Compound, composition, anisotropic dye film, and optical element

Abstract

A compound represented by formula (1). (In formula (1),-XA represents a monovalent organic group. -RA1 and-RA2 each independently represent an alkyl group having or not having a substituent. -RA1 and-RA2 may be integrated to form a ring, but the-RA1 and-RA2 moieties of the ring formed by-RA1 and-RA2 are formed solely from a hydrocarbon chain. -A1-,-A2-,-A3-, and-A4-each independently represents a 1, 4-phenylene group having or not having a substituent group. And n represents 0, 1 or 2. When n is 2, the plurality of-A3-may be the same as or different from each other. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a compound and a composition useful for a polarizing film or the like provided in a display element such as a light-adjusting element, a liquid crystal element (LCD), or an organic electroluminescent element (OLED), and also to an anisotropic dye film and an optical element using the composition. Background Art

[0002] 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.

[0003] Conventionally, as such a polarizing film, for example, a polarizing film obtained by dyeing polyvinyl alcohol (PVA) with low-concentration iodine (iodine-PVA polarizing film) is known (Patent Document 1).

[0004] However, 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.

[0005] On the other hand, it is also known that an anisotropic dye film formed by applying a liquid crystal composition containing a dye functions as a polarizing film (Patent Document 2).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 1-105204

[0009] Patent Document 2: Japanese Patent Application Publication No. 2013-210624 Summary of the invention

[0010] Problems to be solved by the invention

[0011] When an anisotropic dye film is used as a polarizing element, it is important for the anisotropic dye film to have excellent optical properties, particularly a good dichroic ratio, and light resistance, and development of an anisotropic dye film having high optical properties and light resistance is desired.

[0012] An object of the present invention is to provide a compound and a composition in which the obtained anisotropic dye film exhibits a high dichroic ratio and is excellent in light resistance, an anisotropic dye film obtained from the composition, and an optical element including the anisotropic dye film.

[0013] Means for solving problems

[0014] The present inventors have found that a compound having a specific structure can solve the above-mentioned problems.

[0015] The first aspect of the present invention has the following aspects.

[0016] [1-1] A compound represented by the following formula (1).

[0017] [Chemistry 1]

[0018]

[0019] (In formula (1),

[0020] -XA represents a monovalent organic group.

[0021] -RA 1 and-RA 2 Each independently represents an alkyl group which may have a substituent. 1 and-RA 2 Optionally, they can be combined to form a ring, but -RA 1 and-RA 2 The formed ring -RA 1 and-RA 2 Some are formed only by hydrocarbon chains.

[0022] -A 1 -、-A 2 -、-A 3 -and-A 4 - each independently represents a 1,4-phenylene group which may have a substituent.

[0023] n represents 0, 1, or 2.

[0024] When n is 2, multiple -A 3 - can be the same or different from each other. )

[0025] [1-2] The compound according to [1-1], wherein -XA in the above formula (1) is a hydrogen atom, -Ra, -O-Ra, -NH-Ra, -C(=O)-Ra, -C(=O)-O-Ra, -C(=O)-NH-Ra, -C(=O)-N(-Rb)-Ra, -OC(=O)-Ra, -NH-C(=O)-Ra, -N(-Rb)-C(=O)-Ra, or -S-Ra (-Ra and -Rb each independently represent an alkyl group having 1 to 15 carbon atoms which may or may not have a branch, a cycloalkyl group having 5 to 14 atoms constituting the ring, or an aryl group having 5 to 14 atoms constituting the ring, and the above alkyl group, cycloalkyl group and aryl group may or may not have a substituent. In addition, -Ra and -Rb may be combined to form a ring having 2 to 15 carbon atoms, and the ring may or may not have a substituent).

[0026] [1-3] The compound according to [1-1] or [1-2], wherein -RA in the above formula (1) 1 and-RA 2 Each is independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.

[0027] [1-4] A composition comprising a compound represented by the following formula (2) and a polymerizable liquid crystal compound.

[0028] [Chemistry 2]

[0029]

[0030] (In formula (2),

[0031] -XB represents a monovalent organic group.

[0032] -RB 1 and-RB 2 Each independently represents an alkyl group which may have a substituent. 1 and-RB 2 They may be integrated to form a ring.

[0033] -B 1 -and-B 2 - each independently represents a 1,4-phenylene group which may have a substituent.

[0034] -B 3 -and-B 4 - each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent.

[0035] n represents 0, 1, or 2.

[0036] When n is 2, multiple -B 3 - can be the same or different from each other. )

[0037] [1-5] The composition according to [1-4], wherein -B in the above formula (2) 4 - is 1,4-phenylene which may have a substituent.

[0038] [1-6] The composition according to [1-4] or [1-5], wherein -B in the above formula (2) 3 - is 1,4-phenylene which may have a substituent.

