Anisotropic dye film-forming composition, anisotropic dye film, and optical element

Abstract

The present invention provides an anisotropic dye film-forming composition capable of achieving excellent optical properties, in particular, capable of achieving a sufficient dichroic ratio. The anisotropic dye film-forming composition of the present invention comprises a dye and a polymerizable liquid crystal compound, wherein the dye comprises a compound represented by formula (1). 1 ‑CH=CH‑A 2 ‑(N=N‑A 3 ) n ‑X···(1)(where A 1 represents a monovalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group) or a monovalent group of an aromatic heterocyclic ring which may have a substituent (excluding a sulfo group); A 2 and A 3 Each independently represents a divalent group of an aromatic hydrocarbon ring optionally having a substituent (excluding a sulfo group) or a divalent group of an aromatic heterocyclic ring optionally having a substituent (excluding a sulfo group); X represents a monovalent organic group; and n represents 1, 2 or 3.

Description

Technical Field

[0001] The present invention relates to an anisotropic dye film formed by applying a liquid crystal composition, and more particularly to an anisotropic dye film-forming composition showing high dichroism, which is useful for a polarizing film provided in a display element such as a light-adjusting element, a liquid crystal element (LCD), and an organic electroluminescent element (OLED), an anisotropic dye film, and an optical element.

[0002] This application claims priority based on Japanese Patent Application No. 2019-037800 filed in Japan on March 1, 2019, and the contents are cited herein. Background Art

[0003] In LCD, linear polarization film and circular polarization film are used to control optical rotation and birefringence during display, and in OLED, circular polarization film is used to prevent reflection of external light in bright places.

[0004] Conventionally, as such a polarizing film, for example, a polarizing film made of polyvinyl alcohol (PVA) dyed with low-concentration iodine (iodine-PVA polarizing film) is known (Patent Document 1).

[0005] In addition, it is also known that an anisotropic dye film formed by coating a liquid crystal composition containing a dye functions as a polarizing film (Patent Document 2). However, there is no disclosure of a polarizing film containing a dichroic dye having a maximum absorption in the wavelength range of 380nm to 520nm and having a sufficient dichroic ratio.

[0006] In addition, an anisotropic dye film using a non-polymerizable polymer liquid crystal and a stilbene azo dye as a dichroic dye is also known (Non-Patent Document 1). However, in combination with a polymer liquid crystal, a sufficient dichroic ratio as a polarizing film cannot be obtained.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 1-105204

[0010] Patent Document 2: Japanese Patent Application No. 2007-510946

[0011] Non-patent literature

[0012] Non-patent document 1: Jae Bok Chang et al., "Optimized molecular structures of guest-host system for highly efficient coatable polarizer", Dyes and Pigments (2015), 121, 265-275 Summary of the invention

[0013] Problems to be solved by the invention

[0014] However, such a low-concentration iodine-PVA polarizing plate has problems such as iodine sublimation, deterioration, and color change, and warping due to the relaxation of PVA during stretching, depending on the usage environment.

[0015] In addition, there is a problem that a polarizing film formed by applying a liquid crystal composition containing a dye cannot obtain high light absorption selectivity.

[0016] Under such circumstances, a polarizing film having high light absorption selectivity even in the form of a thin film is desired.

[0017] In order to improve the dichroism of the anisotropic dye film formed from the anisotropic dye film-forming composition, it is conceivable to increase the ratio of the major axis to the minor axis of the dichroic dye contained in the anisotropic dye film-forming composition, that is, to extend the π conjugated system and increase the molecular major-minor ratio.

[0018] However, when the π conjugated system of the dichroic pigment molecule is expanded and the molecular aspect ratio is increased, although the dichroism increases, it becomes a pigment that absorbs in the long-wavelength visible range. On the other hand, in order to have absorption in the short-wavelength visible light range, the π conjugated system needs to be shortened. The yellow dichroic pigment that absorbs in the short-wavelength visible light range tends to have a small molecular aspect ratio and low dichroism. Therefore, it is particularly difficult to obtain a polarizing film with high light absorption selectivity in the short-wavelength visible light range of 380nm to 520nm. On the other hand, for polarizing films covering the entire visible light range, it is known that due to the low dichroic ratio in the short-wavelength visible light range, light in the blue range cannot be fully shielded and is transmitted, which is the so-called "blue leakage".

[0019] In addition, it is known that in a polarizing film formed by applying a liquid crystal composition containing a dye, the dichroic ratio varies depending on the combination of liquid crystal molecules and dichroic dyes, and it is important to combine dichroic dyes that match the liquid crystal molecules to be used.

[0020] Under such circumstances, it is desired to develop a dichroic dye molecule that enables an anisotropic dye film to exhibit high dichroism and an anisotropic dye film-forming composition containing the same.

[0021] An object of the present invention is to provide an anisotropic dye film-forming composition capable of achieving excellent optical performance, particularly a sufficient dichroic ratio.

[0022] Another object of the present invention is to provide an anisotropic dye film capable of achieving excellent optical performance, in particular, a sufficient dichroic ratio.

[0023] Another object of the present invention is to provide an optical element including an anisotropic dye film capable of achieving excellent optical performance, in particular, a sufficient dichroic ratio.

[0024] Solution to the problem

[0025] The present inventors have found that the above-mentioned problems can be solved by using a compound having a specific structure as a dye in combination with an anisotropic dye film-forming composition containing a dye and a polymerizable liquid crystal compound.

[0026] That is, the present invention has the following aspects.

[0027] [1] A composition for forming an anisotropic dye film, comprising a dye and a polymerizable liquid crystal compound,

[0028] The pigment comprises a compound represented by formula (1),

[0029] A 1 -CH=CH-A 2 -(N=NA 3 ) n -X…(1)

[0030] (Where,

[0031] A 1 represents a monovalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group) or a monovalent group of an aromatic heterocyclic ring which may have a substituent (excluding a sulfo group);

[0032] A 2 and A 3 Each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group) or a divalent group of an aromatic heterocyclic ring which may have a substituent (excluding a sulfo group);

[0033] X represents a monovalent organic group;

[0034] n is 1, 2, or 3. )

[0035] [2] The anisotropic dye film-forming composition according to [1], wherein A 3 It is a phenylene group which may have a substituent (excluding a sulfo group).

[0036] [3] The anisotropic dye film-forming composition according to [1] or [2], wherein A 2 It is a divalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group).

[0037] [4] The anisotropic dye film-forming composition according to any one of [1] to [3], wherein A 1 It is a monovalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group).

[0038] [5] The anisotropic dye film-forming composition according to any one of [1] to [4], wherein

[0039] X is -O-(R x ) or -N(-R x )-R y ;

[0040] R x and R y Each independently represents an optionally branched alkyl group having 1 to 15 carbon atoms or an aryl group having 5 to 14 atoms constituting a ring;

[0041] R x and R y Optionally, they are combined to represent an alkylene group having 2 to 15 carbon atoms which may have a branch;

[0042] The optionally branched alkyl group having 1 to 15 carbon atoms and the aryl group having 5 to 14 ring atoms each optionally have a substituent;

[0043] One or more methylene groups contained in the optionally branched alkylene group having 2 to 15 carbon atoms may be replaced by an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, -CF- 2 -、-CHCl-、-CCl 2 -Structure replaced;

[0044] The amine nitrogen atom is -NH- or -N(R z )-;

[0045] R z It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0046] [6] The anisotropic dye film-forming composition according to any one of [1] to [5], wherein

[0047] The number of ring structures (r n1) and the number of ring structures (r n2 ) ratio (r n1 / r n2 ) is 0.7~1.5.

[0048] [7] The anisotropic dye film-forming composition according to any one of [1] to [6], wherein

[0049] The polymerizable liquid crystal compound is a compound having a carbon-carbon triple bond.

[0050] [8] The anisotropic dye film-forming composition according to any one of [1] to [7], further comprising a polymerization initiator.

[0051] [9] The anisotropic dye film-forming composition according to any one of [1] to [8], wherein

[0052] The pigment further contains one or more compounds whose absorption curve in the wavelength range of 380 nm to 780 nm shows a maximum wavelength longer than the wavelength at which the compound represented by the formula (1) shows a maximum wavelength in the absorption curve in the wavelength range of 380 nm to 780 nm.

[0053]

[10] An anisotropic dye film formed using the anisotropic dye film-forming composition according to any one of [1] to [9].

[0054]

[11] An optical element comprising the anisotropic pigment film described in

[10] .

[0055] Effects of the Invention

[0056] The anisotropic dye film-forming composition of the present invention can achieve excellent optical performance, particularly a sufficient dichroic ratio.

[0057] The anisotropic dye film of the present invention is formed using the anisotropic dye film-forming composition of the present invention, and therefore can achieve excellent optical performance, particularly a sufficient dichroic ratio.

[0058] The optical element of the present invention includes the anisotropic dye film of the present invention and can therefore achieve excellent optical performance, in particular, a sufficient dichroic ratio. DETAILED DESCRIPTION

[0059] Hereinafter, although embodiment of the present invention is described concretely, the present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist thereof.

[0060] The anisotropic pigment film in the present invention refers to a pigment film having anisotropy in electromagnetic properties in any two directions selected from a total of three directions in a three-dimensional coordinate system formed by the thickness direction of the anisotropic pigment film and any two directions orthogonal in the plane. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance.

[0061] Examples of films having optical anisotropy such as absorption and refraction include polarizing films such as linear polarizing films and circular polarizing films, retardation films, and conductive anisotropic dye films. The anisotropic dye film of the present invention is preferably used as a polarizing film or a conductive anisotropic dye film, and more preferably used as a polarizing film.

[0062] [Anisotropic dye film-forming composition]

[0063] The anisotropic dye film-forming composition of the present invention contains a dye and a polymerizable liquid crystal compound.

[0064] The anisotropic dye film-forming composition of the present invention may be a solution, a liquid crystal, or a dispersed state as long as it is in a state where phase separation does not occur. As the anisotropic dye film-forming composition, a solution is preferred from the viewpoint of easy coating on a substrate. On the other hand, from the viewpoint of orientation on a substrate as described later, the solid component obtained by removing the solvent from the anisotropic dye film-forming composition is preferably in a liquid crystal phase at any temperature.

[0065] It should be noted that in the present invention, the state of liquid crystal phase specifically refers to a liquid crystal state that exhibits the properties of both liquid and crystal or intermediate properties as described in pages 1 to 16 of "Fundamentals and Applications of Liquid Crystals" (written by Masakazu Matsumoto and Ichiyoshi Kakuda in 1991), which refers to a nematic phase, a smectic phase, a cholesteric phase, or a discotic phase.

[0066] (pigment)

[0067] In the present invention, the pigment refers to a substance or compound that absorbs at least a part of the wavelength in the visible light range (380 nm to 780 nm).

[0068] As the pigment that can be used in the present invention, dichroic pigment can be enumerated.It should be noted that dichroic pigment refers to that the absorbance on the major axis direction of the molecule has the pigment of different properties with the absorbance on the minor axis direction.In addition, the pigment can be a pigment with liquid crystallinity, or it may not have liquid crystallinity.It should be noted that having liquid crystallinity refers to showing liquid crystal phase at any temperature.

[0069] The dye contained in the anisotropic dye film-forming composition of the present invention contains at least a compound represented by formula (1).

[0070] A 1 -CH=CH-A 2 -(N=NA 3 ) n -X…(1)

[0071] In the formula,

[0072] A 1 represents a monovalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group) or a monovalent group of an aromatic heterocyclic ring which may have a substituent (excluding a sulfo group);

[0073] A 2 and A 3 Each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group) or a divalent group of an aromatic heterocyclic ring which may have a substituent (excluding a sulfo group);

[0074] X represents a monovalent organic group;

[0075] n represents 1, 2, or 3.

[0076] By making the pigment contained in the anisotropic dye film-forming composition of the present invention have a structure represented by formula (1), it has a molecular major-minor axis ratio large enough to make the dichroic ratio good, and at the same time, the expansion of the π conjugated system is suppressed, so that it has absorption in the short-wavelength visible range. In addition, for the structure represented by formula (1), the combination with the liquid crystal molecules and the intermolecular interaction between the liquid crystal molecules and the pigment molecules are also good, so the molecular orientation of the liquid crystal molecules will not be disordered, and a higher dichroic ratio can be displayed. According to these effects, the pigment with the structure represented by formula (1) can have both a high dichroic ratio and absorption in the short-wavelength visible range, which is a conventional subject.

[0077] A 1 It represents a monovalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group) or a monovalent group of an aromatic heterocyclic ring which may have a substituent.

[0078] A 1 The aromatic hydrocarbon ring in is preferably a monocyclic or condensed aromatic hydrocarbon ring. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 or more, and preferably 20 or less, more preferably 16 or less, and further preferably 10 or less. By being within these ranges, there is a tendency for the combination with liquid crystal to become good. For example, the number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 16, and further preferably 6 to 10.

[0079] The number of rings in the case of a condensed ring is not particularly limited, but is preferably 2 or more and 5 or less because the combination with liquid crystal tends to be good.

[0080] Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc.

[0081] Among them, as A 1 The monovalent group of an aromatic hydrocarbon ring is preferably a monovalent group of a benzene ring (phenyl) or a monovalent group of a naphthalene ring (naphthyl), and is more preferably a phenyl group from the viewpoint of improving the linearity of the molecule.

[0082] A 1 The aromatic heterocycle in is a monocyclic or condensed aromatic heterocycle. The number of carbon atoms in the aromatic heterocycle is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more, and preferably 20 or less, more preferably 13 or less, and further preferably 9 or less. By being within these ranges, there is a tendency for the combination with liquid crystal to become good. For example, the number of carbon atoms in the aromatic heterocycle is preferably 2 to 20, more preferably 3 to 13, and further preferably 4 to 9.

[0083] The number of rings in the case of a condensed ring is not particularly limited, but is preferably 2 or more and 5 or less because the combination with liquid crystal tends to be good.

[0084] Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, thienothiazole ring, benzo Azole ring, benzyl isocyanate azole ring, benzothiazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, quinazoline ring, quinazolinone ring and the like.

[0085] Among them, as A 1 The aromatic heterocyclic ring is preferably a furan ring, a thiophene ring, a thienothiazole ring, a benzothiazole ring, etc. from the viewpoint of improving the linearity of the molecule. azole ring, benzothiazole ring, benzimidazole ring, particularly preferably thienothiazole ring, benzo Azole ring, benzothiazole ring, benzimidazole ring.

[0086] As A 1 The substituents other than sulfo group permitted for the monovalent aromatic hydrocarbon ring group or the monovalent aromatic heterocyclic group in the formula (a) include: -R A 、-OH、-ORA 、-OC(=O)-R A 、-NH 2 、-NH-R A 、-N(-R B )-R A 、-C(=O)-R A 、-C(=O)-OR A 、-C(=O)-NH 2 , -C(=O)-NH-R A 、-C(=O)-N(-RB)-R A , -SH, -SR A , trifluoromethyl, sulfamoyl, carboxyl, cyano, nitro, halogen. A and R B Each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms. One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms may be replaced by an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, -CF- 2 -、-CHCl-、-CCl 2 The structure in which the substituted group is substituted with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group or a glycidyloxy group.

[0087] Among them, as A 1 The permissible substituent other than the sulfo group of the monovalent aromatic hydrocarbon ring group or the monovalent aromatic heterocyclic group in the is preferably -R A 、-OR A Examples thereof include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 5,5-dimethyl-3-methylhexyloxy, and 11-(acryloyloxy)undecyloxy.

[0088] It should be noted that the above-mentioned amine nitrogen atom represents -NH-, -N(R z )-,R z It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0089] As A 1 From the viewpoint of showing a high dichroic ratio, it is preferably a monovalent group of an aromatic hydrocarbon ring, more preferably a phenyl group or a naphthyl group, and from the viewpoint of improving linearity, it is further preferably a phenyl group. 1 The substituent is preferably selected from -R A 、-OR A and -C(=O)-OR AThe substituents are preferably selected from -R A AND-OR A By having the above-mentioned substituent, there is a tendency that the combination with liquid crystal becomes good.

[0090] A 2 and A 3 Each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group) or a divalent group of an aromatic heterocyclic ring which may have a substituent.

[0091] A 2 and A 3 The aromatic hydrocarbon ring in 1 The aromatic hydrocarbon rings in are the same.

[0092] As A 2 The divalent group of an aromatic hydrocarbon ring is preferably a divalent group of a benzene ring (phenylene) or a divalent group of a naphthalene ring (naphthylene), more preferably 1,4-phenylene, 1,4-naphthylene, 2,6-naphthylene, and further preferably 1,4-phenylene.

[0093] As A 3 The divalent group of the aromatic hydrocarbon ring is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,4-phenylene group.

[0094] By making A 2 and / or A 3 The above groups can provide an effect of increasing the major-minor axis ratio of the molecule and tend to provide a favorable combination with liquid crystals.

[0095] A 2 and A 3 The aromatic heterocyclic ring in 1 The aromatic heterocycles in are the same.

[0096] As A 2 and A 3 The substituents other than sulfo groups permitted by the divalent aromatic hydrocarbon ring group or the divalent aromatic heterocyclic group in A 1 The permissible substituents other than the sulfo group of the monovalent aromatic hydrocarbon ring or the monovalent aromatic heterocyclic ring in are the same.

