Polymerizable liquid crystal compound, polymerizable liquid crystal composition, phase difference film, elliptically polarizing plate, and organic EL display device

Abstract

The present invention relates to a polymerizable liquid crystal compound represented by formula (I).

Description

Technical Field

[0001] The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, a retardation film composed of a cured product of the polymerizable liquid crystal composition, and an elliptically polarizing plate and an organic EL display device containing the retardation film. Background Art

[0002] Optical films such as retardation films used in flat panel displays (FPDs) include those obtained by applying a coating solution obtained by dissolving a polymerizable liquid crystal compound in a solvent onto a supporting substrate and then polymerizing the solution. Known polymerizable liquid crystal compounds for forming such optical films include, for example, nematic liquid crystal compounds having a rod-like structure formed by connecting multiple six-membered rings (e.g., Patent Document 1).

[0003] On the other hand, one of the characteristics of retardation films is the ability to perform uniform polarization conversion across the entire wavelength range. For example, it is known that theoretically, uniform polarization conversion can be performed in a wavelength range where the value [Re(λ) / Re(550)] obtained by dividing the retardation value Re(λ) at a certain wavelength λ by the retardation value Re(550) at 550 nm is close to 1, and in a wavelength range where [Re(450) / Re(550)] < 1 is exhibited. Polymerizable liquid crystal compounds that can form such retardation films are disclosed, for example, in Patent Document 2.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2010-24438

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2011-207765 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] The coating liquid used in optical film production may lack solubility in solvents due to the molecular structure of the polymerizable liquid crystal compound. Such low-solubility polymerizable liquid crystal compounds may precipitate or crystallize and precipitate in the coating liquid. Such precipitation or precipitation of the polymerizable liquid crystal compound not only reduces film-forming properties but also causes alignment defects in the resulting optical film.

[0010] Therefore, an object of the present invention is to provide a polymerizable liquid crystal compound that can independently exhibit high solubility in a solvent.

[0011] Means for solving problems

[0012] The present invention provides the following preferred embodiments.

[0013] [1] A polymerizable liquid crystal compound represented by formula (I).

[0014] [Chemical Formula 1]

[0015] PE a -L 1 -A 1 -B 1 -MB 2 -A 2 -L 2 -E b -P (I)

[0016] [In formula (I),

[0017] M represents a divalent alicyclic hydrocarbon group, wherein the hydrogen atoms contained in the divalent alicyclic hydrocarbon 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, and the carbon atoms constituting the divalent alicyclic hydrocarbon group may be replaced with an oxygen atom, a sulfur atom, or a nitrogen atom,

[0018] B 1 and B 2 each independently represents an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -、-R a3 COOR a4 -、-R a5 OCOR a6 -、-R a7 OC=OOR a8 -、-OR b O-, -C(=O)-NR c -、-N=N-、-CR c =CR d -or-C≡C-, where R a1 ~R a8 Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, R b is an alkylene group having 1 to 4 carbon atoms, R c and R d represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom,

[0019] A 1 and A 2each independently represents a divalent alicyclic hydrocarbon group or an aromatic group, in which 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, and the carbon atoms constituting the divalent alicyclic hydrocarbon group or aromatic group may be replaced with an oxygen atom, a sulfur atom or a nitrogen atom

[0020] L 1 and L 2 each independently represents -O-, -COO- or -OCO-

[0021] E a and E b each independently represents an alkane diyl group having 1 to 12 carbon atoms, in which the hydrogen atoms contained in the alkane diyl group may be substituted with an alkyl group having 1 to 4 carbon atoms or a halogen atom, and the -CH2- not adjacent to L 1 or L 2 may be replaced with -O- or -S- (wherein when there are a plurality of -O- and / or -S- in E a and E b , they are not adjacent to each other), and P is acryloyloxy or methacryloyloxy

[0022] When the sum of the number of carbon atoms in the group represented by E a and the sum of the number of carbon atoms in the group represented by E b are set such that the smaller one is N1 and the larger one is N2, N1 is 2 to 6, N2 is 6 to 12, and the relationship 1 < N2 - N1 < 10 is satisfied

[0023] [2] The polymeric liquid crystal compound according to [1] above, wherein M is a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms

[0024] [3] The polymeric liquid crystal compound according to [1] or [2] above, wherein A 1 and A 2 each independently represents a divalent aromatic group, in which the hydrogen atoms contained in the divalent 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, and the carbon atoms constituting the divalent aromatic group may be replaced with an oxygen atom, a sulfur atom or a nitrogen atom

[0025] [4] The polymeric liquid crystal compound according to any one of [1] to [3] above, wherein B 1 and B 2 are each independently -COO- or -OCO-

[0026] [5] A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to any one of [1] to [4] above and a polymerizable liquid crystal compound represented by formula (II).

[0027] [Chemical Formula 2]

[0028] P 1 -E c -L 5 -A 3 -L 3 -G 1 -B 3 -Ar-B 4 -G 2 -L 4 -A 4 -L 6 -E d -P 2 (II)

[0029] [In formula (II), Ar is a divalent group having at least one aromatic ring, and the aromatic ring constituting the divalent group may contain at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. The total number of π electrons contained in the aromatic ring constituting Ar is N π is 12 or more and less than 36,

[0030] G 1 and G 2 Each independently represents a divalent alicyclic hydrocarbon group, wherein the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted by 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, and the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S- or -NH-,

[0031] B 3 and B 4 Each independently represents a single bond or a divalent linking group,

[0032] A 3 and A 4 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, wherein the hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, an alkoxy group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, a cyano group or a nitro group, and the -CH2- contained in the alicyclic hydrocarbon group may be substituted by -O-, -S- or -NR 1 -, the -CH(-)- contained in the alicyclic hydrocarbon group can be replaced by -N(-)-, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0033] L 3 ~L 6 Each independently represents -O-, -COO- or -OCO-,

[0034] E c and E d Each independently represents an alkanediyl group having 1 to 17 carbon atoms, wherein the hydrogen atoms contained in the alkanediyl group may be substituted by halogen atoms, and the -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-,

[0035] P 1 and P 2 each independently represents a polymerizable group]

[0036] [6] The polymerizable liquid crystal composition according to [5], wherein the polymerizable liquid crystal compound represented by formula (II) exhibits maximum absorption in a wavelength range of 300 nm to 400 nm.

[0037] [7] The polymerizable liquid crystal composition according to [5] or [6], wherein the polymerizable liquid crystal compound represented by formula (II) is contained in an amount of 0.1 parts by mass to 50 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound represented by formula (I).

[0038] [8] A phase difference film comprising a liquid crystal cured film, wherein the liquid crystal cured film is a cured product of the polymerizable liquid crystal composition according to any one of [5] to [7] above, and is formed by curing the polymerizable liquid crystal compound in the polymerizable liquid crystal composition in an aligned state.

[0039] [9] The phase difference film according to [8], wherein the liquid crystal cured film has the optical properties represented by formulas (1), (2), and (3).

[0040] Re(450) / Re(550)≤1.00 (1)

[0041] 1.00≤Re(650) / Re(550) (2)

[0042] 100nm≤Re(550)≤180nm (3)

[0043] [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)]

[0044]

[10] The phase difference film according to [8] above, wherein the liquid crystal cured film has the optical properties represented by formulas (4), (5) and (6).

[0045] Rth(450) / Rth(550)≤1.00 (4)

[0046] 1.00≤Rth(650) / Rth(550) (5)

[0047] -100nm≤Rth(550)≤-40nm (6)

[0048] [wherein, Rth(λ) represents the retardation value in the thickness direction at a wavelength of λ nm of the liquid crystal cured film, 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)]

[0049]

[11] An elliptically polarizing plate comprising the phase difference film according to any one of [8] to

[10] and a polarizing film.

[0050]

[12] An organic EL display device comprising the elliptically polarizing plate described in

[11] .

[0051]

[13] A flexible image display device comprising the elliptically polarizing plate described in

[11] .

[0052]

[14] The flexible image display device described in

[13] above further includes a window and a touch panel touch sensor.

[0053] Effects of the Invention

[0054] According to the present invention, a polymerizable liquid crystal compound capable of independently exhibiting high solubility in a solvent can be provided. DETAILED DESCRIPTION

[0055] Hereinafter, embodiments of the present invention will be described in detail. However, the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention.

[0056] <Polymerizable Liquid Crystal Compound>

[0057] The polymerizable liquid crystal compound of the present invention is represented by formula (I).

[0058] [Chemical Formula 3]

[0059] PE a -L 1 -A 1 -B 1 -MB 2 -A 2 -L 2 -E b -P (I)

[0060] Hereinafter, the polymerizable liquid crystal compound represented by formula (I) is also referred to as "polymerizable liquid crystal compound (I)".

[0061] M in formula (I) represents a divalent alicyclic hydrocarbon group. The hydrogen atoms contained in the divalent alicyclic hydrocarbon 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. Furthermore, the carbon atoms constituting the divalent alicyclic hydrocarbon group may be replaced with an oxygen atom, a sulfur atom, or a nitrogen atom.

[0062] Examples of the divalent alicyclic hydrocarbon group in M ​​in formula (I) include divalent alicyclic hydrocarbon groups having 3 to 18 carbon atoms. The divalent alicyclic hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 10 carbon atoms, further preferably 5 to 8 carbon atoms, and particularly preferably 5 or 6 carbon atoms.

[0063] The hydrogen atoms contained in the divalent alicyclic hydrocarbon group may each independently 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.

[0064] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom, a chlorine atom or a bromine atom is preferred.

[0065] Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. An alkyl group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 or 2 carbon atoms is more preferred, and a methyl group is further preferred.

[0066] Examples of the fluoroalkyl group having 1 to 4 carbon atoms include groups in which hydrogen atoms contained in the aforementioned alkyl group having 1 to 4 carbon atoms are substituted with fluorine atoms.

[0067] Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy. An alkoxy group having 1 to 3 carbon atoms is preferred, an alkoxy group having 1 or 2 carbon atoms is more preferred, and a methoxy group is further preferred.

[0068] The carbon atoms contained in the divalent alicyclic hydrocarbon group may be independently replaced by an oxygen atom, a sulfur atom or a nitrogen atom. One carbon atom may be replaced by an oxygen atom, a sulfur atom or a nitrogen atom, or two or more carbon atoms may be replaced by an oxygen atom, a sulfur atom or a nitrogen atom. For example, the -CH2- (methylene) contained in the divalent alicyclic hydrocarbon group may be independently replaced by -O-, -S-, -NH- or -NR 1 -, the -CH(-)- contained in the alicyclic hydrocarbon group may be independently replaced by -N(-)-. 1 It represents an alkyl group having 1 to 4 carbon atoms, wherein hydrogen atoms contained in the alkyl group may each independently be substituted by a fluorine atom.

[0069] Examples of the divalent alicyclic hydrocarbon group include groups represented by the following formulae (m-1) to (m-4). 1 Examples of the divalent alicyclic hydrocarbon group in which -CH(-)- is replaced by -N(-)- include groups represented by the following formulas (m-5) to (m-8). Examples of the divalent alicyclic hydrocarbon group in which -CH(-)- contained in the alicyclic hydrocarbon group is replaced by -N(-)- include groups represented by the following formulas (m-9) and (m-10). These are preferably a 5-membered or 6-membered alicyclic hydrocarbon group.