[0039] [1-7] The composition according to any one of [1-4] to [1-6], wherein -XB in the above formula (2) is a hydrogen atom, -Ra, -O-Ra, -NH-Ra, -C(=O)-Ra, -C(=O)-O-Ra, -C(=O)-NH-Ra, -C(=O)-N(-Rb)-Ra, -OC(=O)-Ra, -NH-C(=O)-Ra, -N(-Rb)-C(=O)-Ra, or -S-Ra (-Ra and -Rb each independently represent an alkyl group having 1 to 15 carbon atoms which may or may not have a branch, a cycloalkyl group having 5 to 14 atoms constituting the ring, or an aryl group having 5 to 14 atoms constituting the ring, and the above alkyl group, cycloalkyl group and aryl group may or may not have a substituent. In addition, -Ra and -Rb may be combined to form a ring having 2 to 15 carbon atoms, and the ring may or may not have a substituent).

[0040] [1-8] The composition according to any one of [1-4] to [1-7], wherein -RB in the above formula (2) 1 and-RB 2 Each is independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.

[0041] [1-9] An anisotropic dye film formed using the composition according to any one of [1-4] to [1-8].

[0042] [1-10] An optical element comprising the anisotropic dye film described in [1-9].

[0043] The present inventors have found that a composition containing a polymerizable liquid crystal compound and a dye showing a specific maximum absorption wavelength characteristic can solve the above-mentioned problems.

[0044] The second aspect of the present invention has the following aspects.

[0045] [2-1] A composition comprising a polymerizable liquid crystal compound and a pigment, wherein:

[0046] The maximum absorption wavelength of the above-mentioned pigment satisfies the following relational expression (11).

[0047] λ max2 -λ max1 <0 (11)

[0048] (In formula (11), λ max1 represents the maximum absorption wavelength of the above-mentioned pigment in the solvent, λ max2 It represents the maximum absorption wavelength of the above-mentioned pigment in the pigment film formed using the above-mentioned composition.

[0049] [2-2] The composition according to [2-1], wherein the pigment is an azo pigment.

[0050] [2-3] The composition according to [2-2], wherein the pigment is a compound represented by the following formula (12).

[0051] X 20 (-A 21 ) m1 (-N=NA 22 ) n1 -N=NA 23 -Y 20 (12)

[0052] (In formula (12),

[0053] -A 21 -、-A 22 -、-A 23 - each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocyclic ring which may have a substituent,

[0054] -X 20 , -Y 20 Each independently represents a monovalent arbitrary substituent,

[0055] m1 means 1 or 2,

[0056] n1 represents 0, 1, 2, or 3.

[0057] When m1 is 2, -A 21 - can be the same or different from each other.

[0058] When n1 is 2 or 3, -A 22 - can be the same or different from each other. )

[0059] [2-4] The composition according to [2-3], wherein in the above formula (12), -A 21 -、-A 23 - are each independently a divalent group of an aromatic hydrocarbon ring which may have a substituent.

[0060] [2-5] The composition according to [2-3] or [2-4], wherein in the above formula (12), -A 22 - is a divalent group of an aromatic hydrocarbon ring which may have a substituent.

[0061] [2-6] The composition according to any one of [2-3] to [2-5], wherein in the above formula (12), -Y 20 It is represented by the following formula (12a).

[0062] -N-(R y )-R x (12a)

[0063] (In formula (12a), -R x , -R y Each independently represents an alkyl group or an aryl group which may or may not have a branch, and the alkyl group or the aryl group may or may not have a substituent. x and -R y They may be combined with N to form a ring having 2 to 15 carbon atoms, and the ring may have a substituent.

[0064] [2-7] The composition according to any one of [2-1] to [2-6], wherein the polymerizable liquid crystal compound is a low-molecular polymerizable liquid crystal compound having no copolymer structure.

[0065] [2-8] An anisotropic dye film formed using the composition according to any one of [2-1] to [2-7].

[0066] [2-9] An optical element comprising the anisotropic dye film described in [2-8].

[0067] Effects of the Invention

[0068] According to the compound and composition of the present invention, an anisotropic dye film having a high dichroic ratio and excellent light resistance can be provided. DETAILED DESCRIPTION

[0069] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof.

[0070] Hereinafter, the "first invention" and the "second invention" are collectively referred to as the "present invention".

[0071] 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 of two directions orthogonal to each other in any plane, the thickness direction of the anisotropic pigment film and any in-plane direction. Examples of the electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance.

[0072] Examples of films having optical anisotropy such as absorption and refraction include polarizing films such as linear polarizing films and circular polarizing films, phase difference films, and conductive anisotropic dye films. The anisotropic dye film using the compound of the present invention and the composition of the present invention is preferably used as a polarizing film or a conductive anisotropic dye film, and more preferably as a polarizing film.

[0073] 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 (350 nm to 800 nm).

[0074] As the pigment that can use in the present invention, can enumerate dichroic pigment.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, pigment can be the pigment with liquid crystallinity, also can not have liquid crystallinity.It should be noted that having liquid crystallinity refers to showing liquid crystal phase at any temperature.

[0075] [Compound of the First Invention]

[0076] The compound of the first invention is a compound represented by the following formula (1) (hereinafter sometimes referred to as "compound (1)").

[0077] [Chemistry 3]

[0078]

[0079] (In formula (1),

[0080] -XA represents a monovalent organic group.