[0097] As A 2, from the viewpoint of showing a high dichroic ratio, preferably a divalent group of an aromatic hydrocarbon ring optionally having a substituent (excluding a sulfo group), more preferably a phenylene group or a naphthylene group optionally having a substituent (excluding a sulfo group), further preferably a 1,4-phenylene group or a 1,4-naphthylene group optionally having a substituent (excluding a sulfo group), and from the viewpoint of improving linearity, even more preferably a 1,4-phenylene group having no substituent.

[0098] As A 3 , from the viewpoint of showing a high dichroic ratio, preferably a divalent group of an aromatic hydrocarbon ring optionally having a substituent (excluding a sulfo group). Among them, more preferably a phenylene group or a naphthylene group optionally having a substituent (excluding a sulfo group), and further preferably a 1,4-phenylene group or a 1,4-naphthylene group optionally having a substituent (excluding a sulfo group). In particular, from the viewpoint of improving linearity, a 1,4-phenylene group without a substituent is particularly preferred.

[0099] In the above A 1 , A 2 and A 3 In the case where the substituent is a sulfonic group, the compatibility with liquid crystal and solvent is reduced, so there is a risk that the dichroic ratio is reduced and the pigment is precipitated, thereby greatly impairing the performance as an anisotropic pigment film.

[0100] X represents a monovalent organic group.

[0101] Examples of the monovalent organic group in X include a hydrogen atom, a hydroxyl group, an amino group, a cyano group, a carbamoyl group, a nitro group, a halogen atom, and -R x 、-OR x 、-NH-R x 、-N(-R y )-R x , -C(=O)-R x 、-C(=O)-OR x , -C(=O)-NH-R x 、-C(=O)-N(-R y )-R x 、-OC(=O)-R x 、-NH-C(=O)-R x 、-N(-R y )-C(=O)-R x It should be noted that R x and R y Each independently represents an optionally branched alkyl group having 1 to 15 carbon atoms or an aryl group having 5 to 14 atoms constituting a ring; R x and Ry It may be combined to represent an alkylene group having 2 to 15 carbon atoms which may have a branch.

[0102] The optionally branched alkyl group having 1 to 15 carbon atoms and the aryl group having 5 to 14 atoms constituting the ring may each have a substituent. The one or more methylene groups contained in the optionally branched alkyl group having 1 to 15 carbon atoms and the optionally branched alkylene group having 2 to 15 carbon atoms may be replaced by an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, -CF- 2 -、-CHCl-、-CCl 2 -substituted (displaced) structure. It should be noted that the above-mentioned amine nitrogen atom represents -NH-, -N(R z )-, R z It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0103] As R x Permissible substituents of the optionally branched alkyl group having 1 to 15 carbon atoms include -OH, -OR A 、-OC(=O)-R A 、-NH 2 、-NH-R A 、-N(-R B )-R A , -C(=O)-R A 、-C(=O)-OR A 、-C(=O)-NH 2 , -C(=O)-NH-R A 、-C(=O)-N(-R B )-R A , -SH, -SR A , sulfamoyl, carboxyl, cyano, nitro, halogen. Here, R A and R B Each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms. One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms may be replaced by an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, -CF- 2 -、-CHCl-、-CCl 2 -substituted structure. In addition, one or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms may be substituted with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group or a glycidyloxy group.

[0104] Among them, as Rx The permissible substituent of the optionally branched alkyl group having 1 to 15 carbon atoms in the alkyl group is preferably -OR because it tends to provide a pigment that is well combined with a liquid crystal. A Examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, acryloyloxy, methacryloyloxy and glycidyloxy.

[0105] It should be noted that the above-mentioned amine nitrogen atom is -NH-, -N(R z )-, R z It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0106] As R x The permissible substituents of the aryl group wherein the number of atoms constituting the ring is 5 to 14 include: -R A 、-OH、-OR A 、-OC(=O)-R A 、-NH 2 、-NH-R A 、-N(-R B )-R A , -C(=O)-R A 、-C(=O)-OR A 、-C(=O)-NH 2 , -C(=O)-NH-R A 、-C(=O)-N(-R B )-R A , -SH, -SR A , trifluoromethyl, sulfamoyl, carboxyl, cyano, nitro, halogen. A and R B Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms.

[0107] Among them, as R x The permissible substituent of the aryl group having 5 to 14 atoms constituting the ring is preferably -R A 、-OR A Examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, and 5,5-dimethyl-3-methylhexyloxy.

[0108] Examples of the aryl group having 5 to 14 atoms constituting the ring include A of the formula (1): 1A monovalent group of a ring exemplified as the aromatic hydrocarbon ring or the aromatic heterocyclic ring.

[0109] The monovalent group of the aromatic hydrocarbon ring is preferably a monovalent group of a benzene ring (phenyl) or a monovalent group of a naphthalene ring (naphthyl). The monovalent group of the aromatic heterocyclic ring is preferably a monovalent group of a furan ring, a monovalent group of a thiophene ring, a monovalent group of a thienothiazole ring, a benzothiophene ... The monovalent groups of the oxazole ring, the monovalent groups of the benzothiazole ring, and the monovalent groups of the benzimidazole ring. The monovalent groups of the aromatic hydrocarbon ring and the aromatic heterocyclic ring have a tendency to increase the linearity of the molecule. Among them, phenyl is more preferred from the viewpoint of showing a high dichroic ratio.

[0110] As R x and R y , which has a tendency to obtain a pigment that is well combined with a liquid crystal, and is preferably an alkyl group having 1 to 15 carbon atoms and optionally having a branched chain, or R x and R y is an alkylene group having 2 to 15 carbon atoms and optionally having a branch; more preferably an alkyl group having 1 to 6 carbon atoms and optionally having a branch, or R x and R y is an alkylene group having 2 to 10 carbon atoms and optionally having a branch; more preferably an alkyl group having 1 to 3 carbon atoms and optionally having a branch, or R x and R y It is an alkylene group having 2 to 6 carbon atoms which is integrated and may have a branch.

[0111] As the monovalent organic group in X, -OR is preferred because it tends to combine well with liquid crystals. x 、-NH-R x 、-N(-R y )-R x , more preferably -OR x 、-N(-R y )-R x , more preferably -N(-R y )-R x Specifically, for example, dimethylamino, diethylamino, di-n-propylamino, ethylmethylamino, methylpropylamino, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, morpholinyl, piperazinyl, and thiomorpholinyl are more preferred, and diethylamino, pyrrolidinyl, and piperidinyl are more preferred.

[0112] n represents 1, 2, or 3.

[0113] Since n tends to be a dye having a sufficiently large molecular major-minor axis ratio and absorption in a short wavelength range, it is preferably 1 or 2, and more preferably 1.

[0114] When n represents 2 or 3, each A 3 It can be the same or different.

[0115] From the viewpoint of increasing the molecular major-minor axis ratio, -CH=CH- in formula (1) is preferably a trans form.

[0116] From the viewpoint of increasing the molecular major-minor axis ratio, -N=N- in formula (1) is preferably a trans form.

[0117] Specifically, examples of the compound represented by formula (1) include the following compounds, but the compound is not limited thereto.

[0118] [Chemical formula 1]

[0119]

[0120] [Chemical formula 2]

[0121]

[0122] [Chemical formula 3]

[0123]

[0124] [Chemical formula 4]

[0125]

[0126] [Chemical formula 5]

[0127]

[0128] [Chemical formula 6]

[0129]

[0130] [Chemical formula 7]

[0131]

[0132] [Chemical formula 8]

[0133]

[0134] [Chemical formula 9]

[0135]

[0136] [Chemical formula 10]

[0137]

[0138] The compound represented by formula (1) contained in the anisotropic dye film-forming composition of the present invention can have a maximum absorption (λ) at any wavelength in the anisotropic dye film produced by the method described below. max1 ), preferably having a maximum absorption in the range of 350 to 550 nm, more preferably having a maximum absorption in the range of 410 to 530 nm, and further preferably having a maximum absorption in the range of 430 to 520 nm.

[0139] In addition, the compound represented by formula (1) contained in the anisotropic dye film-forming composition of the present invention preferably has an absorption maximum (λ max2 ) compared to the maximum absorption in the anisotropic pigment film (the above λ max1 ) exists at long wavelengths. This long wavelength shift is a phenomenon that occurs when the compound represented by formula (1) is dispersed in a polymer having units based on a polymerizable liquid crystal compound and / or a polymerizable liquid crystal compound, and the compound represented by formula (1) and the polymer having units based on a polymerizable liquid crystal compound and / or a polymerizable liquid crystal compound show strong intermolecular interactions. It is believed that through this strong intermolecular interaction, the compound represented by formula (1) can exhibit a high dichroic ratio. Long wavelength shift refers to the phenomenon that the difference in absorption is extremely large (λ max1 -λ max2 ) is a positive value. From the viewpoint of exhibiting high dichroism, the difference is preferably 5 nm or more, more preferably 10 nm or more, and further preferably 15 nm or more. In addition, the upper limit is not particularly limited, and for example, 50 nm or less can be cited.

[0140] The anisotropic dye film-forming composition of the present invention may contain other pigments in addition to the compound represented by formula (1). Examples of other pigments include azo pigments, quinone pigments (including naphthoquinone pigments, anthraquinone pigments, etc.), stilbene pigments, anthocyanin pigments, phthalocyanine pigments, indigo pigments, condensed polycyclic pigments (including perylene pigments, Among these pigments, azo pigments are preferred because they can obtain high molecular arrangement in anisotropic pigment films.

[0141] An azo dye refers to a dye having at least one azo group (-N=N-), and from the viewpoint of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of manufacture, the number of azo groups in one molecule is preferably 1 or more, more preferably 2 or more, and is preferably 6 or less, more preferably 4 or less, and further preferably 3 or less.

[0142] Examples of the azo dye include compounds represented by formula (A).

[0143] R 11 -D 1 -N=N-(D 2 -N=N) p -D 3 -R 12 …(A)

[0144] In formula (A),

[0145] D 1 , D 2 and D 3 each independently represents a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent;

[0146] P represents an integer from 0 to 4;

[0147] When p is an integer greater than 2, a plurality of D 2 Optionally the same or different from each other;

[0148] R 11 and R 12 Each independently represents a monovalent organic group.

[0149] D 1 , D 2 and D 3 Each independently represents a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent.

[0150] As the substitution position of the phenylene group, 1,4-phenylene group is preferred in order to increase the linearity of the molecule.

[0151] As the substitution position of the naphthylene group, in order to increase the linearity of the molecule, a 1,4-naphthylene group or a 2,6-naphthylene group is preferred.

[0152] As a divalent heterocyclic group, from the viewpoint of solubility in solvents, compatibility with liquid crystal compounds, color tone and ease of production, the number of carbon atoms forming a ring is preferably 3 or more and 14 or less, and more preferably 10 or less. In particular, since there is a tendency for the major-minor axis ratio of the molecule to increase, a monocyclic or bicyclic heterocyclic group is preferred.

[0153] Examples of atoms other than carbon constituting the divalent heterocyclic group include at least one selected from a nitrogen atom, a sulfur atom, and an oxygen atom. When the heterocyclic group has a plurality of atoms other than carbon constituting the ring, they may be the same or different.

[0154] Specific examples include pyridinediyl, quinolinediyl, isoquinolinediyl, thiazolediyl, benzothiazolediyl, thienothiazolediyl, thienothiphenediyl, benzimidazolonediyl, benzofurandiyl, phthalimidediyl, Azoles, benzo Oxadiazole, etc.

[0155] As D 1 , D 2 and D 3 The substituents optionally possessed by the phenylene group, naphthylene group and divalent heterocyclic group include: alkyl groups having 1 to 4 carbon atoms; alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy and butoxy; fluoroalkyl groups having 1 to 4 carbon atoms such as trifluoromethyl; cyano; nitro; hydroxyl; halogen atoms; substituted or unsubstituted amino groups such as amino, diethylamino and pyrrolidino.

[0156] It should be noted that the substituted amino group is an amino group having one or two alkyl groups having 1 to 4 carbon atoms, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms. 2 . It should be noted that examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, and butyl. Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl.

[0157] From the viewpoint of high molecular linearity, when unsubstituted or substituted, the group is preferably substituted with a methyl group, a methoxy group, a hydroxyl group, a fluorine atom, a chlorine atom, a dimethylamino group, a pyrrolidinyl group or a piperidinyl group.

[0158] P represents an integer of 0 to 4. From the viewpoint of solubility in a solvent, compatibility with a liquid crystal compound, color tone, and ease of production, it is preferably 1 or more and preferably 4 or less, and more preferably 3 or less.

[0159] R 11 and R 12 represent the same or different monovalent organic groups.

[0160] As R 11 and R 12The monovalent organic group in the formula (a) includes a hydrogen atom, an alkyl group having 1 to 15 carbon atoms and optionally having a branch; an alicyclic alkyl group having 1 to 15 carbon atoms; an alkoxy group having 1 to 15 carbon atoms and optionally having a branch, such as a methoxy group, an ethoxy group, and a butoxy group; a fluoroalkyl group having 1 to 15 carbon atoms and optionally having a branch, such as a trifluoromethyl group; a cyano group; a nitro group; a hydroxyl group; a halogen atom; a substituted or unsubstituted amino group, such as an amino group, a diethylamino group, and a pyrrolidino group; a carboxyl group; an alkyloxycarbonyl group having 1 to 15 carbon atoms and optionally having a branch, such as a butoxycarbonyl group; -(4-butylphenyl)vinyl and other alkylphenyl alkenyl groups; carbamoyl; alkylcarbamoyl groups having 1 to 15 carbon atoms, which may be branched, such as butylcarbamoyl; sulfamoyl; alkylsulfamoyl groups having 1 to 15 carbon atoms, which may be branched, such as butylsulfamoyl; acylamino groups having 1 to 15 carbon atoms, which may be branched, such as butylcarbonylamino; acyloxy groups having 1 to 15 carbon atoms, which may be branched, such as butylcarbonyloxy; sulfonyl; alkylsulfonyl groups having 1 to 15 carbon atoms, such as butylsulfonyl; Q in the polymerizable liquid crystal compound described later 1 -R 1 - and Q 2 -R 2 -.

[0161] It should be noted that the substituted amino group refers to an amino group having one or two optionally branched alkyl groups having 1 to 15 carbon atoms, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 15 carbon atoms. 2 . It should be noted that examples of the alkyl group having 1 to 15 carbon atoms include methyl, ethyl, and butyl. Examples of the alkanediyl group having 2 to 15 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl.

[0162] As R 11 and R 12 , examples include: hydrogen atoms, chain groups, aliphatic organic groups ("aliphatic organic groups" include chain groups and cyclic groups), aliphatic organic groups in which part of carbon is replaced by nitrogen and / or oxygen, etc. In one embodiment, hydrogen atoms and chain groups are preferred, and in another embodiment, hydrogen atoms and aliphatic organic groups are preferred, and in another embodiment, hydrogen atoms and aliphatic organic groups in which part of carbon is replaced by nitrogen and / or oxygen are preferred.

[0163] It should be noted that the above-mentioned "aliphatic organic group in which a part of carbon is substituted by nitrogen and / or oxygen" includes chain groups and cyclic groups, including groups in which a part of the methyl groups of the aliphatic organic group are replaced by hydroxyl groups, oxo groups (=O), amino groups, imino groups, etc.

[0164] Examples of the chain group include the above-mentioned alkyl group having 1 to 15 carbon atoms and optionally having a branch; an alkoxy group having 1 to 15 carbon atoms and optionally having a branch; a fluoroalkyl group having 1 to 15 carbon atoms and optionally having a branch; a substituted or unsubstituted amino group; a carboxyl group; an alkyloxycarbonyl group having 1 to 15 carbon atoms and optionally having a branch; a carbamoyl group; an alkylcarbamoyl group having 1 to 15 carbon atoms and optionally having a branch; a sulfamoyl group; an alkylsulfamoyl group having 1 to 15 carbon atoms and optionally having a branch; an acylamino group having 1 to 15 carbon atoms and optionally having a branch; an acyloxy group having 1 to 15 carbon atoms and optionally having a branch; a sulfanyl group; an alkylsulfonyl group having 1 to 15 carbon atoms and the like.

[0165] It should be noted that the above-mentioned substituted amino group refers to an amino group having one or two optionally branched alkyl groups having 1 to 15 carbon atoms. 2 .

[0166] Examples of the aliphatic organic group include the above-mentioned optionally branched alkyl group having 1 to 15 carbon atoms, alicyclic alkyl group having 1 to 15 carbon atoms, and the like.

[0167] Examples of the aliphatic organic group in which a portion of carbon is replaced by nitrogen and / or oxygen include: the above-mentioned alkoxy group having 1 to 15 carbon atoms and optionally having a branch; a substituted or unsubstituted amino group; a carboxyl group; an alkyloxycarbonyl group having 1 to 15 carbon atoms and optionally having a branch; a carbamoyl group; an alkylcarbamoyl group having 1 to 15 carbon atoms and optionally having a branch; an acylamino group having 1 to 15 carbon atoms and optionally having a branch; and an acyloxy group having 1 to 15 carbon atoms and optionally having a branch.

[0168] It should be noted that the substituted amino group refers to an amino group having one or two optionally branched alkyl groups having 1 to 15 carbon atoms, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 15 carbon atoms. 2 . It should be noted that examples of the alkyl group having 1 to 15 carbon atoms include methyl, ethyl, and butyl. Examples of the alkanediyl group having 2 to 15 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl.

[0169] As R 11and R 12 , from the viewpoint of high molecular linearity, it is preferred that each independently be substituted by a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or an alkoxy group having 1 to 10 carbon atoms, such as a butoxy group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a diethylamino group, a pyrrolidino group, or a piperidinyl group. In addition, Q in the polymerizable liquid crystal compound described later is also preferred. 1 -R 1 - and Q 2 -R 2 -.