[0070] [Chemical Formula 4]

[0071]

[0072] From the viewpoint of wavelength dispersibility, the divalent alicyclic hydrocarbon group is preferably a cycloalkanediyl group represented by formula (M-1), more preferably a cyclohexane-1,4-diyl group, and even more preferably a trans-cyclohexane-1,4-diyl group.

[0073] B in formula (I) 1 and B 2 are each independently an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -、-R a3 COOR a4 -、-R a5 OCOR a6 -、-R a7 OC=OOR a8 -、-OR b O-, -C(=O)-NR c -、-N=N-、-CR c =CR d -or-C≡C-. R a1 ~R a8Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, R b is an alkylene group having 1 to 4 carbon atoms, R c and R d It is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

[0074] B 1 and B 2 Each is independently preferably -OR a2-1 -、-CH2-、-CH2CH2-、-COOR a4-1 -or-OCOR a6-1 -. Here, R a2-1 、R a4-1 、R a6-1 Each independently represents a single bond, -CH2-, and -CH2CH2-. 1 and B 2 Each independently is more preferably -O-, -CH2CH2-, -COO-, -COOCH2CH2- or -OCO-, further preferably -O-, -COO- or -OCO-, and particularly preferably -COO- or -OCO-. In formula (I), B 1 and B 2 They can be the same or different from each other. 1 With B 2 The same as each other means that B when M is regarded as the center 1 With B 2 The structures are the same as each other. 1 With A 2 , L 1 With L 2 、E a With E b The same is true for the relationship.

[0075] A in formula (I) 1 and A 2 Each independently represents 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. Furthermore, the carbon atoms constituting the divalent alicyclic hydrocarbon group or aromatic group may be replaced with oxygen atoms, sulfur atoms, or nitrogen atoms.

[0076] As A in formula (I) 1 and A 2Examples of the divalent alicyclic hydrocarbon group in M ​​include the groups exemplified above as the divalent alicyclic hydrocarbon group in M. Examples of the divalent aromatic group include divalent aromatic hydrocarbon groups having about 6 to 20 carbon atoms represented by the following formulas (a-1) to (a-8).

[0077] [Chemical Formula 5]

[0078]

[0079] A portion of the hydrogen atoms in the groups represented by the above formulae (a-1) to (a-8) may be replaced by an alkyl group having about 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group or a tert-butyl group; an alkoxy group having about 1 to 4 carbon atoms, such as a methoxy group or an ethoxy group; a trifluoromethyl group; a trifluoromethyloxy group; a cyano group; a nitro group; or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

[0080] A in formula (I) 1 and A 2 Each of them is independently preferably a divalent aromatic group, wherein the hydrogen atoms contained in the divalent aromatic group may be substituted by 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, and the carbon atoms constituting the divalent aromatic group may be replaced by an oxygen atom, a sulfur atom or a nitrogen atom. 1 and A 2 Each of them is independently more preferably a 1,4-phenylenediyl group 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, further preferably a 1,4-phenylenediyl group which may be substituted with a methyl group, and particularly preferably an unsubstituted 1,4-phenylenediyl group. 1 and A 2 They may be the same or different from each other. 1 and A 2 At least one of the groups is a divalent aromatic group, and from the viewpoint of exhibiting good liquid crystallinity, it is more preferred that A 1 and A 2 All of them are 1,4-phenylenediyl.

[0081] L in formula (I) 1 and L 2 Each independently represents -O-, -COO- or -OCO-.

[0082] E in formula (I) a and E b Each independently represents an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atoms contained in the alkanediyl group may be substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom. 1 or L 2The adjacent -CH2- can be replaced by -O- or -S-. Among them, E a and E b When there are multiple -O- and / or -S- in, they are not adjacent to each other.

[0083] E a and E b The number of carbon atoms in the alkylene group represented by is preferably 2 or more, more preferably 3 or more, and further preferably 11 or less, more preferably 8 or less, independently of each other.

[0084] In formula (I), when the total number of carbon atoms in the group represented by E a and the total number of carbon atoms in the group represented by E b are set as N1 for the smaller one and N2 for the larger one, N1 is 2 to 6 and N2 is 6 to 12. In addition, N1 and N2 satisfy the relationship of 1 < N2 - N1 < 10. When the group represented by E a in formula (I) and the group represented by E b each have the aforementioned specific number of carbon atoms and the number of carbon atoms of both is in a relationship of higher than 1 and lower than 10, the solubility in various solvents (for example, cyclopentanone, o-xylene, 2-methylpyrrolidone, chloroform) is likely to be improved. Although the reason is not clear, it is considered that: since the compound has an asymmetric structure, it is difficult to precipitate, and as a result, the solubility is improved. The value of N2 - N1 is preferably 2 or more, more preferably 3 or more, and further preferably 9 or less, more preferably 8 or less, and still more preferably 7 or less.

[0085] It should be noted that in this specification, the total number of carbon atoms in the group represented by the aforementioned E a and the total number of carbon atoms in the group represented by E b each refer to the total number of carbon atoms constituting the main chain of the compound represented by formula (I), and the carbon atoms constituting the main chain do not include the number of carbon atoms included as substituents.

[0086] In formula (I), P is acryloyloxy or methacryloyloxy.

[0087] In formula (I), E a and E b have different structures from each other. Therefore, the polymeric liquid crystal compound (I) has a structure centered on the divalent alicyclic hydrocarbon group represented by M, and P-E a -L 1 -A 1 -B 1 - represented and -B 2 -A 2 -L 2 -E b-P represents an asymmetric molecular structure. For the polymerizable liquid crystal compound (I), it is preferred that the ring structures symmetrically related to the divalent alicyclic hydrocarbon group represented by M are the same, that is, A 1 With A 2 The same, more preferably PE in formula (I) a -L 1 -A 1 -B 1 - indicates the structure and -B 2 -A 2 -L 2 -E b -P represents the structure that makes the asymmetric molecular structure only in E a With E b The structure is asymmetric, that is, B 1 With B 2 、A 1 With A 2 and L 1 With L 2 The structures are identical to each other.

[0088] Examples of the polymerizable liquid crystal compound (I) include compounds represented by the following formulae (Ia) to (Ig).

[0089] [Chemical Formula 6]

[0090]

[0091] The method for producing the polymerizable liquid crystal compound (I) of the present invention is not particularly limited, and the compound can be produced by appropriately combining known organic synthesis reactions described in organic chemistry methods, organic reactions, organic syntheses, comprehensive organic synthesis, and new experimental chemistry lectures, etc. (for example, condensation reaction, esterification reaction, Williamson ether reaction, Ullmann reaction, Wittig reaction, Schiff base synthesis reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedel-Crafts reaction, Heck reaction, aldol condensation reaction, etc.) according to its structure.

[0092] For example, B in formula (I) 1 and B 2The polymerizable liquid crystal compound represented by the following formula (I') *-COO- (* indicates a bonding site with M) can be obtained by an esterification reaction of a carboxylic acid compound represented by the following formula (I-1) and an alcohol compound represented by the following formula (I-2).

[0093] [Chemical Formula 7]

[0094]

[0095] [In formula (I'), M, A 1 、A 2 、L 1 、L 2 、E a 、E b and P each represent the same as M, A in formula (I) 1 、A 2 、L 1 、L 2 、E a 、E b and P have the same meaning.]

[0096] [Chemical Formula 8]

[0097]

[0098] [In formula (I-1), M, B 1 、A 1 、L 1 、E a and P represents the same as M and B in formula (I) 1 、A 1 、L 1 、E a and P have the same meaning.]

[0099] [Chemical Formula 9]

[0100] PE b -L 2 -A 2 -OH (I-2)

[0101] [In formula (I-2), A 2 、L 2 、E b and P represents the same as A in formula (I) 2 、L 2 、E b and P have the same meaning.]

[0102] M and B in formula (I-1) 1 、A 1 、L 1 、E aand P, and A in formula (I-2) 2 , L 2 、E b and P can be determined according to the corresponding molecular structure of the desired polymerizable liquid crystal compound (I).

[0103] The compound represented by formula (I-1) and the compound represented by formula (I-2) can be prepared by replacing M, B 1 、A 1 , L 1 、E a and P, or A 2 , L 2 、E b The structural units of P and P are synthesized and bonded in a manner of appropriately combining known organic synthesis reactions according to their structures. Specifically, for example, it can be prepared from a compound having a structure corresponding to the structure of the desired polymerizable liquid crystal compound (I) according to the method described in Japanese Patent Application Laid-Open No. 2010-24438.

[0104] For example, B in formula (I-1) 1 In the case of -COO-, the compound represented by the formula (I-1) can be obtained by an esterification reaction of a dicarboxylic acid compound (I-1a) represented by the following formula (I-1a) and an alcohol compound (I-1b) represented by the following formula (I-1b).

[0105] [Chemical Formula 10]

[0106]

[0107] [In formula (I-1a), M has the same meaning as M in formula (I).]

[0108] [Chemical Formula 11]

[0109] PE a -L 1 -A 1 -OH (I-1b)

[0110] [In formula (I-1b), A 1 , L 1 、E a and P represents the same as A in formula (I) 1 , L 1 、E a and P have the same meaning.]

[0111] Examples of the compound represented by formula (I-2) include compounds in which two carboxyl groups are bonded to a divalent alicyclic hydrocarbon group corresponding to the alicyclic hydrocarbon group M in formula (I) in the desired polymerizable liquid crystal compound (I).

[0112] The esterification reaction of the carboxylic acid compound (I-1) and the alcohol compound (I-2) is preferably carried out in the presence of a condensing agent. By carrying out the esterification reaction in the presence of a condensing agent, the esterification reaction can be carried out efficiently and rapidly.

[0113] Examples of the condensing agent include 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide methyl p-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (water-soluble carbodiimide: commercially available as WSC), bis(2,6-diisopropylphenyl)carbodiimide, and the like. Carbodiimide and carbodiimide compounds such as bis(trimethylsilyl)carbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphoryl azide, 1-(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinylphosphonium hexafluorophosphate, 1H-benzotriazol-1-yl Oxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide, N-benzyloxycarbonylsuccinimide, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate (4-Chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium p-toluenesulfonate, 2-fluoro-1-methylpyridinium p-toluenesulfonate and pentachlorophenyl trichloroacetate, etc.

[0114] The polymerizable liquid crystal compound (I) of the present invention has good solubility in a solvent even when it is formulated in a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by the following formula (II) (hereinafter also referred to as “polymerizable liquid crystal compound (II)”).