[0081] -RA 1 and-RA 2 Each independently represents an alkyl group which may have a substituent. 1 and-RA 2 Optionally, they can be combined to form a ring, but -RA 1 and-RA 2 The formed ring -RA 1 and-RA 2 Some are formed only by hydrocarbon chains.

[0082] -A 1 -、-A 2 -、-A 3 -and-A 4 - each independently represents a 1,4-phenylene group which may have a substituent.

[0083] n represents 0, 1, or 2.

[0084] When n is 2, multiple -A 3 - can be the same or different from each other. )

[0085] <Relationship between the structure and effect of compound (1)>

[0086] The details of the mechanism by which the compound (1) exerts the effect of the first invention are not clear, but are presumed as follows.

[0087] By including the compound (1) having a specific structure represented by formula (1) as a dye, the dye association state in the anisotropic dye film is optimized, and an anisotropic dye film having excellent optical properties such as dichroic ratio and high light resistance when used as a polarizing element can be obtained.

[0088] <-XA>

[0089] -XA represents a monovalent organic group.

[0090] Preferred organic groups for -XA include hydrogen atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups, carbamoyl groups, -Ra, -O-Ra, -NH-Ra, -C(=O)-Ra, -C(=O)-O-Ra, -C(=O)-NH-Ra, -C(=O)-N(-Rb)-Ra, -OC(=O)-Ra, -NH-C(=O)-Ra, -N(-Rb)-C(=O)-Ra, or -S-Ra (-Ra and -Rb each independently represent an alkyl group having 1 to 15 carbon atoms which may be branched, a cycloalkyl group having 5 to 14 atoms constituting the ring, or an aryl group having 5 to 14 atoms constituting the ring, and the above alkyl group, cycloalkyl group and aryl group may each have a substituent. -Ra and -Rb may be combined to form a ring having 2 to 15 carbon atoms, and the ring may have a substituent).

[0091] As the monovalent organic group in -XA, from the viewpoint of making the molecular orientation with the polymerizable liquid crystal compound good, it is preferred not to have the polymerizable group described below. On the other hand, as the monovalent organic group in -XA, from the viewpoint of improving the mechanical strength of the anisotropic dye film, it is preferred to have the polymerizable group described below.

[0092] The branched or unbranched alkyl group having 1 to 15 carbon atoms, the cycloalkyl group having 5 to 14 ring atoms, and the aryl group having 5 to 14 ring atoms in -Ra and -Rb may have a substituent.

[0093] In addition, one or more methylene groups contained in an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 5 to 14 atoms constituting the ring, or a ring formed by combining -Ra and -Rb may be replaced by -O-, -S-, -NH-, -N(R z )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -、-CHCl-、-CCl 2 -substituted (displaced) structure, and may be substituted with a polymerizable group of acryloyloxy, methacryloyloxy, or glycidyloxy.z It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0094] Permissible substituents for the branched or unbranched alkyl group having 1 to 15 carbon atoms in -Ra and -Rb include -OH, -OR f 、-OC(=O)-R f 、-NH 2 、-NH-R f 、-N(-R g )-R f , -C(=O)-R f 、-C(=O)-OR f 、-C(=O)-NH 2 , -C(=O)-NH-R f 、-C(=O)-N(-R g )-R f , -SH, -SR f , sulfamoyl, carboxyl, cyano, nitro, halogen, etc. Here, -R f and -R g Each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.

[0095] One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms may be replaced by -O-, -S-, -NH-, -N(R h )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -、-CHCl-、-CCl 2 -substituted (displaced) structure, and may also be substituted with a polymerizable group of acryloyloxy, methacryloyloxy, or glycidyloxy. h It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0096] Among these, as the permissible substituent for the branched or unbranched alkyl group having 1 to 15 carbon atoms in -Ra and -Rb, -OR f Examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, acryloyloxy, methacryloyloxy and glycidyloxy.

[0097] Permissible substituents for the cycloalkyl group or aryl group having 5 to 14 ring atoms in -Ra and -Rb include -R i 、-OH、-OR i、-OC(=O)-R i 、-NH 2 、-NH-R i 、-N(-R j )-R i , -C(=O)-R i 、-C(=O)-OR i 、-C(=O)-NH 2 , -C(=O)-NH-R i 、-C(=O)-N(-R j )-R i , -SH, -SR i , trifluoromethyl, sulfamoyl, carboxyl, cyano, nitro, halogen. -R i and -R j Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.

[0098] Among these, as the permissible substituents for the cycloalkyl group or aryl group having 5 to 14 ring atoms in -Ra and -Rb, -R i 、-OR i , for example, 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, 5,5-dimethyl-3-methylhexyloxy and the like.

[0099] Examples of the cycloalkane ring of the cycloalkyl group having 5 to 14 atoms constituting the ring of -Ra and -Rb include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, camphane ring, adamantane ring, tetralin ring, bicyclo[2.2.2]octane ring and the like.

[0100] Examples of the aryl group having 5 to 14 atoms constituting the ring of -Ra and -Rb include monovalent groups of aromatic hydrocarbon rings or aromatic heterocycles.

[0101] Examples of the aromatic hydrocarbon ring of the monovalent group 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.

