I-2)"), and at least one compound defined based on the structure of the polymerizable liquid crystal compound (I-1) represented by formula (I-3): [In formula (I-3), M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 are the same as M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 in the above formula (I-1), respectively. E2 is the same as E2 in the above formula (I-2), and the two E2 in formula (I-3) are the same] The polymerizable liquid crystal compound represented by (hereinafter also referred to as "polymerizable liquid crystal compound (I-3)"). In the present invention, when the polymerizable liquid crystal mixed composition contains a plurality of compounds corresponding to the above-mentioned formula (I-1), the polymerizable liquid crystal compound corresponding to the compound represented by formula (I-1) in which the carbon number of the alkanediyl group represented by Ea and Eb is the smallest is referred to as "polymerizable liquid crystal compound (I-1)". Furthermore, when the alkanediyl group represented by Ea and Eb has a substituent, "the carbon number of the alkanediyl group represented by Ea and Eb" means the carbon number of the alkanediyl group represented by Ea and Eb that constitutes the main chain of the compound represented by formula (I-1).

[0011] The three polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) constituting the polymerizable liquid crystal hybrid composition of the present invention differ only in the structure of the alkanediyl group represented by E1 and / or E2 in the portion other than M1 (hereinafter, the M1 portion is also referred to as the "core portion," and the portion other than M1 is also referred to as the "mesogen portion") in each of the formulas (I-1), (I-2), and (I-3). By making the structures of the polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) similar to each other, the polymerizable liquid crystal compounds are more easily mixed with each other, thereby improving the solubility of the hybrid composition in solvents. Therefore, compared to dissolving the polymerizable liquid crystal compound (I-1), (I-2), or (I-3) individually in a solvent, a larger amount of the polymerizable liquid crystal compound can be easily dissolved in the same or a smaller amount of solvent. Furthermore, even in solvents that cannot dissolve the polymerizable liquid crystal compound (I-1), (I-2), or (I-3) individually, the mixed composition can be dissolved. This reduces the likelihood of undissolved polymerizable liquid crystal compound remaining in the coating liquid, ensuring high coating properties during film formation, resulting in a polymerizable liquid crystal mixed composition with excellent film-forming properties. Furthermore, this advantageously reduces the amount of solvent required to prepare the coating liquid and increases the number of solvents available, thus increasing options related to the substrate, alignment film, and manufacturing conditions. Furthermore, by increasing the solubility of the polymerizable liquid crystal compound in the solvent, precipitation or stacking of the polymerizable liquid crystal compound in the coating liquid can be suppressed. This can suppress the occurrence of alignment defects caused by undissolved polymerizable liquid crystal compounds or precipitates, improve storage stability, suppress the reduction of the optical properties that the polymerizable liquid crystal compounds used can originally exhibit, and form a film, thereby obtaining a polymerizable liquid crystal composition suitable for manufacturing a phase difference plate with excellent optical properties.

[0012] The polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) are respectively represented by formula (I): The polymerizable liquid crystal compound represented by formula (I) is a polymerizable liquid crystal compound that exhibits birefringence with reverse wavelength dispersion when polymerized in a state of unidirectional alignment, and can undergo uniform polarization conversion over a wide wavelength range. Therefore, by using the polymerizable liquid crystal compound represented by formula (I), a polymerizable liquid crystal composition can be obtained that can impart excellent display properties when used in display devices.

[0013] In formula (I), B1 and B2 are each independently a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -Ra1OR2-, -Ra3COOR4-, -Ra5OCOR6-, -Ra7OC=OOR8-, -ORbO-, -C(=O)-NRc-, -N=N-, -CRc=CRd-, or -C≡C-. Here, Ra1 to Ra8 are each independently a single bond or an alkylene group having 1 to 4 carbon atoms, Rb is an alkylene group having 1 to 4 carbon atoms, and Rc and Rd are alkyl groups having 1 to 4 carbon atoms or a hydrogen atom. Preferably, B1 and B2 are each independently a single bond, -OR2-1-, -CH2-, -CH2CH2-, -COOR4-1-, or -OCOR6-1-. Here, Ra2-1, Ra4-1, and Ra6-1 each independently represent a single bond, -CH2-, or -CH2CH2-. B1 and B2 each independently represent preferably a single bond, -O-, -CH2CH2-, -COO-, -COOCH2CH2-, or -OCO-. In formula (I), B1 and B2 may be the same or different. Furthermore, B1 and B2 being identical means that the structures of B1 and B2 are identical when M1 is considered the center. The same applies to the relationships between G1 and G2, L1 and L2, and Ea and Eb.

[0014] G1 and G2 each independently represent a divalent alicyclic hydrocarbon group or an aromatic group. The hydrogen atoms contained in the divalent alicyclic hydrocarbon group or aromatic group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atoms constituting the divalent alicyclic hydrocarbon group or aromatic group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. When n1 and / or n2 is 2, the two G1s and / or two G2s may be the same or different. G1 and G2 are preferably each independently 1,4-phenylenediyl which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, or 1,4-cyclohexanediyl which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms. They are more preferably methyl-substituted 1,4-phenylenediyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl. They are particularly preferably unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-trans-cyclohexanediyl. In formula (I), G1 and G2 may be the same or different. When there are two G1 and G2, it is preferred that at least one of them is a divalent alicyclic hydrocarbon group. Furthermore, it is more preferred that at least one of G1 and G2 bonded to B1 or B2 is a divalent alicyclic hydrocarbon group. In particular, from the perspective of exhibiting good liquid crystallinity, it is further preferred that both G1 and G2 bonded to B1 or B2 are 1,4-trans-cyclohexanediyl. It is particularly preferred that both G1 and G2 bonded to B1 or B2 are 1,4-trans-cyclohexanediyl, and both G1 and G2 not adjacent to B1 or B2 are 1,4-phenylenediyl.

[0015] L1 and L2 each independently represent a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -Ra1OR2-, -Ra3COOR4-, -Ra5OCOR6-, -Ra7OC=OOR8-, -ORbO-, -C(=O)-NRc-, -N=N-, -CRc=CRd-, or -C≡C-. Here, Ra1 to Ra8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, Rb represents an alkylene group having 1 to 4 carbon atoms, and Rc and Rd represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. When n1 and / or n2 is 2, the two L1s and / or two L2s may be the same or different. L 1 and L 2 are preferably each independently a single bond, -OR a2-1-, -CH 2-, -CH 2CH 2-, -COOR a4-1-, or OCOR a6-1-. Here, R a2-1, R a4-1, and R a6-1 each independently represent a single bond, -CH 2-, or -CH 2CH 2-. L 1 and L 2 are further preferably each independently a single bond, -O-, -CH 2CH 2-, -COO-, -COOCH 2CH 2-, -OCO-, or -OCOCH 2CH 2-. In formula (I), L 1 and L 2 may be the same as or different from each other.

[0016] Ea and Eb each independently represent an alkanediyl group having 1 to 20 carbon atoms. Here, the hydrogen atoms contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms or a halogen atom, and the -CH2- contained in the alkanediyl group may be substituted with -O- or -S- (wherein, when multiple -O- and / or -S- groups are present, they are not adjacent to each other). Ea and Eb each independently represent an alkanediyl group having 4 to 20 carbon atoms, more preferably an alkanediyl group having 4 to 11 carbon atoms. The three polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) constituting the polymerizable liquid crystal mixed composition of the present invention differ from each other in the structure of the group corresponding to the structure represented by Ea and / or Eb in formula (I).

[0017] P is an acryloxy group or a methacryloyloxy group. In formula (I), two Ps are the same.

[0018] n1 and n2 are each independently 1 or 2. From the viewpoint of expressing specific wavelength dispersion characteristics, it is preferred that n1 and n2 are the same number, and more preferably n1=2 and n2=2.

[0019] In formula (I), M1 is a divalent linking group comprising at least one aromatic hydrocarbon ring or aromatic heterocycle. The aromatic hydrocarbon ring and aromatic heterocycle referred to herein refer to those having a ring structure having [4n+2] π electrons (n represents an integer) according to Huckel's law (in the case of an aromatic heterocycle, this includes non-covalently bonded electron pairs on heteroatoms such as -N= or -S-, satisfying Huckel's law). The divalent linking group M1 may also have two or more π electrons, such as those exemplified in (M1-1) to (M1-23) below, through a divalent linking group. The divalent linking group M1 may comprise one aromatic hydrocarbon ring or aromatic heterocycle, or two or more. When comprising one aromatic hydrocarbon ring or aromatic heterocycle, the divalent linking group M1 may be a divalent aromatic hydrocarbon group that may have substituents, or a divalent aromatic heterocyclic group that may have substituents. When containing two or more aromatic hydrocarbon rings or aromatic heterocycles, the compound may contain only a plurality of aromatic hydrocarbon rings, or only a plurality of aromatic heterocycles, or may contain one or more aromatic hydrocarbon rings and one or more aromatic heterocycles respectively. The two or more aromatic hydrocarbon rings and / or aromatic heterocycles may be bonded to each other via a single bond, a divalent bonding group such as -CO-O-, or -O-.

[0020] Examples of aromatic hydrocarbon rings that may be included in M include benzene rings, naphthalene rings, and anthracene rings, with benzene rings and naphthalene rings being preferred. Examples of aromatic heterocyclic rings include furan rings, benzofuran rings, pyrrole rings, indole rings, thiophene rings, benzothiophene rings, pyridine rings, pyrrolidine rings, pyrimidine rings, triazole rings, trithionine rings, pyrroline rings, imidazole rings, pyrazole rings, thiazole rings, benzothiazole rings, thienothiazole rings, oxazole rings, benzooxazole rings, and phenanthroline rings. When M includes a nitrogen atom, it is preferred that the nitrogen atom have π electrons.

[0021] Among them, M1 is preferably an aromatic heterocyclic ring containing at least two heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, more preferably a thiazole ring, a benzothiazole ring, or a benzofuran ring, and even more preferably a benzothiazole ring. Furthermore, when M1 has an aromatic heterocyclic ring containing at least two heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, the aromatic heterocyclic ring may be directly bonded to B1 and B2 in formula (I) to form a divalent linking group, or may be included as a substituent of the divalent linking group directly bonded to B1 and B2. It is preferred that the entire M1 group containing the aromatic heterocyclic ring is sterically arranged in a direction substantially orthogonal to the molecular alignment direction.

[0022] In formula (I), the total number Nπ of π electrons contained in the divalent linking group represented by M1 and comprising at least one aromatic hydrocarbon ring or aromatic heterocycle is preferably 16 or more, more preferably 18 or more, and particularly preferably 20 or more. Furthermore, it is preferably less than 36, more preferably 30 or less, further preferably 26 or less, and particularly preferably 24 or less.

[0023] Examples of the divalent linking group represented by M1 include the following groups.

[0024] In formulas (M1-1) to (M1-23), the * symbol represents a linking moiety, and Z0, Z1, and Z2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an N-alkylamino group having 1 to 12 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylaminosulfonyl group having 1 to 12 carbon atoms, or an N,N-dialkylaminosulfonyl group having 2 to 12 carbon atoms. Furthermore, Z0, Z1, and Z2 may contain a polymerizable group.

[0025] Q 1 and Q 2 each independently represent -CR 2 'R 3 '-, -S-, -NH-, -NR 2 '-, -CO- or O-, and R 2 ' and R 3 ' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0026] J 1 and J 2 each independently represent a carbon atom or a nitrogen atom.

[0027] Y 1, Y 2 and Y 3 each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

[0028] W1 and W2 each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.