[0115] [Chemical Formula 12]

[0116] P 1 -E c -L 5 -A 3 -L 3 -G 1 -B 3 -Ar-B 4 -G 2 -L 4 -A4 -L 6 -E d -P 2 (II)

[0117] Ar in formula (II) is a divalent group having at least one aromatic ring, and the aromatic ring constituting the divalent group may contain at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of the divalent group having an aromatic ring include a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group that may have a substituent. In the present invention, a divalent aromatic hydrocarbon group that may have a substituent refers to a divalent group containing at least one aromatic hydrocarbon ring, and a divalent aromatic heterocyclic group that may have a substituent refers to a divalent group containing at least one aromatic heterocyclic ring. The aromatic hydrocarbon ring and aromatic heterocyclic ring referred to herein refer to a ring structure having a number of π electrons of [4n+2] (n represents an integer) according to the Huckel rule (in the case of an aromatic heterocyclic ring, the Huckel rule is satisfied, including non-covalent bond electron pairs on heteroatoms such as -N= and -S-). Ar may contain one aromatic hydrocarbon ring or aromatic heterocyclic ring, or may contain two or more aromatic hydrocarbon rings or aromatic heterocyclic rings. When Ar contains one aromatic hydrocarbon ring or aromatic heterocycle, Ar may be a divalent aromatic hydrocarbon group which may have a substituent, or may be a divalent aromatic heterocyclic group which may have a substituent. When Ar contains two or more aromatic hydrocarbon rings or aromatic heterocycles, Ar may contain a plurality of aromatic hydrocarbon rings alone, or a plurality of aromatic heterocycles alone, or may contain one or more aromatic hydrocarbon rings and one or more aromatic heterocycles. The two or more aromatic hydrocarbon rings and / or aromatic heterocycles may be bonded to each other by a single bond, a divalent bonding group such as -CO-O-, or -O-.

[0118] As the aromatic hydrocarbon ring included in Ar, for example, benzene ring, naphthalene ring, anthracene ring etc. can be enumerated, preferably benzene ring, naphthalene ring.As aromatic heterocycle, furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazole ring, triazine ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole (thienothiazole) ring, oxazole ring, benzoxazole ring and phenanthroline ring etc. can be enumerated.Wherein, preferably there is thiazole ring, benzothiazole ring or benzofuran ring, further preferably there is benzothiazolyl.In addition, when Ar comprises nitrogen atom, this nitrogen atom preferably has π electrons.

[0119] In formula (II), the total number of π electrons contained in Ar is N π It is preferably 12 or more, more preferably 14 or more, and even more preferably 16 or more. It is preferably less than 40, more preferably 36 or less, even more preferably 34 or less, and particularly preferably 32 or less.

[0120] Examples of the aromatic group represented by Ar include the following groups.

[0121] [Chemical Formula 13]

[0122]

[0123] In formula (Ar-1) to formula (Ar-23), the symbol * represents a connecting portion, and Z 0 , Z 1 and Z 2 Each independently represents 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-alkylsulfamoyl group having 1 to 12 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms. In addition, Z 0 , Z 1 and Z 2 A polymerizable group may be contained.

[0124] Q 1 and Q 2 Each independently represents -CR 2’ R 3’ -、-S-、-NH-、-NR 2’ -, -CO- or -O-, R 2’ and R 3’ Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0125] J 1 and J 2 Each independently represents a carbon atom or a nitrogen atom.

[0126] Y 1 、Y 2 and Y 3 Each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

[0127] W 1 and W 2 Each independently represents a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0-6.

[0128] As Y 1 、Y 2 and Y 3Examples of the aromatic hydrocarbon group in the group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, phenanthrenyl, and biphenyl, preferably phenyl and naphthyl, and more preferably phenyl. 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, preferably furyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl.

[0129] Y 1 、Y 2 and Y 3 Each independently may be a substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. A polycyclic aromatic hydrocarbon group refers to a fused polycyclic aromatic hydrocarbon group or a group derived from an aggregate of aromatic rings. A polycyclic aromatic heterocyclic group refers to a fused polycyclic aromatic heterocyclic group or a group derived from an aggregate of aromatic rings.

[0130] Z 0 , Z 1 and Z 2 Each of them is independently preferably 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, 0 More preferably, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyano group, Z 1 and Z 2 More preferably, Z is a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group. 0 , Z 1 and Z 2 A polymerizable group may be contained.

[0131] Q 1 and Q 2 Preferred are -NH-, -S-, and -NR 2’ -、-O-,R 2’ A hydrogen atom is preferred, and among them, -S-, -O-, and -NH- are particularly preferred.

[0132] Among formulae (Ar-1) to (Ar-23), formulae (Ar-6) and (Ar-7) are preferred from the viewpoint of molecular stability.

[0133] In the formulas (Ar-16) to (Ar-23), Y 1 The nitrogen atom and Z 0Together they form an aromatic heterocyclic group. Examples of the aromatic heterocyclic group include the heterocyclic rings described above as aromatic heterocyclic rings that Ar may have, such as a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine 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. In addition, Y 1 It can also be bonded to the nitrogen atom and Z 0 Together they form the aforementioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group, for example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, and the like.

[0134] As G in formula (II) 1 and G 2 , which can be exemplified by the following: 1 and A 2 The same groups as those exemplified for the divalent alicyclic hydrocarbon group in G 1 and G 2 , preferably a 5-membered or 6-membered alicyclic hydrocarbon group, more preferably an alicyclic hydrocarbon group formed by a 6-membered ring, further preferably a cyclohexane-1,4-diyl group, and particularly preferably a trans-cyclohexane-1,4-diyl group. In formula (II), G 1 and G 2 They can be the same or different from each other.

[0135] B in formula (II) 3 and B 4 Each independently represents a single bond or a divalent linking group. 3 and B 4 The divalent linking group in the formula (I) of the polymerizable liquid crystal compound (I) can be exemplified by the following: 1 and B 2 The groups exemplified are the same groups. 3 and B 4 Each of them is independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -、-R a3 COOR a4 -、-R a5 OCOR a6 -、-R a7 OC=OOR a8 -、-N=N-、-CR c =CR d -or-C≡C-. Here, R a1 ~R a8 Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, Rc and R d represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. 3 and B 4 More preferably, each independently represents a single bond, -OR a2-1 -、-CH2-、-CH2CH2-、-COOR a4-1 -, or -OCOR a6-1 -(R a2-1 、R a4-1 、R a6-1 Each independently represents a single bond, -CH2-, or -CH2CH2-), more preferably a single bond, -O-, -CH2CH2-, -COO-, -COOCH2CH2-, or -OCO-, and particularly preferably -COO- or -OCO-. In formula (II), B 3 and B 4 They can be the same or different from each other.

[0136] A in formula (II) 3 and A 4 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. The hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, an alkoxy group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, a cyano group, or a nitro group. In addition, the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, or -NR 1 -, the -CH(-)- contained in the alicyclic hydrocarbon group may be replaced by -N(-)-. 1 It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0137] As A in formula (II) 3 and A 4 The alicyclic hydrocarbon group and the aromatic hydrocarbon group in the polymerizable liquid crystal compound (I) include 1 and A 2 The groups exemplified are the same groups. In formula (II), A 3 and A 4Each of them is independently preferably a 1,4-phenylenediyl group 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 a 1,4-cyclohexanediyl group 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, more preferably a 1,4-phenylenediyl group substituted with a methyl group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-cyclohexanediyl group, and particularly preferably an unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4-cyclohexanediyl group. In formula (II), A 1 and A 2 They may be the same as or different from each other.

[0138] L in formula (II) 3 ~L 6 Each independently represents -O-, -COO- or -OCO-. In formula (II), L 3 ~L 6 They may be the same as or different from each other.

[0139] E in formula (II) c and E d Each independently represents an alkanediyl group having 1 to 17 carbon atoms. The hydrogen atoms contained in the alkanediyl group may be substituted by halogen atoms, and the -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. In formula (II), E c and E d Each of them is independently preferably an alkanediyl group having 4 to 17 carbon atoms which may be substituted, and more preferably an alkanediyl group having 4 to 12 carbon atoms which may be substituted. c and E d They may be the same as or different from each other.

[0140] P in formula (II) 1 and P 2 Each independently represents a polymerizable group. 1 or P 2 The polymerizable group represented by includes epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, oxetanyl and the like. Among them, acryloyloxy, methacryloyloxy, vinyl and vinyloxy are preferred, acryloyloxy and methacryloyloxy are more preferred, and acryloyloxy is still more preferred. In formula (II), P 1 and P 2 Can be the same or different.

[0141] Examples of the polymerizable liquid crystal compound (II) include compounds described in JP-A-2011-207765, JP-A-2008-107767, WO2014 / 010325, and JP-A-2019-003177.

[0142] The polymerizable liquid crystal compound (II) is preferably a polymerizable liquid crystal compound that shows maximum absorption in the range of more than 300nm and less than 400nm of wavelength. In the case of including a photopolymerization initiator in the polymerizable liquid crystal composition, there is concern about the polymerization reaction and gelation of the polymerizable liquid crystal compound during long-term storage. However, if the maximum absorption wavelength of the polymerizable liquid crystal compound (II) is within the range of more than 300nm and less than 400nm, even if it is exposed to ultraviolet light during storage, it is possible to effectively suppress the generation of reactive species from the photopolymerization initiator and the polymerization reaction and gelation of the polymerizable liquid crystal compound caused by the reactive species. Therefore, it becomes advantageous from the perspective of the long-term stability of the polymerizable liquid crystal composition, and it is possible to improve the orientation of the obtained liquid crystal cured film and the uniformity of the film thickness. It should be noted that the maximum absorption wavelength of the polymerizable liquid crystal compound (II) can be measured using an ultraviolet-visible spectrophotometer in a solvent. The solvent is a solvent that can dissolve the polymerizable liquid crystal compound (II), and for example, chloroform can be mentioned.

[0143] The polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound (I) and a polymerizable liquid crystal compound (II). Each of the polymerizable liquid crystal compound (I) and the polymerizable liquid crystal compound (II) may be comprised of only one type or a combination of two or more types.

[0144] As for the polymerizable liquid crystal composition of the present invention, the solubility of the polymerizable liquid crystal compound in the solvent is high, therefore, the effect of suppressing the generation of orientation defects caused by the precipitation, separation, etc. of the polymerizable liquid crystal compound in the undissolved polymerizable liquid crystal compound, the polymerizable liquid crystal compound in storage is excellent. Therefore, by using the polymerizable liquid crystal composition of the present invention, it is possible to carry out film making when the optical characteristics that the polymerizable liquid crystal compound can originally present are reduced, and a liquid crystal cured film with excellent optical characteristics can be obtained. In addition, compared with the case where the polymerizable liquid crystal compound (I) is dissolved in the solvent alone, it is possible to easily dissolve more polymerizable liquid crystal compounds relative to the solvent of the same amount or less amount. In addition, sometimes it can also be dissolved in a solvent that is almost or completely insoluble even when the polymerizable liquid crystal compound (I) or (II) is alone. Thus, it is not easy to leave undissolved polymerizable liquid crystal compounds in the coating liquid, it is possible to ensure high coating properties during film making, and to become a polymerizable liquid crystal composition with excellent film making properties. In addition, it is possible to reduce the amount of solvent required for preparing the coating liquid, and the range of choice of the substrate, alignment film, manufacturing conditions, etc. used is increased due to the variety of selectable solvents, which is also advantageous in the above aspects.

[0145] From the viewpoint of easily improving the compatibility with the polymerizable liquid crystal compound (I) and easily improving the solubility of the polymerizable liquid crystal compound (II) in the solvent, it is preferred that the polymerizable liquid crystal compound (I) and the polymerizable liquid crystal compound (II) have similar structures to each other, and it is preferred that B in formula (II) 3 and B 4 Respectively with B in formula (I) 1 and B 2 Same, G in formula (II) 1 and G 2 Respectively with A in formula (I) 1 and A 2 Same, L in formula (II) 3 and L 4 Respectively with L in formula (I) 1 and L 2 Same, P in formula (II) 1 and P 2 are respectively the same as P in formula (I).