[0102] Examples of the aromatic heterocyclic ring as a monovalent group 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, a thiazole ring, an isothiazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furofuran ring, a furatothiazole ring, a thienofuran ring, a thienothiazole ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, and an azulene ring.

[0103] -Ra and -Rb are preferably an alkyl group having 1 to 15 carbon atoms which may or may not have a branch, or -Ra and -Rb are combined to form a ring having 2 to 15 carbon atoms which may or may not have a substituent. Furthermore, -Ra and -Rb are more preferably an alkyl group having 1 to 9 carbon atoms which may or may not have a branch, or -Ra and -Rb are combined to form a ring having 2 to 10 carbon atoms; further preferably, an alkyl group having 1 to 5 carbon atoms which may or may not have a branch, or -Ra and -Rb are combined to form a ring having 2 to 6 carbon atoms; particularly preferably, an alkyl group having 1 to 3 carbon atoms which may not have a branch, or -Ra and -Rb are combined to form a ring having 2 to 6 carbon atoms. By adopting the above-mentioned embodiment, the molecular orientation of compound (1) tends to be good.

[0104] -XA is preferably -Ra, -O-Ra, or -C(=O)-O-Ra, more preferably -Ra or -O-Ra, and further preferably -Ra.

[0105] <-RA 1 and-RA 2 >

[0106] -RA 1 and-RA 2 Each independently represents an alkyl group which may have a substituent. 1 and-RA 2 Optionally, they can be combined to form a ring, but -RA 1 and-RA 2 The formed ring -RA 1 and-RA 2 Some are formed only by hydrocarbon chains.

[0107] -RA 1 and-RA 2 The alkyl group of the alkyl group which may or may not have a substituent may be linear or branched, and the groups exemplified as -Ra and -Rb may be mentioned, and the preferred groups are also the same. When having a substituent, a fluorine atom is preferred.

[0108] -RA 1 and-RA 2 When they are integrated to form a ring, the number of carbon atoms in the ring is preferably 3 to 8, more preferably 4 to 5.

[0109] AS-RA 1 and-RA 2 Alkyl or -RA 1 and-RA 2 As the substituent which the ring formed by integrating them may have, there may be mentioned the substituents exemplified as the substituent which -Ra and -Rb may have.

[0110] AS-RA 1 and-RA 2 From the viewpoint of molecular orientation, an alkyl group having 1 to 10 carbon atoms which may be substituted is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is further preferred.

[0111] As -N(-RA 1 )RA 2 , specifically, dimethylamino, diethylamino, dipropylamino, dibutylamino, ethylmethylamino, methylpropylamino, methylbutylamino, ethylpropylamino, ethylbutyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl or the above-mentioned groups with fluorine atoms can be cited as preferred groups. Among them, diethylamino, isopropyl (methyl) amino, ethyl (isopropyl) amino, pyrrolidinyl, piperidinyl or the above-mentioned groups with fluorine atoms are more preferred. Among the above-mentioned groups with fluorine atoms, di (fluoroethyl) amino, di (fluoropropyl) amino, fluoroethyl (isopropyl) amino, ethyl (fluoroisopropyl) amino are more preferred.

[0112] By adopting the above embodiment, the molecular orientation of the compound (1) tends to be improved.

[0113] <-A 1 -、-A 2 -、-A 3 -and-A 4 ->

[0114] -A 1 -、-A 2 -、-A 3 -and-A 4 - each independently represents a 1,4-phenylene group which may have a substituent.

[0115] -A 1 -、-A 2 -、-A 3 -and-A4 When the 1,4-phenylene group of - has a substituent, examples of the substituent 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. Here, -R A and -R B Each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms. A and -R B The number of carbon atoms is preferably 1 to 12, and more preferably 1 to 9, from the viewpoint of achieving good molecular alignment with the polymerizable liquid crystal compound used in the first invention.

[0116] The one or more methylene groups contained in the linear or branched alkyl group may be replaced by etheric oxygen atoms, thioetheric sulfur atoms, amine nitrogen atoms (-NH-, -N(R z )-: Here, R z represents a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms), a carbonyl group, an ester bond, an amide bond, -CHF-, -CF 2 -、-CHCl-、-CCl 2 The structure formed by - substitution may be substituted by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group or a glycidyloxy group.

[0117] Among these, the permissible substituents for 1,4-phenylene are preferably -R A 、-OR A , trifluoromethyl, fluoro. A Examples of the substituent include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 5,5-dimethyl-3-methylhexyl, etc. The presence of the substituent tends to improve the molecular orientation of the dye of the compound (1).

[0118] Since the absorption transition moment of compound (1) tends to be consistent with the long axis direction of the compound, the dichroic ratio can be improved. 1 -、-A 2 -、-A 3 -and-A 4 - are preferably 1,4-phenylene groups having no substituent.

[0119] (n)

[0120] n represents 0, 1, or 2.

[0121] n is preferably 0 or 1, more preferably 1. In the above embodiment, the molecular orientation of the compound (1) tends to be good.

[0122] When n is 2, each -A 3 -Can be the same or different.