[0029] Examples of the aromatic hydrocarbon group in Y1, Y2, and Y3 include aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, phenanthrenyl, and biphenyl. Phenyl and naphthyl are preferred, and phenyl is more preferred. Examples of the aromatic heterocyclic group include aromatic heterocyclic groups having 4 to 20 carbon atoms, such as furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl, which contain at least one heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom. Furyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl are preferred.

[0030] Y1, Y2, and Y3 may each independently be a substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. A polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aggregate of aromatic rings. A polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aggregate of aromatic rings.

[0031] Z0, Z1, and Z2 are preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, or an alkoxy group having 1 to 12 carbon atoms. Z0 is further preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyano group. Z1 and Z2 are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group. Z0, Z1, and Z2 may also contain a polymerizable group.

[0032] Q 1 and Q 2 are preferably -NH-, -S-, -NR 2 '-, or -O-, and R 2 ' is preferably a hydrogen atom, particularly preferably -S-, -O-, or -NH-.

[0033] In formulas (M1-16) to (M1-23), Y1, together with the nitrogen atom to which it is bonded and Z0, may form an aromatic heterocyclic group. Examples of the aromatic heterocyclic group include those described above as aromatic heterocyclic rings that M1 may possess, such as a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrrolidine ring, a pyrimidine ring, an indole ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring. The aromatic heterocyclic group may have a substituent. Furthermore, Y1, together with the nitrogen atom to which it is bonded and Z0, may represent a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group that may be substituted as described above. Examples include a benzofuran ring, a benzothiazole ring, and a benzoxazole ring.

[0034] Among formulas (M1-1) to (M1-23), formula (M1-6), formula (M1-7), and formula (M1-16) are preferred from the viewpoint of molecular stability.

[0035] The polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) constituting the polymerizable liquid crystal hybrid composition of the present invention differ from each other only in the structure of the alkanediyl groups represented by Ea and / or Eb in the structure represented by formula (I). Based on the structure of the polymerizable liquid crystal compound (I-1) constituting the polymerizable liquid crystal hybrid composition, the polymerizable liquid crystal compound (I-2) differs from the polymerizable liquid crystal compound (I-1) only in the structure of one of the alkanediyl groups corresponding to Ea and Eb in formula (I) [E2 in formula (I-2)] constituting the mesogen. Furthermore, the polymerizable liquid crystal compound (I-3) differs from the polymerizable liquid crystal compound (I-1) only in the structure of the two alkanediyl groups corresponding to Ea and Eb in formula (I) [E2 in formula (I-3)] constituting the mesogen. Furthermore, the polymerizable liquid crystal compound (I-3) differs from the polymerizable liquid crystal compound (I-2) only in the structure of the alkanediyl group represented by E1 in formula (I-2), which constitutes the mesogen. By using at least three polymerizable liquid crystal compounds having similar but different structures, the polymerizable liquid crystal compounds are easily mixed with each other, improving the solubility of the mixed composition in solvents, and thus providing a polymerizable liquid crystal mixed composition with excellent film-forming properties.

[0036] In the polymerizable liquid crystal compound (I-1) serving as the basis for the structure of the polymerizable liquid crystal compound constituting the polymerizable liquid crystal hybrid composition of the present invention, examples of M1, B1, B2, G1, G2, L1, L2, P, n1, and n2 in formula (I-1) include the same examples as those exemplified for M1, B1, B2, G1, G2, L1, L2, P, n1, and n2 in formula (I). Examples of E1 in formula (I-1) include the same examples as those exemplified for Ea and Eb in formula (I), and E1 in formula (I-1) are the same as each other.

[0037] In the polymerizable liquid crystal compound (I-1), the ring structures in the mesogens other than M1 are preferably symmetrical in number, with the divalent linking group (core portion) represented by M1 as the center. Therefore, in formula (I-1), n1 and n2 are preferably the same.

[0038] Furthermore, it is more preferred that the ring structures of the mesogens in a symmetrical relationship with the core as the center are identical to each other. Therefore, in formula (I-1), when n1 and n2 are each 1, it is more preferred that G1 and G2 are identical to each other. When n1 and n2 are each 2, it is more preferred that G1 bonded to B1 and G2 bonded to B2 are identical to each other, and the other G1 and G2 (not adjacent to B1 or B2) are identical to each other. Furthermore, it is more preferred that the molecular structures of the mesogens in a symmetrical relationship with the core portion as the center are identical to each other. In formula (I-1), when n1 and n2 are both 1, it is more preferred that L1 and L2 are the same as each other. When n1 and n2 are each 2, it is more preferred that L1 and L2 respectively bonded to E1 are identical to each other, and the other L1 and L2 are identical to each other. In a preferred embodiment of the present invention, it is particularly preferred that the mesogens other than M1 have a symmetrical molecular structure with the core as the center. In formula (I-1), it is particularly preferred that B1 and B2 are the same, G1 and G2 are the same, L1 and L2 are the same, n1 and n2 are the same, In formula (I-1), it is particularly preferred that B1 and B2 are the same, G1 and G2 are the same, L1 and L2 are the same, and n1 and n2 are both 2. Liquid crystal compounds with highly symmetrical molecular structures tend to have poor solubility. However, in the present invention, by forming a mixture of liquid crystal compounds with similar structures, the solubility in solvents is improved. Therefore, the present invention is suitable for utilizing polymerizable liquid crystal compounds with highly symmetrical molecular structures, which previously had insufficient solvent solubility when used alone. Furthermore, the phrase "B1 and B2 are identical" means that when M1 is considered the center, the structures of B1 and B2 are identical. For example, when B1 is -O-CO-*1, B2 identical to B1 is *2-CO-O- (*1 and *2 each independently represent a bond to M1). The same applies to the relationships between G1 and G2, and between L1 and L2.

[0039] In the present invention, examples of the polymerizable liquid crystal compound (I-1) include compounds described in Japanese Patent Application Laid-Open No. 2019-003177.

[0040] In the polymerizable liquid crystal compound represented by formula (I-2), M1, B1, B2, G1, G2, L1, L2, E1, P, n1, and n2 in formula (I-2) are the same as M1, B1, B2, G1, G2, L1, L2, E1, P, n1, and n2 in formula (I-1) contained in the polymerizable liquid crystal mixed composition. E2 in formula (I-2) is an alkanediyl group having 1 to 20 carbon atoms, which is different from E1 in formula (I-1), and can be the same as those exemplified as Ea and Eb in formula (I). In formula (I-2), since E1 and E2 constituting the mesogen part have different structures, the polymerizable liquid crystal compound (I-2) has a mesogen part with an asymmetric structure centered on M1 of the core part.

[0041] The polymerizable liquid crystal compound (I-2) has a molecular structure in which the mesogens other than M1 are asymmetric with the divalent linking group (core) represented by M1 as the center. It is more preferred that the ring structures of the mesogens in a symmetrical relationship with the core as the center are identical to each other, and it is further preferred that only the structures of E1 and E2 in formula (I-2) are asymmetric. Therefore, in formula (I-2), it is preferred that n1 and n2 are identical. When n1 and n2 are both 1, it is more preferable that G1 and G2 are the same. When n1 and n2 are each 2, it is more preferred that G1 bonded to B1 and G2 bonded to B2 are the same, and the other G1 and G2 are the same. In formula (I-2), when n1 and n2 are each 1, it is more preferred that L1 and L2 are the same. When n1 and n2 are each 2, it is more preferred that L1 and L2 respectively bonded to E1 are identical to each other, and the other L1 and L2 are identical to each other. Particularly preferably, B1 and B2 are the same, G1 and G2 are the same, L1 and L2 are the same, and n1 and n2 are the same. In the present invention, the structure of the polymerizable liquid crystal compound (I-2) is specified in relation to the polymerizable liquid crystal compound (I-1) contained together in the polymerizable liquid crystal mixed composition. The polymerizable liquid crystal compound (I-2) differs from the polymerizable liquid crystal compound (I-1) only in the structure of one -E1- in formula (I-1) [-E2- in formula (I-2)] corresponding to the structure constituting the mesogen. The polymerizable liquid crystal mixed composition of the present invention may contain only one type of polymerizable liquid crystal compound (I-2) or two or more types. Furthermore, when the core portion M1 in formula (I-2) is a divalent linking group with an asymmetric structure, the polymerizable liquid crystal compound (I-2) includes a compound represented by formula (I-2a) and a compound represented by formula (I-2b).

[0042] In the present invention, in the polymerizable liquid crystal compound represented by formula (I-3), M1, B1, B2, G1, G2, L1, L2, P, n1, and n2 in formula (I-3) are the same as M1, B1, B2, G1, G2, L1, L2, P, n1, and n2 in formula (I-1) contained together with the polymerizable liquid crystal compound (I-1) in the polymerizable liquid crystal mixed composition. E2 in formula (I-3) is the same as E2 in formula (I-2) contained together with the polymerizable liquid crystal compound (I-2) in the polymerizable liquid crystal mixed composition, and the two E2s in formula (I-3) are the same as each other.

[0043] The polymerizable liquid crystal compound (I-3) is preferably a compound having a divalent linking group (core) represented by M1 as the center, and the ring structures of the mesogens in a symmetrical relationship with the core as the center are identical to each other, and more preferably has a molecular structure with symmetry of the mesogens other than M1. Therefore, in formula (I-3), it is preferred that n1 and n2 are the same, When n1 and n2 are both 1, it is more preferable that G1 and G2 are the same. When n1 and n2 are each 2, it is more preferred that G1 bonded to B1 and G2 bonded to B2 are the same, and the other G1 and G2 are the same. In formula (I-3), when n1 and n2 are each 1, it is more preferred that L1 and L2 are the same. When n1 and n2 are each 2, it is more preferred that L1 and L2 respectively bonded to E1 are identical to each other, and the other L1 and L2 are identical to each other. Particularly preferably, B1 and B2 are the same, G1 and G2 are the same, L1 and L2 are the same, and n1 and n2 are the same. In the present invention, the structure of the polymerizable liquid crystal compound (I-3) is specified in relation to the polymerizable liquid crystal compounds (I-1) and (I-2) contained together in the polymerizable liquid crystal mixed composition. The polymerizable liquid crystal compound (I-3) differs from the polymerizable liquid crystal compound (I-1) only in the structure corresponding to -E1- in formula (I-1) [-E2- in formula (I-3)] constituting the mesogen portion, and differs from the polymerizable liquid crystal compound (I-2) only in the structure corresponding to -E1- in formula (I-2) [one -E2- in formula (I-3)] constituting the mesogen portion. The polymerizable liquid crystal compound (I-3) contained in the polymerizable liquid crystal mixed composition of the present invention may be only one type or two or more types.