[0146] In the polymerizable liquid crystal composition of the present invention, relative to 100 parts by mass of polymerizable liquid crystal compound (Ⅰ), the amount of polymerizable liquid crystal compound (Ⅰ) is preferably 1 part by mass or less and 70 parts by mass or less, more preferably 1 part by mass or less and 50 parts by mass or less, and further preferably 2 parts by mass or less and 30 parts by mass or less. When the content of the polymerizable liquid crystal compound (Ⅰ) relative to the polymerizable liquid crystal compound (Ⅰ) is above the above lower limit, it is preferred from the viewpoint of wavelength dispersion. In addition, when it is below the above upper limit, it is easy to fully improve solubility.

[0147] As long as the effects of the present invention are not affected, the polymerizable liquid crystal composition of the present invention may also contain polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (I) and the polymerizable liquid crystal compound (II). As such polymerizable liquid crystal compounds, for example, E in formula (I) can be cited. a With E b The same polymerizable liquid crystal compound generally exhibits positive wavelength dispersion.

[0148] When the polymerizable liquid crystal composition of the present invention contains polymerizable liquid crystal compounds other than polymerizable liquid crystal compounds (I) and (II), from the viewpoint of obtaining a liquid crystal cured film having excellent optical properties, the total mass of the polymerizable liquid crystal compounds (I) and (II) is preferably 51% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and can be 100% by mass, relative to the total mass of all polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition.

[0149] Relative to 100 parts by mass of the solid component of the polymerizable liquid crystal composition, the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal 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 further preferably 90 to 95 parts by mass. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the resulting liquid crystal cured film. It should be noted that, in this specification, the so-called solid component of the polymerizable liquid crystal composition refers to all the components after removing volatile components such as organic solvents from the polymerizable liquid crystal composition.

[0150] The polymerizable liquid crystal composition of the present invention may contain, in addition to the polymerizable liquid crystal compounds (I) and (II), additives such as a photopolymerization initiator, an organic solvent, a polymerization inhibitor, a photosensitizer, and a leveling agent. These components may be used alone or in combination of two or more.

[0151] The polymerizable liquid crystal composition of the present invention preferably includes a polymerization initiator. A polymerization initiator is a compound that generates reactive species by applying heat or light and can initiate a polymerization reaction of a polymerizable liquid crystal, etc. As reactive species, active species such as free radicals, cations or anions can be mentioned. Among them, from the viewpoint of easy control of the reaction, a photopolymerization initiator that generates free radicals by light irradiation is preferred.

[0152] Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, iodonium salts, and sulfonium 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 Industries, Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Chemical Co., Ltd.), and ADEKA OPTOMER. SP-152, ADEKA OPTOMER SP-170, ADEKA OPTOMER N-1717, ADEKA OPTOMER N-1919, ADEKA ARKLS NCI-831, ADEKA ARKLSNCI-930 (the above are made by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (the above are made by Japan Siber Hegner Co., Ltd.) and TAZ-104 (the above are made by Sanwa Chemical Co., Ltd.).

[0153] In the present invention, the polymerizable liquid crystal composition preferably contains at least one photopolymerization initiator, and may contain two or more photopolymerization initiators.

[0154] The photopolymerization initiator preferably has a maximum absorption wavelength of 300 nm to 400 nm, more preferably 300 nm to 380 nm, in order to fully utilize the energy emitted from the light source and achieve excellent productivity. Among them, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferred.

[0155] Examples of α-acetophenone-based polymerization initiators include 2-methyl-2-morpholino-1-(4-methylthiophenyl)-1-propanone, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzyl-1-butanone, and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)-1-butanone. More preferred examples include 2-methyl-2-morpholino-1-(4-methylthiophenyl)-1-propanone and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzyl-1-butanone. 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 Industries, Ltd.).

[0156] Oxime-based photopolymerization initiators generate methyl radicals by irradiation with light. Through these methyl radicals, the polymerization of the polymerizable liquid crystal compound in the deep part of the formed liquid crystal cured film is appropriately carried out. In addition, from the perspective of more efficiently carrying out the polymerization reaction in the deep part of the formed liquid crystal cured film, it is preferred to use a photopolymerization initiator that can efficiently utilize ultraviolet rays with a wavelength of 350nm or more. As photopolymerization initiators that can efficiently utilize ultraviolet rays with a wavelength of 350nm or more, triazine compounds and oxime ester carbazole compounds are preferred. From the perspective of sensitivity, oxime ester carbazole compounds are more preferred. As oxime ester carbazole compounds, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime) and the like can be mentioned. Examples of commercially available oxime ester carbazole compounds include Irgacure OXE-01, Irgacure OXE-02, and Irgacure OXE-03 (all manufactured by BASF Japan Ltd.), ADEKA OPTOMER N-1919, and ADEKA ARKLS NCI-831 (all manufactured by ADEKA Corporation).

[0157] The amount of the photopolymerization initiator added is generally 0.1 to 30 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound, preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, more preferably 15 parts by mass or less. Within the above range, the reaction of the polymerizable group proceeds sufficiently and the orientation of the polymerizable liquid crystal compound is not easily disturbed.

[0158] In the present invention, the polymerizable liquid crystal composition is usually applied to a substrate or the like in a state dissolved in a solvent, and therefore preferably contains a solvent. As the solvent, it is preferably a solvent that can dissolve the polymerizable liquid crystal compounds (I) and (II) and other polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition, and it is also preferably a solvent that is inactive in the polymerization reaction of the polymerizable liquid crystal compound. Examples of the solvent include alcohol solvents such as water, 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.

[0159] Relative to 100 parts by mass of polymerizable liquid crystal compound, the content of the solvent in the polymerizable liquid crystal compound is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass. Therefore, the solid content shared in 100 parts by mass of the polymerizable liquid crystal compound is preferably 2 to 50 parts by mass, more preferably 5 to 30 parts by mass. When the solid content is 50 parts by mass or less, there is a tendency that the viscosity of the polymerizable liquid crystal compound tends to become lower, the thickness of the film becomes roughly uniform, and it is not easy to produce unevenness. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be manufactured.

[0160] The polymerization reaction of a polymerizable liquid crystal compound can be controlled by adding a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone and hydroquinones substituted with alkyl ethers, etc.; catechols substituted with alkyl ethers, such as butyl catechol; free radical scavengers such as pyrogallols and 2,2,6,6-tetramethyl-1-piperidinyloxy radicals; thiophenols; β-naphthylamines, and β-naphthols. To polymerize a 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 more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0161] Furthermore, the use of a sensitizer can enhance the sensitivity of the photopolymerization initiator. Examples of photosensitizers include xanthones such as xanthone and thioxanthone; anthracenes and anthracenes having substituents such as alkyl ethers; phenothiazine; and rubrene. Examples of photosensitizers include xanthones such as xanthone and thioxanthone; anthracenes and anthracenes having substituents such as alkyl ethers; phenothiazine; 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 more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0162] The polymerizable liquid crystal composition of the present invention may also contain a leveling agent. A leveling agent is an additive that adjusts the fluidity of the polymerizable liquid crystal composition and makes the film obtained by coating the composition flatter. Examples of such leveling agents 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 Corporation), 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, and fluorinert FC-43, 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), 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.

[0163] The content of the leveling agent in the polymerizable liquid crystal composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, it is easier to align the polymerizable liquid crystal compound and the resulting liquid crystal cured film tends to be smoother, which is preferred. The polymerizable liquid crystal composition may contain two or more leveling agents.

[0164] The polymerizable liquid crystal composition of the present invention can be prepared by adding a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, or other additives as needed to the polymerizable liquid crystal compounds (I) and (II), and stirring and mixing at a predetermined temperature.

[0165] <Phase difference film>

[0166] With regard to the polymerizable liquid crystal composition of the present invention, the solubility of the polymerizable liquid crystal compound in the solvent is high, therefore, the effect of suppressing the generation of orientation defects caused by the precipitation of the polymerizable liquid crystal compound in the undissolved polymerizable liquid crystal compound, the polymerizable liquid crystal compound in storage, the precipitation, the separation, etc. is excellent. Therefore, by using the polymerizable liquid crystal composition of the present invention, it is possible to carry out film making when the optical characteristics that the polymerizable liquid crystal compound can originally present are reduced, and it is easy to obtain a liquid crystal cured film with excellent optical characteristics. Therefore, the present invention further relates to a phase difference film, which includes a liquid crystal cured film, and the liquid crystal cured film is the cured product of the polymerizable liquid crystal composition of the present invention, and is formed by curing under the state that the polymerizable liquid crystal compound in the polymerizable liquid crystal composition has been oriented. The phase difference film constituted by the aforementioned liquid crystal cured film can fully present the optical characteristics that the polymerizable liquid crystal compound used can originally play, and can become a phase difference film with high optical performance.

[0167] The liquid crystal cured film constituting the retardation film of the present invention may be composed of a homopolymer of the polymerizable liquid crystal compound (I) and a homopolymer of the polymerizable liquid crystal compound (II) in an oriented state, or may be composed of a copolymer of a mixture of the polymerizable liquid crystal compounds (I) and (II) in an oriented state. The liquid crystal cured film constituting the retardation film of the present invention is preferably composed of a copolymer of a mixture of the polymerizable liquid crystal compounds (I) and (II) in an oriented state, because the polymerization reaction is easy and a uniform liquid crystal cured film is easily obtained.

[0168] In one embodiment of the present invention, the retardation film of the present invention includes a liquid crystal cured film, which is a cured product of the polymerizable liquid crystal composition of the present invention and has the optical properties represented by the following formulas (1), (2), and (3). The liquid crystal cured film is usually a cured product formed by curing the polymerizable liquid crystal compounds (I) and (II) in a state where they are oriented in a direction parallel to the plane of the liquid crystal cured film (hereinafter also referred to as a "horizontally oriented liquid crystal cured film").

[0169] Re(450) / Re(550)≤1.00 (1)

[0170] 1.00≤Re(650) / Re(550) (2)

[0171] 100nm≤Re(550)≤180nm (3)

[0172] [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.]

[0173] When the horizontally aligned liquid crystal curing film satisfies formulas (1) and (2), the horizontally aligned liquid crystal curing film exhibits so-called reverse wavelength dispersion, that is, 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 film, 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. In addition, Re (650) / Re (550) is preferably 1.00 or more, more preferably 1.01 or more, and further preferably 1.02 or more.

[0174] The above-mentioned in-plane retardation value can be adjusted by the thickness d of the horizontally aligned liquid crystal cured film. The in-plane retardation value is determined by the above-mentioned formula: Re(λ) = (nx(λ) -ny(λ)) × d. Therefore, 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)), it is sufficient to adjust the three-dimensional refractive index and the film thickness d.

[0175] In addition, when the horizontally aligned liquid crystal cured film satisfies formula (3), the retardation film containing the horizontally aligned liquid crystal cured film functions as a λ / 4 plate, and when the elliptically polarizing plate including the retardation film containing the liquid crystal cured film is used in an optical display or the like, the effect of improving the front reflected hue (effect of suppressing coloration) is excellent. A more preferred range of the in-plane retardation value is 120 nm ≤ Re (550) ≤ 170 nm, and an even more preferred range is 130 nm ≤ Re (550) ≤ 150 nm.