[0123] (-N=N-)

[0124] From the viewpoint of improving the linearity of the compound (1), -N=N- in the formula (1) is preferably a trans form.

[0125] (Molecular weight of compound (1))

[0126] The molecular weight of the compound (1) 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 compound (1) is preferably 300 to 1500, more preferably 350 to 1200, and further preferably 380 to 1000. By being within the above range, the molecular length and volume are appropriately obtained, and thus the molecular orientation as a pigment tends to be good.

[0127] (Specific example of compound (1))

[0128] Specific examples of the compound (1) include the following compounds, but are not limited to these.

[0129] [Chemistry 4]

[0130]

[0131] [Chemistry 5]

[0132]

[0133] [Chemistry 6]

[0134]

[0135] (Method for producing compound (1))

[0136] Compound (1) can be produced by combining known chemical reactions such as alkylation reaction, esterification reaction, amidation reaction, etherification reaction, in-situ substitution reaction, diazotization coupling reaction, coupling reaction using a metal catalyst, and the like.

[0137] For example, compound (1) can be synthesized by the method described in the examples described below, "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).

[0138] [Composition of the first invention]

[0139] The composition of the first invention is a composition containing a compound represented by the following formula (2) (hereinafter sometimes referred to as "compound (2)") and a polymerizable liquid crystal compound.

[0140] [Chemistry 7]

[0141]

[0142] (In formula (2),

[0143] -XB represents a monovalent organic group.

[0144] -RB 1 and-RB 2 Each independently represents an alkyl group which may have a substituent. 1 and-RB 2 They may be integrated to form a ring.

[0145] -B 1 -and-B 2 - each independently represents a 1,4-phenylene group which may have a substituent.

[0146] -B 3 -and-B 4 - each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent.

[0147] n represents 0, 1, or 2.

[0148] When n is 2, multiple -B 3 - can be the same or different from each other. )

[0149] The composition of the first invention may be a solution, a liquid crystal, or a dispersed state as long as it does not phase separate. As the composition for forming an anisotropic dye film, a solution is preferred from the viewpoint of easy application to the substrate. On the other hand, from the viewpoint of orientation on the substrate as described later, the solid component obtained by removing the solvent from the composition for forming anisotropic dye film is preferably in a liquid crystal phase at any temperature.

[0150] In the present invention, the state of liquid crystal phase specifically refers to a liquid crystal state that exhibits properties of both liquid and crystal or intermediate properties as described on pages 1 to 16 of "Fundamentals and Applications of Liquid Crystals" (written by Masakazu Matsumoto and Ichiyoshi Kakuda in 1991), and refers to a nematic phase, a smectic phase, a cholesteric phase, or a discotic phase.

[0151] <Compound (2)>

[0152] The composition of the first invention contains compound (2) as a pigment. By containing compound (2) having a specific structure represented by the above formula (2) as a pigment, it is presumed that the pigment association state in the anisotropic pigment film is optimized, and an anisotropic pigment film having excellent optical properties such as dichroic ratio when used as a polarizing element and high light resistance can be obtained.

[0153] The composition of the first invention may contain only one compound (2) or two or more compounds (2).

[0154] (-XB)

[0155] -XB represents a monovalent organic group, and examples of -XB include the same groups as -XA in the above formula (1), and preferred groups are also the same.

[0156] (-RB 1 and-RB 2 )

[0157] -RB 1 and-RB 2 Each independently represents an alkyl group which may have a substituent, -RB 1 and-RB 2 They may be integrated to form a ring.

[0158] AS-RB 1 and-RB 2 , which can be exemplified by -RA in the above formula (1) 1 and-RA 2 The same groups are preferred.

[0159] (-B 1 -and-B 2 -)

[0160] -B 1 -and-B 2 - each independently represents a 1,4-phenylene group which may have a substituent, and examples of the substituent which the 1,4-phenylene group may have include -A in formula (1): 1 -、-A 2 -、-A 3 -and-A 4 The substituents exemplified as the substituents which the 1,4-phenylene group may have are also the same as the preferred substituents.

[0161] For the same reason as in compound (1), as -B 1 -and-B 2 -, preferably 1,4-phenylene having no substituent.

[0162] (-B 3 -and-B 4 -)

[0163] -B 3 -and-B 4 - each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent.

[0164] Examples of the aromatic hydrocarbon ring of the divalent group of the aromatic hydrocarbon ring which may have a substituent 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.

[0165] As the divalent group of the aromatic hydrocarbon ring, since the absorption transition moment of the compound (2) tends to coincide with the long axis direction of the pigment and the dichroic ratio can be improved, the divalent group of the benzene ring (phenylene) and the divalent group of the naphthalene ring (naphthylene) are preferred, and the divalent group of the benzene ring (phenylene) is more preferred. In particular, as the divalent group of the aromatic hydrocarbon ring, 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene are more preferred, 1,4-phenylene is further preferred, and 1,4-phenylene without a substituent is particularly preferred. By adopting the above-mentioned mode, the absorption transition moment of the compound (2) tends to coincide with the long axis direction of the compound and the dichroic ratio can be improved.