[0170] The dye other than the compound represented by formula (1) contained in the anisotropic dye film-forming composition of the present invention is not particularly limited, and a known dye may be used.

[0171] Examples of known pigments include pigments (dichroic pigments, dichroic dyes) described in Patent Document 1, Japanese Patent No. 5982762, Japanese Patent Application Publication No. 2017-025317, and Japanese Patent Application Publication No. 2014-095899.

[0172] Specifically, the pigments described below can be mentioned, but the pigments are not limited to these.

[0173] [Chemical formula 11]

[0174]

[0175] [Chemical formula 12]

[0176]

[0177] [Chemical formula 13]

[0178]

[0179] [Chemical formula 14]

[0180]

[0181] In addition, as a dye other than the compound represented by formula (1) contained in the anisotropic dye film-forming composition of the present invention, it is preferable that the wavelength showing a maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm is longer than the wavelength showing a maximum value in the absorption curve of the compound represented by formula (1) contained in the anisotropic dye film-forming composition in the wavelength range of 380 nm to 780 nm. It is more preferable that the wavelength showing a maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm is longer than the wavelength showing a maximum value in the absorption curve of the compound represented by formula (1) contained in the anisotropic dye film-forming composition in the wavelength range of 380 nm to 780 nm. It is further preferable that the wavelength showing a maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm is longer than the wavelength showing a maximum value in the absorption curve of the compound represented by formula (1) contained in the anisotropic dye film-forming composition in the wavelength range of 380 nm to 780 nm. When the wavelength showing a maximum value in the absorption curve of the dye other than the compound represented by formula (1) in the wavelength range of 380 nm to 780 nm is within the above range, there is a tendency that the color tone adjustment becomes easy.

[0182] The molecular weight of the pigment contained in the anisotropic dye film-forming composition of the present invention (when two or more pigments are used in combination, the molecular weight of each pigment) is preferably 300 or more, more preferably 350 or more, and further preferably 380 or more, and is preferably 1500 or less, more preferably 1200 or less, and further preferably 1000 or less. Specifically, the molecular weight of the pigment contained in the anisotropic dye film-forming composition of the present invention is preferably 300 to 1500, more preferably 350 to 1200, and further preferably 380 to 1000. By being in the above range, there is a tendency for the molecular major-minor axis ratio to increase.

[0183] The content of the pigment (dichroic pigment) in the anisotropic dye film-forming composition (the sum of the contents of each pigment when two or more pigments are used in combination) is, for example, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 30 parts by mass or less, more preferably 10 parts by mass or less, relative to the solid content (100 parts by mass) of the anisotropic dye film-forming composition. Specifically, the content of the pigment (dichroic pigment) in the anisotropic dye film-forming composition is, for example, 0.01 to 30 parts by mass, preferably 0.05 to 10 parts by mass, relative to the solid content (100 parts by mass) of the anisotropic dye film-forming composition.

[0184] When the content occupied by the pigment (dichroic pigment) is within the above range, there is a tendency to polymerize the compound contained in the anisotropic pigment film-forming composition of the present invention without disturbing the orientation of the liquid crystal compound contained in the anisotropic pigment film-forming composition of the present invention. In addition, when the content occupied by the pigment (dichroic pigment) is above the above lower limit, sufficient light absorption can be obtained, and there is a tendency to obtain sufficient polarization performance. In addition, when the content occupied by the pigment (dichroic pigment) is below the above upper limit, there is a tendency to easily suppress the orientation obstruction of the liquid crystal molecules.

[0185] Depending on the purpose, the dye (dichroic dye) may be used alone or in combination with the compound represented by formula (1) and other dyes. As described above, as the dye contained in the anisotropic dye film-forming composition of the present invention, it is preferred to use the compound represented by formula (1) in combination with one or more compounds having a wavelength showing a maximum in the absorption curve in the wavelength range of 380 nm to 780 nm longer than the wavelength showing a maximum in the absorption curve in the wavelength range of 380 nm to 780 nm of the compound represented by formula (1) contained in the anisotropic dye film-forming composition. In particular, when the anisotropic dye film is formed into a polarizing element such as a display using the anisotropic dye film-forming composition, it is preferred from the viewpoint of showing polarization characteristics in a wide range of the visible light region.

[0186] The dye contained in the anisotropic dye film-forming composition of the present invention can be produced by combining known chemical reactions such as alkylation reaction, esterification reaction, amidation reaction, etherification reaction, in situ (ipso) substitution reaction, diazotization coupling reaction, and coupling reaction using a metal catalyst.

[0187] For example, the dye contained in the anisotropic dye film-forming composition of the present invention can be synthesized by the method described in the examples, for example, the method described in "New Dye Chemistry" (written by Yutaka Hosoda, December 21, 1950, Gihodo), "General Theory of Synthetic Dyes" (written by Hiroshi Horiguchi, 1968, Sankyo Publishing), and "Theoretical Manufacturing Dye Chemistry" (written by Yutaka Hosoda, 1957, Gihodo).

[0188] (Polymerizable Liquid Crystal Compound)

[0189] In the present invention, the liquid crystal compound refers to a substance that exhibits a liquid crystal state, specifically, a compound that does not directly change from a crystal to a liquid but becomes a liquid through an intermediate state that exhibits the properties of both a crystal and a liquid, as described in pages 1 to 28 of the "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2001).

[0190] The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention is a liquid crystal compound having a polymerizable group as described later.

[0191] In the polymerizable liquid crystal compound, the polymerizable group may be arranged at any position in the liquid crystal compound molecule, but is preferably substituted at the terminal of the liquid crystal compound molecule because it tends to facilitate polymerization between molecules.

[0192] In the polymerizable liquid crystal compound, one or more polymerizable groups may be present in the liquid crystal compound molecule. When two or more polymerizable groups are present, they are preferably present at both ends of the liquid crystal compound molecule.

[0193] In addition, the polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond in the liquid crystal compound molecule. In the case of a compound having a carbon-carbon triple bond, the carbon-carbon triple bond can become the core of the liquid crystal molecule while performing rotational motion, and there is a tendency that the mobility of the molecule is high, and the intermolecular interaction between the liquid crystal molecules and the compound having a π conjugated system such as the pigment molecule is strong, and the molecular orientation increases.

[0194] As the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention, any liquid crystal compound having a polymerizable group can be used without particular limitation.

[0195] For example, as the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention, there can be mentioned a compound represented by formula (2).

[0196] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2)

[0197] (Where,

[0198] Q 1 represents a hydrogen atom or a polymerizable group;

[0199] Q 2 represents a polymerizable group;

[0200] R 1 and R 2 Each independently represents a chain organic group;

[0201] A 11 and A 13Each independently represents a partial structure represented by the following formula (3), a divalent organic group, or a single bond;

[0202] A 12 represents a partial structure or a divalent organic group represented by the following formula (3);

[0203] -Y 1 -and-Y 2 - each independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH 2 CH 2 -, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH 2 O-、-OCH 2 -、-CH 2 S-, or -SCH 2 -;

[0204] A 11 and A 13 One of them is a partial structure or a divalent organic group represented by the following formula (3);

[0205] K is 1 or 2. )

[0206] -Cy-X 2 -C≡CX 1 -…(3)

[0207] (Where,

[0208] Cy represents a hydrocarbon ring group or a heterocyclic group;

[0209] -X 1 - means -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH 2 CH 2 -, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH 2 O-、-OCH 2 -、-CH 2 S-, or -SCH 2 -;

[0210] -X 2 - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH 2 CH 2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH 2 O-、-OCH 2 -、-CH 2 S-, or -SCH 2 -. )

[0211] It should be noted that in A 11 In the case of the partial structure represented by formula (3), formula (2) can be expressed as follows.

[0212] Q 1 -R 1 -Cy-X 2 -C≡CX 1 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2A)

[0213] Q 1 -R 1 -X 1 -C≡CX 2 -Cy-Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2B)

[0214] In addition, in A 12 In the case of the partial structure represented by formula (3), formula (2) can be expressed as follows.

[0215] Q 1 -R 1 -A 11 -Y 1 -Cy-X 2 -C≡CX 1 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2C)

[0216] Q 1 -R 1 -A 11 -Y 1 -X 1 -C≡CX 2 -Cy-(Y 2-A 13 ) k -R 2 -Q 2 …(2D)

[0217] In addition, in A 13 In the case of the partial structure represented by formula (3), formula (2) can be expressed as follows.

[0218] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -Cy-X 2 -C≡CX 1 ) k -R 2 -Q 2 …(2E)

[0219] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -X 1 -C≡CX 2 -Cy) k -R 2 -Q 2 …(2F)

[0220] Similarly, in A 11 , A 12 and A 13 When there are two or more partial structures represented by formula (1), the orientations of the partial structures represented by formula (1) can be flipped independently of each other.

[0221] In addition, as mentioned above, A 11 , A 12 and A 13 Each independently represents a partial structure or a divalent organic group represented by formula (1); in addition, A 11 and A 13 Can be a single bond, but A 11 and A 13 Not single bond at the same time.

[0222] The hydrocarbon ring group in Cy includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.

[0223] The aromatic hydrocarbon ring group includes a non-bonded aromatic hydrocarbon ring group and a bonded aromatic hydrocarbon ring group.

[0224] The non-bonded aromatic hydrocarbon ring group is a monocyclic or condensed divalent aromatic hydrocarbon ring group, and preferably has 6 to 20 carbon atoms. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc.

[0225] The connecting aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond and have a bonding arm on the atoms constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 6 to 20. For example, a monocyclic or condensed first aromatic hydrocarbon ring having 6 to 20 carbon atoms is bonded by a single bond to a monocyclic or condensed second aromatic hydrocarbon ring having 6 to 20 carbon atoms, and has a first bonding arm on an atom constituting the ring of the monocyclic or condensed first aromatic hydrocarbon ring having 6 to 20 carbon atoms, and has a second bonding arm on an atom constituting the ring of the monocyclic or condensed second aromatic hydrocarbon ring having 6 to 20 carbon atoms. As the connecting aromatic hydrocarbon ring group, for example, biphenyl-4,4'-diyl can be mentioned.

[0226] As the aromatic hydrocarbon ring group, a non-bonded aromatic hydrocarbon ring group is preferred.

[0227] Among them, as the aromatic hydrocarbon ring group, a divalent group of a benzene ring or a divalent group of a naphthalene ring is preferred, and a divalent group of a benzene ring (phenylene) is more preferred. As the phenylene group, 1,4-phenylene is preferred. By having the above group, there is a tendency that the molecular orientation of the liquid crystal compound becomes good.

[0228] The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.

[0229] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and the number of carbon atoms is preferably 3 to 20. Examples of the non-aromatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a norbornane ring, a camphane ring, an adamantane ring, a tetralin ring, and a bicyclo[2.2.2]octane ring.

[0230] The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring. The non-linked non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group.

[0231] The linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed non-aromatic hydrocarbon rings are bonded by a single bond and have a bonding arm on the atoms constituting the ring; or a divalent group in which one or more rings selected from a monocyclic aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring are bonded by a single bond to a monocyclic or condensed non-aromatic hydrocarbon ring and have a bonding arm on the atoms constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20. For example, a divalent group in which a monocyclic or condensed first non-aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a monocyclic or condensed second non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, and has a first bonding arm on an atom constituting the ring of the monocyclic or condensed first non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and has a second bonding arm on an atom constituting the ring of the monocyclic or condensed second non-aromatic hydrocarbon ring having 3 to 20 carbon atoms; for example, a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded to a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, and has a first bonding arm on an atom constituting the ring of the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and has a second bonding arm on an atom constituting the ring of the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Examples of the linking non-aromatic hydrocarbon ring group include a bis(cyclohexane)-4,4'-diyl group and a 1-cyclohexylbenzene-4,4'-diyl group.

[0232] As the non-aromatic hydrocarbon ring group, from the viewpoint of the molecular alignment of the liquid crystal compound, a non-bonding non-aromatic hydrocarbon ring group is preferred.

[0233] Among them, as the non-aromatic hydrocarbon ring group, a divalent group of cyclohexane (cyclohexanediyl) is preferred. As the cyclohexanediyl, cyclohexane-1,4-diyl is preferred. By having the above group, there is a tendency that the solubility and molecular orientation of the liquid crystal compound become good.

[0234] The heterocyclic group in Cy includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

[0235] The aromatic heterocyclic group includes a non-bonded aromatic heterocyclic group and a bonded aromatic heterocyclic group.

[0236] The non-bonded aromatic heterocyclic group is a monocyclic or condensed divalent aromatic heterocyclic group, and preferably has 4 to 20 carbon atoms. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, thienothiazole ring, benzisocyanate ring azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, quinazoline ring, quinazolinone ring, azulene ring and the like.

[0237] The linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by a single bond and have a bonding arm on the atoms constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a monocyclic or condensed first aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded by a single bond to a monocyclic or condensed second aromatic heterocyclic ring having 4 to 20 carbon atoms, and the first bonding arm is on the atoms constituting the ring of the monocyclic or condensed first aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bonding arm is on the atoms constituting the ring of the monocyclic or condensed second aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0238] The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.

[0239] The non-bonded non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group, and preferably has 4 to 20 carbon atoms. It is a monocyclic or condensed non-aromatic heterocyclic divalent group having 4 to 20 carbon atoms, and examples of the non-aromatic heterocyclic group include tetrahydrofuran ring, tetrahydropyran ring, dihydrogen ... alkane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazolidine ring, tetrahydro oxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring, quinuclidine ring and the like.

[0240] The linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic rings are bonded by a single bond and have a bonding arm on the atoms constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, it is a divalent group in which a first non-aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded by a single bond to a second non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the first bonding arm is on the atom constituting the ring of the first non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bonding arm is on the atom constituting the ring of the second non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0241] The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy are each optionally selected from R z 、-OH、-OR z 、-OC(=O)-R z 、-NH 2 、-NH-Rz 、-N(R z’ )-R z , -C(=O)-R z 、-C(=O)-OR z 、-C(=O)-NH 2 , -C(=O)-NH-R z 、-C(=O)-N(R z’ )-R z , -SH, -SR z , trifluoromethyl, sulfamoyl, carboxyl, sulfonyl, cyano, nitro, and halogen. z and R z’ Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0242] From the viewpoint that the molecular structure has high linearity, the molecules represented by formula (2) are easily associated with each other, and are easy to exhibit a liquid crystal state, the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy are preferably each independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, and are more preferably unsubstituted.

[0243] The substituents possessed by the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group may be the same or different. Furthermore, the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group may all be substituted or all be unsubstituted, or may be partially substituted and partially unsubstituted.

[0244] As Cy, from the viewpoint of solubility and molecular orientation of the liquid crystal compound, a hydrocarbon ring group is preferred, and a phenylene group or a cyclohexanediyl group is more preferred. In addition, from the viewpoint of being able to improve the linearity of the molecular structure of the liquid crystal compound, as Cy, a 1,4-phenylene group or a cyclohexane-1,4-diyl group is further preferred, and a 1,4-phenylene group is particularly preferred.

[0245] From the viewpoint of the linearity of the liquid crystal compound and the tendency to easily perform rotational motion around the minor axis of the molecule, -X 1 -, preferably -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -、-CH 2 S-、-SCH 2-, more preferably -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -. As a way, -X 1 - is -C(=O)O- or -OC(=O)-, in another embodiment, -X 1 -for-CH 2 CH 2 -、-CH 2 O-, or -OCH 2 -.

[0246] From the viewpoint of increasing the core of the liquid crystal compound and increasing the dichroism of the anisotropic dye film formed from the anisotropic dye film-forming composition, it is preferred to connect -Cy- and -C≡C- with a highly linear group. Specifically, -X 2 - is preferably a single bond, or -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH=CH-, -C(=O)NH-, or -NHC(=O)- having a π bond. From the viewpoint of higher linearity, a single bond is more preferred.

[0247] The polymerizable group in the present invention is a group having a partial structure that can be polymerized by light, heat, and / or radiation, and is a functional group or atomic group necessary to ensure the polymerization function. From the viewpoint of production of anisotropic dye film, the polymerizable group is preferably a photopolymerizable group.

[0248] As the polymerizable group, specifically, for example, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, vinyl, vinyloxy, ethynyl, ethynyloxy, 1,3-butadienyl, 1,3-butadienyloxy, oxiranyl, oxetanyl, glycidyl, glycidyloxy, styryl, styryloxy, etc. are listed. Among them, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, oxiranyl, glycidyl, glycidyloxy are preferred, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, glycidyl, glycidyloxy are more preferred, and acryloyloxy, methacryloyloxy, glycidyloxy, glycidyloxy, and acryloyloxy, methacryloyloxy, glycidyloxy, are further preferred. By having the above-mentioned polymerizable group, there is a tendency that the control of polymerization becomes easy.

[0249] R 1 and R 2The chain organic group in is a divalent organic group that does not contain a cyclic structure such as the above-mentioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic heterocycle, etc.

[0250] Examples of such chain organic groups include -(alkylene)-, -O-(alkylene)-, -S-(alkylene)-, -NH-(alkylene)-, -N(alkyl)-(alkylene)-, -OC(=O)-(alkylene)-, and -C(=O)O-(alkylene)-.

[0251] As R 1 and R 2 The chain organic group in is preferably -(alkylene)- or -O-(alkylene)-. 1 and R 2 The chain organic group in is -(alkylene)-. In another embodiment, such a chain organic group is -O-(alkylene)-.