[0044] The polymerizable liquid crystal compounds (I-1) and (I-3) constituting the polymerizable liquid crystal hybrid composition of the present invention preferably have a molecular structure in which the divalent linking group (core portion) represented by M1 in formula (I-1) or (I-3) is symmetrical, with the portion other than M1 (mesogen portion) being the center. On the other hand, the polymerizable liquid crystal compound (I-2) has a molecular structure in which the divalent linking group (core portion) represented by M1 in formula (I-2) is asymmetrical, with the portion other than M1 (mesogen portion) being the center. When the polymerizable liquid crystal hybrid composition of the present invention comprises at least three polymerizable liquid crystal compounds having similar structures: the polymerizable liquid crystal compounds (I-1) and (I-3) having mesogen portions with a symmetrical structure centered on the core portion, and the polymerizable liquid crystal compound (I-2) having a mesogen portion with an asymmetric structure centered on the core portion, the polymerizable liquid crystal compounds are easily mixed with each other, thereby further improving the solubility of the hybrid composition in solvents. Therefore, compared to dissolving the polymerizable liquid crystal compound (I-1), (I-2), or (I-3) individually in a solvent, a larger amount of the polymerizable liquid crystal compound can be easily dissolved in the same or a smaller amount of solvent. Furthermore, even in solvents that cannot dissolve the polymerizable liquid crystal compound (I-1), (I-2), or (I-3) individually, the mixed composition can be dissolved. This reduces the likelihood of undissolved polymerizable liquid crystal compound remaining in the coating liquid, ensuring high coating properties during film formation, resulting in a polymerizable liquid crystal mixed composition with excellent film-forming properties. Furthermore, this is advantageous in reducing the amount of solvent required to prepare the coating liquid and increasing the number of solvents available, thereby increasing the options for substrates, alignment films, and manufacturing conditions. Furthermore, by increasing the solubility of the polymerizable liquid crystal compound in the solvent, precipitation or stacking of the polymerizable liquid crystal compound in the coating liquid can be suppressed. This can suppress the occurrence of alignment defects caused by undissolved polymerizable liquid crystal compounds or precipitates, improve storage stability, and allow film formation without degrading the inherent optical properties of the polymerizable liquid crystal compounds used. Furthermore, by simply varying the length of the alkyl chain (the number of carbon atoms in Ea and Eb in formula (I)) in the mesogen portion of the polymerizable liquid crystal compound, there is also the advantage of maintaining the reactivity of the polymerizable liquid crystal compound during synthesis, making it easier to obtain a polymerizable liquid crystal mixed composition containing the polymerizable liquid crystal compounds in the desired composition ratio.

[0045] In the polymerizable liquid crystal hybrid composition of the present invention, preferably, each E1 in formula (I-1) and formula (I-2) and each E2 in formula (I-2) and formula (I-3) are all alkanediyl groups having 4 to 20 carbon atoms. More preferably, each E1 in formula (I-1) and formula (I-2) and each E2 in formula (I-2) and formula (I-3) are both alkanediyl groups having 4 to 20 carbon atoms, and the difference between the number of carbon atoms of the alkanediyl groups represented by each E1 in formula (I-1) and formula (I-2) and the number of carbon atoms of the alkanediyl groups represented by each E2 in formula (I-2) and formula (I-3) is 2 or more. If the difference in the carbon number of the above-mentioned alkanediyl groups is 2 or more, the solubility of each polymerizable liquid crystal compound in the solvent can be effectively improved as a liquid crystal mixed composition, thereby obtaining a polymerizable liquid crystal mixed composition with excellent coating and film-forming properties, which is suitable for the high-efficiency production of optical films. The upper limit of the difference between the number of carbon atoms in the alkanediyl group represented by each E1 in formula (I-1) and formula (I-2) and the number of carbon atoms in the alkanediyl group represented by each E2 in formula (I-2) and formula (I-3) is usually 20 or less, preferably 9 or less, and more preferably 7 or less. Furthermore, the phrase "the difference in the number of carbon atoms is 2 or more" means that when there are a plurality of polymerizable liquid crystal compounds (I-2) and / or (I-3), the number of carbon atoms in the alkanediyl group represented by E2 in all of these polymerizable liquid crystal compounds (I-2) and / or (I-3) differs by 2 or more from the number of carbon atoms in the alkanediyl group represented by each E1 in formula (I-1) and formula (I-2).

[0046] Combinations of polymerizable liquid crystal compounds represented by formula (I) that constitute the polymerizable liquid crystal hybrid composition of the present invention include, for example, the combinations listed in Tables 1 to 4 below. The polymerizable liquid crystal hybrid compositions listed in each table contain three or more polymerizable liquid crystal compounds that differ only in Ea and / or Eb in the structures listed as the basic structure.

[0047] [Table 1] Basic structure of polymerizable liquid crystal compounds Polymerizable liquid crystal mixed composition No. polymerizable liquid crystal compounds E a E b 1 (I-1) Butyl Butyl (I-2) Butyl Shinji Shinji Butyl (I-3) Shinji Shinji 2 (I-1) Shinji Shinji (I-2) Shinji Shinki Shinki Shinji (I-3) Shinki Shinki 3 (I-1) Butyl Butyl (I-2) Butyl Shinki Shinki Butyl (I-3) Shinki Shinki 4 (3 types mixed) (I-1) Butyl Butyl (I-2) Butyl Shinji Butyl Shinki Others (I) Shinji Shinki (I-2) Shinji Butyl Shinki Butyl Others (I) Shinki Shinji (I-3) Shinji Shinji Shinki Shinki

[0048] [Table 2] Basic structure of polymerizable liquid crystal compounds Polymerizable liquid crystal mixed composition No. polymerizable liquid crystal compounds E a E b 5 (I-1) Butyl Butyl (I-2) Butyl Shinji Shinji Butyl (I-3) Shinji Shinji 6 (I-1) Shinji Shinji (I-2) Shinji Shinki Shinki Shinji (I-3) Shinki Shinki 7 (I-1) Butyl Butyl (I-2) Butyl Shinki Shinki Butyl (I-3) Shinki Shinki 8 (3 types mixed) (I-1) Butyl Butyl (I-2) Butyl Shinji Butyl Shinki Others (I) Shinji Shinki (I-2) Shinji Butyl Shinki Butyl Others (I) Shinki Shinji (I-3) Shinji Shinji Shinki Shinki

[0049] [Table 3] Basic structure of polymerizable liquid crystal compounds Polymerizable liquid crystal mixed composition No. polymerizable liquid crystal compounds E a E b 9 (I-1) Butyl Butyl (I-2) Butyl Shinji Shinji Butyl (I-3) Shinji Shinji 10 (I-1) Shinji Shinji (I-2) Shinji Shinki Shinki Shinji (I-3) Shinki Shinki 11 (I-1) Butyl Butyl (I-2) Butyl Shinki Shinki Butyl (1-3) Shinki Shinki 12 (3 types mixed) (I-1) Butyl Butyl (I-2) Butyl Shinji Butyl Shinki Others (I) Shinji Shinki (I-2) Shinji Butyl Shinki Butyl Others (I) Shinki Shinji (I-3) Shinji Shinji Shinki Shinki

[0050] [Table 4] Basic structure of polymerizable liquid crystal compounds Polymerizable liquid crystal mixed composition No. polymerizable liquid crystal compounds E a E b 13 (I-1) Butyl Butyl (I-2) Butyl Shinji Shinji Butyl (I-3) Shinji Shinji 14 (I-1) Shinji Shinji (I-2) Shinji Shinki Shinki Shinji (I-3) Shinki Shinki 15 (I-1) Butyl Butyl (I-2) Butyl Shinki Shinki Butyl (I-3) Shinki Shinki 16 (3 types mixed) (I-1) Butyl Butyl (I-2) Butyl Shinji Butyl Shinki Others (I) Shinji Shinki (I-2) Shinji Butyl Shinki Butyl Others (I) Shinki Shinji (I-3) Shinji Shinji Shinki Shinki

[0051] [Table 5] Basic structure of polymerizable liquid crystal compounds Polymerizable liquid crystal mixed composition No. polymerizable liquid crystal compounds E a E b 17 (I-1) Butyl Butyl (I-2) Butyl Shinji Shinji Butyl (I-3) Shinji Shinji 18 (I-1) Shinji Shinji (I-2) Shinji Shinki Shinki Shinji (I-3) Shinki Shinki 19 (I-1) Butyl Butyl (I-2) Butyl Shinki Shinki Butyl (I-3) Shinki Shinki 20 (3 types mixed) (I-1) Butyl Butyl (I-2) Butyl Shinji Butyl Shinki Others (I) Shinji Shinki (I-2) Shinji Butyl Shinki Butyl Others (I) Shinki Shinji (I-3) Shinji Shinji Shinki Shinki

[0052] The polymerizable liquid crystal mixed composition of the present invention preferably comprises at least 10 mol% of each of the polymerizable liquid crystal compound represented by formula (I-1), the polymerizable liquid crystal compound represented by formula (I-2), and the polymerizable liquid crystal compound represented by formula (I-3), relative to the total molar amount of the polymerizable liquid crystal compounds represented by formula (I) wherein M1, B1, B2, G1, G2, L1, L2, P, n1, and n2 are identical to each other [i.e., the molecular structures are identical except for the structures corresponding to the structures represented by Ea and / or Eb in formula (I)]. By including at least 10 mol% of each of the three polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) having similar molecular structures, the three polymerizable liquid crystal compounds can be easily mixed without significant variation in content, thereby effectively improving the solubility of each polymerizable liquid crystal compound in a solvent.

[0053] In one aspect of the present invention, the polymerizable liquid crystal hybrid composition of the present invention preferably contains more polymerizable liquid crystal compound (I-2) than polymerizable liquid crystal compound (I-1), and the ratio of polymerizable liquid crystal compound (I-1) to (I-2) in the polymerizable liquid crystal hybrid composition [molar ratio, (I-1): (I-2)] is preferably 1:1 to 1:5, more preferably 1:1 to 1:2. Furthermore, preferably, the content of polymerizable liquid crystal compound (I-2) is greater than the content of polymerizable liquid crystal compound (I-3), and the ratio of polymerizable liquid crystal compound (I-2) to (I-3) in the polymerizable liquid crystal hybrid composition [molar ratio, (I-2): (I-3)] is preferably 1:8 to 8:1, more preferably 1:4 to 4:1. Furthermore, when the polymerizable liquid crystal mixed composition contains a plurality of polymerizable liquid crystal compounds (I-1), (I-2) and / or (I-3), the above content ratio is calculated as the total amount of the compounds equivalent to each polymerizable liquid crystal compound.

[0054] The method for producing the polymerizable liquid crystal compounds represented by formula (I), such as the polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) constituting the polymerizable liquid crystal hybrid composition of the present invention, is not particularly limited and can be produced by appropriately combining known organic synthesis reactions described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, and New Experimental Chemistry Lectures (e.g., condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedel-Crafts reaction, Heck reaction, and aldol reaction, according to their structures. Specifically, it can be prepared by an esterification reaction of an alcohol compound having a structure corresponding to the structure of the desired polymerizable liquid crystal compound and a carboxylic acid compound according to the production method of a polymerizable liquid crystal compound described in, for example, Japanese Patent Laid-Open No. 2019-003177.

[0055] The polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) that constitute the polymerizable liquid crystal mixed composition of the present invention can be prepared separately and then mixed to form a liquid crystal mixture. Alternatively, a liquid crystal mixture containing the polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) can be prepared by the following method: the method comprises reacting the reactive group R2 of the compound represented by the following formula (III-1), the reactive group R2 of the compound represented by (III-2), and R1 of the compound represented by (III-3). [wherein, R 1 and R 2 independently represent reactive groups, M1, L1, L2, G1, G2, P, n1 and n2 have the same meanings as M1, L1, L2, G1, G2, P, n1 and n2 in formula (I-1). E1 represents the same meaning as E1 in formula (I-1), E2 has the same meaning as E2 in formula (I-2)] From the perspective of simple synthesis and more efficient production of the polymerizable liquid crystal hybrid composition, the latter method is preferred.

[0056] M1, L1, L2, G1, G2, E1, E2, P, n1 and n2 in formulas (III-1), (III-2) and (III-3) are determined according to the molecular structures corresponding to the desired polymerizable liquid crystal compounds (I-1), (I-2) and (I-3).

[0057] R1 in formula (III-3) and R2 in formulas (III-1) and (III-2) can react with each other to form the structures represented by B1 and B2 in formulas (I-1) to (I-3) representing polymerizable liquid crystal compounds (I-1) to (I-3). For example, the reactive groups represented by R1 and / or R2 include hydroxyl groups, carboxyl groups, and amino groups. The reactive groups represented by R1 and R2 can be selected based on the reaction used to produce the polymerizable liquid crystal compound.