[0176] In another embodiment of the present invention, the retardation film of the present invention comprises a liquid crystal cured film, which is a cured product of the polymerizable liquid crystal composition of the present invention and has the optical properties represented by the following formulas (4), (5), and (6). The liquid crystal cured film is usually a cured product formed by curing the polymerizable liquid crystal compounds (I) and (II) in a state in which they are oriented in a direction perpendicular to the plane of the liquid crystal cured film (hereinafter also referred to as a "vertically aligned liquid crystal cured film").

[0177] Rth(450) / Rth(550)≤1.00 (4)

[0178] 1.00≤Rth(650) / Rth(550) (5)

[0179] -100nm≤Rth(550)≤-40nm (6)

[0180] [Wherein, Rth(λ) represents the retardation value in the thickness direction at a wavelength of λ nm of the liquid crystal cured film, 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).]

[0181] When the vertically aligned liquid crystal cured film satisfies formulas (4) and (5), in an elliptically polarizing plate having a retardation film including the vertically aligned liquid crystal cured film, the decrease in ellipticity on the short wavelength side can be suppressed, and the oblique reflection hue can be improved. The value of Rth(450) / Rth(550) in the vertically aligned liquid crystal cured 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 even more preferably 0.85 or less. In addition, Rth(650) / Rth(550) is preferably 1.0 or more, more preferably 1.01 or more, and further preferably 1.02 or more.

[0182] In addition, when the vertically aligned liquid crystal cured film satisfies formula (6), the oblique reflection hue can be improved when an elliptically polarizing plate including a retardation film containing the vertically aligned liquid crystal cured film is used in an organic EL display device. The retardation value Rth(550) in the thickness direction of the vertically aligned liquid crystal cured film is more preferably not less than -90 nm, further preferably not less than -80 nm, and more preferably not more than -50 nm.

[0183] The retardation value in the thickness direction can be adjusted by the thickness d of the liquid crystal cured film. This retardation value is determined by the formula Rth = ((nx(λ) + ny(λ)) / 2-nz) × d. Therefore, to obtain the desired retardation value (Rth(λ): the retardation value in the thickness direction of the liquid crystal cured film at wavelength λ (nm)), the three-dimensional refractive index and film thickness d can be adjusted.

[0184] The retardation film of the present invention can be produced, for example, by a method including the following steps:

[0185] a step of forming a coating film of the polymerizable liquid crystal composition of the present invention, drying the coating film, and aligning the polymerizable liquid crystal compound in the polymerizable liquid crystal composition; and

[0186] A step of polymerizing a polymerizable liquid crystal compound by light irradiation while maintaining the aligned state to form a liquid crystal cured film.

[0187] The coating film of the polymerizable liquid crystal composition can be formed by applying the polymerizable liquid crystal composition on a substrate or an alignment film described later.

[0188] As the substrate, for example, a glass substrate, a film substrate, etc. can be mentioned. From the viewpoint of processability, a resin film substrate is preferred. As the resin constituting the film substrate, for example, polyolefins such as polyethylene, polypropylene, and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; cellulose esters such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; plastics such as polyphenylene sulfide and polyphenylene ether. Such resins can be made into a substrate by forming a film using known means such as a solvent casting method and a melt extrusion method. On the surface of the substrate, there can be a protective layer formed of an acrylic resin, a methacrylic resin, an epoxy resin, an oxetane resin, a polyurethane resin, a melamine resin, etc., and a surface treatment such as a release treatment such as a silicone treatment, a corona treatment, or a plasma treatment can also be implemented.

[0189] As the substrate, commercially available products can be used. Examples of commercially available cellulose ester substrates include Fujitack Film, a cellulose ester substrate manufactured by Fuji Photo Film Co., Ltd.; and KC8UX2M, KC8UY, and KC4UY, manufactured by Konica Minolta Opto Co., Ltd. Examples of commercially available cyclic olefin resins include Topas (registered trademark), a cyclic olefin resin manufactured by Ticona (Germany); ARTON (registered trademark), a cyclic olefin resin manufactured by JSR Corporation; ZEONOR (registered trademark) and ZEONEX (registered trademark), manufactured by Zeon Co., Ltd.; and Apel (registered trademark), a cyclic olefin resin manufactured by Mitsui Chemicals, Inc. Commercially available cyclic olefin resin substrates may also be used. Examples of commercially available cyclic olefin resin substrates include "Escena (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.

[0190] The thickness of the substrate is usually 5 to 300 μm, preferably 10 to 150 μm, from the viewpoints of thinning the retardation film, ease of peeling the substrate, and handleability of the substrate.

[0191] Examples of methods for applying the polymerizable liquid crystal composition to a substrate include known methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and coater coating, and printing methods such as flexographic printing.

[0192] Then, the solvent is removed by drying, thereby forming a dry coating. As a drying method, natural drying method, ventilation drying method, heat drying and reduced pressure drying method etc. can be cited. At this time, by heating the coating obtained by the polymerizable liquid crystal composition, it is possible to make the polymerizable liquid crystal compound oriented along the desired direction (for example, horizontal or vertical direction) relative to the coating plane while the solvent is dried and removed from the coating. The heating temperature of the coating can be appropriately determined considering the material of the polymerizable liquid crystal compound used and the substrate to be formed with respect to the coating. In order to make the polymerizable liquid crystal compound phase transition into a liquid crystal phase state, it is generally necessary to be a temperature above the liquid crystal phase transition temperature. In order to remove the solvent contained in the polymerizable liquid crystal composition, make the polymerizable liquid crystal compound become the desired orientation state, for example, it is possible to heat to a temperature above the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound contained in the aforementioned polymerizable liquid crystal composition. It should be noted that the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA) and the like having a temperature regulating stage. The above-mentioned phase transition temperature of the polymerizable liquid crystal composition of the present invention comprising at least a polymerizable liquid crystal compound (I) and a polymerizable liquid crystal compound (II) refers to a temperature measured using a mixture of the following polymerizable liquid crystal compounds, wherein the mixture of the polymerizable liquid crystal compounds is obtained by mixing all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition with the same ratio as the composition in the polymerizable liquid crystal composition.

[0193] The polymerizable liquid crystal compound of the present invention includes at least 2 kinds of polymerizable liquid crystal compounds (I) and (II), usually, liquid crystal phase transition can be carried out at a temperature lower than the temperature of the liquid crystal phase of each independent polymerizable liquid crystal compound (I) or (II).Therefore, in the manufacture of the phase difference film using the polymerizable liquid crystal compound of the present invention, it is possible to suppress the excessive consumption of thermal energy, it is possible to improve production efficiency.In addition, by being able to carry out liquid crystal phase transition with heating at a lower temperature, there is also the such advantage that the range of selection of the supporting substrate for coating polymerizable liquid crystal compound is widened.

[0194] The heating time can be appropriately determined depending on the heating temperature, the type of polymerizable liquid crystal compound used, the type of solvent, its boiling point, and its amount, and is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.

[0195] The removal of the solvent from the coating film can be carried out simultaneously with the heating of the polymerizable liquid crystal compound to more than the liquid crystal phase transition temperature, or it can be carried out independently, but from the viewpoint of improving productivity, it is preferably carried out simultaneously. Before carrying out the heating of the polymerizable liquid crystal compound to more than the liquid crystal phase transition temperature, it is possible to provide a pre-drying process for appropriately removing the solvent in the coating film under the condition that the polymerizable liquid crystal compound contained in the coating film obtained by the polymerizable liquid crystal composition is not polymerized. As the drying method in the pre-drying process, natural drying method, ventilation drying method, heating drying and reduced pressure drying method etc. can be cited, and the drying temperature (heating temperature) in the drying process can be appropriately determined according to the kind of the polymerizable liquid crystal compound used, the kind of solvent, its boiling point and its amount etc.

[0196] Then, in the obtained dry coating, while maintaining the orientation state of the polymerizable liquid crystal compound, the polymerizable liquid crystal compound is polymerized by light irradiation, thereby forming a polymer of the polymerizable liquid crystal compound in the desired orientation state, i.e., a liquid crystal cured film. As for the polymerizable liquid crystal composition of the present invention, since it can be highly polymerized by light irradiation of high-intensity ultraviolet rays while suppressing damage to the polymerizable liquid crystal compound, photopolymerization is generally used as a polymerization method. In photopolymerization, the light irradiated to the dry coating can be appropriately selected according to the type of polymerization initiator contained in the dry coating, the type of polymerizable liquid crystal compound and its amount. As a specific example, one or more light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α rays, β rays and γ rays, and active electron beams can be cited. Among them, from the aspect of easily controlling the progress of the polymerization reaction, the aspect of being able to use a device widely used in the art as a photopolymerization device, preferably ultraviolet light, preferably in a manner that can utilize ultraviolet light for photopolymerization, the type of polymerizable liquid crystal compound and polymerization initiator contained in the polymerizable liquid crystal composition is preselected. In addition, when polymerization, by carrying out light irradiation while utilizing appropriate cooling means to cool dry coating, it is also possible to control polymerization temperature.If by adopting such cooling means and implementing the polymerization of polymerizable liquid crystal compound with lower temperature, then even if using the lower base material of heat resistance as base material, it is also possible to suitably form liquid crystal cured film. In addition, in the scope of the undesirable condition (deformation etc. that base material occurs because of heat) caused by the heat when not occurring by light irradiation, it is also possible to promote polymerization reaction by raising polymerization temperature. In the time of photopolymerization, by shielding, developing etc., it is also possible to obtain patterned cured film.

[0197] As light sources for the aforementioned active energy rays, for example, there can be mentioned 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 lamps, gallium lamps, excimer lasers, LED light sources emitting light in the wavelength range of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.

[0198] The UV radiation intensity is usually 10 to 3,000 mW / cm 2 The intensity of ultraviolet irradiation is preferably an intensity in the wavelength region effective for activating the photopolymerization initiator. The irradiation time is usually 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 irradiation is performed once or multiple times with such an ultraviolet irradiation intensity, the cumulative light amount is 10 to 3,000 mJ / cm 2 , preferably 50 to 2,000 mJ / cm 2 , more preferably 100 to 1,000 mJ / cm 2 .

[0199] The thickness of the liquid crystal cured film can be appropriately selected depending on the optical display to which it is applied, and is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm.

[0200] The coating film of the polymerizable liquid crystal composition can be formed on an alignment film. The alignment film has an alignment control force that causes the polymerizable liquid crystal compound to perform liquid crystal orientation in the desired direction. For example, there are horizontal alignment films with an alignment control force that causes the polymerizable liquid crystal compound to align in the horizontal direction, vertical alignment films with an alignment control force that causes the polymerizable liquid crystal compound to align in the vertical direction, and the like. The alignment control force can be arbitrarily adjusted by the type of alignment film, the surface state, the friction conditions, etc. When the alignment film is formed of a photo-alignable polymer, it can be arbitrarily adjusted by the polarized light irradiation conditions, etc.

[0201] The alignment film preferably has solvent resistance such that it does not dissolve due to application of the polymerizable liquid crystal composition, and also has heat resistance during the heat treatment used for solvent removal and alignment of the polymerizable liquid crystal compound described later. Examples of the alignment film include alignment films comprising an aligning polymer, photoalignment films, groove alignment films having a concave-convex pattern and multiple grooves on the surface, and stretched films stretched along the alignment direction. From the perspective of alignment angle accuracy and quality, photoalignment films are preferred.