[0252] Examples of the alkylene group in these chain organic groups include linear or branched alkylene groups having 1 to 25 carbon atoms. A portion of the carbon-carbon bonds of the alkylene group may be unsaturated bonds, and one or more methylene groups contained in the alkylene group may be replaced by ether oxygen atoms, thioether sulfur atoms, amine nitrogen atoms, carbonyl groups, ester bonds, amide bonds, -CHF-, -CF- 2 -、-CHCl-、-CCl 2 -Structure formed by replacement.

[0253] Examples of the aminic nitrogen atom include -NH-, -N(R z ), R z It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0254] As the alkylene group in these chain organic groups, a straight-chain alkylene group having 1 to 25 carbon atoms is preferred from the viewpoint of high molecular linearity, and the alkylene group may have a structure in which a part of the carbon atoms of the alkylene group is an unsaturated bond, and one or more methylene groups contained in the alkylene group are substituted (displaced) by the above-mentioned groups.

[0255] The number of atoms in the main chain (the longest chain portion in the chain organic group) of the chain organic group is preferably 3-25, more preferably 5-20, and even more preferably 6-20.

[0256] The chain organic group is preferably -(CH 2 ) n -CH2 -、-O-(CH 2 ) n -CH 2 -、-(O) n1 -(CH 2 CH 2 O) n2 -(CH 2 ) n3 -、-(O) n1 -(CH 2 ) n2 -(CH 2 CH 2 O) n3 -. It should be noted that n in these formulas is an integer of 1 to 24, preferably an integer of 2 to 24, more preferably an integer of 4 to 19, and further preferably an integer of 5 to 19. In addition, n1, n2, and n3 in these formulas each independently represent an integer, and the number of atoms in the main chain (referring to the longest chain part in the chain organic group) in the chain organic group is preferably appropriately adjusted to 3 to 25, more preferably 5 to 20, and further preferably 6 to 20.

[0257] R 1 and R 2 Preferably, they are independently -(alkylene)- or -O-(alkylene)-, and more preferably -(alkylene)- or -O-(alkylene)-. The above molecular structure tends to improve the molecular alignment of the liquid crystal compound.

[0258] In formula (2B) and formula (2E), X 1 With R 1 or X 1 With R 2 When bonded together, and for example in formula (2B) A 13 In the case of a single bond, in formula (2E) 11 As in the case of a single bond, R 1 or R 2 With Y 1 or Y 2 When the liquid crystal compound is bonded together, from the viewpoint of improving the molecular orientation of the liquid crystal compound, 1 or Y 1 or Y 2 Bonded R 1 or R 2 Preferred is -(alkylene)-.

[0259] In addition to the above, from the viewpoint of improving the molecular orientation of the liquid crystal compound, 1 or Y 1 or Y 2 Bonded R1 or R 2 Preferred is -O-(alkylene)-.

[0260] A 11 , A 12 and A 13 The divalent organic group in is preferably a group represented by the following formula (4).

[0261] -Q 3 -…(4)

[0262] In formula (4),

[0263] Q 3 represents a hydrocarbon ring group or a heterocyclic group.

[0264] Q 3 The hydrocarbon ring group in includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.

[0265] The aromatic hydrocarbon ring group includes a non-bonded aromatic hydrocarbon ring group and a bonded aromatic hydrocarbon ring group.

[0266] The non-linked aromatic hydrocarbon ring group is a monocyclic or condensed divalent aromatic hydrocarbon ring group, and preferably has 6 to 20 carbon atoms. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc.

[0267] The connecting aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond and have a bonding arm on the atoms constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 6 to 20. For example, a monocyclic or condensed first aromatic hydrocarbon ring having 6 to 20 carbon atoms is bonded by a single bond to a monocyclic or condensed second aromatic hydrocarbon ring having 6 to 20 carbon atoms, and has a first bonding arm on an atom constituting the ring of the monocyclic or condensed first aromatic hydrocarbon ring having 6 to 20 carbon atoms, and has a second bonding arm on an atom constituting the ring of the monocyclic or condensed second aromatic hydrocarbon ring having 6 to 20 carbon atoms. As the connecting aromatic hydrocarbon ring group, for example, biphenyl-4,4'-diyl can be mentioned.

[0268] As the aromatic hydrocarbon ring group, a non-bonded aromatic hydrocarbon ring group is preferred.

[0269] Among them, as the aromatic hydrocarbon ring group, a divalent group of a benzene ring or a divalent group of a naphthalene ring is preferred, and a divalent group of a benzene ring (phenylene) is more preferred. As the phenylene group, 1,4-phenylene is preferred. By having the above group, there is a tendency that the molecular orientation of the liquid crystal compound becomes good.

[0270] The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.

[0271] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and the number of carbon atoms is preferably 3 to 20. Examples of the non-aromatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a norbornane ring, a camphane ring, an adamantane ring, a tetralin ring, and a bicyclo[2.2.2]octane ring.

[0272] The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring. The non-linked non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group.

[0273] The linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed non-aromatic hydrocarbon rings are bonded by a single bond and have a bonding arm on the atoms constituting the ring; or a divalent group in which one or more rings selected from a monocyclic aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring are bonded by a single bond to a monocyclic or condensed non-aromatic hydrocarbon ring and have a bonding arm on the atoms constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20. For example, a bivalent group in which a monocyclic or condensed first non-aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a monocyclic or condensed second non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, and has a first bonding arm on an atom constituting the ring of the monocyclic or condensed first non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and has a second bonding arm on an atom constituting the ring of the monocyclic or condensed second non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. In addition, for example, a bivalent group in which a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, and has a first bonding arm on an atom constituting the ring of the monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms, and has a second bonding arm on an atom constituting the ring of the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0274] Examples of the linking non-aromatic hydrocarbon ring group include a bis(cyclohexane)-4,4'-diyl group and a 1-cyclohexylbenzene-4,4'-diyl group.

[0275] As the non-aromatic hydrocarbon ring group, a non-bonded non-aromatic hydrocarbon ring group is preferred.

[0276] Among them, as the non-aromatic hydrocarbon ring group, a divalent group of cyclohexane (cyclohexanediyl) is preferred. As the cyclohexanediyl group, from the viewpoint of solubility and molecular orientation of the liquid crystal compound, a cyclohexane-1,4-diyl group is preferred.

[0277] Q3 The heterocyclic group in the formula (A) includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

[0278] The aromatic heterocyclic group includes a non-bonded aromatic heterocyclic group and a bonded aromatic heterocyclic group.

[0279] The non-bonded aromatic heterocyclic group is a monocyclic or condensed divalent aromatic heterocyclic group, and preferably has 4 to 20 carbon atoms. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, thienothiazole ring, benzisocyanate ring azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, quinazoline ring, quinazolinone ring, azulene ring and the like.

[0280] The linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by a single bond and have a bonding arm on the atoms constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a monocyclic or condensed first aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded by a single bond to a monocyclic or condensed second aromatic heterocyclic ring having 4 to 20 carbon atoms, and the first bonding arm is on the atoms constituting the ring of the monocyclic or condensed first aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bonding arm is on the atoms constituting the ring of the monocyclic or condensed second aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0281] The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.

[0282] The non-bonded non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group, and preferably has 4 to 20 carbon atoms. It is a monocyclic or condensed non-aromatic heterocyclic divalent group having 4 to 20 carbon atoms, and examples of the non-aromatic heterocyclic group include tetrahydrofuran ring, tetrahydropyran ring, dihydrogen ... alkane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazolidine ring, tetrahydro oxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring, quinuclidine ring and the like.

[0283] The linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic rings are bonded by a single bond and have a bonding arm on the atoms constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, it is a divalent group in which a first non-aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded by a single bond to a second non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the first bonding arm is on the atom constituting the ring of the first non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bonding arm is on the atom constituting the ring of the second non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0284] Q 3 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in R are each optionally selected from z 、-OH、-OR z 、-OC(=O)-R z 、-NH 2 、-NH-R z 、-N(R z’ )-R z , -C(=O)-R z 、-C(=O)-OR z 、-C(=O)-NH 2 , -C(=O)-NH-R z 、-C(=O)-N(R z’ )-R z , -SH, -SR z , trifluoromethyl, sulfamoyl, carboxyl, sulfo, cyano, nitro, and halogen. z and R z’ Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0285] From the viewpoint that the molecular structure has high linearity, the molecules represented by formula (2) are easily associated with each other, and a liquid crystal state is easily exhibited, Q 3 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group in are each independently preferably unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom or a bromine atom, and more preferably unsubstituted.

[0286] The substituents possessed by the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group may be the same or different. Furthermore, the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group may all be substituted or all be unsubstituted, or may be partially substituted and partially unsubstituted.

[0287] In addition, A11 , A 12 , and A 13 The substituents having a divalent organic group in A may be the same or different. 11 , A 12 , and A 13 The divalent organic groups in may be all substituted or all unsubstituted, or may be partially substituted and partially unsubstituted.

[0288] As Q 3 , preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group. In addition, from the viewpoint of being able to improve the linearity of the molecular structure of the liquid crystal compound, Q 3 , and more preferably 1,4-phenylene and cyclohexane-1,4-diyl.

[0289] As a divalent organic group, Q3 is preferably a hydrocarbon ring group, that is, a hydrocarbon ring group as a divalent organic group is preferred. In addition, as a divalent organic group, a phenylene group or a cyclohexanediyl group is more preferred, and from the viewpoint of being able to improve the linearity of the molecular structure of the liquid crystal compound, a 1,4-phenylene group or a cyclohexane-1,4-diyl group is further preferred.

[0290] As formula (2), in A 11 , A 12 and A 13 It is preferred that one of them is a partial structure represented by formula (3), and the other two are each independently a divalent organic group, in A 11 , A 12 and A 13 In the partial structure represented by formula (3), it is preferred that Cy is a hydrocarbon ring group, and it is particularly preferred that the divalent organic group is a hydrocarbon ring group. In addition, the hydrocarbon ring group is preferably 1,4-phenylene or cyclohexane-1,4-diyl. In addition, it is preferred that A 11 and A 13 One of them is cyclohexane-1,4-diyl.

[0291] In addition, in A 11 and A 13 It is preferred that one of them is a partial structure represented by formula (3), and the other one and A 12 is a divalent organic group. In this case, 11 and A 13 Among them, one of the divalent organic groups is preferably a cyclohexane-1,4-diyl group, and A is particularly preferred. 12 The above structure tends to improve the molecular orientation of the liquid crystal compound.

[0292] From the viewpoint of the linearity of the liquid crystal compound and the tendency to easily perform rotational motion around the short axis of the molecule, -Y 1 -and-Y 2 -, each independently preferably a single bond with small π-bond properties, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH 2 CH 2 -, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH 2 O-、-OCH 2 -、-CH 2 S-, or -SCH 2 , more preferably a single bond, -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -.

[0293] In formula (2A), formula (2C), formula (2D), formula (2F), X 1 With Y 1 or X 1 With Y 2 When bonded together, with X 1 Bonded Y 1 or with X 1 Bonded Y 2 Preferably a single bond; -X 1 -and-Y 1 -and-Y 2 The other of - is preferably -C(=O)O- or -OC(=O)-.

[0294] In addition, in formula (2B) and formula (2E), X 1 With Y 1 and Y 2 When both are not bonded, -X 1 -Preferably -CH 2 CH 2 -、-CH 2 O-, or -OCH 2 -;-Y 1 -and-Y 2 - is preferably -C(=O)O- or -OC(=O)-. The above structure tends to improve the molecular orientation of the liquid crystal compound.

[0295] As the formula (2), the above-mentioned formula (2A), the above-mentioned formula (2B), the above-mentioned formula (2E), and the above-mentioned formula (2F) are preferable.

[0296] In addition, as another embodiment, as formula (2), in A 11 , A 12 and A 13 In the embodiment of the present invention, one of them is preferably 1,4-phenylene, and the other two are each independently a divalent organic group, and the divalent organic group is particularly preferably a hydrocarbon ring group. In addition, the hydrocarbon ring group is preferably 1,4-phenylene or cyclohexane-1,4-diyl. By being the above structure, there is a tendency that the molecular linearity increases.

[0297] k is 1 or 2. In one embodiment, k is preferably 1. In another embodiment, k is preferably 2. By setting it to the above value, there is a tendency that the molecular orientation of the liquid crystal compound becomes good.

[0298] When k is 2, each Y 2 They can be the same or different. 13 They can be the same as each other or different.

[0299] Specific examples of the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention include the polymerizable liquid crystal compounds described below, but are not limited thereto. 5 H 11 refers to n-pentyl, C 6 H 13 It refers to n-hexyl.

[0300] [Chemical formula 15]

[0301]

[0302] [Chemical formula 16]

[0303]

[0304] [Chemical formula 17]

[0305]

[0306] [Chemical formula 18]

[0307]

[0308] [Chemical formula 19]

[0309]

[0310] [Chemical formula 20]

[0311]

[0312] [Chemical formula 21]

[0313]

[0314] [Chemical formula 22]

[0315]

[0316] [Chemical formula 23]

[0317]

[0318] [Chemical formula 24]

[0319]

[0320] [Chemical formula 25]

[0321]

[0322] [Chemical formula 26]

[0323]

[0324] [Chemical formula 27]

[0325]

[0326] [Chemical formula 28]

[0327]

[0328] The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention may be used alone or in combination of two or more.

[0329] From a process standpoint, the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention has an isotropic phase appearance temperature of preferably 160°C or less, more preferably 140°C or less, further preferably 115°C or less, further preferably 110°C or less, and particularly preferably 105°C or less.

[0330] It should be noted that the isotropic phase appearance temperature here refers to the phase transition temperature from liquid crystal to liquid and the phase transition temperature from liquid to liquid crystal. In the present invention, preferably at least one of these phase transition temperatures is within the above range, and more preferably both of these phase transition temperatures are within the above range.

[0331] The liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention can be produced by combining known chemical reactions such as alkylation reaction, esterification reaction, amidation reaction, etherification reaction, autosubstitution reaction, and coupling reaction using a metal catalyst.

[0332] For example, the liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention can be synthesized by the method described in Examples or the method described in “Liquid Crystal Handbook” (Maruzen Co., Ltd., published on October 30, 2001, pp. 449 to 468).

[0333] (Relationship between the polymerizable liquid crystal compound and the compound represented by formula (1))

[0334] From the viewpoint of improving the orientation of an anisotropic dye film formed using an anisotropic dye film-forming composition, in the anisotropic dye film-forming composition, the smaller the difference between the molecular length of the liquid crystal compound and the molecular length of the dye, the stronger the intermolecular interaction between the liquid crystal molecules and the dye molecules, and the less likely the dye molecules are to hinder the association of the liquid crystal molecules with each other, and therefore it is preferred.

[0335] Therefore, in the anisotropic dye film-forming composition of the present invention, the number of ring structures (r n1 ) and the number of ring structures (r n2 ) ratio (r n1 / r n2 ) is preferably 0.7 to 1.5.

[0336] In addition, a fused ring in which two or more rings are fused is counted as one ring structure.

[0337] Here, the number of ring structures (r) possessed by the compound represented by formula (1) n2 ) refers to A in the formula 1 , A 2 and A 3 Specifically, when n is 1, r n2 is 3; when n is 2, r n2 is 4; when n is 3, r n2 is 5.

[0338] It should be noted that even if X is a cyclic functional group such as pyrrolidinyl or piperidinyl, the ring structure contained in X is not included in the number of ring structures (r n2 )middle.

[0339] More specifically, when n is 1, r n2 is 3, so r n1 is 3 or 4; when n is 2, r n2 is 4, so r n1 is 3, 4, 5 or 6; when n is 3, r n2is 5, so r n1 is 4, 5, 6 or 7. In this case, the number of ring structures (r n1 ) and the number of ring structures (r n2 ) ratio (r n1 / r n2 ) is 0.7 to 1.5, so it is preferred.

[0340] The number of ring structures (r n1 ) does not include a ring structure (for example, an oxirane ring, an oxetane ring, etc.) contained in a polymerizable group in a polymerizable liquid crystal compound.

[0341] (Polymerization initiator)

[0342] The anisotropic dye film-forming composition of the present invention may contain a polymerization initiator as necessary.

[0343] The polymerization initiator is a compound that can initiate a polymerization reaction of a polymerizable liquid crystal compound. As the polymerization initiator, a photopolymerization initiator that generates active radicals by the action of light is preferred.

[0344] As the polymerization initiator that can be used, for example, there are titanocene derivatives; biimidazole derivatives; halomethylated Oxadiazole derivatives; halomethyl-s-triazine derivatives; alkylphenone derivatives; oxime ester derivatives; benzoin; benzophenone derivatives; acylphosphine oxide derivatives; iodine onium salts; sulfonium salts; anthraquinone derivatives; acetophenone derivatives; thioxanthone derivatives; benzoate derivatives; acridine derivatives; phenazine derivatives; anthrone derivatives, etc.

[0345] Among these photopolymerization initiators, alkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferred.

[0346] Specifically, examples of the titanocene derivatives include biscyclopentadienyl titanium dichloride, biscyclopentadienyl diphenyl titanium, biscyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, biscyclopentadienyl bis(2,3,5,6-tetrafluorophenyl-1-yl)titanium, biscyclopentadienyl bis(2,4,6-trifluorophenyl-1-yl)titanium, biscyclopentadienyl bis(2,6-difluorophenyl-1-yl)titanium, biscyclopentadienyl bis(2,4-difluorophenyl-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl-1-yl)titanium, and biscyclopentadienyl titanium [2,6-difluoro-3-(pyrrol-1-yl)-phenyl-1-yl].