[0058] From the perspectives of ease of reaction, material handling, and availability, the polymerizable liquid crystal mixture of the present invention can typically be produced by, for example, an esterification reaction using an alcohol compound in which R 1 is a hydroxyl group in formula (III-3) as a compound represented by formula (III-3) and a carboxylic acid compound in which R 2 is a carboxyl group in formulas (III-1) and (III-2) as compounds represented by formulas (III-1) and (III-2). This esterification reaction can be carried out using the same method as the esterification reaction used to produce the polymerizable liquid crystal compound represented by formula (I), and can employ, for example, the method and conditions described in Japanese Patent Application Laid-Open No. 2019-003177.

[0059] By adjusting the amounts of the compound represented by formula (III-1) and the compound represented by formula (III-2) used in the preparation, the contents of polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) in the resulting liquid crystal mixture can be controlled. By using multiple carboxylic acid compounds in the aforementioned method of reacting R1 and R2, a large number of compounds can be synthesized simultaneously. If the total amount of carboxylic acid compounds is set to 1, and the molar fractions of the carboxylic acid compounds are An, Bn, and Cn, respectively, then, when the total amount of polymerizable liquid crystal compounds (I-1) and (I-2) is set to 1, the theoretical molar fraction Sn of polymerizable compound (I-1) is as follows. Sn=Σ(An 2+Bn 2+Cn 2) The theoretical molar fraction of the polymerizable compound (I-2) is also represented by 1-Sn.

[0060] The polymerizable liquid crystal mixed composition of the present invention may also contain polymerizable liquid crystal compounds other than polymerizable liquid crystal compounds (I-1), (I-2), and (I-3), as long as the effects of the present invention are not affected. Examples of polymerizable liquid crystal compounds other than polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) include polymerizable liquid crystal compounds having a molecular structure represented by formula (I) but not belonging to either of polymerizable liquid crystal compounds (I-2) or (I-3) in relation to the polymerizable liquid crystal compound represented by formula (I-1). Examples include polymerizable liquid crystal compounds that generally exhibit positive wavelength dispersion, such as compounds having a polymerizable group listed in "3.8.6 Network (Completely Cross-linked Type)" and "6.5.1 Liquid Crystal Materials b. Polymerizable Nematic Liquid Crystal Materials" of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000).

[0061] When the polymerizable liquid crystal mixed composition of the present invention contains polymerizable liquid crystal compounds other than the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3), the content thereof is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 50 parts by mass or less, relative to 100 parts by mass of the total of the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3). In particular, excessive amounts of liquid crystal compounds with significantly different molecular structures may cause phase separation, significantly impairing the appearance. Therefore, the polymerizable liquid crystal compound constituting the polymerizable liquid crystal hybrid composition of the present invention is preferably substantially composed of a polymerizable liquid crystal compound represented by formula (I), and more preferably substantially composed of a polymerizable liquid crystal compound in which M1, B1, B2, G1, G2, L1, L2, P, n1, and n2 in formula (I) are identical to M1, B1, B2, G1, G2, L1, L2, P, n1, and n2 in formula (I-1). Furthermore, the phrase "substantially composed" means that the content of the polymerizable liquid crystal compound represented by formula (I) and the like is 90% by mass or greater relative to the total mass of the polymerizable liquid crystal compounds contained in the polymerizable liquid crystal hybrid composition of the present invention.

[0062] The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal hybrid composition (the total amount of all polymerizable liquid crystal compounds) is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solids content of the polymerizable liquid crystal hybrid composition. A content of the polymerizable liquid crystal compound within this range is advantageous in terms of the alignment properties of the resulting liquid crystal cured film. Furthermore, in this specification, the solids content of the polymerizable liquid crystal hybrid composition refers to all components obtained from the polymerizable liquid crystal hybrid composition after removing volatile components such as organic solvents.

[0063] The polymerizable liquid crystal hybrid composition of the present invention may further contain additives such as an organic solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, and a leveling agent, in addition to the polymerizable liquid crystal compounds (I-1), (I-2), and (I-3). These components may be used alone or in combination of two or more.

[0064] In the present invention, the polymerizable liquid crystal hybrid composition is typically applied to a substrate or the like while dissolved in a solvent, and therefore preferably contains a solvent. The solvent is preferably one that can dissolve the polymerizable liquid crystal compounds (I-1) to (I-3) and other polymerizable liquid crystal compounds that constitute the polymerizable liquid crystal hybrid composition, and is preferably one that is inert to the polymerization reaction of the polymerizable liquid crystal compounds. Examples of the solvent include water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorinated solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone; and the like. These solvents can be used alone or in combination of two or more. Among them, organic solvents are preferred, and alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents are more preferred.

[0065] The solvent content in the polymerizable liquid crystal hybrid composition is preferably 50-98 parts by mass, more preferably 70-95 parts by mass, per 100 parts by mass of the polymerizable liquid crystal hybrid composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal hybrid composition is preferably 2-50 parts by mass, more preferably 5-30 parts by mass. If the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal hybrid composition decreases, resulting in a generally uniform film thickness and less prone to unevenness. The solid content can be appropriately determined based on the thickness of the desired liquid crystal cured film.

[0066] The polymerizable liquid crystal mixed composition of the present invention preferably contains a polymerization initiator. A polymerization initiator is a compound that generates reactive species with the aid of heat or light, thereby initiating the polymerization reaction of the polymerizable liquid crystal. Examples of reactive species include free radicals, cations, and anions. Among these, photopolymerization initiators that generate free radicals upon irradiation with light are preferred for ease of reaction control.

[0067] Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, trisulphuric acid compounds, iodonium salts, and coronium salts. Specific examples include Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, and Irgacure 379EG (all manufactured by BASF Japan Co., Ltd.), Seikuol BZ, Seikuol Z, and Seikuol BEE (all manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Chemical), Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, and Adeka Ark1s. NCI-831, Adeka Arkls NCI-930 (all manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (all manufactured by Nihon SiberHegner Co., Ltd.), and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.). In the present invention, the polymerizable liquid crystal mixed composition preferably contains at least one photopolymerization initiator, and may also contain two or more photopolymerization initiators.

[0068] The photopolymerization initiator can fully utilize the energy emitted by the light source and has excellent productivity. The maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm. Among them, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferred.

[0069] Examples of α-acetophenone compounds include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butane-1-one. More preferred examples include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one. Commercially available α-acetophenone compounds include Irgacure 369, 379EG, and 907 (all manufactured by BASF Japan Co., Ltd.) and Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.).

[0070] Oxime-based photopolymerization initiators generate methyl radicals upon exposure to light. These methyl radicals facilitate polymerization of the polymerizable liquid crystal compound deep within the formed liquid crystal cured film. Furthermore, to more efficiently promote polymerization deep within the formed liquid crystal cured film, it is preferable to use a photopolymerization initiator that can effectively utilize ultraviolet light with a wavelength of 350 nm or longer. Preferred photopolymerization initiators that can effectively utilize ultraviolet light with a wavelength of 350 nm or longer are tris(phosphonium) compounds or oxime ester-type carbazole compounds. Oxime ester-type carbazole compounds are more preferred for their sensitivity. Examples of oxime ester carbazole compounds include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyl oxime). Commercially available oxime ester carbazole compounds include Irgacure OXE-01, Irgacure OXE-02, and Irgacure OXE-03 (all manufactured by BASF Japan Co., Ltd.), Adeka Optomer N-1919, and Adeka Arkls NCI-831 (all manufactured by ADEKA Co., Ltd.).

[0071] The amount of photopolymerization initiator added is generally 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. Within this range, the reaction of the polymerizable groups proceeds sufficiently, and the alignment of the polymerizable liquid crystal compound is less likely to be disturbed.

[0072] The polymerization reaction of polymerizable liquid crystal compounds can be controlled by adding a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone and hydroquinones substituted with alkyl ethers, etc.; butylcatechol and other alkyl ether-substituted catechols; pyrogallols; free radical scavengers such as 2,2,6,6-tetramethyl-1-piperidinyloxy radicals; thiophenols; β-naphthylamines and β-naphthols. To polymerize the polymerizable liquid crystal compound without disrupting its alignment, the polymerization inhibitor content is typically 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound.

[0073] Furthermore, by using a sensitizer, the photopolymerization initiator can be made highly sensitive. Examples of photosensitizers include thiophene, 9-oxothiophene, Anthracene and anthracene with alkyl ether and other substituents; phenanthrene; rubrene. Examples of photosensitizers include anthracene, 9-oxothiophene Ketones; anthracenes and anthracenes having substituents such as alkyl ethers; phenanthrene; and rubrene. The content of the photosensitizer is typically 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0074] Furthermore, the polymerizable liquid crystal hybrid composition of the present invention may also contain a leveling agent. Leveling agents are additives that adjust the fluidity of the polymerizable liquid crystal hybrid composition, thereby making the resulting film smoother. Examples include silicone-based, polyacrylate-based, and perfluoroalkyl-based leveling agents. Specific examples include DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, and FZ2123 (all manufactured by Dow Corning Toray Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, and KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (all manufactured by Momentive Advanced Materials Japan Co., Ltd.), fluorinert (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, and fluorinert FC-3283 (all manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) R-08, MEGAFAC R-30, MEGAFAC R-90, MEGAFAC F-410, MEGAFAC F-411, MEGAFAC F-443, MEGAFAC F-445, MEGAFAC F-470, MEGAFAC F-477, MEGAFAC F-479, MEGAFAC F-482, MEGAFAC F-483 (all manufactured by DIC Corporation), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.), trade name E1830, trade name E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names; manufactured by BM Chemie), etc.Among them, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

[0075] The content of the leveling agent in the polymerizable liquid crystal hybrid composition is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. A leveling agent content within this range is preferred because it facilitates alignment of the polymerizable liquid crystal compound and tends to make the resulting liquid crystal cured film smoother. The polymerizable liquid crystal hybrid composition may also contain two or more leveling agents.

[0076] The polymerizable liquid crystal hybrid composition of the present invention can be prepared by adding additives such as a solvent, a polymerization initiator, a polymerization inhibitor, a photosensitizer, or a leveling agent to the polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) as needed, and stirring and mixing them at a specific temperature.

[0077] <Phase Difference Plate> The polymerizable liquid crystal hybrid composition of the present invention has high solvent solubility, excellent coating and film-forming properties, and can therefore suppress the occurrence of alignment defects caused by undissolved polymerizable liquid crystal compounds or precipitates during storage. Therefore, by using the polymerizable liquid crystal hybrid composition of the present invention, a film can be formed without degrading the optical properties inherent to the polymerizable liquid crystal compounds, resulting in a liquid crystal cured film with excellent optical properties. Therefore, the present invention also relates to a phase difference plate comprising a liquid crystal cured film, which is a cured product of the polymerizable liquid crystal hybrid composition of the present invention, cured while the polymerizable liquid crystal compounds in the polymerizable liquid crystal hybrid composition are aligned. A phase difference plate comprising this liquid crystal cured film can fully exhibit the optical properties inherent to the polymerizable liquid crystal compounds used, resulting in a phase difference plate with high optical performance.

[0078] The liquid crystal cured film constituting the phase difference plate of the present invention may also include an aligned homopolymer of the polymerizable liquid crystal compound (I-1), a homopolymer of the polymerizable liquid crystal compound (I-2), and a homopolymer of the polymerizable liquid crystal compound (I-3). Furthermore, it may include an aligned copolymer of a mixture of the polymerizable liquid crystal compounds (I-1), (I-2), and (I-3). Because the polymerization reaction is relatively easy, making it easier to obtain a uniform liquid crystal cured film, the liquid crystal cured film constituting the phase difference plate of the present invention preferably includes an aligned copolymer of a mixture of the polymerizable liquid crystal compounds (I-1), (I-2), and (I-3).