[0202] Examples of the oriented polymer include polyamides having an amide bond in the molecule, gelatins, polyimides having an imide bond in the molecule, and polyamic acid as their hydrolyzates, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinyl pyrrolidone, polyacrylic acid, and polyacrylates. Among these, polyvinyl alcohol is preferred. The oriented polymer can be used alone or in combination of two or more.

[0203] An oriented film containing an oriented polymer can generally be obtained by applying a composition obtained by dissolving the oriented polymer in a solvent (hereinafter also referred to as an "oriented polymer composition") to a substrate and removing the solvent; or by applying the oriented polymer composition to a substrate, removing the solvent, and rubbing (rubbing method). Examples of the solvent include the same solvents as those previously exemplified as solvents that can be used in polymerizable liquid crystal compositions.

[0204] The concentration of the oriented polymer in the oriented polymer composition may be such that the oriented polymer material can be completely dissolved in the solvent, and is preferably 0.1 to 20%, more preferably about 0.1 to 10%, in terms of solid content relative to the solution.

[0205] As the oriented polymer composition, a commercially available oriented film material can be used as it is. Examples of commercially available oriented film materials include SUNEVER (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).

[0206] Examples of a method for applying the oriented polymer composition to a substrate include the same methods as those exemplified as the method for applying the polymerizable liquid crystal composition to a substrate.

[0207] Examples of a method for removing the solvent contained in the oriented polymer composition include natural drying, ventilation drying, heat drying, and reduced-pressure drying.

[0208] To impart an orientation-controlling force to the alignment film, a rubbing treatment (rubbing method) may be performed as needed. Examples of methods for imparting orientation-controlling force using rubbing methods include the following: An oriented polymer film formed on the surface of a substrate by coating an oriented polymer composition on the substrate and annealing the resulting film is brought into contact with a rotating rubbing roller wrapped with a rubbing cloth. By masking the rubbing treatment, multiple regions (patterns) with different orientation directions can be formed on the alignment film.

[0209] A photo-alignment film is typically obtained by applying a composition containing a polymer or monomer having a photoreactive group 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). The photo-alignment film is also advantageous in that the direction of the alignment-controlling force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

[0210] The so-called photoreactive group refers to a group that generates liquid crystal orientation ability by light irradiation. Specifically, groups that participate in the photoreaction of the orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction of molecules that occur by light irradiation, which becomes the source of liquid crystal orientation ability, can be cited. Among them, the group that participates in the dimerization reaction or photocrosslinking reaction is preferred from the aspect of excellent orientation. As a photoreactive group, it is preferably a group having an unsaturated bond, especially a double bond, and it is particularly preferably a group 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).

[0211] Examples of photoreactive groups having a C=C bond include vinyl, polyenyl, stilbene, stilbazole, stilbazolium, chalcone, and cinnamoyl 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, disazo, formazan, 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 have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and halogenated alkyl groups.

[0212] Among these, photoreactive groups that participate in the photodimerization reaction are preferred. Cinnamoyl and chalcone groups are preferred because they require a low dose of polarized light for photoalignment and can easily produce a photoalignment film with excellent thermal stability and temporal stability. Polymers having photoreactive groups are particularly preferred, such as those having cinnamoyl groups where the terminal end of the polymer side chain has a cinnamic acid structure.

[0213] A photo-alignment inducing layer can be formed on a substrate by applying the photo-alignment film-forming composition to the substrate. Examples of the solvent included in the composition include the same solvents previously exemplified as solvents that can be used in polymerizable liquid crystal compositions, and can be appropriately selected based on the solubility of the polymer or monomer having a photoreactive group.

[0214] The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending 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 to 10% by mass, relative to the mass of the composition. The composition for forming a photo-alignment film may also contain a polymer material such as polyvinyl alcohol or polyimide, and a photosensitizer, within a range that does not significantly impair the properties of the photo-alignment film.

[0215] The method for applying the photo-alignment film-forming composition to the substrate may be the same as the method for applying the aligning polymer composition to the substrate. The method for removing the solvent from the applied photo-alignment film-forming composition may include, for example, natural drying, air drying, heat drying, and reduced pressure drying.

[0216] When irradiating with polarized light, the method may be to directly irradiate the product obtained after removing the solvent from the composition for forming a photo-alignment film applied on the substrate with polarized UV light, or to irradiate with polarized light from the substrate side and transmit the polarized light. In addition, it is particularly preferred that the polarized light is substantially parallel light. The wavelength of the polarized light irradiated is preferably a wavelength in the wavelength region where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) with a wavelength range of 250 to 400 nm is particularly preferred. As the light source used in the polarized light irradiation, xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF can be cited, and high-pressure mercury lamps, ultra-high-pressure mercury lamps and metal halide lamps are more preferred. Among them, high-pressure mercury lamps, ultra-high-pressure mercury lamps and metal halide lamps are preferred because of the high luminous intensity of ultraviolet light with a wavelength of 313 nm. Polarized UV light can be irradiated by passing the light from the above-mentioned light source through an appropriate polarizer. As the polarizer, a polarizing filter, a polarizing prism such as a Glan-Thompson or Glan-Taylor polarizer, or a wire grid polarizer can be used.

[0217] In addition, if shielding is performed during rubbing or polarized light irradiation, a plurality of regions (patterns) in which the directions of liquid crystal alignment are different can be formed.

[0218] Groove alignment films have a concavo-convex pattern or multiple grooves (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.

[0219] Methods for obtaining a grooved oriented film include: exposing the surface of a photosensitive polyimide film through an exposure mask having a slit in a pattern shape, and then developing and rinsing to form a concave-convex pattern; forming a layer of a UV-curable resin before curing on a plate-like original having grooves on its surface, transferring the formed resin layer to a substrate, and then curing; and pressing a roll-like original having a plurality of grooves against a film of a UV-curable resin before curing formed on a substrate to form concave-convex patterns, and then curing the film.

[0220] The thickness of the alignment film (alignment film or photoalignment film containing an aligning polymer) is usually 10 to 10,000 nm, preferably 10 to 1,000 nm, more preferably 10 to 500 nm, further preferably 10 to 300 nm, and particularly preferably 50 to 250 nm.

[0221] <Elliptical polarizing plate>

[0222] The present invention includes an elliptically polarizing plate comprising the retardation film of the present invention and a polarizing film.

[0223] Polarizing films are films with polarizing functions, and examples thereof include stretched films adsorbed with anisotropic absorption dyes, films coated with anisotropic absorption dyes as polarizers, etc. Examples of anisotropic absorption dyes include dichroic dyes.

[0224] A film comprising a stretched film adsorbed with an anisotropic absorption dye as a polarizer is generally produced by sandwiching a transparent protective film on at least one side of the following polarizer via an adhesive, wherein the polarizer is produced by the following steps: a step of uniaxially stretching a polyvinyl alcohol-based resin film; a step of dyeing the polyvinyl alcohol-based resin film with a dichroic dye so that the film adsorbs the dichroic dye; a step of treating the polyvinyl alcohol-based resin film adsorbed with the dichroic dye with an aqueous boric acid solution; and a step of washing the film with water after the treatment with the aqueous boric acid solution.

[0225] Polyvinyl alcohol-based resins are obtained by saponifying polyvinyl acetate-based resins. As polyvinyl acetate-based resins, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith can also be used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

[0226] The degree of saponification of polyvinyl alcohol resins is generally about 85 to 100 mol%, preferably 98 mol% or higher. Polyvinyl alcohol resins may be modified; for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may also be used. The degree of polymerization of polyvinyl alcohol resins is generally about 1,000 to 10,000, preferably 1,500 to 5,000.

[0227] Films made of such polyvinyl alcohol-based resins can be used as polarizing film raw films. The method for forming a polyvinyl alcohol-based resin into a film is not particularly limited, and a known method can be used. The film thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 μm.

[0228] Uniaxial stretching of the polyvinyl alcohol resin film 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. Alternatively, 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 performed dry in the air or wet while the polyvinyl alcohol resin film is swollen with a solvent. The stretch ratio is typically approximately 3 to 8 times.

[0229] The polyvinyl alcohol-based resin film can be dyed with a dichroic dye by, for example, a method of immersing the polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic dye.

[0230] As the dichroic pigment, specifically, iodine and dichroic organic dyes can be used. Examples of dichroic organic dyes include dichroic direct dyes formed from disazo compounds such as CI Direct Red 39, and dichroic direct dyes formed from compounds such as triazo and tetrakis azo. The polyvinyl alcohol-based resin film is preferably immersed in water before dyeing.

[0231] When iodine is used as a dichroic pigment, a method of dyeing a polyvinyl alcohol-based resin film by immersing it in an aqueous solution containing iodine and potassium iodide can generally be adopted. The iodine content in the aqueous solution is generally about 0.01 to 1 mass part relative to 100 mass parts of water. In addition, the potassium iodide content is generally about 0.5 to 20 mass parts relative to 100 mass parts of water. The temperature of the aqueous solution used for dyeing is generally about 20 to 40°C. In addition, the immersion time (dyeing time) in the aqueous solution is generally about 20 to 1,800 seconds.

[0232] On the other hand, when a dichroic organic dye is used as the dichroic pigment, a method of dyeing the polyvinyl alcohol-based resin film by immersing the film in an aqueous solution containing a water-soluble dichroic dye can generally be adopted. The content of the dichroic organic dye in the aqueous solution is generally 1×10 -4 ~10 parts by mass, preferably 1×10 -3 ~1 mass part, more preferably 1×10 -3 ~1×10 -2 parts by mass. The aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The temperature of the dichroic dye aqueous solution used for dyeing is generally about 20 to 80°C. In addition, the immersion time (dyeing time) in the aqueous solution is generally about 10 to 1,800 seconds.

[0233] Boric acid treatment after dyeing with a dichroic pigment can usually be carried out by immersing the dyed polyvinyl alcohol-based resin film in an aqueous solution of boric acid. The content of boric acid in the aqueous solution of boric acid is usually about 2 to 15 parts by mass relative to 100 parts by mass of water, and preferably 5 to 12 parts by mass. When iodine is used as a dichroic pigment, the aqueous solution of boric acid preferably contains potassium iodide, and the content of potassium iodide in this case is usually about 0.1 to 15 parts by mass relative to 100 parts by mass of water, and preferably 5 to 12 parts by mass. The immersion time in the aqueous solution of boric acid is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid treatment is usually above 50°C, preferably 50 to 85°C, and more preferably 60 to 80°C.

[0234] Typically, the polyvinyl alcohol-based resin film treated with boric acid can be washed with water. For example, the water washing process can be performed by immersing the polyvinyl alcohol-based resin film treated with boric acid in water. The water temperature during the water washing process is typically about 5 to 40°C. The immersion time is typically about 1 to 120 seconds.

[0235] After washing with water, a drying process can be performed to obtain a polarizer. The drying process can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying process is usually about 30 to 100° C., preferably 50 to 80° C. The time of the drying process is usually about 60 to 600 seconds, preferably 120 to 600 seconds. By drying, the moisture content of the polarizer can be reduced to a practical level. The moisture content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. When the moisture content is within the above range, it is easy to obtain a polarizer with moderate flexibility and excellent thermal stability.

[0236] The thickness of the polarizer 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.

[0237] Examples of films coated with a pigment having absorption anisotropy include films coated with a composition containing a dichroic pigment having liquid crystal properties, or a composition containing a dichroic pigment and a polymerizable liquid crystal compound. The film preferably has a protective film on one or both sides. Examples of the protective film include the same resin films exemplified above as substrates that can be used in the manufacture of liquid crystal cured films.