[0347] Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0348] In addition, as halomethyl Oxadiazole derivatives include: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4- Oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4- oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuranyl)vinyl)]-1,3,4- Oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4- Diazole, etc.

[0349] Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0350] Examples of the alkylphenone derivatives include diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0351] In addition, examples of oxime ester derivatives include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, oxime ester derivatives described in Japanese Unexamined Patent Publication No. 2000-80068, Japanese Unexamined Patent Publication No. 2006-36750, International Publication No. WO2009 / 131189, and the like.

[0352] Moreover, as a benzoin, benzoin, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, etc. are mentioned.

[0353] Examples of benzophenone derivatives include benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

[0354] Examples of the acylphosphine oxide derivatives include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0355] In addition, iodine Salts include: diphenyl iodide Tetrakis(pentafluorophenyl)borate, diphenyl iodide Hexafluorophosphate, diphenyl iodide Hexafluoroantimonate, di(4-nonylphenyl)iodide Hexafluorophosphate, etc.

[0356] Examples of sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4,4'-bis[diphenylsulfonium]diphenyl sulfide bishexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenylsulfonium]diphenyl sulfide bishexafluoroantimonate, 4,4'-bis[bis(β-hydroxyethoxy)phenylsulfonium]diphenyl sulfide bishexafluorophosphate. salt, 7-[di(p-tolyl)sulfonium]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-tolyl)sulfonium]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonium diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylsulfonium diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-tolyl)sulfonium diphenyl sulfide tetrakis(pentafluorophenyl)borate, and the like.

[0357] Examples of anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone.

[0358] Examples of acetophenone derivatives include 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4′-methylthiophenyl)-2-morpholino-1-propanone, and 1,1,1-trichloromethyl-(p-butylphenyl)ketone.

[0359] Examples of thioxanthone derivatives include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0360] In addition, benzoic acid ester derivatives; ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, etc. are mentioned.

[0361] Examples of acridine derivatives include 9-phenylacridine and 9-(p-methoxyphenyl)acridine.

[0362] In addition, examples of phenazine derivatives include 9,10-dimethylbenzophenazine and the like.

[0363] Examples of anthrone derivatives include benzanthrone and the like.

[0364] The polymerization initiator may be used alone or in combination of two or more.

[0365] As the polymerization initiator, a commercially available product may be used.

[0366] Examples of commercially available products include IRGACURE (registered trademark, hereinafter the same) 250, IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 819, IRGACURE 784, OXE-01, and OXE-02 (all manufactured by BASF); SEIKUOR (registered trademark) BZ, Z, and BEE (manufactured by Seiko Chemical Co., Ltd.); KAYACURE (registered trademark) BP100 and UVI-6992 (manufactured by Dow Chemical); ADEKA OPTEMER SP-152 and SP-170 (manufactured by ADEKA); TAZ-A and TAZ-PP (manufactured by NIHON SIBER HEGNER Co., Ltd.); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.); TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (manufactured by Changzhou TRONLY NEW ELECTRONIC MATERIALS CO., LTD.).

[0367] When the composition of the present invention contains a polymerization initiator, from the viewpoint of not easily disturbing the orientation of the polymerizable liquid crystal compound, the content of the polymerization initiator in the composition of the present invention is generally 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0368] A polymerization accelerator may be used in combination with the polymerization initiator as required. Examples of the polymerization accelerator include N,N-dialkylaminobenzoic acid alkyl esters such as ethyl N,N-dimethylaminobenzoate; 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, The invention also includes mercapto compounds having a heterocyclic ring such as oxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic multifunctional mercapto compounds, and the like.

[0369] In addition, in order to improve the sensitivity, a sensitizing dye can be used in combination as needed. The sensitizing dye can be used appropriately according to the wavelength of the exposure light source, and examples thereof include: xanthene dyes described in Japanese Patent Laid-Open No. 4-221958, Japanese Patent Laid-Open No. 4-219756, etc.; coumarin dyes with heterocyclic rings described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, etc.; 3-coumarin ketone dyes described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, etc.; pyrromethene dyes described in Japanese Patent Laid-Open No. 6-19240, etc.; Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 5-289335, etc. Pigments having a dialkylaminobenzene skeleton as described in JP-A-54-155292, JP-B-45-37377, JP-B-48-84183, JP-A-52-112681, JP-B-58-15503, JP-B-60-88005, JP-B-59-56403, JP-B-2-69, JP-B-57-168088, JP-B-5-107761, JP-B-5-210240, JP-B-4-288818, and the like.

[0370] The sensitizing dye may be used alone or in combination of two or more.

[0371] (Solvent)

[0372] The anisotropic dye film-forming composition of the present invention may contain a solvent as necessary.

[0373] The solvent that can be used is not particularly limited as long as it is a solvent that can fully disperse or dissolve the pigment or other additives in the liquid crystal compound. For example, alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether can be listed; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate can be listed; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-pentanone, and methyl isobutyl ketone can be listed; aliphatic hydrocarbon solvents such as pentane, ethane, and heptane can be listed; aromatic hydrocarbon solvents such as toluene and xylene can be listed; nitrile solvents such as acetonitrile can be listed; ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether can be listed; fluorine-containing solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, and hexafluoro-2-propanol can be listed; and chlorine-containing solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene can be listed.

[0374] These solvents may be used alone or in combination of two or more.

[0375] The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound and the pigment, and more preferably a solvent capable of completely dissolving the polymerizable liquid crystal compound and the pigment. In addition, it is preferably a solvent inactive to the polymerization reaction. In addition, from the viewpoint of applying the anisotropic dye film-forming composition of the present invention described later, it is preferably a solvent having a boiling point in the range of 50 to 200°C.

[0376] When the anisotropic dye film-forming composition of the present invention contains a solvent, the content ratio of the solvent in the anisotropic dye film-forming composition is preferably 50 to 98% by mass relative to the total amount (100% by mass) of the composition of the present invention. In other words, the solid content in the anisotropic dye film-forming composition of the present invention is preferably 2 to 50% by mass.

[0377] When the solid content in the anisotropic dye film-forming composition is at most the upper limit, the viscosity of the anisotropic dye film-forming composition does not become too high, the thickness of the obtained polarizing film becomes uniform, and there is a tendency that unevenness is less likely to occur in the polarizing film.

[0378] The solid content can be determined in consideration of the thickness of the polarizing film to be produced.

[0379] The viscosity of the anisotropic dye film composition of the present invention is not particularly limited as long as a uniform film without uneven thickness can be produced by the coating method described later. From the viewpoint of obtaining uniformity of thickness over a large area, productivity such as coating speed, and in-plane uniformity of optical properties, the viscosity is preferably 0.1 mPa·s or more, and preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and further preferably 50 mPa·s or less.

[0380] (Other additives)

[0381] The anisotropic dye film-forming composition of the present invention may further contain other additives such as polymerization inhibitors, polymerization aids, polymerizable non-liquid crystal compounds, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, organic / inorganic fillers, organic / inorganic nanosheets, organic / inorganic nanofibers, and metal oxides as needed. By including additives, the coating properties and stability of the anisotropic dye film-forming composition may be improved, and the stability of the anisotropic dye film formed from the anisotropic dye film-forming composition may be improved.

[0382] [Method for producing anisotropic dye film-forming composition]

[0383] The method for producing the anisotropic dye film composition of the present invention is not particularly limited. For example, the dye, polymerizable liquid crystal compound, solvent added as needed, other additives, etc. are mixed, stirred and shaken at 0 to 80° C. to dissolve the dye. In the case of poor solubility, a homogenizer, a bead mill disperser, etc. can be used.

[0384] The method for producing the composition for anisotropic dye films of the present invention may include a filtration step in order to remove foreign matter and the like in the composition.

[0385] The composition for forming an anisotropic dye film of the present invention may or may not be a liquid crystal at any temperature after the solvent is removed from the composition for forming an anisotropic dye film, but preferably exhibits liquid crystal properties at any temperature. From the viewpoint of the coating process described below, the composition after the solvent is removed from the composition for forming an anisotropic dye film preferably has an isotropic phase appearance temperature of less than 160°C, more preferably less than 140°C, further preferably less than 115°C, further preferably less than 110°C, and particularly preferably less than 105°C.

[0386] [Anisotropic pigment film]

[0387] The anisotropic dye film of the present invention is formed using the anisotropic dye film-forming composition of the present invention. Therefore, the anisotropic dye film of the present invention includes one or both of a polymerizable liquid crystal compound and a polymer having units based on the polymerizable liquid crystal compound, and a dye, and the dye includes a compound represented by formula (1).

[0388] The anisotropic pigment film of the present invention may contain non-polymerizable liquid crystal compounds, polymerization initiators, inhibitors, polymerization aids, polymerizable non-liquid crystal compounds, non-polymerizable non-liquid crystal compounds, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, organic / inorganic fillers, organic / inorganic nanosheets, organic / inorganic nanofibers, metal oxides, etc.

[0389] The anisotropic dye film of the present invention can be formed using the anisotropic dye film-forming composition of the present invention.

[0390] The anisotropic dye film in the present invention can function as a polarizing film that obtains linear polarized light, circular polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption. In addition, it can also function as various anisotropic dye films such as refractive anisotropy and conductive anisotropy by selecting the film formation process and the substrate and the composition containing the organic compound (pigment, transparent material).

[0391] When the anisotropic dye film of the present invention is used as a polarizing element for liquid crystal display applications and anti-reflection films for OLEDs, the orientation characteristics of the anisotropic dye film can be expressed using the dichroic ratio. When the dichroic ratio is 8 or more, it functions as a polarizing element, preferably 15 or more, more preferably 20 or more, further preferably 25 or more, particularly preferably 30 or more, and further preferably 40 or more. In addition, the higher the dichroic ratio, the better. By making the dichroic ratio above the above lower limit, it is useful as an optical element described later, especially a polarizing element.

[0392] When used as a polarizing element of an anti-reflection film for OLED, even if the performance of peripheral materials such as phase difference film is low, as long as the performance of the polarizing element is high, the characteristics of the anti-reflection film can be improved. Therefore, if the performance of the polarizing element is high, it is easy to simplify the layer structure, even if it is a thin film structure, it is easy to give full play to the function, and it can also be preferably used for the purpose of using deformation including bending and bending. In addition, the cost can also be suppressed to be relatively low.

[0393] The dichroic ratio (D) in the present invention is represented by the following formula when the dyes are uniformly oriented.

[0394] D=A z / A y

[0395] Among them, A z A is the absorbance observed when the polarization direction of light incident on the anisotropic dye film is parallel to the orientation direction of the anisotropic dye. y It is the absorbance observed when the polarization direction of light incident on the anisotropic dye film is perpendicular.

[0396] Each absorbance (A z , A y ) As long as the absorbance at the same wavelength is used, there is no particular limitation and any wavelength can be selected according to the purpose. In the case of expressing the degree of orientation of anisotropic pigment films, it is preferred to use a value corrected by the luminescence coefficient in a specific wavelength range of 380nm to 780nm of the anisotropic pigment film, or a value at the maximum absorption wavelength in the visible light range.

[0397] Furthermore, the transmittance of the anisotropic dye film of the present invention is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more at the target wavelength to be used. The upper limit of the transmittance may be determined according to the intended use.

[0398] When the anisotropic pigment film of the present invention is used as a pigment film having anisotropy in the entire visible light wavelength range, the transmittance of the anisotropic pigment film in the visible light wavelength range is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more. In addition, the upper limit of the transmittance can be adjusted according to the application. For example, in the case of increasing the degree of polarization, the transmittance is preferably 50% or less. By making the transmittance within the above range, it is useful as an optical element described later, especially as an optical element for liquid crystal display applications used for color display and an anti-reflection film composed of a combination of anisotropic pigment film and phase difference film.

[0399] The film thickness of the anisotropic dye film is preferably 10 nm or more, more preferably 100 nm or more, and further preferably 500 nm or more in terms of dry film thickness. On the other hand, it is preferably 30 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 3 μm or less. By making the film thickness of the anisotropic dye film within the above range, there is a tendency to obtain uniform orientation of the dye and uniform film thickness in the film.

[0400] [Method for producing anisotropic dye film]

[0401] The anisotropic dye film of the present invention is preferably produced by a wet film-forming method using the anisotropic dye film-forming composition of the present invention.

[0402] The wet film-forming method of the present invention refers to a method of coating an anisotropic dye film composition on a substrate by any method and orienting it. Therefore, the anisotropic dye film composition may or may not contain a solvent as long as it has fluidity. From the perspective of viscosity and film uniformity during coating, it is more preferable to contain a solvent.

[0403] The orientation of the liquid crystal and the pigment in the anisotropic dye film can be oriented by shearing during the coating process, or by the solvent drying process. In addition, it is also possible to heat after coating and drying, and orient and stack the liquid crystal, the pigment, etc. on the substrate through the process of reorienting the liquid crystal, the pigment, etc. In the wet film-forming method, when the anisotropic dye film composition is given on the substrate, in the anisotropic dye film composition, or in the process of solvent drying, or after the solvent is completely removed, the pigment and the liquid crystal compound have produced a small area orientation due to self-association (molecular association state such as liquid crystal state). By applying an external field to this state, it can be oriented in a certain direction in the macro region to obtain an anisotropic dye film with desired performance. In this regard, it is different from the method of dyeing and stretching a polyvinyl alcohol (PVA) film with a solution containing a pigment and only orienting the pigment through a stretching process as a principle. It should be noted that here, the external field can list the influence of the orientation treatment layer applied on the substrate in advance, shear force, magnetic field, electric field, heat, etc., which can be used alone or in combination. If necessary, it can also be heated.

[0404] The process of applying the anisotropic dye film composition to the substrate to form a film, the process of applying an external field to perform alignment, and the process of drying the solvent may be performed sequentially or simultaneously.

[0405] Examples of methods for applying the anisotropic dye film-forming composition to a substrate in a wet film-forming method include coating, dipping, LB film formation, and known printing methods. In addition, there is a method of transferring the anisotropic dye film thus obtained to another substrate.

[0406] Among these, it is preferred to apply the anisotropic dye film-forming composition to the substrate using a coating method.

[0407] The orientation direction of the anisotropic dye film may be different from the coating direction. It should be noted that in the present invention, the orientation direction of the anisotropic dye film refers to the transmission axis (polarization axis) or absorption axis of polarized light in the case of a polarizing film, and refers to the fast axis or slow axis in the case of a retardation film.

[0408] The method for applying the composition for anisotropic dye film to obtain an anisotropic dye film is not particularly limited, and examples thereof include the method described in pages 253 to 277 of "Coating Engineering" by Yuji Harasaki (Asakura Shoten Co., Ltd., published on March 20, 1971), the method described in pages 118 to 149 of "Creation and Application of Molecular Coordination Materials" edited by Kunihiro Ichimura (published by CMC Corporation, published on March 3, 1998), and a method of applying the composition to a substrate having a height difference structure (optionally subjected to a pre-alignment treatment) by slit die coating, spin coating, spray coating, rod coating, roll coating, blade coating, curtain coating, injection coating, dip coating, etc. Among them, the slit die coating method and the rod coating method are preferred because a highly uniform anisotropic dye film can be obtained.

[0409] The die coater used in the slot die coating method is generally equipped with a coating machine for ejecting a coating liquid, i.e., a so-called slot die head. For example, slot die heads are disclosed in Japanese Patent Laid-Open No. 2-164480, Japanese Patent Laid-Open No. 6-154687, Japanese Patent Laid-Open No. 9-131559, "Basics and Applications of Dispersion / Coating / Drying" (2014, Technosys, ISBN 9784924728707C305), "Wet Coating Technology for Displays / Optical Components" (2007, Information Agency (Information Agency), ISBN 9784901677752), "Precision Coating / Drying Technology in the Electronic Field" (2007, Technical Information Association (Technical Information Association), ISBN 9784861041389), etc. These known slot dies can apply coating even to flexible members such as films and tapes, and hard members such as glass substrates.

[0410] As the substrate used for forming the anisotropic dye film of the present invention, glass, triacetyl cellulose, acrylic acid, polyester, polyimide, polyetherimide, polyetheretherketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetyl cellulose or urethane film can be listed. In addition, for the surface of the substrate, in order to control the orientation direction of the dye, the known methods described in "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2001) pp. 226 to 239 (rubbing method, method of forming grooves (fine groove structure) on the surface of the alignment film, method using polarized ultraviolet light / polarized laser (photo-alignment method), alignment method based on LB film formation, alignment method based on oblique evaporation of inorganic substances, etc.) can be applied to the alignment treatment (alignment film). In particular, the alignment treatment based on the rubbing method and the photo-alignment method can be preferably cited. As the material used in the rubbing method, polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, acrylic resin, etc. can be listed. Materials used in the photo-alignment method include polycinnamate, polyamic acid / polyimide, azobenzene, etc. When an alignment treatment layer is provided, it is believed that the liquid crystal compound and the dye are aligned by the influence of the alignment treatment of the alignment treatment layer and the shear force applied to the anisotropic dye film composition during coating.

[0411] When applying the anisotropic dye film composition, the supply method and supply interval of the anisotropic dye film composition are not particularly limited. Sometimes the supply operation of the coating liquid becomes complicated, and the coating film thickness changes when the coating liquid is started and stopped. Therefore, when the film thickness of the anisotropic dye film is thin, it is desirable to apply the anisotropic dye film while continuously supplying the anisotropic dye film composition.