[0079] In one embodiment of the present invention, the phase difference plate of the present invention is a cured product of the polymerizable liquid crystal hybrid composition of the present invention, comprising a liquid crystal cured film having the optical properties represented by the following formulas (1), (2), and (3). The liquid crystal cured film is generally a cured product formed by curing the polymerizable liquid crystal compound in a state aligned in a direction horizontal to the plane of the liquid crystal cured film (hereinafter also referred to as a "horizontally aligned liquid crystal cured film"). Re(450) / Re(550)≦1.00 (1) 1.00≦Re(650) / Re(550) (2) 100 nm ≦ Re (550) ≦ 180 nm (3) [Wherein, Re(λ) represents the in-plane retardation of the liquid crystal cured film at a wavelength of λ nm, Re = (nx(λ) - ny(λ)) × d (d represents the thickness of the liquid crystal cured film, nx represents the principal refractive index at a wavelength of λ nm in a direction parallel to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film, and ny represents the refractive index at a wavelength of λ nm in a direction parallel to the plane of the liquid crystal cured film and orthogonal to the direction of nx in the refractive index ellipsoid formed by the liquid crystal cured film.]

[0080] When the horizontal alignment liquid crystal cured film satisfies equations (1) and (2), the horizontal alignment liquid crystal cured film exhibits so-called reverse wavelength dispersion, in which the in-plane phase difference value at a short wavelength is smaller than the in-plane phase difference value at a long wavelength. In order to improve the reverse wavelength dispersion and further improve the optical properties of the phase difference plate, Re(450) / Re(550) is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0.92 or less, more preferably 0.90 or less, further preferably 0.87 or less, particularly preferably 0.86 or less, and more particularly preferably 0.85 or less. Furthermore, Re(650) / Re(550) is preferably 1.00 or more, more preferably 1.01 or more, and further preferably 1.02 or more.

[0081] The aforementioned in-plane retardation value can be adjusted by adjusting the thickness d of the horizontally aligned liquid crystal cured film. Since the in-plane retardation value is determined by the formula Re(λ) = (nx(λ) -ny(λ)) × d, to obtain the desired in-plane retardation value (Re(λ): the in-plane retardation value of the horizontally aligned liquid crystal cured film at wavelength λ (nm)), simply adjust the three-dimensional refractive index and the film thickness d.

[0082] Furthermore, when a horizontally aligned liquid crystal cured film satisfies formula (3), when an elliptically polarizing plate having a phase difference plate including the horizontally aligned liquid crystal cured film is applied to an organic EL display device, the effect of improving the frontal reflection hue (the effect of suppressing coloration) is excellent. The in-plane phase difference value is more preferably in the range of 120 nm ≤ Re (550) ≤ 170 nm, and even more preferably in the range of 130 nm ≤ Re (550) ≤ 150 nm.

[0083] In one embodiment of the present invention, the phase difference plate of the present invention is a cured product of the polymerizable liquid crystal hybrid composition of the present invention, comprising a liquid crystal cured film having the optical properties represented by the following formulas (4), (5), and (6). The liquid crystal cured film is generally a cured product formed by curing the polymerizable liquid crystal compound in a state of being aligned perpendicular to the plane of the liquid crystal cured film (hereinafter also referred to as a "vertically aligned liquid crystal cured film"). Rth(450) / Rth(550)≦1.00 (4) 1.00≦Rth(650) / Rth(550) (5) -100 nm≦Rth(550)≦-40 nm (6) [Wherein, Rth(λ) represents the retardation value of the liquid crystal cured film in the thickness direction at a wavelength of λ nm, Rth = ((nx(λ) + ny(λ)) / 2-nz) × d (d represents the thickness of the liquid crystal cured film, nx represents the principal refractive index at a wavelength of λ nm in a direction parallel to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film, ny represents the refractive index at a wavelength of λ nm in a direction parallel to the plane of the liquid crystal cured film and perpendicular to the direction of nx in the refractive index ellipsoid formed by the liquid crystal cured film, and nz represents the refractive index at a wavelength of λ nm in a direction perpendicular to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film.]

[0084] When the vertically aligned liquid crystal curing film satisfies equations (4) and (5), in an elliptically polarizing plate having a phase difference plate including the vertically aligned liquid crystal curing film, the decrease in ellipticity can be suppressed on the short wavelength side, and the oblique reflection hue can be improved. The value of Rth(450) / Rth(550) in the vertically aligned liquid crystal curing film is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0.92 or less, more preferably 0.90 or less, further preferably 0.87 or less, particularly preferably 0.86 or less, and further particularly preferably 0.85 or less. Furthermore, Rth(650) / Rth(550) is preferably 1.0 or more, more preferably 1.01 or more, and further preferably 1.02 or more.

[0085] Furthermore, when a vertically aligned liquid crystal cured film satisfies formula (6), when an elliptically polarizing plate having a phase difference plate including the vertically aligned liquid crystal cured film is applied to an organic EL display device, the oblique reflection hue can be improved. The phase difference value Rth(550) in the thickness direction of the vertically aligned liquid crystal cured film is preferably not less than -90 nm, further preferably not less than -80 nm, and further preferably not more than -50 nm.

[0086] The phase difference plate of the present invention can be manufactured, for example, by a method comprising the following steps: The steps of forming a coating film of the polymerizable liquid crystal hybrid composition of the present invention, drying the coating film, and aligning the polymerizable liquid crystal compound in the polymerizable liquid crystal hybrid composition; and The step of polymerizing the polymerizable liquid crystal compound by light irradiation while maintaining the alignment state to form a liquid crystal cured film.

[0087] The coating film of the polymerizable liquid crystal hybrid composition can be formed by coating the polymerizable liquid crystal composition on a substrate or an alignment film described below. Examples of substrates include glass substrates and film substrates. From the perspective of processability, resin film substrates are preferred. Examples of resins constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norolefin polymers; cycloolefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylates; polyacrylates; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; and plastics such as polyphenylene sulfide and polyphenylene ether. These resins can be formed into films using known methods such as solvent casting and melt extrusion to create the substrate. The substrate surface may also have a protective layer formed from acrylic resin, methacrylic resin, epoxy resin, oxetane resin, urethane resin, melamine resin, etc., and may also be subjected to surface treatment such as release treatment such as silicone treatment, corona treatment, plasma treatment, etc.

[0088] Commercially available products can also be used as substrates. Examples of commercially available cellulose ester substrates include Fujifilm Co., Ltd.'s cellulose ester substrates, such as Fujitac Film; and KC8UX2M, KC8UY, and KC4UY, manufactured by Konica Minolta Opto Co., Ltd. Examples of commercially available cycloolefin resins include Topas (registered trademark) manufactured by Ticona AG of Germany; ARTON (registered trademark) manufactured by JSR Corporation; ZEONOR (registered trademark) and ZEONEX (registered trademark) manufactured by Zeon Co., Ltd. of Japan; and APEL (registered trademark) manufactured by Mitsui Chemicals, Inc. Commercially available cycloolefin resin substrates can also be used. Examples of commercially available cycloolefin resin substrates include "S-SINA (registered trademark)" and "SCA40 (registered trademark)" manufactured by Sekisui Chemical Co., Ltd.; "Zeonor Film (registered trademark)" manufactured by Optes Co., Ltd.; and "Arton Film (registered trademark)" manufactured by JSR Corporation.

[0089] From the perspectives of thinning the phase difference plate, easy peeling of the substrate, and substrate processing properties, the thickness of the substrate is generally 5-300 μm, preferably 10-150 μm.

[0090] Examples of methods for coating the polymerizable liquid crystal mixed composition on a substrate include known methods such as spin coating, extrusion, gravure coating, die coating, rod coating, and applicator coating, and printing methods such as flexographic printing.

[0091] Next, the solvent is removed by drying, etc., to form a dried coating. Examples of drying methods include natural drying, ventilation drying, heat drying, and reduced-pressure drying. By heating the coating obtained from the polymerizable liquid crystal composition, the solvent can be dried out of the coating and the polymerizable liquid crystal compound can be aligned in a desired direction (e.g., horizontal or vertical) relative to the plane of the coating. The heating temperature of the coating can be appropriately determined based on the polymerizable liquid crystal compound used and the material of the substrate forming the coating. A temperature above the liquid crystal phase transition temperature is generally required to induce the polymerizable liquid crystal compound to transition to a liquid crystal state. To simultaneously remove the solvent contained in the polymerizable liquid crystal composition and achieve the desired alignment of the polymerizable liquid crystal compound, the coating can be heated to a temperature above the liquid crystal phase transition temperature (smectic or nematic) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal mixed composition. Furthermore, the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control platform, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), etc. The phase transition temperature of the polymerizable liquid crystal mixed composition of the present invention comprising at least three polymerizable liquid crystal compounds refers to the temperature measured using a mixture of the polymerizable liquid crystal compounds comprising the polymerizable liquid crystal composition in the same ratio as in the composition of the polymerizable liquid crystal composition.

[0092] The polymerizable liquid crystal hybrid composition of the present invention comprises at least three polymerizable liquid crystal compounds (I-1), (I-2), and (I-3). It can generally undergo liquid crystal phase transition at a temperature lower than the temperature at which each polymerizable liquid crystal compound (I-1), (I-2), or (I-3) transitions to a liquid crystal phase. Therefore, when using the polymerizable liquid crystal hybrid composition of the present invention to manufacture phase difference plates, excessive heat consumption can be suppressed, thereby improving production efficiency. Furthermore, by performing liquid crystal phase transition at a relatively low heating temperature, there is also the advantage of increasing the options for supporting substrates on which the polymerizable liquid crystal hybrid composition can be applied.

[0093] The heating time can be appropriately determined according to the heating temperature, the type of polymerizable liquid crystal compound used, the type or boiling point of the solvent, and its amount, and is generally 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.

[0094] Removal of the solvent from the coating film can be performed simultaneously with or separately from heating to a temperature above the liquid crystal phase transition temperature of the polymerizable liquid crystal compound. From the perspective of improving productivity, simultaneous removal is preferred. Before heating to a temperature above the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, a pre-drying step can be performed to appropriately remove the solvent from the coating film obtained from the polymerizable liquid crystal mixed composition while the polymerizable liquid crystal compound contained therein remains unpolymerized. Drying methods in this pre-drying step include natural drying, ventilation drying, heating drying, and reduced pressure drying. The drying temperature (heating temperature) in this drying step can be appropriately determined based on the type of polymerizable liquid crystal compound used, the type of solvent, its boiling point, and its amount.

[0095] Next, the resulting dried coating film is polymerized by irradiating the polymerizable liquid crystal compound with light while maintaining its alignment, thereby forming a polymerized liquid crystal compound in the desired alignment, i.e., a cured liquid crystal film. The polymerizable liquid crystal composition of the present invention is typically polymerized using photopolymerization because it minimizes damage to the polymerizable liquid crystal compound and allows for high-level polymerization by irradiation with high-intensity light, such as ultraviolet light. During photopolymerization, the light irradiated on the dried coating film is appropriately selected based on the type of polymerization initiator, the type of polymerizable liquid crystal compound, and its amount. Specific examples include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays, or active electron beams. Ultraviolet light is preferred because it allows for easy control of the polymerization reaction and because the photopolymerization apparatus can be used by a wide range of users in the field. It is preferred to select the type of polymerizable liquid crystal compound or polymerization initiator contained in the polymerizable liquid crystal mixed composition so that photopolymerization can proceed using ultraviolet light. Furthermore, during polymerization, the polymerization temperature can be controlled by cooling the dried coating film using an appropriate cooling method while irradiating the film with light. By employing this cooling method, polymerization of the polymerizable liquid crystal compound can be performed at a lower temperature, allowing for the formation of a suitable liquid crystal cured film even on substrates with relatively low heat resistance. Furthermore, the polymerization reaction can be accelerated by raising the polymerization temperature within a range that does not cause abnormalities (such as thermal deformation of the substrate) caused by the heat of light irradiation. During photopolymerization, masking or development can be performed to obtain a patterned cured film.