[0166] Permissible substituents for the divalent aromatic hydrocarbon ring include -A 1 -、-A 2 -、-A 3 -and-A 4 The substituents exemplified as the substituents which the 1,4-phenylene group may have are also the same as the preferred substituents.

[0167] (n)

[0168] n represents 0, 1, or 2.

[0169] n is preferably 0 or 1, more preferably 1. In this embodiment, the molecular orientation of the compound (2) tends to be good.

[0170] When n is 2, each -B 3 -Can be the same or different.

[0171] (-N=N-)

[0172] From the viewpoint of improving the linearity of the compound (2), -N=N- in the formula (2) is preferably a trans form.

[0173] (Preferred examples of compound (2))

[0174] Preferred examples of the compound (2) include the above-mentioned compound (1).

[0175] (Specific example of compound (2))

[0176] Specific examples of the compound (2) include the following compounds in addition to the specific examples of the compound (1) described above, but are not limited to these.

[0177] [Chemistry 8]

[0178]

[0179] [Chemistry 9]

[0180]

[0181] [Composition of the Second Invention]

[0182] The composition of the second invention contains a dye having a maximum absorption wavelength satisfying the following relational expression (11) (hereinafter, sometimes referred to as "the dye of the second invention") and a polymerizable liquid crystal compound.

[0183] The composition of the second invention may contain only one kind of the dye of the second invention, or may contain two or more kinds.

[0184] λ max2 -λ max1 <0 (11)

[0185] (In formula (11), λ max1 represents the maximum absorption wavelength of the above-mentioned pigment in the solvent, λ max2 It represents the maximum absorption wavelength of the above-mentioned pigment in the pigment film formed using the above-mentioned composition.

[0186] The composition of the second invention may be a solution, a liquid crystal, or a dispersed state as long as it does not phase separate. As the composition for forming an anisotropic dye film, from the viewpoint of easy coating on the substrate, a solution is preferred. On the other hand, from the viewpoint of orientation on the substrate as described later, the solid component obtained by removing the solvent from the composition for forming anisotropic dye film is preferably in a state of liquid crystal phase at any temperature.

[0187] In the present invention, the state of liquid crystal phase specifically refers to a liquid crystal state that exhibits properties of both liquid and crystal or intermediate properties as described on pages 1 to 16 of "Fundamentals and Applications of Liquid Crystals" (written by Masakazu Matsumoto and Ichiyoshi Kakuda in 1991), and refers to a nematic phase, a smectic phase, a cholesteric phase, or a discotic phase.

[0188] <The maximum absorption wavelength of the pigment λ max1 and the maximum absorption wavelength λ max2 Relationship with effect>

[0189] It is presumed that the composition of the second invention contains a pigment satisfying the above relational expression (11), that is, contains a maximum absorption wavelength λ of the pigment in the solvent. max1 The maximum absorption wavelength λ of the pigment in the pigment film formed using the composition of the second invention max2 Satisfy λ max2 -λ max1 <0, the dye association state in the obtained anisotropic dye film is optimized, and an anisotropic dye film having excellent optical properties such as dichroic ratio when used as a polarizing element and high light resistance can be obtained.

[0190] The pigment of the second invention satisfies λ max2 -λ max1 <0, i.e. λ max2 Less than λ max1 That is, for λ max1 With λ max2 The difference in is not particularly limited. From the viewpoint of optical properties such as the dichroic ratio and light resistance of the anisotropic dye film formed, the dye of the second invention preferably satisfies the following relational expression (11A).

[0191] In addition, since the optical performance such as dichroic ratio tends to be better, λ max1 and λ max2 It is more preferable to satisfy the following relational expression (11B), and it is even more preferable to satisfy the following relational expression (11C).

[0192] λ max2 -λ max1 ≤-1(11A)

[0193] λmax2 -λ max1 ≤-10(11B)

[0194] λ max2 -λ max1 ≤-20(11C)

[0195] The maximum absorption wavelength of the measured pigment is max1 The solvent is not particularly limited, as long as it is a solvent in which the pigment is dissolved to form a uniform solution. In the case of a pigment dissolved in chloroform, chloroform is used as a solvent, and the maximum absorption wavelength λ of the pigment is measured for a solution in which the pigment of the second invention is dissolved at a concentration of about 3ppm to 30ppm. max1 , that is, the wavelength λ at which the absorbance of the pigment becomes maximum max1 .

[0196] The maximum absorption wavelength λ of the pigment in the pigment film max2 The wavelength λ at which the orthogonal absorbance of the pigment in the pigment membrane reaches a maximum max2 .

[0197] In the second invention, the maximum absorption wavelength λ max1 , max2 Specifically, it is measured by a spectrophotometer.

[0198] The maximum absorption wavelength λ of the dye of the second invention max1 , max2 The values ​​of are not particularly limited as long as they satisfy the above relational expression (11). The maximum absorption wavelength λ of the pigment of the second invention is max1 The wavelength is preferably in the range of 380 nm to 800 nm, more preferably in the range of 400 nm to 750 nm, and even more preferably in the range of 410 nm to 700 nm.