[0412] The speed of coating the anisotropic dye film composition is usually 0.001 m / min or more, preferably 0.01 m / min or more, more preferably 0.1 m / min or more, further preferably 1.0 m / min or more, and particularly preferably 5.0 m / min or more, and is usually 400 m / min or less, preferably 200 m / min or less, more preferably 100 m / min or less, and further preferably 50 m / min or less. By setting the coating speed within the above range, the anisotropy of the anisotropic dye film can be obtained, and there is a tendency that the coating can be uniformly applied.

[0413] The coating temperature of the anisotropic dye film composition is usually 0° C. or higher and 100° C. or lower, preferably 80° C. or lower, and more preferably 60° C. or lower.

[0414] The humidity during application of the anisotropic dye film composition is preferably 10% RH or more and preferably 80 RH% or less.

[0415] The anisotropic dye film may be subjected to an insolubilization treatment. Insolubilization refers to a treatment for improving the stability of the film by reducing the solubility of the compound in the anisotropic dye film and controlling the elution of the compound from the anisotropic dye film.

[0416] Specifically, from the viewpoint of easiness of post-processing, durability of the anisotropic dye film, etc., film polymerization, surface coating, etc. are preferred.

[0417] When polymerizing the film, the film in which the liquid crystal molecules and the dye molecules are aligned is polymerized using light, heat, and / or radiation.

[0418] When polymerization is performed using light or radiation, it is preferred to irradiate with active energy rays having a wavelength in the range of 190 to 450 nm.

[0419] The light source of the active energy line with a wavelength of 190 to 450 nm is not particularly limited, and examples thereof include: xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, fluorescent lamps and other lamp light sources; argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, semiconductor lasers and other laser light sources, etc. When used by irradiating light of a specific wavelength, a filter can also be used. The exposure amount of the active energy line is preferably 10 to 10,000 J / m 2 .

[0420] When the polymerization is performed using heat, it is preferably performed at a temperature in the range of 50 to 200°C, more preferably in the range of 60 to 150°C.

[0421] The polymerization can be carried out using light, heat and / or radiation, but photopolymerization or a combination of photopolymerization and thermal polymerization is preferably used from the viewpoint of shortening the film formation process time and simplifying the equipment.

[0422] [Optical components]

[0423] The optical element of the present invention includes the anisotropic dye film of the present invention.

[0424] The optical element in the present invention refers to a polarizing element that utilizes the anisotropy of light absorption to obtain linear polarized light, circular polarized light, elliptically polarized light, etc., a phase difference element, an element having functions such as refractive anisotropy and conductive anisotropy. These functions can be appropriately adjusted by selecting the anisotropic dye film formation process and the substrate and the composition containing the organic compound (dye, transparent material).

[0425] The optical element of the present invention is most preferably used as a polarizing element.

[0426] From the viewpoint that a polarizing element can be obtained by forming an anisotropic dye film on a substrate by coating or the like, the optical element of the present invention can also be preferably used for applications such as flexible displays.

[0427] In order to maintain or improve the function of the anisotropic pigment film, the optical element may be provided with other layers. Examples thereof include: a layer having a function of shielding a specific wavelength, a layer having a function of blocking a specific substance (barrier films such as oxygen barrier films and water vapor barrier films, etc.) used to improve durability such as light resistance, heat resistance, and water resistance; a wavelength cutoff filter used to change the color gamut and improve optical characteristics; and a layer containing a material that absorbs a specific wavelength.

[0428] [Polarizing element]

[0429] The polarizing element of the present invention may have any other film (layer) as long as it has the anisotropic dye film of the present invention. For example, it can be produced by providing an alignment film on a substrate and forming the anisotropic dye film of the present invention on the surface of the alignment film.

[0430] In addition, the polarizing element is not limited to the anisotropic dye film, and can also be used in combination with the following layers: a surface coating having functions of improving polarization performance, improving mechanical strength, etc.; an adhesive layer or an antireflection layer; an orientation film; a layer having optical functions such as a phase difference film, a brightness improvement film, a reflection or antireflection film, a semi-transmissive reflection film, and a diffusion film, etc. Specifically, the layers having the above-mentioned various functions can be laminated by coating and laminating, so as to form a laminated body for use.

[0431] These layers can be appropriately arranged according to the manufacturing process, characteristics and functions, and the position and order of the stacking are not particularly limited. For example, the positions of the layers can be formed on the anisotropic pigment film or on the opposite side of the substrate provided with the anisotropic pigment film. In addition, the order of forming the layers can be before the anisotropic pigment film is formed or after the anisotropic pigment film is formed.

[0432] The layers having these optical functions can be formed by the following various methods.

[0433] The layer having the function of a phase difference film can be formed by coating the phase difference film, laminating it to other layers constituting the polarizing element, etc. The phase difference film can be formed, for example, by performing a stretching treatment described in Japanese Patent Laid-Open No. 2-59703, Japanese Patent Laid-Open No. 4-230704, etc., or a treatment described in Japanese Patent Laid-Open No. 7-230007, etc.

[0434] The layer having the function of a brightness enhancement film can be formed by coating and laminating the brightness enhancement film to other layers constituting the polarizing element, etc. The brightness enhancement film can be formed, for example, by forming micropores using the method described in Japanese Patent Application Laid-Open No. 2002-169025 and Japanese Patent Application Laid-Open No. 2003-29030, or by stacking two or more cholesteric liquid crystal layers having different central wavelengths of selective reflection.

[0435] The layer having a function as a reflective film or a semi-transmissive reflective film can be formed by, for example, applying a metal thin film obtained by vapor deposition, sputtering, etc., and bonding it to other layers constituting the polarizing element.

[0436] The layer having a function as a diffusion film can be formed by, for example, applying a resin solution containing fine particles to other layers constituting the polarizing element.

[0437] The layer having the function of a phase difference film or an optical compensation film can be formed by applying a liquid crystal compound such as a discotic liquid crystal compound, a nematic liquid crystal compound, a smectic liquid crystal compound, or a cholesteric liquid crystal compound to other layers constituting the polarizing element and orienting them. In this case, an orientation film can also be provided on the substrate, and a phase difference film or an optical compensation film can be formed on the surface of the orientation film.

[0438] When the anisotropic dye film of the present invention is used as an anisotropic dye film in various display elements such as liquid crystal elements (LCDs) and organic electroluminescent elements (OLEDs), the anisotropic dye film of the present invention can be directly formed on the surface of an electrode substrate constituting these display elements, or the substrate on which the anisotropic dye film of the present invention is formed can be used as a structural member of these display elements.

[0439] Example

[0440] The present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples unless the scope of the invention exceeds the scope of the invention.

[0441] In the following description, "parts" means "parts by weight".

[0442] [Method for Identifying Liquid Crystal Phase]

[0443] The liquid crystal properties of the obtained anisotropic dye film-forming composition were observed by differential scanning calorimetry ("DSC220CU" manufactured by Seiko Instruments), X-ray structural analysis ("NANO-Viewer" manufactured by Rigaku), and a polarizing microscope ("ECLIPSE LV100N POL" manufactured by Nikon Instech) attached to a heating stage ("HCS302-LN190" manufactured by TOYO Corporation), and the liquid crystal was identified according to the method described in pages 9 to 50 and pages 117 to 176 of the "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2001).

[0444] [Measurement of transmittance of polarized light in the absorption axis / polarization axis direction of anisotropic dye film and dichroic ratio]

[0445] The transmittance of the obtained anisotropic dye film with respect to polarized light in the absorption axis / polarization axis direction was measured using a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., product name “RETS-100”) equipped with a Glan-Thompson polarizer.

[0446] Linearly polarized measurement light is made incident on the anisotropic dye film, and the transmittance of the anisotropic dye film for polarized light in the absorption axis direction and the transmittance of the anisotropic dye film for polarized light in the polarization axis direction are measured, and the dichroic ratio (D) is calculated by the following formula.

[0447] D=A z / A y

[0448] (Where,

[0449] A y = -log(T y );

[0450] A z = -log(T z );

[0451] T z is the transmittance of the anisotropic pigment film for polarized light in the absorption axis direction;

[0452] T y is the transmittance of the anisotropic pigment film for polarized light in the direction of the polarization axis. )

[0453] Specifically, the composition for anisotropic dye film was injected in an isotropic phase into a sandwich cell (cell gap: 8.0 μm, 10.0 μm, the formed polyimide film was previously rubbed with cloth) of an oriented film (LX1400, manufactured by HD MicroSystems) formed on glass as a substrate, and cooled to 80°C at 5°C / min to obtain an anisotropic dye film. The dichroic ratio was measured at each temperature while further cooling to 0°C at 5°C / min. The dichroic ratio at the temperature and wavelength showing the maximum dichroic ratio was determined as the dichroic ratio of the anisotropic dye film. In addition, in the measurement at this temperature, the dichroic ratio at the wavelength at which the absorbance at the orthogonal position (absorption axis direction) showed a maximum value in the anisotropic dye film (the dichroic ratio at the wavelength at which the absorbance in the film showed a maximum value) was also measured.

[0454] [Synthesis of polymerizable liquid crystal compounds]

[0455] <Liquid crystal compound (I-1)>

[0456] The liquid crystal compound (I-1) was synthesized according to a method based on the compound described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[0457] The structure was confirmed by NMR, and the results are shown below.

[0458] 1 H NMR (CDCl 3 , 400MHz) δ1.23-1.72 (m, 38H), 1.76-1.86 (m, 2H), 2.11-2.23 (m, 4H), 2.48-2.60 (m, 1H) ), 3.20-3.30 (m, 1H), 3.47 (t, 2H, J=6.8Hz), 4.04 (t, 2H, J=6.8Hz), 4.15 (t, 2H, J=6.8H z), 5.82 (d, 2H, J = 10.4Hz), 6.12 (dd, 2H, J = 10.4, 17.4Hz), 6.40 (d, 2H, J = 17.4Hz), 6.9 7(d, 2H, J=9.2Hz), 7.11 (d, 2H, J=9.2Hz), 7.21 (d, 2H, J=9.0Hz), 8.13 (d, 2H, J=9.0Hz)

[0459] [Chemical formula 29]

[0460]

[0461] <Liquid crystal compound (I-2)>

[0462] The liquid crystal compound (I-2) was synthesized according to the synthesis method described below.

[0463] [Chemical formula 30]

[0464]

[0465] Synthesis of (I-2-a):

[0466] To a solution of p-iodophenol (11.0 g, 50 mmol) in N,N-dimethylformamide (150 mL), ethyl propiolate (9.7 g, 99 mmol) and copper (I) oxide (7.5 g, 94 mmol) were added, stirred at 110 ° C for 9 hours, and cooled naturally to room temperature. After filtering and separating the precipitate, ethyl acetate was added, and washed with water and saturated brine in turn. Purification was performed by silica gel column chromatography (hexane / ethyl acetate) to obtain 7.3 g of brown crystals (I-2-a).

[0467] Synthesis of (I-2-b):

[0468] (I-2-a) (4.20 g, 22.1 mmol), 11-bromo-1-undecanol (5.55 g, 22.1 mmol), potassium carbonate (6.10 g, 44.2 mmol), N,N-dimethylformamide (30 mL) were mixed and stirred at 80°C for 4 hours. After filtering and separating the precipitate, ether was added, and the mixture was washed with water and saturated brine in sequence. Purification was performed by silica gel column chromatography (hexane / ethyl acetate) to obtain 5.5 g of an orange solid (I-2-b).

[0469] Synthesis of (I-2-c):

[0470] (I-2-b) (3.6 g, 10 mmol), potassium hydroxide (1.7 g, 30 mmol), and water (20 mL) were mixed and stirred at 100°C for 2 hours. Water (20 mL) was added, and the mixture was acidified with concentrated hydrochloric acid, and then the precipitate was separated by filtration. The precipitate was washed with acetonitrile to obtain 3.2 g of a milky white solid (I-2-c).

[0471] Synthesis of (I-2-d):

[0472] (I-2-c) (2.33 g, 7.0 mmol) and tetrahydrofuran (20 mL) were mixed, and then N, N-dimethylaniline (1.02 g, 8.4 mmol) and 2,5-di-tert-butylphenol (54 mg) were added. After cooling in an ice bath, acryloyl chloride (0.76 g, 8.4 mmol) was slowly added. After stirring for 6 hours in an ice bath, dichloromethane was added and washed in the order of 1 mol / L hydrochloric acid, saturated sodium bicarbonate water, and saturated brine. Purification was performed by silica gel column chromatography (chloroform / methanol) to obtain 2.0 g of a white solid (I-2-d).

[0473] Synthesis of (I-2-e):

[0474] (I-2-e) was synthesized by the synthesis method described in JP-A-2014-262884.

[0475] Synthesis of (I-2-f):

[0476] (I-2-d) (2.00 g, 5.17 mmol), (I-2-e) (1.01 g, 5.17 mmol), N, N-dimethylamino-4-pyridine (0.13 g, 1.03 mmol), 2,5-di-tert-butylphenol (58 mg), and dichloromethane (30 mL) were mixed, cooled in an ice bath, and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (1.09 g, 5.69 mmol) was added. After standing overnight, the mixture was washed with saturated aqueous ammonium chloride solution and saturated brine in turn. Purification was performed by silica gel column chromatography (hexane / ethyl acetate) to obtain 1.9 g of a white solid (I-2-f).

[0477] Synthesis of (I-2-g):

[0478] (I-2-f) (2.6 g, 4.62 mmol), pyridinium p-toluenesulfonate (0.23 g, 0.92 mmol), 2,5-di-tert-butylphenol (44 mg), and ethanol (20 mL) were mixed and stirred at 50° C. for 2 hours. The reaction solution was drained into water, and the precipitate was filtered out and dried to obtain 2.0 g of a white solid (I-2-g).

[0479] Synthesis of (I-2-h):

[0480] Compound (I-2-h) was synthesized according to the synthesis method described below.

[0481] [Chemical formula 31]

[0482]

[0483] Liquid crystal compound (I-2-i) was synthesized according to a method based on the compound described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[0484] Next, (I-2-i) (trans isomer only) (42.9 g, 107.6 mmol), p-toluenesulfonic acid pyridinium salt (2.6 g, 10.8 mmol), and ethanol (430 mL) were mixed and stirred at 78°C for 2 hours. The solvent was distilled off, dissolved in ethyl acetate (150 mL), hexane (750 mL) was added, and the mixture was cooled. The precipitate was separated by filtration, washed with hexane, and dried to obtain 29.2 g of a white solid (I-2-j).

[0485] Mix (I-2-j) (37.2 g, 118.3 mmol), N,N-dimethylaniline (21.5 g, 177.5 mmol), 2,5-di-tert-butylphenol (0.24 g), and tetrahydrofuran (380 mL). After cooling in an ice bath, slowly add acryloyl chloride (16.1 g, 177.5 mmol). After dropping, stir at 50 ° C for 2 hours, then distill to remove the solvent until the liquid volume reaches 190 mL, and discharge it into 1 mol / L hydrochloric acid under ice-cooling. The precipitate was separated by filtration and washed with water and hexane. Purification by silica gel column chromatography (hexane / ethyl acetate) gave 39.4 g of a white solid (I-2-h).

[0486] Synthesis of (I-2):

[0487] (I-2-g) (494 mg, 1.03 mmol), (I-2-h) (400 mg, 1.09 mmol), N, N-dimethylamino-4-pyridine (27 mg, 0.22 mmol), 2,5-di-tert-butylphenol (2 mg), dichloromethane (10 mL) were mixed, cooled in an ice bath, and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (230 mg, 1.19 mmol) was added. After stirring for 4 hours in an ice bath, it was washed with saturated ammonium chloride aqueous solution and saturated brine in sequence. Purification was performed by silica gel column chromatography (hexane / ethyl acetate) to obtain 530 mg of liquid crystal compound (I-2) as a white solid.

[0488] The results of liquid chromatography-mass spectrometry analysis of this compound are shown below.

[0489] LC-MS (APCI) m / z 851.5 (M+Na + )

[0490] In addition, the structure was confirmed by NMR, and the results are shown below.

[0491] 1 H NMR (CDCl 3 , 400MHz) δ1.20-1.70 (m, 38H), 1.74-1.85 (m, 2H), 2.05-2.25 (m, 4H), 2.49-2.57 (m, 1H ), 3.21-3.29 (m, 1H), 3.46 (t, 2H, J=6.8Hz), 3.99 (t, 2H, J=6.8Hz), 4.15 (t, 4H, J=6.8H z), 5.80 (d, 2H, J = 10.4Hz), 6.12 (dd, 2H, J = 17.2, 10.4Hz), 6.39 (d, 2H, J = 17.2Hz), 6.8 9 (d, 2H, J = 6.8Hz), 7.10 (d, 2H, J = 6.8Hz), 7.19 (d, 2H, J = 6.8Hz), 7.55 (d, 2H, J = 6.8Hz)

[0492] For the liquid crystal compound (I-1) and the liquid crystal compound (I-2), the isotropic phase appearance temperature (phase transition temperature from liquid crystal to liquid and phase transition temperature from liquid to liquid crystal) was determined by differential scanning calorimetry. It should be noted that in the differential scanning calorimetry, 0.2 parts by weight of 4-methoxyphenol as a polymerization inhibitor was added to 100 parts by weight of the liquid crystal compound.

[0493] The results are shown in Table 1.

[0494] It should be noted that polarizing microscope observation and X-ray structural analysis confirmed that this temperature is the isotropic phase appearance temperature.