[0096] Examples of light sources for the active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten filament lamps, gallium lamps, excimer lasers, LED (Light Emitting Diode) light sources with an emission wavelength range of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.

[0097] The UV irradiation intensity is typically 10-3,000 mW / cm². The UV irradiation intensity is preferably within the wavelength range effective for activating the photopolymerization initiator. The irradiation duration is typically 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and even more preferably 0.1 second to 1 minute. When irradiated once or multiple times at this UV irradiation intensity, the cumulative amount of light is 10-3,000 mJ / cm², preferably 50-2,000 mJ / cm², and more preferably 100-1,000 mJ / cm².

[0098] The thickness of the liquid crystal cured film can be appropriately selected according to the display device to which it is applied, and is preferably 0.2-3 μm, more preferably 0.2-2 μm.

[0099] A coating of the polymerizable liquid crystal hybrid composition can also be formed on an alignment film. The alignment film has an alignment-controlling force that aligns the polymerizable liquid crystal compound in the desired direction. An alignment film that has an alignment-controlling force that aligns the polymerizable liquid crystal compound horizontally is sometimes referred to as a horizontal alignment film, while an alignment film that has an alignment-controlling force that aligns the polymerizable liquid crystal compound vertically is sometimes referred to as a vertical alignment film. The alignment-controlling force can be arbitrarily adjusted based on the type of alignment film, surface condition, and friction conditions. When the alignment film is formed from a photoalignable polymer, it can be arbitrarily adjusted by, for example, polarized light irradiation conditions.

[0100] Alignment films are preferably solvent-resistant, preventing dissolution during application of the polymerizable liquid crystal hybrid composition, and heat-resistant to heat treatments used for solvent removal and alignment of the polymerizable liquid crystal compound described below. Examples of alignment films include those containing an aligning polymer, photo-alignment films, groove-alignment films with a concave-convex pattern or multiple grooves on the surface, and stretched films extending in the alignment direction. Photo-alignment films are preferred for their accuracy and quality in terms of alignment angle.

[0101] Examples of aligning polymers include polyamides or gelatins having amide bonds within their molecules, polyimides having imide bonds within their molecules and their hydrolyzates, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylates. Among these, polyvinyl alcohol is preferred. Aligning polymers can be used alone or in combination of two or more.

[0102] An alignment film comprising an alignment polymer is typically obtained by applying a composition obtained by dissolving the alignment polymer in a solvent (hereinafter sometimes referred to as an "alignment polymer composition") to a substrate and removing the solvent, or by applying the alignment polymer composition to a substrate, removing the solvent, and then rubbing the substrate (rubbing method). Examples of the solvent include the same solvents listed above as examples of solvents that can be used in the polymerizable liquid crystal hybrid composition.

[0103] The concentration of the alignment polymer in the alignment polymer composition can be within the range where the alignment polymer material can be completely dissolved in the solvent, and is preferably 0.1-20%, more preferably about 0.1-10%, calculated relative to the solid content of the solution.

[0104] Commercially available alignment film materials can also be used directly as the alignment polymer composition. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).

[0105] Examples of a method for coating the aligning polymer composition on a substrate include the same methods as those exemplified for the method for coating the polymerizable liquid crystal mixed composition on a substrate.

[0106] Examples of methods for removing the solvent contained in the alignment polymer composition include natural drying, ventilation drying, heat drying, and reduced pressure drying.

[0107] To impart an alignment-regulating force to the alignment film, a rubbing treatment (rubbing method) may be performed as needed. One method for imparting alignment-regulating force by rubbing is to bring an alignment polymer film formed on the substrate surface by coating an alignment polymer composition on the substrate and then annealing it into contact with a rotating rubbing roller wrapped with a rubbing cloth. By masking during the rubbing treatment, multiple regions (patterns) with different alignment directions can be formed on the alignment film.

[0108] Photo-alignment films are typically obtained by applying a composition containing a polymer or monomer having photoreactive groups and a solvent (hereinafter referred to as a "photo-alignment film-forming composition") to a substrate, removing the solvent, and then irradiating the substrate with polarized light (preferably polarized UV light). Photo-alignment films are also advantageous in that the direction of the alignment-regulating force can be arbitrarily controlled by selecting the polarization direction of the irradiated light.

[0109] A photoreactive group refers to a group that induces liquid crystal alignment upon exposure to light. Specifically, groups that participate in photoreactions such as molecular alignment induction, isomerization reactions, dimerization reactions, photocrosslinking reactions, or photodecomposition reactions that are the source of the liquid crystal alignment ability can be listed. Groups that participate in dimerization reactions or photocrosslinking reactions are preferred due to their excellent alignment properties. Preferred photoreactive groups are those having an unsaturated bond, particularly a double bond, and particularly those having at least one selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond).

[0110] Examples of photoreactive groups having a C=C bond include vinyl, polyenyl, stilbene, stilbazolyl, stilbazolium, chalcone, and cinnamyl groups. Examples of photoreactive groups having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of photoreactive groups having an N=N bond include azophenyl, azonaphthyl, aromatic heterocyclic azo groups, disazo groups, formazan groups, and groups having an oxyazobenzene structure. Examples of photoreactive groups having a C=O bond include benzophenone, coumarin, anthraquinone, and maleimide groups. These groups may also have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and alkyl halides.

[0111] Among these, photoreactive groups that participate in photodimerization reactions are preferred. Cinnamoyl and chalcone groups are particularly preferred because they require relatively low amounts of polarized light for photoalignment and can easily produce photoalignment films with excellent thermal and temporal stability. Polymers containing photoreactive groups are particularly preferred because they have cinnamoyl groups at the end of their side chains, forming a cinnamic acid structure.

[0112] By applying the photo-alignment film-forming composition onto a substrate, a photo-alignment inducing layer can be formed on the substrate. Examples of the solvent contained in the composition include the same solvents listed above as those usable in the polymerizable liquid crystal mixed composition, and can be appropriately selected based on the solubility of the polymer or monomer having a photoreactive group.

[0113] The content of the polymer or monomer containing photoreactive groups in the photo-alignment film-forming composition can be adjusted appropriately based on the type of polymer or monomer and the desired thickness of the photo-alignment film. It is preferably at least 0.2% by mass, and more preferably in the range of 0.3-10% by mass, relative to the mass of the photo-alignment film-forming composition. The photo-alignment film-forming composition may also contain polymer materials such as polyvinyl alcohol or polyimide, or a photosensitizer, within a range that does not significantly degrade the properties of the photo-alignment film.

[0114] Methods for applying the photo-alignment film-forming composition to a substrate include the same methods as those for applying the aligning polymer composition to a substrate. Methods for removing the solvent from the applied photo-alignment film-forming composition include, for example, natural drying, air drying, heat drying, and reduced-pressure drying.

[0115] Polarized light irradiation can be performed by directly irradiating the photo-alignment film-forming composition coated on the substrate with the solvent removed with polarized UV light, or by irradiating the polarized light from the substrate side and transmitting the polarized light. The polarized light is preferably substantially parallel light. The wavelength of the polarized light irradiated can be within the wavelength range where the photoreactive groups of the polymer or monomer having photoreactive groups can absorb light energy. Specifically, ultraviolet light (UV) with a wavelength of 250-400 nm is particularly preferred. Examples of light sources used for polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF. High-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are more preferred. Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferred due to their higher luminous intensity of ultraviolet light with a wavelength of 313 nm. Polarized UV can be irradiated by passing the light from the above light source through an appropriate polarizing element. The polarizing element can be a polarizer, a polarizing prism such as Glenn-Thompson or Glenn-Taylor, or a wire grid type polarizing element.

[0116] Furthermore, if shielding is performed during rubbing or polarized light irradiation, multiple regions (patterns) with different liquid crystal alignment directions can also be formed.

[0117] Groove alignment films have a concave-convex pattern or multiple grooves on their surface. When a polymerizable liquid crystal compound is applied to a film with multiple linear grooves arranged at equal intervals, the liquid crystal molecules align along the grooves.

[0118] Methods for obtaining a grooved alignment film include: a method of exposing a photosensitive polyimide film through an exposure mask having patterned slits on its surface, followed by development and rinsing to form a concave-convex pattern; a method of forming a layer of UV-curable resin before curing on a plate-like master having grooves on its surface, and then transferring the formed resin layer to a substrate and curing it; and a method of pressing a roller-like master having a plurality of grooves against a film of UV-curable resin before curing formed on a substrate to form concave-convex patterns, and then curing it.

[0119] Furthermore, as materials that exhibit an alignment restraining force that causes the polymerizable liquid crystal compound to align in a direction perpendicular to the plane of the liquid crystal cured film, in addition to the above-mentioned alignment polymers, fluorine-based polymers such as perfluoroalkyl groups, silane compounds, and polysiloxane compounds obtained by condensation reactions thereof can also be used.

[0120] When using a silane compound as a material for forming an alignment film, compounds containing Si and C as constituent elements are preferred from the perspective of easily reducing surface tension and improving adhesion with layers adjacent to the alignment film. Silane compounds are particularly suitable. Silane compounds can be ionic compounds containing silane, and their use can enhance vertical alignment limiting forces. Silane compounds can be used alone, in combination of two or more, or mixed with other materials. When the silane compound is a non-ionic silane compound, compounds having an alkyl group at the molecular end are preferred from the perspective of easily improving vertical alignment limiting forces, and silane compounds having an alkyl group with 3 to 30 carbon atoms are more preferred.

[0121] The thickness of the alignment film (including an alignment film of an alignment polymer or a photo-alignment film) is generally in the range of 10 to 10,000 nm, preferably in the range of 10 to 1,000 nm, more preferably 10 to 500 nm or less, further preferably 10 to 300 nm, and particularly preferably 50 to 250 nm.

[0122] The present invention includes an elliptically polarizing plate comprising the phase difference plate of the present invention and a polarizing film. Polarizing films are films with polarizing functions, and examples thereof include stretched films adsorbed with anisotropic absorption dyes or films coated with anisotropic absorption dyes as polarizing elements. Examples of anisotropic absorption dyes include dichroic dyes.

[0123] A film comprising a stretched film adsorbed with an anisotropic absorption pigment as a polarizing element is usually produced by sandwiching at least one surface of a polarizing element manufactured through the following steps between transparent protective films via an adhesive: a step of uniaxially stretching a polyvinyl alcohol resin film; a step of dyeing the polyvinyl alcohol resin film with a dichroic pigment to thereby adsorb the dichroic pigment; a step of treating the polyvinyl alcohol resin film adsorbed with the dichroic pigment with an aqueous boric acid solution; and a step of washing with water after the treatment with the aqueous boric acid solution.

[0124] Polyvinyl alcohol resins can be obtained by saponifying polyvinyl acetate resins. Polyvinyl acetate resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other copolymerizable monomers. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides containing ammonium groups.

[0125] The saponification degree of polyvinyl alcohol resin is typically around 85-100 mol%, preferably 98 mol% or higher. Polyvinyl alcohol resin can be modified; for example, aldehyde-modified polyvinyl formal or polyvinyl acetal can be used. The degree of polymerization of polyvinyl alcohol resin is typically around 1,000-10,000, preferably 1,500-5,000.

[0126] A film of this polyvinyl alcohol-based resin is used as a precursor for the polarizing film. The method for forming the polyvinyl alcohol-based resin film is not particularly limited, and known methods can be used. The thickness of the polyvinyl alcohol-based film can be, for example, approximately 10 to 150 μm.