[0199] The maximum absorption wavelength λ of the dye of the second invention is max2 The wavelength is preferably in the range of 350 nm to 800 nm, more preferably in the range of 380 nm to 750 nm, and even more preferably in the range of 400 nm to 700 nm.

[0200] [Dye of the second invention]

[0201] The pigment of the second invention is not particularly limited as long as it satisfies the above-mentioned relational expression (11), preferably satisfies the above-mentioned relational expression (11A), more preferably satisfies the above-mentioned relational expression (11B), and further preferably satisfies the above-mentioned relational expression (11C). From the viewpoint of optical properties such as dichroic ratio, it is preferably an azo pigment. Among azo pigments, the compound represented by the following formula (12) (hereinafter sometimes referred to as "compound (12)") has a tendency to have better optical properties such as dichroic ratio and is preferred.

[0202] X 20 (-A 21 ) m1 (-N=NA 22 ) n1 -N=NA 23 -Y 20 (12)

[0203] (In formula (12),

[0204] -A 21 -、-A 22 -、-A 23 - each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocyclic ring which may have a substituent,

[0205] -X 20 , -Y 20 Each independently represents a monovalent arbitrary substituent,

[0206] m1 means 1 or 2,

[0207] n1 represents 0, 1, 2, or 3.

[0208] When m1 is 2, -A 21 - can be the same or different from each other.

[0209] When n1 is 2 or 3, -A 22 - can be the same or different from each other. )

[0210] Next, compound (12) is described.

[0211] (-A 21 -、-A 22 -、-A 23 -)

[0212] -A 21 -、-A 22 -、-A 23 - each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocyclic ring which may have a substituent.

[0213] A divalent group of an aromatic hydrocarbon ring which may have a substituent:

[0214] Examples of the aromatic hydrocarbon ring of the divalent group of the aromatic hydrocarbon ring which may have a substituent 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.

[0215] As the divalent group of the aromatic hydrocarbon ring, since the absorption transition moment of the compound (12) tends to be consistent with the long axis direction of the pigment and the dichroic ratio can be improved, the divalent group of the benzene ring (phenylene) and the divalent group of the naphthalene ring (naphthylene) are preferred, and the divalent group of the benzene ring (phenylene) is more preferred. In particular, 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene are more preferred, 1,4-phenylene is further preferred, and 1,4-phenylene without a substituent is particularly preferred. By adopting the above-mentioned mode, the absorption transition moment of the compound (12) tends to be consistent with the long axis direction of the compound, and the dichroic ratio can be improved.

[0216] Permissible substituents for the divalent aromatic hydrocarbon ring 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. Here, -R A and -R B Each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms. A and -R B The number of carbon atoms is preferably 1 to 12, more preferably 1 to 9, from the viewpoint of achieving good molecular alignment with the polymerizable liquid crystal compound used in the present invention.

[0217] The one or more methylene groups contained in the linear or branched alkyl group may be replaced by etheric oxygen atoms, thioetheric sulfur atoms, amine nitrogen atoms (-NH-, -N(R z )-: Here, R z represents a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms), a carbonyl group, an ester bond, an amide bond, -CHF-, -CF 2 -、-CHCl-、-CCl 2 The structure formed by - substitution may be substituted by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group or a glycidyloxy group.

[0218] Among these, as the permissible substituent for the divalent aromatic hydrocarbon ring, -R A 、-OR A , trifluoromethyl, fluoro. A Examples of the substituent include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 5,5-dimethyl-3-methylhexyl, etc. By having the substituent, the molecular orientation of the dye of compound (2) tends to be improved.

[0219] Aromatic heterocyclic divalent group which may have a substituent:

[0220] Examples of the aromatic heterocyclic ring of the divalent group of the aromatic heterocyclic ring which may have a substituent include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furofuran ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, and an azulene ring.

[0221] Permissible substituents for the divalent aromatic heterocyclic group include the same substituents as the substituents which the divalent aromatic hydrocarbon ring group may have, and preferred substituents are also the same.

[0222] (-A 21 -、-A 22 -、-A 23 -Preferred mode)

[0223] From the perspective of optical properties such as dichroic ratio and the optimal pigment association state, -A 21 -、-A 22 -、-A 23 -A in 21 -、-A 23 - each independently preferably is a divalent group of an aromatic hydrocarbon ring which may have a substituent, more preferably each independently is a phenylene group which may have a substituent, particularly preferably a 1,4-phenylene group which may have a substituent, and particularly preferably an unsubstituted 1,4-phenylene group.

[0224] About-A 22-, from the viewpoint of optical properties such as dichroic ratio, it is also preferably a divalent group of an aromatic hydrocarbon ring which may have a substituent, more preferably a phenylene which may have a substituent, particularly preferably a 1,4-phenylene which may have a substituent, and particularly preferably a 1,4-phenylene which may have a substituent.

[0225] (-X 20 , -Y 20 )

[0226] -X 20 , -Y 20 Each independently represents a monovalent arbitrary substituent.