[0495] Table 1

[0496] Liquid crystal compounds I-1 I-2 Phase transition temperature from liquid crystal to liquid (℃) 111.0 103.1 Phase transition temperature from liquid to liquid crystal (℃) 109.4 101.9

[0497] [Synthesis of polymerizable liquid crystal compounds]

[0498] <Liquid crystal compound (I-3)>

[0499] The liquid crystal compound (I-3) was synthesized according to the synthesis method described below.

[0500] [Chemical formula 32]

[0501]

[0502] Synthesis of (I-3-a):

[0503] Liquid crystal compound (I-3-a) was synthesized according to a method based on the compound described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[0504] Synthesis of (I-3-b):

[0505] 4-iodophenol (3.62g, 16.5mmol), (I-3-a) (6.43g, 16.1mmol), N, N-dimethylamino-4-pyridine (0.39g, 3.20mmol), dichloromethane (80mL) were mixed, cooled in an ice bath, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) (3.39g, 17.7mmol) was added, and stirred for 5 minutes. Then, it was stirred at room temperature for 2 hours, and washed with saturated ammonium chloride aqueous solution and saturated brine in sequence. The solution was concentrated and purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 8.49g of a white solid (I-3-b).

[0506] Synthesis of (I-3-c):

[0507] After adding (I-3-b) (5.00 g, 8.33 mmol) to diisopropylamine (70 mL) and dissolving it completely, dichlorobis(triphenylphosphine)palladium (II) (58 mg, 0.08 mmol) and copper (I) iodide (48 mg, 0.25 mmol) were mixed, and trimethylsilyl acetylene (0.98 g, 9.99 mmol) was added. After stirring at room temperature for 30 minutes, the mixture was extracted with water-ethyl acetate and washed with saturated brine. The solution was concentrated and purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 4.30 g of a white solid (I-3-c).

[0508] Synthesis of (I-3-d):

[0509] (I-3-c) (4.30 g, 7.53 mmol) and chloroform (100 mL) were mixed, cooled in an ice bath, and tetrabutylammonium fluoride (TBAF) tetrahydrofuran solution (1 mol / L, 9 mL) was added. After stirring for 20 minutes, the mixture was extracted with water-chloroform and washed with saturated brine. The solution was concentrated and purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 3.80 g of a white solid (I-3-d).

[0510] Synthesis of (I-3-e):

[0511] (I-3-b) (3.56 g, 5.93 mmol), tetrakistriphenylphosphine palladium (0) (68 mg, 0.06 mmol), copper (I) iodide (34 mg, 0.18 mmol), diisopropylamine (120 mL) were mixed, cooled in an ice bath, and a diisopropylamine (40 mL) solution of (I-3-d) (2.96 g, 5.93 mmol) was added. After stirring at room temperature for 1 hour, the mixture was extracted with water-chloroform and washed with saturated brine. The solution was concentrated and purified by silica gel column chromatography (chloroform) to obtain a white solid (I-3-e).

[0512] Synthesis of (I-3-f):

[0513] The (I-3-e) obtained by the above operation and tetrahydrofuran (60 mL) were mixed, and after being completely dissolved at 50°C, ethanol (60 mL) was added. Pyridinium p-toluenesulfonate (PPTS) (0.54 g, 2.13 mmol) was added to the slurry solution, heated at 60°C for 2 hours, and then left overnight. The next day, it was heated to 60°C again to completely dissolve, and the reaction solution was added to ice water. Extracted with chloroform, the solution was concentrated, and the obtained solid was washed with hexane to obtain 4.02 g of a white solid (I-3-f).

[0514] Synthesis of (I-3):

[0515] (I-3-f) (4.00 g, 4.98 mmol), acrylic acid (0.72 g, 9.96 mmol, N,N-dimethyl-4-aminopyridine (0.12 g, 0.10 mmol), and dichloromethane (100 mL) were mixed and cooled in an ice bath, and then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (2.10 g, 11.0 mmol) was added. After stirring for 2 hours, acrylic acid (0.36 g, 4.98 mmol) and EDC (1.05 g, 5.5 mmol) were added, and acrylic acid (0.36 g, 4.98 mmol) and EDC (1.05 g, 5.5 mmol) were further added 18 hours later, and the mixture was stirred for 5 hours. The reaction solution was washed with a saturated aqueous ammonium chloride solution and a saturated saline solution in sequence, and purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 2.30 g of a white solid (I-3).

[0516] The structure was confirmed by NMR, and the results are shown below.

[0517] 1H NMR (CDCl3, 400MHz) δ7.52 (d, 4H, J = 8.8Hz), 7.06 (d, 4H, J = 8.8Hz), 6.40 (d, 2H, J = 17.2Hz), 6.12 (dd, 2H, J = 10.4, 17.2Hz), 5.81 (d, 2H, J = 10.4Hz) ), 4.15 (t, 4H, J = 6.8Hz), 3.46 (t, 4H, J = 9.2Hz), 3.30-3.20 (m, 2H), 2.60 -2.45(m, 2H), 2.22-2.10(m, 8H), 1.70-1.50(m, 8H), 1.45-1.25(m, 36H)

[0518] The fact that the compound (I-3) exhibits liquid crystallinity was confirmed by observing birefringence at 70° C. using a polarizing microscope attached to a heating stage using 0.2 parts by weight of 4-methoxyphenol as a polymerization inhibitor added to 100 parts by weight of the liquid crystal compound.

[0519] [Synthesis of pigments]

[0520] <Pigment (II-1)>

[0521] The pigment (II-1) was synthesized according to the synthesis method described below.

[0522] [Chemical formula 33]

[0523]

[0524] Synthesis of (II-1-a):

[0525] Tetrahydrofuran (100 mL) and sodium hydride (purity 60%, 6.7 g, 168.0 mmol) were added to the ice-cooled reactor, and a mixture of diethyl (4-nitrobenzyl)phosphonate (18.0 g, 65.9 mmol), 4-butylbenzaldehyde (9.1 g, 56.1 mmol) and tetrahydrofuran (50 mL) was added dropwise over 10 minutes, washed with tetrahydrofuran (30 mL), and stirred at 50°C for 0.5 hours. The reaction solution was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was dissolved in ethyl acetate (20 mL) by heating, and hexane (50 mL) was added to cool, and the precipitate was separated by filtration, washed with hexane, and dried under reduced pressure to obtain 15.0 g of (II-1-a).

[0526] Synthesis of (II-1-b):

[0527] (II-1-a) (15.0 g, 53.3 mmol), tetrahydrofuran (150 mL), iron powder (13.9 g, 248.9 mmol) were mixed, and ammonium chloride (13.3 g, 248.6 mmol) dissolved in water (30 mL) was added dropwise, and stirred at 50 ° C for 3 hours. Filtered using diatomaceous earth, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was suspended in hexane, the precipitate was separated by filtration, washed with hexane and dried to obtain (II-1-b) 10.9 g.

[0528] Synthesis of (II-1):

[0529] Mix (II-1-b) (2.51 g, 10.0 mmol), N-methylpyrrolidone (40 mL), concentrated hydrochloric acid (2.2 mL), and water (20 mL), cool to 3°C, add sodium nitrite (789 mg, 11.4 mmol), and stir at 15°C for 3.5 hours.

[0530] 1-Phenylpyrrolidine (1.47 g, 10.0 mmol), methanol (60 mL), and water (30 mL) were mixed and the pH was adjusted to 3.5 with concentrated hydrochloric acid. A sodium hydroxide aqueous solution was added, and the above-mentioned diazonium salt-containing liquid was added dropwise while maintaining the pH at 3-5, followed by stirring at 15°C for 3 hours.

[0531] The obtained precipitate was filtered, washed with water, and dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / dichloromethane) to obtain 3.06 g of a red solid (II-2).

[0532] The maximum absorption wavelength (λ max ) is 459nm, and the gram absorption coefficient is 107.6Lg -1 cm -1 .

[0533] In addition, the structure was confirmed by NMR, and the results are shown below.

[0534] 1 H-NMR (CDCl 3,400MHz)δ0.94(t,3H,J=7.2Hz),1.32-1.43(m,2H),1.55-1.68(m,2H),2 .00-2.12(m, 4H), 2.62(t, 2H, J=7.6Hz), 3.41(t, 4H, J=6.4Hz), 6.63(d, 2H , J=8.8Hz), 7.14 (d, 2H, J=8.8Hz), 7.19 (d, 2H, J=8.0Hz), 7.45 (d, 2H, J=8 .0Hz), 7.60 (d, 2H, J = 8.4Hz), 7.84 (d, 2H, J = 8.4Hz), 7.88 (d, 2H, J = 9.2Hz)

[0535] The solubility of the compound in cyclopentanone was determined.

[0536] In cyclopentanone 97mg, add pigment (II-1) 3mg, stirred 5 minutes at 80 ℃.Then, at room temperature leave standstill 1 hour, use the syringe that possesses syringe filter (Membrane Solutions company system, PTFE13045, caliber 0.45 μ m) to filter the mixed solution that obtains, obtained the cyclopentanone saturated solution of pigment (II-1) thus.Dilute this solution with tetrahydrofuran (THF) 800mg, use HPLC (Hitachi High-Tech company system L-2300 series) to determine concentration.Make pigment (II-1) 0.1 % by weight to be dissolved in the solution that tetrahydrofuran (THF) obtains, made calibration curve under absorption wavelength 254nm.Use this calibration curve to measure the concentration of cyclopentanone saturated solution, the result is 1.0%.

[0537] <Pigment (II-2)>

[0538] The pigment (II-2) was synthesized according to the synthesis method described below.

[0539] [Chemical formula 34]

[0540]

[0541] Synthesis of (II-2):

[0542] A mixture of (II-1-b) (1.26 g, 5.0 mmol), N-methylpyrrolidone (20 mL), concentrated hydrochloric acid (1.1 mL) and water (20 mL) was cooled to 3°C, sodium nitrite (380 mg, 5.5 mmol) was added, and the mixture was stirred at 15°C for 3.5 hours.

[0543] N,N-diethylaniline (751 mg, 5.0 mmol), methanol (40 mL), and water (20 mL) were mixed and the pH was adjusted to 3.5 with concentrated hydrochloric acid. A sodium hydroxide aqueous solution was added, and the above diazonium salt liquid was added dropwise while maintaining the pH at 3-6, followed by stirring at 15°C for 1 hour.

[0544] The obtained precipitate was filtered, washed with water, and dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / dichloromethane) to obtain 1.15 g of a red solid (II-2).

[0545] The maximum absorption wavelength (λ max ) is 458nm, and the gram absorption coefficient is 105.7Lg -1 cm -1 .

[0546] In addition, the structure was confirmed by NMR, and the results are shown below.

[0547] 1 H-NMR (CDCl 3 ,400MHz) δ0.96 (t, 3H, J=7.2Hz), 1.24 (t, 6H, J=7.2Hz), 1.33-1.44 (m, 2H) , 1.57-1.67 (m, 2H), 2.64 (t, 2H, J=7.2Hz), 3.47 (q, 4H, J=7.2Hz), 6.74 (d, 2H, J=9.2Hz), 7.15 (d, 2H, J=8.0Hz), 7.20 (d, 2H, J=8.0Hz), 7.47 (d, 2H, J= 8.0Hz), 7.61 (d, 2H, J=8.8Hz), 7.85 (d, 2H, J=8.0Hz), 7.88 (d, 2H, J=8.8Hz)

[0548] The solubility of this compound in cyclopentanone was measured by the same method as that of the dye (II-1) (detection absorption wavelength: 254 nm) and found to be 3.0% or more.

[0549] <Pigment (II-3)>

[0550] The pigment (II-3) was synthesized according to the synthesis method described below.

[0551] [Chemical formula 35]

[0552]

[0553] Synthesis of (II-3-a):

[0554] Tetrahydrofuran (200 mL) and sodium hydroxide (purity 60%, 10.1 g, 252.6 mmol) were added to an ice-cooled reactor, and a mixture of diethyl (4-nitrobenzyl)phosphonate (23.0 g, 84.2 mmol), 4-heptyloxybenzaldehyde (18.6 g, 84.2 mmol) and tetrahydrofuran (200 mL) was added dropwise over 10 minutes. The mixture was washed with tetrahydrofuran (30 mL) and stirred at 50°C for 2 hours. The reaction solution was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was dissolved in ethyl acetate (35 mL) by heating, and hexane (80 mL) was added to cool the mixture. The precipitate was separated by filtration, washed with hexane, and dried under reduced pressure to obtain 23.1 g of (II-3-a).

[0555] Synthesis of (II-3-b):

[0556] (II-3-a) (23.1 g, 68.1 mmol), tetrahydrofuran (200 mL), iron powder (19.0 g, 340.5 mmol) were mixed, and ammonium chloride (18.2 g, 340.5 mmol) dissolved in water (50 mL) was added dropwise, and stirred at 50 ° C for 5 hours. Filtered using diatomaceous earth, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. After purifying the obtained crude product by silica gel column chromatography (hexane / ethyl acetate), it was suspended in hexane, the precipitate was filtered out, and washed with hexane. Drying under reduced pressure gave 10.7 g of (II-3-b).

[0557] Synthesis of (II-3):

[0558] A mixture of (II-3-b) (1.6 g, 5.0 mmol), N-methylpyrrolidone (20 mL), concentrated hydrochloric acid (1.1 mL) and water (20 mL) was cooled to 3°C, sodium nitrite (380 mg, 5.5 mmol) was added, and stirred at 15°C for 5 hours.

[0559] N,N-diethylaniline (751 mg, 5.0 mmol), methanol (40 mL), and water (20 mL) were mixed and the pH was adjusted to 3.5 with concentrated hydrochloric acid. A sodium hydroxide aqueous solution was added, and the above-mentioned diazonium salt-containing liquid was added dropwise while maintaining the pH at 7, followed by stirring at 15°C for 1 hour.

[0560] The obtained precipitate was filtered, washed with water, and dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / dichloromethane) to obtain 152 mg of an orange solid (II-2).

[0561] The maximum absorption wavelength (λmax ) is 459nm, and the gram absorption coefficient is 96.4Lg -1 cm -1 .

[0562] In addition, the structure was confirmed by NMR, and the results are shown below.

[0563] 1 H-NMR (CDCl 3 ,400MHz) δ0.90 (t, 3H, J=7.0Hz), 1.30 (t, 6H, J=7.0Hz), 1.28-1.41 (m, 6H), 1.4 2-1.52 (m, 2H), 1.74-1.86 (m, 2H), 3.45 (q, 4H, J=7.2Hz), 3.98 (t, 2H, J=6.6Hz) , 6.73 (d, 2H, J = 9.6Hz), 6.90 (d, 2H, J = 8.8Hz), 7.01 (d, 1H, J = 16.4Hz), 7.13 (d, 1H, J=16.4Hz), 7.46 (d, 2H, J=8.8Hz), 7.58 (d, 2H, J=8.4Hz), 7.80-7.87 (m, 4H)

[0564] The solubility of this compound in cyclopentanone was measured by the same method as that of the dye (II-1) (detection absorption wavelength: 254 nm) and found to be 3.0% or more.

[0565] <Pigment (II-4)>

[0566] The pigment (II-4) was synthesized according to the synthesis method described below.

[0567] [Chemical formula 36]

[0568]

[0569] Synthesis of (II-4):

[0570] (II-1-b) (1.0 g, 4.0 mmol) and N-methylpyrrolidone (13 mL) were mixed, concentrated hydrochloric acid (1.0 g, 10.0 mmol) was added, and after cooling in an ice bath, sodium nitrite (0.3 g, 4.4 mmol) dissolved in water (1.3 mL) was added and stirred for 1 hour. The reaction solution was coupled with 1-phenylpiperidine (0.6 g, 4.0 mmol) dissolved in methanol (25 mL) and water (6.5 mL) at pH = 7, and the precipitate was separated by filtration, washed with water, and dried under reduced pressure. The crude product was purified by silica gel column chromatography (hexane / dichloromethane) to obtain 760 mg of an orange solid (II-4).

[0571] The maximum absorption wavelength (λ max ) is 431nm, and the gram absorption coefficient is 94.3Lg -1 cm -1 .

[0572] In addition, the structure was confirmed by NMR, and the results are shown below.

[0573] 1 H-NMR (CDCl 3 , 400MHz) δ0.94 (t, 3H, J=7.4Hz), 1.30-1.44 (m, 2H), 1.57-1.75 (m, 8H), 2.62 (t, 2H, J=8.0Hz), 3.37 (t, 4H, J=5. 2Hz), 6.96 (d, 2H, J=9.2Hz), 7.13-7.20 (m, 4H), 7.45 (d, 2H, J=8.0Hz), 7.60 (d, 2H, J=8.4Hz), 7.84-7.87 (m, 4H)

[0574] The solubility of this compound in cyclopentanone was measured by the same method as that of the dye (II-1) (detection absorption wavelength: 254 nm) and the result was 2.4%.

[0575] <Pigment (II-5)>

[0576] The pigment (II-5) was synthesized according to the method described in Color Materials, 73, 221-226 (2000).

[0577] [Chemical formula 37]

[0578]

[0579] The maximum absorption wavelength (λ max ) is 459nm, and the gram absorption coefficient is 52.6Lg -1 cm -1 .

[0580] In addition, the structure was confirmed by NMR, and the results are shown below.