[0127] Uniaxial stretching of polyvinyl alcohol-based resin films can be performed before, simultaneously with, or after dyeing with a dichroic dye. When uniaxial stretching is performed after dyeing, it can be performed before or during the boric acid treatment. Furthermore, uniaxial stretching can be performed in multiple stages. Uniaxial stretching can be performed between rollers with different circumferential speeds or using heated rollers. Uniaxial stretching can be dry stretching in air or wet stretching using a solvent while the polyvinyl alcohol-based resin film is swollen. The stretching ratio is typically around 3 to 8 times.

[0128] The polyvinyl alcohol-based resin film can be dyed with a dichroic dye by, for example, immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.

[0129] Specifically, iodine or a dichroic organic dye is used as the dichroic dye. Examples of dichroic organic dyes include dichroic direct dyes containing disazo compounds such as CI Direct Red 39, and dichroic direct dyes containing trisazo and tetrakisazo compounds. The polyvinyl alcohol-based resin film is preferably immersed in water before dyeing.

[0130] When using iodine as a dichroic dye, the dyeing method typically involves immersing the polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide. The iodine content of this aqueous solution is typically 0.01 to 1 part by mass per 100 parts by mass of water. The potassium iodide content is typically 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is typically around 20 to 40°C. Furthermore, the immersion time (dyeing time) in this aqueous solution is typically around 20 to 1,800 seconds.

[0131] On the other hand, when using a dichroic organic dye as the dichroic pigment, a dyeing method is typically employed in which the polyvinyl alcohol-based resin film is immersed in an aqueous solution containing a water-soluble dichroic dye. The content of the dichroic organic dye in this aqueous solution is typically approximately 1×10-4 to 10 parts by mass per 100 parts by mass of water, preferably 1×10-3 to 1 part by mass, and even more preferably 1×10-3 to 1×10-2 parts by mass. The aqueous solution may also contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The temperature of the dichroic dye aqueous solution used for dyeing is typically approximately 20 to 80°C. Furthermore, the immersion time in the aqueous solution (dyeing time) is typically approximately 10 to 1,800 seconds.

[0132] Boric acid treatment after dyeing with a dichroic dye is typically performed by immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The boric acid content in the aqueous boric acid solution is typically 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. When iodine is used as the dichroic dye, the aqueous boric acid solution preferably contains potassium iodide. In this case, the potassium iodide content is typically 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. The immersion time in the aqueous boric acid solution is typically 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature for the boric acid treatment is typically above 50°C, preferably 50 to 85°C, and more preferably 60 to 80°C.

[0133] The polyvinyl alcohol-based resin film treated with boric acid is typically washed with water. This washing process can be performed, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water. The water temperature during the washing process is typically around 5-40°C. The immersion time is typically around 1-120 seconds.

[0134] After washing with water, a drying treatment is performed to obtain a polarizing element. The drying treatment can be performed using, for example, a hot air dryer or a far-infrared heater. The drying temperature is generally around 30-100°C, preferably 50-80°C. The drying time is generally around 60-600 seconds, preferably 120-600 seconds. The drying treatment reduces the moisture content of the polarizing element to a practical level. The moisture content is generally around 5-20% by mass, preferably 8-15% by mass. If the moisture content is lower than 5% by mass, the flexibility of the polarizing element may be lost, and the polarizing element may be damaged or broken after drying. In addition, if the moisture content exceeds 20% by mass, the thermal stability of the polarizing element may deteriorate.

[0135] The thickness of the polarizing element obtained by uniaxially stretching the polyvinyl alcohol-based resin film, dyeing it with a dichroic dye, treating it with boric acid, washing it with water, and drying it is preferably 5 to 40 μm.

[0136] Examples of films coated with a dye having absorption anisotropy include films obtained by coating a composition containing a dichroic dye having liquid crystal properties, or a composition containing a dichroic dye and a polymerizable liquid crystal. Preferably, the film has a protective film on one or both sides. Examples of such protective films include the same resin films listed above as substrates useful in the production of liquid crystal cured films.

[0137] The film coated with the anisotropic absorption dye is preferably thin. However, if it is too thin, the strength tends to decrease and the processability deteriorates. The thickness of the film is generally 20 μm or less, preferably 5 μm or less, and more preferably 0.5-3 μm.

[0138] Specific examples of the film coated with the dye having absorption anisotropy include films described in Japanese Patent Application Laid-Open No. 2012-33249 and the like.

[0139] A polarizing film is obtained by laminating a transparent protective film onto at least one surface of the polarizing element obtained in this manner via an adhesive. The transparent protective film can be preferably a transparent film similar to the resin film exemplified above as a substrate for producing a liquid crystal cured film.

[0140] The elliptically polarizing plate of the present invention comprises the phase difference plate of the present invention and a polarizing film. For example, the elliptically polarizing plate of the present invention can be obtained by laminating the phase difference plate of the present invention and the polarizing film via an adhesive layer or a pressure-sensitive adhesive layer.

[0141] In one embodiment of the present invention, when the phase difference plate of the present invention including a horizontally aligned liquid crystal cured film and a polarizing film are laminated, it is preferred that the phase difference plate is laminated in such a manner that the angle formed by the slow phase axis (optical axis) of the horizontally aligned liquid crystal cured film constituting the phase difference plate and the absorption axis of the polarizing film becomes 45±5°.

[0142] The elliptically polarizing plate of the present invention may also have the same configuration as conventional elliptically polarizing plates, polarizing films, and retardation plates. Examples of such configurations include adhesive layers (sheets) used to attach the elliptically polarizing plate to display devices such as organic EL, and protective films used to protect the surfaces of polarizing films or retardation plates from damage or contamination.

[0143] The elliptically polarizing plate of the present invention can be used in various display devices. A display device is a device having a display element, including a light-emitting element or light-emitting device as a light source. Examples of display devices include liquid crystal displays, organic electroluminescent (EL) displays, inorganic electroluminescent (EL) displays, touch panel displays, electron emission displays (e.g., field emission displays (FEDs) and surface field emission displays (SEDs)), electronic paper (displays using electronic ink or electrophoretic elements), plasma displays, projection displays (e.g., grating light valve (GLV) displays and displays with digital micromirror devices (DMDs)), and piezoelectric ceramic displays. Liquid crystal displays include transmissive, semi-transmissive, reflective, direct-view, and projection liquid crystal displays. These display devices can display two-dimensional images or three-dimensional images. In particular, the elliptically polarizing plate of the present invention is well-suited for use in organic and inorganic electroluminescent (EL) displays, while the laminate of the present invention is well-suited for use in liquid crystal displays and touch panel displays. These displays, by incorporating the elliptically polarizing plate of the present invention, which exhibits excellent optical properties, can exhibit superior image display characteristics. [Example]

[0144] The present invention is described in more detail below with reference to Examples. Furthermore, "%" and "parts" in the examples refer to mass % and mass parts, respectively, unless otherwise specified.

[0145] [Example 1: Preparation of Liquid Crystal Mixture (A-1)] A liquid crystal mixture represented by the following formula (A-1) (hereinafter referred to as "liquid crystal mixture (A-1)") was synthesized according to the following process.

[0146] A 100 mL four-necked flask equipped with a Dai condenser and a thermometer was placed under a nitrogen atmosphere, and 2.70 parts of the compound represented by formula (E-1) synthesized with reference to the patent document (Japanese Patent Application Laid-Open No. 2010-31223), 2.88 parts of the compound represented by formula (E-2) [the molar ratio of the compound represented by formula (E-1) to the compound represented by formula (E-2) = 50:50], 2 parts of the compound represented by formula (G-1) synthesized with reference to the patent document (Japanese Patent Application Laid-Open No. 2019-003177), 0.02 parts of dimethylaminopyridine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.2 parts of dibutylhydroxytoluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 30 parts of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added and mixed, and then 1.92 parts of IPC (manufactured by Wako Pure Chemical Industries, Ltd.) was further added using a dropping funnel. g, and allowed to react overnight at 0°C. After the reaction, the insoluble components were removed by filtration. The resulting chloroform solution was added dropwise to a volume of heptane (Wako Pure Chemical Industries, Ltd.) three times the weight of the chloroform contained in the solution, to precipitate a solid. The precipitated solid was then removed by filtration, washed three times with 20 g of heptane, and dried under reduced pressure at 40°C to obtain 5.96 g of liquid crystal mixture (A-1). The yield of liquid crystal mixture (A-1) was 98% based on compound (G-1).

[0147] [Example 2: Preparation of Liquid Crystal Mixture (A-2)] A liquid crystal mixture (A-2) was prepared in the same manner as in Example 1, except that the compound represented by formula (E-3) shown below was used instead of the compound represented by formula (E-2), and the molar ratio of the compound represented by formula (E-1): the compound represented by formula (E-3) was made 50:50.

[0148] [Example 3: Preparation of Liquid Crystal Mixture (A-3)] A liquid crystal mixture (A-3) was prepared in the same manner as in Example 1, except that the compound represented by formula (E-3) shown below was used instead of the compound represented by formula (E-1), and the molar ratio of the compound represented by formula (E-2): the compound represented by formula (E-3) was made 50:50.

[0149] [Example 4: Preparation of Liquid Crystal Mixture (A-4)] In addition to the compound represented by formula (E-1) and the compound represented by formula (E-2), the compound represented by formula (E-3) shown below was used. A liquid crystal mixture (A-4) was prepared in the same manner as in Example 1, except that the molar ratio of the compound represented by formula (E-1), the compound represented by formula (E-2), and the compound represented by formula (E-3) was set to be equal.

[0150] [Example 5: Preparation of Liquid Crystal Mixture (A-5)] A liquid crystal mixture (A-5) was prepared in the same manner as in Example 1, except that the compound represented by the following formula (G-2) was used instead of the compound represented by the formula (G-1).

[0151] [Example 6: Preparation of Liquid Crystal Mixture (A-6)] A liquid crystal mixture (A-6) was prepared in the same manner as in Example 2, except that the compound represented by the following formula (G-2) was used instead of the compound represented by the formula (G-1).

[0152] [Example 7: Preparation of Liquid Crystal Mixture (A-7)] A liquid crystal mixture (A-7) was prepared in the same manner as in Example 3, except that the compound represented by the following formula (G-2) was used instead of the compound represented by the formula (G-1).

[0153] [Example 8: Preparation of Liquid Crystal Mixture (A-8)] A liquid crystal mixture (A-8) was prepared in the same manner as in Example 4, except that the compound represented by the following formula (G-2) was used instead of the compound represented by the formula (G-1).

[0154]

[0155] [Comparative Example 1] A polymerizable liquid crystal compound was synthesized in the same manner as in Example 1, except that 5.40 parts of the compound represented by formula (E-1) was used instead of the compound represented by formula (E-2).

[0156] [Comparative Example 2] A polymerizable liquid crystal compound was synthesized in the same manner as in Example 1, except that 5.96 parts of the compound represented by formula (E-2) was used instead of the compound represented by formula (E-1).

[0157] The resulting liquid crystal mixture and polymerizable liquid crystal compound are shown in Table 6. The polymerizable liquid crystal compound contained in the liquid crystal mixture and the polymerizable liquid crystal compounds synthesized in Comparative Examples 1 and 2 are compounds represented by the following formula (I'). Furthermore, (G1-1) and (G2-1) in Table 6 represent the following partial structures, respectively (where * indicates a bond to an oxygen atom).