[0238] The thinner the film formed by coating the dye having absorption anisotropy, the better. From the viewpoint of strength and processability, the thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

[0239] Specific examples of the film formed by coating a dye having absorption anisotropy include films described in Japanese Patent Application Laid-Open No. 2013-33249 and the like.

[0240] A polarizing film can be obtained by laminating a transparent protective film on at least one side of the polarizer obtained as described above via an adhesive. As the transparent protective film, a transparent film similar to the resin film exemplified above as a base material that can be used in the manufacture of the liquid crystal cured film constituting the phase difference film can be preferably used.

[0241] The elliptically polarizing plate of the present invention comprises the retardation film of the present invention and a polarizing film. For example, the elliptically polarizing plate of the present invention can be obtained by laminating the retardation film of the present invention and the polarizing film via an adhesive layer or a pressure-sensitive adhesive layer.

[0242] In one embodiment of the present invention, when the retardation film of the present invention including a liquid crystal cured film is laminated with a polarizing film, it is preferred that the lamination be performed so that the angle formed by the slow axis (optical axis) of the liquid crystal cured film constituting the retardation film and the absorption axis of the polarizing film becomes 45±5°.

[0243] The elliptically polarizing plate of the present invention may have a structure similar to that of conventional elliptically polarizing plates, polarizing films, and retardation films. Examples of such structures include an adhesive layer (sheet) for attaching the elliptically polarizing plate to a display element constituting an optical display, and a protective film for protecting the surface of the polarizing film or retardation film from damage or contamination.

[0244] The elliptically polarizing plate of the present invention can be used in various display devices.

[0245] A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light source. Examples of display devices include liquid crystal display devices, organic electroluminescent (EL) display devices, inorganic electroluminescent (EL) display devices, flexible image display devices, touch panel display devices, electron emission display devices (e.g., field emission display devices (FED), surface field emission display devices (SED)), electronic paper (display devices using electronic ink or electrophoretic elements), plasma display devices, projection display devices (e.g., grating light valve (GLV) display devices, display devices with digital micromirror devices (DMD)), and piezoelectric ceramic displays. Liquid crystal display devices include any of transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, and projection liquid crystal display devices. These display devices may be display devices that display two-dimensional images or stereoscopic display devices that display three-dimensional images. In particular, the elliptically polarizing plate of the present invention can be suitably used in organic electroluminescent (EL) display devices and inorganic electroluminescent (EL) display devices. These display devices (optical displays) can exhibit excellent image display characteristics by including the elliptically polarizing plate of the present invention having excellent optical properties.

[0246] The flexible image display device including the elliptically polarizing plate of the present invention preferably further includes a window and a touch panel touch sensor.

[0247] A flexible image display device, for example, is formed from a flexible image display device laminate and an organic EL display panel. The flexible image display device laminate is disposed on the viewing side relative to the organic EL display panel, and is configured to be bendable. The flexible image display device laminate may include, in addition to the elliptically polarizing plate of the present invention described above, a window, a touch panel touch sensor, and the like. The order in which these layers are stacked is arbitrary, but preferably, the window, elliptically polarizing plate, and touch panel touch sensor are stacked in this order, or the window, touch panel touch sensor, and elliptically polarizing plate are stacked in this order, starting from the viewing side.

[0248] The presence of an elliptically polarizing plate on the viewing side of the touch panel sensor is preferred because it makes the pattern on the touch panel sensor less easily discernible, improving the visibility of the displayed image. The various components can be laminated using adhesives, pressure-sensitive adhesives, and the like. Furthermore, the laminate for a flexible image display device may include a light-shielding pattern formed on at least one side of any of the aforementioned layers: the window, the elliptically polarizing plate, or the touch panel sensor.

[0249] A window is located on the viewing side of a flexible image display device, protecting other components from external impacts and environmental changes such as temperature and humidity. Conventionally, glass has been used as this protective layer. However, the window in a flexible image display device is not rigid and hard like glass, but rather flexible. The window is formed from a flexible, transparent substrate and may include a hard coating on at least one side.

[0250] The window, touch panel, touch sensor, and the like constituting the laminate for a flexible image display device are not particularly limited, and conventionally known ones can be used.

[0251] Example

[0252] The present invention will be described in more detail below using Examples. It should be noted that, unless otherwise specified, "%" and "parts" in the examples refer to mass % and mass parts, respectively.

[0253] [Example 1: Production of polymerizable liquid crystal compound (A-1)]

[0254] A polymerizable liquid crystal compound represented by the following formula (A-1) (hereinafter referred to as “polymerizable liquid crystal compound (A-1)”) was synthesized according to the following route.

[0255] [Chemical Formula 14]

[0256]

[0257] A 100 mL four-necked flask equipped with a serpentine condenser and a thermometer was filled with nitrogen atmosphere, and 1.00 parts of the compound represented by formula (D-1) synthesized with reference to the patent document (Japanese Patent Application Laid-Open No. 2010-024438), 1.05 parts of the compound represented by formula (E-1), 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. After mixing, 1.92 g of IPC (manufactured by Wako Pure Chemical Industries, Ltd.) was further added using a dropping funnel, and the mixture was reacted at 0°C overnight. After completion of the reaction, the insoluble components were removed by filtration. The obtained chloroform solution was added dropwise to methanol (manufactured by Wako Pure Chemical Industries, Ltd.) 3 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 methanol, and then dried under reduced pressure at 40° C., thereby obtaining 7.49 g of polymerizable liquid crystal compound (A-1). The yield of polymerizable liquid crystal compound (A-1) was 38% based on compound (E-1).

[0258] [Example 2: Production of polymerizable liquid crystal compound (A-2)]

[0259] A polymerizable liquid crystal compound represented by formula (A-2) (hereinafter referred to as "polymerizable liquid crystal compound (A-2)") was produced in the same manner as in Example 1, except that the compound represented by formula (D-2) shown below was used instead of the compound represented by formula (D-1).

[0260] [Chemical Formula 15]

[0261]

[0262] [Chemical Formula 16]

[0263]

[0264] [Example 3: Production of polymerizable liquid crystal compound (A-3)]

[0265] A polymerizable liquid crystal compound represented by formula (A-3) (hereinafter referred to as “polymerizable liquid crystal compound (A-3)”) was produced in the same manner as in Example 1, except that the compound represented by formula (D-4) was used instead of the compound represented by formula (D-1).

[0266] [Chemical Formula 17]

[0267]

[0268] [Comparative Example 1]

[0269] Instead of using the compound represented by formula (E-1), 1.00 parts of the compound represented by formula (F-1) and 1.90 parts of the compound represented by formula (D-1) were used. The same operations as in Example 1 were followed to synthesize a polymerizable liquid crystal compound represented by formula (A-4) (hereinafter referred to as "polymerizable liquid crystal compound (A-4)").

[0270] [Chemical Formula 18]

[0271]

[0272] [Comparative Example 2]

[0273] Instead of using the compound represented by formula (E-1), 1.00 parts of the compound represented by formula (F-1) and 1.90 parts of the compound represented by formula (D-2) were used. The same operations as in Example 1 were followed to synthesize a polymerizable liquid crystal compound represented by formula (A-5) (hereinafter referred to as "polymerizable liquid crystal compound (A-5)").

[0274] [Chemical Formula 19]

[0275]

[0276] [Comparative Example 3]

[0277] Instead of using the compound represented by formula (E-1), 1.00 parts of the compound represented by formula (F-1) and 1.90 parts of the compound represented by formula (D-3) were used. The same operations as in Example 1 were followed to synthesize a polymerizable liquid crystal compound represented by formula (A-6) (hereinafter referred to as "polymerizable liquid crystal compound (A-6)").

[0278] [Chemical Formula 20]

[0279]

[0280] [Comparative Example 4]

[0281] Instead of using the compound represented by formula (E-1), 1.00 parts of the compound represented by formula (F-1) and 1.90 parts of the compound represented by formula (D-4) were used. The same operations as in Example 1 were followed to synthesize a polymerizable liquid crystal compound represented by formula (A-7) (hereinafter referred to as "polymerizable liquid crystal compound (A-7)").

[0282] [Chemical Formula 21]

[0283]

[0284] 〔Solubility determination〕

[0285] A vial was charged with 1 g each of two organic solvents (o-xylene and cyclopentanone) and a stirrer at 25°C. While stirring with a magnetic stirrer (HS-30DN, AS ONE), the polymerizable liquid crystal compound (A-1) of Example 1 was added until a dissolved residue was visually observed. The mixture was then stirred for 2 hours from the time the dissolved residue was observed. The presence of dissolved residue was confirmed in the resulting mixed solution, and the supernatant concentration was analyzed by HPLC to determine the solubility (analyzer: HPLC (Shimadzu Corporation), column used: L-Column ODS 3μm (3mm×150mm), mobile phase A: 0.1% (v / v) trifluoroacetic acid / water, mobile phase B: 0.1% (v / v) trifluoroacetic acid / acetonitrile, injection volume: 5μL, detection wavelength: 220nm, column oven temperature: 40°C, flow rate: 0.5mL / min). The solubility in each organic solvent was measured in the same manner for the polymerizable liquid crystal compounds of Examples 2 and 3 and Comparative Examples 1 to 4. The obtained results are shown in Table 1.

[0286] [Table 1]

[0287] Liquid crystal compounds o-Xylene Cyclopentanone Comparative Example 1 1％ 7％ Comparative Example 2 1％ 4％ Comparative Example 3 0％ 1％ Comparative Example 4 0％ 1％ Example 1 16％ 37％ Example 2 2％ 10％ Example 3 4％ 9％

[0288] It was confirmed that the polymerizable liquid crystal compounds according to the present invention (Examples 1 to 3) have improved solubility compared to the polymerizable liquid crystal compounds of Comparative Examples 1 to 4 having a symmetrical structure centered around the alicyclic hydrocarbon group corresponding to M in formula (I).

[0289] [Preparation of a composition for forming a photo-alignment film]

[0290] The following components were mixed, and the obtained mixture was stirred at 80° C. for 1 hour to obtain a composition (1) for forming a photo-alignment film.

[0291] Polymer with photoreactive groups: 1 part

[0292] [Chemical Formula 22]

[0293]

[0294] (Number average molecular weight about 29000)

[0295] Solvent: Propylene glycol monomethyl ether: 99 parts

[0296] [Preparation of liquid crystal cured film-forming composition (1)]

[0297] The following components were mixed, and the obtained mixture was stirred at 80° C. for 1 hour to obtain a composition for forming a liquid crystal cured film (1).

[0298] The following polymerizable liquid crystal compound (B-1) was synthesized by the method described in JP-A-2010-31223.

[0299] Polymerizable liquid crystal compound (B-1): 26 parts

[0300] [Chemical Formula 23]

[0301]

[0302] Polymerizable liquid crystal compound (A-1) of Example 1: 10 parts

[0303] Polymerization initiator:

[0304] 2 parts of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)-1-butanone (Irgacure (registered trademark) 369; manufactured by Ciba Specialty Chemicals Inc.)