[0581] 1 H-NMR (CDCl 3,400MHz) δ0.98 (t, 3H, J=7.2Hz), 1.16 (t, 6H, J=7.2Hz), 1.39-1.45 (m, 2H), 1.67-1 .71 (m, 2H), 2.74 (t, 2H, J=7.6Hz), 3.38 (q, 4H, J=7.2Hz), 7.20 (d, 1H, J=8.4Hz), 7.3 7(d, 2H, J=8.4Hz), 7.57-7.61(m, 1H), 7.65-7.70(m, 1H), 7.90-7.95(m, 3H), 8.10( d, 2H, J=8.8Hz), 8.17 (d, 2H, J=8.8Hz), 8.31 (d, 1H, J=8.4Hz), 9.05 (d, 1H, J=8.0Hz)

[0582] The solubility of this compound in cyclopentanone was measured by the same method as that of the dye (II-1) (detection absorption wavelength: 254 nm) and found to be 2.2%.

[0583] The chemical structures of the liquid crystal compound and the pigment synthesized above are shown below. 11 H 22 It means a linearly bonded methylene chain of 11 members.

[0584] [Chemical formula 38]

[0585]

[0586] [Chemical formula 39]

[0587]

[0588] [Chemical formula 40]

[0589]

[0590] [Chemical formula 41]

[0591]

[0592] [Chemical formula 42]

[0593]

[0594] [Chemical formula 43]

[0595]

[0596] [Chemical formula 44]

[0597]

[0598] [Chemical formula 45]

[0599]

[0600] [Chemical formula 46]

[0601]

[0602] [Chemical formula 47]

[0603]

[0604] The solubility of the dye (III-1) in cyclopentanone was measured by the same method as that of the dye (II-1) (detection absorption wavelength: 254 nm) and the result was 0.7%.

[0605] The solubility of the dye (III-2) in cyclopentanone was measured by the same method as that of the dye (II-1) (detection absorption wavelength: 254 nm) and the result was 0.8%.

[0606] Example 1

[0607] 20.00 parts of the liquid crystal compound (I-1) and 0.40 parts of the dye (II-1) were added to 399.6 parts of chloroform, stirred and dissolved, and then the solvent was removed to obtain an anisotropic dye film-forming composition 1.

[0608] The fact that the anisotropic dye film-forming composition 1 exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0609] In order to determine the dichroic ratio by the above method using the obtained anisotropic dye film-forming composition 1 , an anisotropic dye film 1 was produced using sandwich cells having a cell gap of 8.0 μm, and the dichroic ratio of the anisotropic dye film 1 was determined.

[0610] The results are shown in Table 2.

[0611] Example 2

[0612] An anisotropic dye film-forming composition 2 and an anisotropic dye film 2 were obtained in the same manner as in Example 1 except that 0.30 parts of the dye (II-2) was used instead of 0.40 parts of the dye (II-1).

[0613] The fact that the anisotropic dye film-forming composition 2 showed liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0614] Regarding anisotropic pigment film 2 , the dichroic ratio of anisotropic pigment film 2 was determined.

[0615] The results are shown in Table 2.

[0616] Example 3

[0617] Anisotropic dye film-forming composition 3 and anisotropic dye film 3 were obtained in the same manner as in Example 1 except that 0.30 parts of dye (II-3) was used instead of 0.40 parts of dye (II-1).

[0618] The fact that the anisotropic dye film-forming composition 3 showed liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0619] Regarding anisotropic dye film 3 , the dichroic ratio of anisotropic dye film 3 was determined.

[0620] The results are shown in Table 2.

[0621] Example 4

[0622] Anisotropic dye film-forming composition 4 and anisotropic dye film 4 were obtained in the same manner as in Example 1 except that 20.00 parts of liquid crystal compound (I-2) was used instead of 20.00 parts of liquid crystal compound (I-1) and 0.28 parts of dye (II-1) was used instead of 0.40 parts of dye (II-1).

[0623] The fact that the anisotropic dye film-forming composition 4 showed liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0624] Regarding anisotropic dye film 4 , the dichroic ratio of anisotropic dye film 4 was determined.

[0625] The results are shown in Table 2.

[0626] Example 5

[0627] An anisotropic dye film-forming composition 5 and an anisotropic dye film 5 were obtained in the same manner as in Example 1, except that 20.00 parts of the liquid crystal compound (I-2) was used instead of 20.00 parts of the liquid crystal compound (I-1), 0.32 parts of the dye (II-4) was used instead of 0.40 parts of the dye (II-1), and a sandwich unit with a cell gap of 10.0 μm was used instead of a sandwich unit with a cell gap of 8.0 μm.

[0628] The fact that the anisotropic dye film-forming composition 5 showed liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0629] Regarding anisotropic dye film 5 , the dichroic ratio of anisotropic dye film 5 was determined.

[0630] The results are shown in Table 2.

[0631] Comparative Example 1

[0632] Anisotropic dye film-forming composition 7 and anisotropic dye film 7 were obtained in the same manner as in Example 1 except that 0.2 parts of dye (II-5) was used instead of 0.40 parts of dye (II-1).

[0633] The fact that the anisotropic dye film-forming composition 7 showed liquid crystallinity was confirmed by observing birefringence at 60° C. using a polarizing microscope attached to a heating stage.

[0634] Regarding anisotropic dye film 7 , the dichroic ratio of anisotropic dye film 7 was confirmed.

[0635] The results are shown in Table 2.

[0636] [Table 2]

[0637]

[0638] Example 6

[0639] To 399.6 parts of chloroform were added 34.28 parts of the liquid crystal compound (I-2), 0.34 parts of an azo dye of the formula (III-1) (manufactured by Hayashibara Co., Ltd.), 0.84 parts of an azo dye of the formula (III-2) (manufactured by Showa Chemical Industry Co., Ltd.), 0.28 parts of an azo dye of the formula (II-1), and 0.21 parts of an azo dye of the formula (II-4), and the mixture was stirred to dissolve, and then the solvent was removed to obtain an anisotropic dye film-forming composition 8.

[0640] The fact that the anisotropic dye film-forming composition 8 showed liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0641] In order to determine the dichroic ratio by the above method using the obtained anisotropic dye film-forming composition 8 , an anisotropic dye film 8 was produced and the dichroic ratio of the anisotropic dye film 8 was determined.

[0642] The maximum dichroic ratio of the anisotropic dye film 8 was 48.7 at 40° C. and a wavelength of 675 nm. The dichroic ratio at a wavelength of 495 nm, where the absorbance of the azo dye of formula (II-1) showed a maximum value in the liquid crystal compound (I-2), was 31.7.

[0643] Example 7

[0644] To 717.9 parts of cyclopentanone were added 243.6 parts of the liquid crystal compound (I-2), 4.35 parts of the azo dye of the formula (II-1), 5.58 parts of IRGACURE (registered trademark) 369 (product of BASF), and 3.62 parts of BYK-361N (manufactured by BYK-Chemie), and after heating and stirring at 80°C, filtration was performed using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, caliber 0.45 μm), thereby obtaining a composition 9 for anisotropic dye film.

[0645] The anisotropic dye film composition 9 was formed into a film by spin coating on a substrate having an alignment film of polyimide formed on glass (LX1400, manufactured by HD MicroSystems, an alignment film formed by a rubbing method), and dried by heating at 120° C., cooled to a liquid crystal phase, and exposed to light at an exposure dose of 500 mj / cm 2 (365 nm standard) was polymerized to obtain anisotropic dye film 9. When the obtained anisotropic dye film 9 was placed on a commercially available polarizing plate and rotated, it showed changes in brightness and darkness, and it was confirmed that it had good performance that could be used as a polarizing film.

[0646] Example 8

[0647] 19.65 parts of the liquid crystal compound (I-2), 0.06 parts of an azo dye of the formula (III-1) (manufactured by Hayashibara Co., Ltd.), 0.15 parts of an azo dye of the formula (III-2) (manufactured by Showa Chemical Industry Co., Ltd.), and 0.05 parts of the dye (II-2) were added to 2615.7 parts of chloroform, stirred to dissolve them, and then the solvent was removed to obtain an anisotropic dye film-forming composition 10.

[0648] The fact that the anisotropic dye film-forming composition 10 exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0649] In order to determine the dichroic ratio by the above method using the obtained anisotropic dye film-forming composition 10 , an anisotropic dye film 10 was produced and the dichroic ratio of the anisotropic dye film 10 was determined.

[0650] The maximum dichroic ratio of the anisotropic dye film 10 was 31.0 at 40° C. and a wavelength of 595 nm. The dichroic ratio at a wavelength of 485 nm, where the absorbance of the dye (II-2) showed a maximum value in the liquid crystal compound (I-2), was 20.4.

[0651] Example 9

[0652] 20.00 parts of the liquid crystal compound (I-2), 0.18 parts of an azo dye of the formula (III-2) (manufactured by Showa Chemical Industry Co., Ltd.), and 0.14 parts of the dye (II-1) were added to 79.67 parts of chloroform, stirred and dissolved, and then the solvent was removed to obtain an anisotropic dye film-forming composition 11.

[0653] The fact that the anisotropic dye film-forming composition 11 exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0654] In order to determine the dichroic ratio by the above method using the obtained anisotropic dye film-forming composition 11 , an anisotropic dye film 11 was produced and the dichroic ratio of the anisotropic dye film 11 was determined.

[0655] The maximum dichroic ratio of the anisotropic dye film 11 was 34.2 at 40° C. and a wavelength of 515 nm. The dichroic ratio at a wavelength of 470 nm, where the absorbance of the dye (II-1) showed a maximum value in the liquid crystal compound (I-2), was 28.7.

[0656] Example 10

[0657] An anisotropic dye film-forming composition 12 and an anisotropic dye film 12 were obtained in the same manner as in Example 9 except that 20.00 parts of the liquid crystal compound (I-3) was used instead of 20.00 parts of the liquid crystal compound (I-1).

[0658] The fact that the anisotropic dye film-forming composition 12 exhibited liquid crystallinity was confirmed by observing birefringence at 70° C. using a polarizing microscope attached to a heating stage.

[0659] In order to determine the dichroic ratio by the above method using the obtained anisotropic dye film-forming composition 12 , an anisotropic dye film 12 was produced and the dichroic ratio of the anisotropic dye film 12 was determined.

[0660] The maximum dichroic ratio of the anisotropic dye film 12 was 28.8 at 70° C. and a wavelength of 515 nm. The dichroic ratio at a wavelength of 470 nm, where the absorbance of the dye (II-1) showed a maximum value in the liquid crystal compound (I-3), was 25.5.

[0661] Comparative Example 2

[0662] An anisotropic dye film-forming composition 13 was obtained in the same manner as in Example 1 except that 0.2 parts of the dye (II-6) was used instead of 0.40 parts of the dye (II-1).

[0663] The solubility of the dye (II-6) in cyclopentanone was measured by the same method as that of the dye (II-1) (detection absorption wavelength: 254 nm) and the result was 0.0%.

[0664] The precipitate of the anisotropic dye film-forming composition 13 was observed at 60° C. using a polarizing microscope attached to a heating stage. It is believed that since the solubility of the dye (II-6) was low, it was difficult to exhibit a sufficient dichroic ratio when an anisotropic dye film was formed from the anisotropic dye film-forming composition 13.

[0665] [Chemical formula 48]

[0666]

[0667] Comparative Example 3

[0668] 20.00 parts of the liquid crystal compound (I-2), 0.18 parts of the azo dye of the formula (III-2) (manufactured by Showa Chemical Industry Co., Ltd.), and 0.15 parts of the dye (II-5) were added to 79.66 parts of chloroform, stirred to dissolve, and then the solvent was removed to obtain an anisotropic dye film-forming composition 14.

[0669] The fact that the anisotropic dye film-forming composition 14 exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0670] In order to determine the dichroic ratio by the above method using the obtained anisotropic dye film-forming composition 14 , an anisotropic dye film 14 was produced and the dichroic ratio of the anisotropic dye film 14 was determined.

[0671] The maximum dichroic ratio of the anisotropic dye film 14 is 6.6 at 40° C. and a wavelength of 485 nm. The dichroic ratio of the dye (II-5) at a wavelength of 465 nm, where the absorbance shows a maximum value among the liquid crystal compounds (I-2), is 6.6.

[0672] Comparative Example 4

[0673] An anisotropic dye film-forming composition 15 and an anisotropic dye film 15 were obtained in the same manner as in Example 10 except that 0.17 parts of the dye (II-5) was used instead of 0.17 parts of the dye (II-1).

[0674] The fact that the anisotropic dye film-forming composition 15 exhibited liquid crystallinity was confirmed by observing birefringence at 70° C. using a polarizing microscope attached to a heating stage.

[0675] In order to determine the dichroic ratio by the above method using the obtained anisotropic dye film-forming composition 15 , an anisotropic dye film 15 was produced and the dichroic ratio of the anisotropic dye film 15 was determined.

[0676] The maximum dichroic ratio of the anisotropic dye film 15 was 4.3 at 70° C. and a wavelength of 485 nm. The dichroic ratio at a wavelength of 465 nm, where the absorbance of the dye (II-5) showed a maximum value among the liquid crystal compounds (I-3), was 3.5.

[0677] Table 3 shows the results of Examples 6, 8 to 10 and Comparative Examples 3 to 4.

[0678] [Table 3]

[0679]

[0680] Industrial Applicability

[0681] The anisotropic dye film-forming composition of the present invention can achieve excellent optical performance, particularly a sufficient dichroic ratio, and can particularly achieve a sufficient dichroic ratio in a wavelength range of 430 nm to 550 nm.

[0682] The anisotropic dye film of the present invention is formed using the anisotropic dye film-forming composition of the present invention, and therefore can achieve excellent optical performance, in particular, a sufficient dichroic ratio.

[0683] The optical element of the present invention includes the anisotropic dye film of the present invention and can therefore achieve excellent optical performance, in particular, a sufficient dichroic ratio.

Claims

1. A composition for forming an anisotropic dye film, comprising a dye and a polymerizable liquid crystal compound, The pigment comprises a compound represented by formula (1), A 1 -CH=CH-A 2 -(N=N-A 3 ) n -X···(1) In the formula, A 1 represents a phenyl group optionally having a substituent, the substituent excluding a sulfo group; A 2 and A 3 each independently represents a phenylene group optionally having a substituent, the substituent excluding a sulfo group; X represents a monovalent organic group; n represents 1, 2, or 3.

2. A composition for forming an anisotropic dye film, comprising a dye and a polymerizable liquid crystal compound, The pigment comprises a compound represented by formula (1), A 1 -CH=CH-A 2 -(N=N-A 3 ) n -X···(1) In the formula, A 1 represents a phenyl group optionally having a substituent, the substituent does not include a sulfo group, and the substituent allowed by the phenyl group is -R A OR A , R A Each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms; A 2 represents a phenylene group optionally having a substituent, the substituent excluding a sulfo group; A 3 represents a 1,4-phenylene group having no substituent; X represents a monovalent organic group; n represents 1, 2, or 3.

3. A composition for forming an anisotropic dye film, comprising a dye and a polymerizable liquid crystal compound, The pigment comprises a compound represented by formula (1), A 1 -CH=CH-A 2 -(N=N-A 3 ) n -X···(1) In the formula, A 1 represents a phenyl group optionally having a substituent, the substituent does not include a sulfo group, and the substituent allowed by the phenyl group is -R A OR A , R A Each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms; A 2 and A 3 Each independently represents an unsubstituted 1,4-phenylene group; X is -N(-R y )-R x , R x and R y are each independently an optionally branched alkyl group having 1 to 3 carbon atoms, or, R x and R y Taken together, they represent an alkylene group having 2 to 6 carbon atoms which may have a branch; n represents 1, 2, or 3.

4. The anisotropic dye film-forming composition according to claim 1, wherein n is 1.

5. The anisotropic dye film-forming composition according to claim 2, wherein n is 1.

6. The anisotropic dye film-forming composition according to claim 3, wherein n is 1.

7. The anisotropic dye film-forming composition according to claim 1 or 4, wherein X is -O-(R x ) or -N(-R x )-R y ; R x and R y Each independently represents an optionally branched alkyl group having 1 to 15 carbon atoms or an aryl group having 5 to 14 atoms constituting a ring; R x and R y Optionally, they are combined to represent an alkylene group having 2 to 15 carbon atoms which may have a branch; The optionally branched alkyl group having 1 to 15 carbon atoms and the aryl group having 5 to 14 ring atoms each optionally have a substituent; One or more methylene groups contained in the optionally branched alkylene group having 2 to 15 carbon atoms are optionally substituted by an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, -CF2-, -CHCl-, or -CCl2-; The amine nitrogen atom is -NH- or -N(R z )-; R z It represents a linear or branched alkyl group having 1 to 6 carbon atoms. 8 . The anisotropic dye film-forming composition according to claim 1 , wherein The number of ring structures (r n1 ) and the number of ring structures (r n2 ) ratio (r n1 / r n2 ) is 0.7~1.

5. 9 . The anisotropic dye film-forming composition according to claim 1 , wherein The polymerizable liquid crystal compound is a compound having a carbon-carbon triple bond. 10 . The anisotropic dye film-forming composition according to claim 1 , further comprising a polymerization initiator. 11 . The anisotropic dye film-forming composition according to claim 1 , wherein The pigment further contains one or more compounds whose absorption curve in the wavelength range of 380 nm to 780 nm shows a maximum wavelength longer than the wavelength at which the compound represented by the formula (1) shows a maximum wavelength in the absorption curve in the wavelength range of 380 nm to 780 nm. 12 . An anisotropic dye film formed using the anisotropic dye film-forming composition according to claim 1 . 13 . An optical element comprising the anisotropic pigment film according to claim 12 .

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