[0158] [Table 6] Polymerizable liquid crystal mixed composition polymerizable liquid crystal compounds Theoretical mixing ratio (%) Carboxylic acid compound mixing ratio (molar ratio) Alkanediyl carbon number M 1 E-1 E-2 E-3 E a E b Comparative Example 1 G1-1 100 0 0 6 6 (I-1) 100 Comparative Example 2 G2-1 100 0 0 6 6 (I-1) 100 Example 1 G1-1 50 50 0 4 4 (I-1) 25 4 6 (I-2) twenty five 6 4 (I-2) twenty five 6 6 (I-3) twenty five Actual example 2 G1-1 50 0 50 6 6 (I-1) twenty five 6 8 (I-2) twenty five 8 6 (I-2) twenty five 8 8 (I-3) twenty five Actual example 3 G1-1 0 50 50 4 4 (I-1) twenty five 4 8 (I-2) twenty five 8 4 (I-2) twenty five 8 8 (I-3) twenty five Actual example 4 G1-1 33 33 33 4 4 (I-1) 11 4 6 (I-2) 11 6 4 (I-2) 11 4 8 (I-2) 11 8 4 (I-2) 11 6 6 (I-3) 11 6 8 Others (I) 11 8 6 Others (I) 11 8 8 (I-3) 11 Example 5 G2-1 50 50 0 4 4 (I-1) 25 4 / 6 (G-2 symmetric structure) (I-2) 50 6 6 (I-3) 25 Example 6 G2-1 50 0 50 6 6 (I-1) 25 6 / 8 (G-2 symmetric structure) (I-2) 50 8 8 (I-3) 25 Example 7 G2-1 0 50 50 4 4 (I-1) 25 4 / 8 (G-2 symmetric structure) (I-2) 50 8 8 (I-3) 25 Example 8 G2-1 33 33 33 4 4 (I-1) 11 4 / 6 (G-2 symmetric structure) (I-2) twenty two 6 / 8 (G-2 symmetric structure) (I-2) twenty two 6 6 (I-3) 11 4 / 8 (G-2 symmetric structure) (I-2) twenty two 8 8 (I-3) 11

[0159] [Determination of solubility] Prepare four organic solvents (o-xylene, toluene, cyclopentane, and N-methyl-2-pyrrolidone) and add 1 g of each organic solvent to a screw-cap bottle. The liquid crystal mixture from Example 1 was added to each screw-cap bottle and visually confirmed to be completely dissolved. The solubility of the liquid crystal mixtures or polymerizable liquid crystal compounds from Examples 2-8 and Comparative Examples 1 and 2 was also measured in the same manner for each organic solvent. The results are shown in Table 7.

[0160] [Table 7] Liquid crystal compounds o-Xylene Toluene Cyclopentanone N-Methyl-2-pyrrolidone Comparative Example 1 0% 0% 4% 7% Comparative Example 2 0% 0% 2% 2% Example 1 5% 7% 20% 26% Example 2 3% 4% 16% twenty four% Example 3 3% 3% 15% twenty two% Example 4 6% 8% 20% 27% Example 5 2% 3% 8% 10% Example 6 2% 2% 7% 9% Example 7 2% 2% 7% 9% Example 8 3% 4% 10% 12%

Claims

1. A polymerizable liquid crystal mixture composition comprising at least three molecules with different molecular structures and of formula (I): [Chemical 1] [In formula (I), M1 represents a divalent linker containing at least one aromatic hydrocarbon ring or aromatic heterocycle, M1 is a divalent linker containing at least one aromatic hydrocarbon ring or aromatic heterocycle whose total number of π electrons is 16 or more but less than 36, B1 and B2 independently represent a single bond, an alkyl group having 1 to 4 carbon atoms, -O-, -S-, -Ra1OR a2-, -Ra3COOR a4-, -Ra5OCOR a6-, -Ra7OC=OOR a8-, -OR bO-, -C(=O)-NR c-, -N=N-, -CR c=CR d- or -C≡C-, where Ra1 to Ra8 are independently single bonds or alkyl groups having 1 to 4 carbon atoms, R b is an alkyl group having 1 to 4 carbon atoms; Rc and Rd represent alkyl groups or hydrogen atoms having 1 to 4 carbon atoms; G1 and G2 independently represent divalent alicyclic hydrocarbon groups or aromatic groups. The hydrogen atoms in these divalent alicyclic hydrocarbon groups or aromatic groups can be replaced by halogen atoms, alkyl groups having 1 to 4 carbon atoms, fluoroalkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, cyano groups, or nitro groups. The carbon atoms constituting these divalent alicyclic hydrocarbon groups or aromatic groups can be replaced by oxygen atoms, sulfur atoms, or nitrogen atoms. When n1 and n2 are both 1, G1 and G2 are identical. When n1 and n2 are both 2, G1 bonded to B1 and G2 bonded to B2 are identical, and another G1 and G2 are identical. L1 and L 2 independently represents a single bond, -O-, -S-, -COO-, -OCO-, -OC=OO-, -C(=O)-NR c-, -N=N-, -CR c=CR d-, or -C≡C-. Here, Rc and Rd represent alkyl or hydrogen atoms with 1 to 4 carbon atoms. When n1 and n2 are both 1, L1 and L2 are identical. When n1 and n2 are both 2, L1 and L2 bonded to E1 are identical, and the other L1 and L2 are identical. Ea and Eb independently represent alkadiyl groups with 1 to 20 carbon atoms. Here, the hydrogen atoms in the alkadiyl group can be replaced by alkyl or halogen atoms with 1 to 4 carbon atoms, and the -CH2- in the alkadiyl group can be replaced by -O- or -S- (wherein, In the case where there are multiple -O- and / or -S- (which are not adjacent to each other), P is acryloxy or methacryloxy, n1 and n2 are independently 1 or 2 respectively. The polymeric liquid crystal compound represented by the above polymeric liquid crystal compound includes polymeric liquid crystal compounds in which Ea and Eb are the same. The polymeric liquid crystal compound in which the number of carbon atoms of the alkadiyl group represented by Ea and Eb is the polymeric liquid crystal compound represented by Ea and Eb is defined as the polymeric liquid crystal compound represented by Ea and Eb. [Chemical 2] [In formula (I-1), M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 are defined in the same way as M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 in formula (I) above, and E1 is the same as Ea and Eb in formula (I) above. When the polymeric liquid crystal compound (I-1) represented by b is defined similarly, and the two E 1s are the same, it includes at least one of the following: [I-2] defined based on the structure of the polymeric liquid crystal compound (I-1): [Chemical 3] [In formula (I-2), M 1, B 1, B 2, G 1, G 2, L 1, L 2, E 1, P, n1 and n2 are the same as M 1, B 1, B 2, G 1, G 2, L 1, L 2, E 1, P, n1 and n2 in formula (I-1) respectively, and E 2 represents an alkyl diyl group with 1 to 20 carbon atoms that is different from E 1 in formula (I-1). Here, the hydrogen atoms contained in the alkyl diyl group can be replaced by alkyl or halogen atoms with 1 to 4 carbon atoms, and the -CH atoms contained in the alkyl diyl group are different from E 1 in formula (I-1). 2- can be replaced by -O- or -S- (wherein, in the case of a plurality of -O- and / or -S-, they are not adjacent to each other)] represents the polymerizable liquid crystal compound (I-2), and at least one polymerizable liquid crystal compound (I-3) defined based on the structure of the polymerizable liquid crystal compound (I-1) above: [Chemical 4] [In formula (I-3), M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 are the same as M1, B1, B2, G1, G2, L1, L2, P, n1 and n2 in formula (I-1) above, E2 is the same as E2 in formula (I-2) above, and the two E2s in formula (I-3) are the same] represents the polymerizable liquid crystal compound (I-3).

2. The polymerizable liquid crystal mixture composition of claim 1, wherein n1 and n2 are the same in formula (I-1).

3. The polymerizable liquid crystal mixture composition of claim 1 or 2, wherein each E1 in formula (I-1) and formula (I-2) and each E2 in formula (I-2) and formula (I-3) are alkyldiyl groups with 4 to 20 carbon atoms, and the difference between the number of carbon atoms of the alkyldiyl group represented by each E1 in formula (I-1) and formula (I-2) and the number of carbon atoms of the alkyldiyl group represented by each E2 in formula (I-2) and formula (I-3) is 2 or more.

4. The polymeric liquid crystal mixture composition of claim 1 or 2, wherein the polymeric liquid crystal compound represented by formula (I) comprises, relative to the total molar amount of the polymeric liquid crystal compounds represented by formula (I) that are identical to each other M1, B1, B2, G1, G2, L1, L2, P, n1 and n2, at least 10 molars of the polymeric liquid crystal compound represented by formula (I-1), the polymeric liquid crystal compound represented by formula (I-2) and the polymeric liquid crystal compound represented by formula (I-3).

5. The polymeric liquid crystal mixture composition of claim 1 or 2, comprising an organic solvent.

6. A phase retardation plate comprising a liquid crystal curing film, wherein the liquid crystal curing film is a cured product of a polymeric liquid crystal mixture composition as claimed in any one of claims 1 to 5, and is cured in a state in which the polymeric liquid crystal compounds in the polymeric liquid crystal mixture composition are aligned.

7. The phase difference plate of claim 6, wherein the liquid crystal curing film has the optical properties represented by formulas (1), (2) and (3), Re(450) / Re(550)≦1.00 (1) 1.00≦Re(650) / Re(550) (2) 100 nm≦Re(550)≦180 nm (3) [where Re(λ) represents the in-plane phase difference value of the liquid crystal curing film at wavelength λ nm, Re=(nx(λ)-ny(λ))×d (d represents the thickness of the liquid crystal curing film, nx represents the principal refractive index at wavelength λ nm in the direction parallel to the plane of the liquid crystal curing film in the refractive index ellipsoid formed by the liquid crystal curing film, and ny represents the refractive index at wavelength λ nm in the direction parallel to the plane of the liquid crystal curing film and orthogonal to the direction of the above nx in the refractive index ellipsoid formed by the liquid crystal curing film).

8. The phase difference plate of claim 6, wherein the liquid crystal curing film has the optical properties represented by equations (4), (5) and (6), Rth(450) / Rth(550)≦1.00 (4) 1.00≦Rth(650) / Rth(550) (5) -100 nm≦Rth(550)≦-40 nm (6) [where Rth(λ) represents the phase difference value of the liquid crystal curing film in the thickness direction at wavelength λ nm, Rth=((nx(λ)+ny(λ)) / 2-nz)×d (d represents the thickness of the liquid crystal curing film, nx represents the refractive index at wavelength λ nm in the direction parallel to the plane of the liquid crystal curing film in the refractive index ellipsoid formed by the liquid crystal curing film, and ny represents the wavelength λ nm in the direction parallel to the plane of the liquid crystal curing film and orthogonal to the direction of the above nx in the refractive index ellipsoid formed by the liquid crystal curing film.] The refractive index at nm, where nz represents the refractive index at wavelength λ nm in the direction perpendicular to the plane of the liquid crystal curing film within the refractive index ellipsoid formed by the liquid crystal curing film.

9. An elliptical polarizing plate comprising a phase retardation plate and a polarizing film as claimed in any one of claims 6 to 8.

10. An organic EL display device having an elliptical polarizing plate as claimed in claim 9.

11. A method for manufacturing a polymerizable liquid crystal mixture composition as claimed in any one of claims 1 to 5, comprising reacting the reactive group R2 of the compound represented by formula (III-1), the reactive group R2 of the compound represented by formula (III-2), and R1 of the compound represented by formula (III-3), [Chemical 5] [wherein, R1 and R2 independently represent reactive groups, M1, L1, L2, G1, G2, P, n1 and n2 have the same meaning as M1, L1, L2, G1, G2, P, n1 and n2 in formula (I-1), E1 has the same meaning as E1 in formula (I-1), and E2 has the same meaning as E2 in formula (I-2).]