[0305] Leveling agent: 0.1 part of polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)

[0306] Polymerization inhibitor: 0.1 part of dibutylhydroxytoluene (produced by Wako Pure Chemical Industries, Ltd.) Solvent: 160 parts of N-methyl-2-pyrrolidone, 240 parts of cyclopentanone

[0307] [Manufacturing of optical films]

[0308] A cycloolefin polymer film (COP) (ZF-14, manufactured by Zeon Co., Ltd.) was treated once using a corona treatment apparatus (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) at an output of 0.3 kW and a treatment speed of 3 m / min. The photo-alignment film-forming composition (1) was applied to the surface subjected to the corona treatment using a bar coater, dried at 80°C for 1 minute, and irradiated with a polarized UV light apparatus (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) at a radiation intensity of 100 mJ / cm 2 Polarized UV light exposure was performed with a cumulative light intensity of 1000 mJ / cm . Subsequently, the composition for forming a liquid crystal curable film (1) was applied to the obtained photo-alignment film using a bar coater, and dried at 120° C. for 1 minute. The film was then irradiated with ultraviolet light (under a nitrogen atmosphere, wavelength: 365 nm, cumulative light intensity at a wavelength of 365 nm: 1000 mJ / cm ) using a high-pressure mercury lamp (uniQure (registered trademark) VB-15201BY-A, manufactured by USHIO Electric Co., Ltd.). 2 ), thereby producing an optical film.

[0309] [Measurement of optical properties]

[0310] The front retardation value of the optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Instruments Co., Ltd.). It should be noted that the cycloolefin polymer film used for the substrate does not have birefringence. Therefore, the value obtained by measuring the above-mentioned optical film including the COP film using the measuring machine is essentially the front retardation value of the liquid crystal cured film produced on the COP film. With respect to the obtained optically measured front retardation value, [Re(450) / Re(550)] (denoted as α) and [Re(650) / Re(550)] (denoted as β) were measured and calculated at wavelengths of 450nm, 550nm, and 650nm, respectively. The results are the values ​​shown below.

[0311] Re(450)=125nm

[0312] Re(550)=135nm

[0313] Re(650)=137nm

[0314] Re(450) / Re(550)=0.91

[0315] Re(650) / Re(550)=1.01

[0316] The obtained optical film had an α value of 1 or less and a β value of 1 or greater, confirming that its refractive index exhibited reverse wavelength dispersion. This demonstrates that the optical film formed from the polymerizable liquid crystal composition of the present invention can uniformly perform polarization conversion over a wide wavelength range.

[0317] Industrial applicability

[0318] According to the present invention, a composition having improved solubility of a polymerizable liquid crystal compound in a solvent can be obtained. In addition, an optical film capable of uniform polarization conversion over a wide wavelength range can be produced from the composition.

Claims

1. A polymerizable liquid crystal compound represented by formula (I), [Chemical Formula 1] P-E a -L 1 -A 1 -B 1 -M-B 2 -A 2 -L 2 -E b -P (I) In formula (I), M represents a divalent alicyclic hydrocarbon group, the hydrogen atoms contained in the divalent alicyclic hydrocarbon group are unsubstituted, and the carbon atoms constituting the divalent alicyclic hydrocarbon group may be replaced by oxygen atoms, sulfur atoms, or nitrogen atoms, B 1 and B 2 each independently represents an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -、-R a3 COOR a4 -、-R a5 OCOR a6 -、-R a7 OC=OOR a8 -、-OR b O-, -C(=O)-NR c -、-N=N-、-CR c =CR d -or-C≡C-, where R a1 、R a2 、R a7 and R a8 Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, R a3 ~R a6 Each is independently a single bond, R b is an alkylene group having 1 to 4 carbon atoms, R c and R d represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, A 1 and A 2 Each independently represents a divalent alicyclic hydrocarbon group or an aromatic group, wherein the hydrogen atoms contained in the divalent alicyclic hydrocarbon group or the 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, and the carbon atoms constituting the divalent alicyclic hydrocarbon group or the aromatic group may be replaced with an oxygen atom, a sulfur atom or a nitrogen atom, L 1 and L 2 Each independently represents -O-, -COO- or -OCO-, E a and E b Each independently represents an alkanediyl group having 1 to 12 carbon atoms, wherein the hydrogen atoms contained in the alkanediyl group may be substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom, and is contained in the alkanediyl group and is not combined with L 1 or L 2 The adjacent -CH2- can be replaced by -O- or -S-, where E a and E b When there are multiple -O- and / or -S- in , they are not adjacent to each other. P is an acryloyloxy group or a methacryloyloxy group, When the total number of carbon atoms in the group represented by E a is set as N1, the smaller one, and the total number of carbon atoms in the group represented by E b is set as N2, the larger one, N1 is 2 to 6, N2 is 6 to 12, and the relationship 1 < N2 - N1 < 10 is satisfied.

2. The polymerizable liquid crystal compound according to claim 1, wherein M is a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms.

3. The polymerizable liquid crystal compound according to claim 1 or 2, wherein A 1 and A 2 Each independently represents a divalent aromatic group, wherein the hydrogen atoms contained in the divalent aromatic group may be substituted by 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, and the carbon atoms constituting the divalent aromatic group may be replaced by an oxygen atom, a sulfur atom or a nitrogen atom.

4. The polymerizable liquid crystal compound according to any one of claims 1 to 3, wherein B 1 and B 2 Each is independently -COO- or -OCO-.

5. A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound represented by formula (I) and a polymerizable liquid crystal compound represented by formula (II), [Chemical Formula 1] P-E a -L 1 -A 1 -B 1 -M-B 2 -A 2 -L 2 -E b -P (I) In formula (I), M represents a divalent alicyclic hydrocarbon group, wherein the hydrogen atoms contained in the divalent alicyclic hydrocarbon 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, and the carbon atoms constituting the divalent alicyclic hydrocarbon group may be replaced with an oxygen atom, a sulfur atom, or a nitrogen atom, B 1 and B 2 each independently represents an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -、-R a3 COOR a4 -、-R a5 OCOR a6 -、-R a7 OC=OOR a8 -、-OR b O-, -C(=O)-NR c -、-N=N-、-CR c =CR d -or-C≡C-, where R a1 ~R a8 Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, R b is an alkylene group having 1 to 4 carbon atoms, R c and R d represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, A 1 and A 2 Each independently represents a divalent alicyclic hydrocarbon group or an aromatic group, wherein the hydrogen atoms contained in the divalent alicyclic hydrocarbon group or the 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, and the carbon atoms constituting the divalent alicyclic hydrocarbon group or the aromatic group may be replaced with an oxygen atom, a sulfur atom or a nitrogen atom, L 1 and L 2 Each independently represents -O-, -COO- or -OCO-, E a and E b Each independently represents an alkanediyl group having 1 to 12 carbon atoms, wherein the hydrogen atoms contained in the alkanediyl group may be substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom, and is contained in the alkanediyl group and is not combined with L 1 or L 2 The adjacent -CH2- can be replaced by -O- or -S-, where E a and E b When there are multiple -O- and / or -S- in , they are not adjacent to each other. P is an acryloyloxy group or a methacryloyloxy group, When the total number of carbon atoms in the group represented by E a is set as N1 and the total number of carbon atoms in the group represented by E b is set as N2, with the smaller value being N1 and the larger value being N2, N1 is 2 to 6, N2 is 6 to 12, and the relationship 1 < N2 - N1 < 10 is satisfied. [Chemical Formula 2] P.S 1 -E c -L 5 -AM 3 -L 3 -G 1 -B 3 -Ar-B 4 -G 2 -L 4 -AM 4 -L 6 -E d -P 2 (II) In formula (II), Ar is a divalent group having at least one aromatic ring. The aromatic ring constituting the divalent group may contain at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. The total number of π electrons contained in the aromatic ring constituting Ar is N π is 12 or more and less than 36, G 1 and G 2 Each independently represents a divalent alicyclic hydrocarbon group, wherein the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted by 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, and the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S- or -NH-, B 3 and B 4 Each independently represents a single bond or a divalent linking group, A 3 and A 4 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, wherein the hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, an alkoxy group having 1 to 4 carbon atoms which may be substituted by a fluorine atom, a cyano group or a nitro group, and the -CH2- contained in the alicyclic hydrocarbon group may be substituted by -O-, -S- or -NR 1 -, the -CH(-)- contained in the alicyclic hydrocarbon group can be replaced by -N(-)-, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 3 ~L 6 Each independently represents -O-, -COO- or -OCO-, E c and E d Each independently represents an alkanediyl group having 1 to 17 carbon atoms, wherein the hydrogen atoms contained in the alkanediyl group may be substituted by halogen atoms, and the -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, P 1 and P 2 Each independently represents a polymerizable group.

6. The polymerizable liquid crystal composition according to claim 5, wherein The polymerizable liquid crystal compound represented by formula (II) exhibits maximum absorption in a wavelength range of 300 nm to 400 nm.

7. The polymerizable liquid crystal composition according to claim 5 or 6, wherein The polymerizable liquid crystal compound represented by formula (II) is contained in an amount of 0.1 parts by mass to 50 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound represented by formula (I).

8. The polymerizable liquid crystal composition according to claim 5 or 6, wherein M is a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms.

9. The polymerizable liquid crystal composition according to claim 5 or 6, wherein A 1 and A 2 Each independently represents a divalent aromatic group, wherein the hydrogen atoms contained in the divalent aromatic group may be substituted by 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, and the carbon atoms constituting the divalent aromatic group may be replaced by an oxygen atom, a sulfur atom or a nitrogen atom.

10. The polymerizable liquid crystal composition according to any one of claims 5 or 6, wherein B 1 and B 2 Each is independently -COO- or -OCO-.

11. A retardation film comprising a liquid crystal cured film, wherein the liquid crystal cured film is a cured product of the polymerizable liquid crystal composition according to any one of claims 5 to 10, and is formed by curing the polymerizable liquid crystal compound in the polymerizable liquid crystal composition in an aligned state.

12. The phase difference film according to claim 11, wherein The liquid crystal cured film has the optical properties shown in formulas (1), (2) and (3). Re(450) / Re(550)≤1.00 (1) 1.00≤Re(650) / Re(550) (2) 100nm≤Re(550)≤180nm (3) In the formula, Re(λ) represents the in-plane retardation value of the liquid crystal cured film at a wavelength of λnm, Re = (nx(λ) - ny(λ)) × d, wherein d represents the thickness of the liquid crystal cured film, nx represents the principal refractive index at a wavelength of λnm 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 λnm 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.

13. The phase difference film according to claim 11, wherein The liquid crystal cured film has the optical properties shown in formulas (4), (5) and (6), Rth(450) / Rth(550)≤1.00 (4) 1.00≤Rth(650) / Rth(550) (5) -100nm≤Rth(550)≤-40nm (6) In the formula, Rth(λ) represents the retardation value in the thickness direction at a wavelength λnm of the liquid crystal cured film, Rth=((nx(λ)+ny(λ)) / 2-nz)×d, wherein d represents the thickness of the liquid crystal cured film, nx represents the refractive index at a wavelength λnm 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 λnm 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, and nz represents the refractive index at a wavelength λnm 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. 14 . An elliptically polarizing plate comprising the retardation film according to claim 11 and a polarizing film. 15 . An organic EL display device comprising the elliptically polarizing plate according to claim 14 . 16 . A flexible image display device comprising the elliptically polarizing plate according to claim 14 . 17 . The flexible image display device according to claim 16 , further comprising a window and a touch panel touch sensor.

Images