[0227] As-X 20 , -Y 20 The monovalent substituent in the group may be, for example, a hydroxyl group, an amino group, a cyano group, a carbamoyl group, a nitro group, a halogen atom, -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 . -R x and -R y Each independently represents an alkyl group, a cycloalkyl group or an aryl group which may or may not have a branch, and which may or may not have a substituent. The alkyl group preferably has 1 to 15 carbon atoms, the cycloalkyl group preferably has 5 to 14 ring atoms, and the aryl group preferably has 5 to 14 ring atoms.

[0228] -R x and -R y They may be combined to form a ring having preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms.

[0229] As-X 20 , -Y 20 The monovalent substituent in -X preferably does not have a polymerizable group described below from the viewpoint of achieving good molecular orientation with the polymerizable liquid crystal compound used in the second invention. 20 , -Y 20The monovalent substituent in preferably has a polymerizable group described below from the viewpoint of improving the mechanical strength of the anisotropic dye film.

[0230] The alkyl group having 1 to 15 carbon atoms which may or may not have a branch has preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. The cycloalkyl group having 5 to 14 ring atoms has preferably 5 to 10 ring atoms, and more preferably 5 to 6 ring atoms, and further preferably 6 ring atoms. The aryl group having 5 to 14 ring atoms has preferably 5 to 10 ring atoms, and more preferably 5 to 6 ring atoms, and further preferably 6 ring atoms. By adopting the above-mentioned embodiment, optical properties such as dichroic ratio tend to be good and the state of association of the dye tends to be optimal.

[0231] The branched or unbranched alkyl group having 1 to 15 carbon atoms, the cycloalkyl group having 5 to 14 ring atoms, and the aryl group having 5 to 14 ring atoms may have a substituent.

[0232] In addition, an alkyl group having 1 to 15 carbon atoms which may be branched or not, a cycloalkyl group having 5 to 14 atoms constituting the ring, or -R x and -R y One or more methylene groups contained in the ring formed by integration may be replaced by -O-, -S-, -NH-, -N(R z )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -、-CHCl-、-CCl 2 -substituted (displaced) structure, or may be substituted with a polymerizable group of acryloyloxy, methacryloyloxy, or glycidyloxy. z It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0233] AS-R x and -R y The substituents permitted for the branched or unbranched alkyl group having 1 to 15 carbon atoms include -OH, -OR f 、-OC(=O)-R f 、-NH 2 、-NH-R f 、-N(-R g )-R f 、-C(=O)-R f 、-C(=O)-OR f 、-C(=O)-NH 2 , -C(=O)-NH-R f 、-C(=O)-N(-Rg )-R f , -SH, -SR f , sulfamoyl, carboxyl, cyano, nitro, halogen, etc. Here, -R f and -R g Each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.

[0234] The one or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms may be replaced by -O-, -S-, -NH-, -N(R h )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -、-CHCl-、-CCl 2 -substituted (displaced) structure, or a structure substituted with a polymerizable group of acryloyloxy, methacryloyloxy, or glycidyloxy. h It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0235] Among these, as -R x and -R y The permissible substituents of the branched or unbranched alkyl group having 1 to 15 carbon atoms are preferably -OR f Examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, acryloyloxy, methacryloyloxy and glycidyloxy.

[0236] AS-R x and -R y The permissible substituents of the cycloalkyl group or aryl group wherein the number of atoms constituting the ring is 5 to 14 include -R i 、-OH、-OR i 、-OC(=O)-R i 、-NH 2 、-NH-R i 、-N(-R j )-R i 、-C(=O)-R i 、-C(=O)-OR i 、-C(=O)-NH 2 , -C(=O)-NH-R i 、-C(=O)-N(-R j )-R i , -SH, -SR i, trifluoromethyl, sulfamoyl, carboxyl, cyano, nitro, halogen. -R i and -R j Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.

[0237] Among these, as -R x and -R y The number of atoms constituting the ring in the cycloalkyl group is 5 to 14, or the substituent group permitted by the aryl group is preferably -R i 、-OR i , for example, 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, 5,5-dimethyl-3-methylhexyloxy and the like.

[0238] AS-R x and -R y Examples of the cycloalkane ring of the cycloalkyl group having 5 to 14 ring atoms include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, camphane ring, adamantane ring, tetralin ring and bicyclo[2.2.2]octane ring.

[0239] AS-R x and -R y The aryl group having 5 to 14 atoms constituting the ring includes -A 21 -、-A 22 -、-A 23 - is a monovalent group of the ring exemplified by the aromatic heterocyclic ring and the aromatic hydrocarbon ring.

[0240] AS-R x and -R y , preferably an alkyl group having 1 to 15 carbon atoms which may or may not have a branch, or -R x and -R y They are combined to form a ring having 2 to 15 carbon atoms which may have a substituent. Furthermore, it is more preferably an alkyl group having 1 to 6 carbon atoms which may have a branch or not, or -R x and -R y are formed into a ring having 2 to 10 carbon atoms; more preferably, an alkyl group having 1 to 3 carbon atoms which may or may not have a branch, or -R x and -R y are combined to form a ring having 2 to 6 carbon atoms; particularly preferably an unbranched alkyl group having 1 to 3 carbon atoms, or -R x and -R yThey are united to form a ring having 2 to 6 carbon atoms. By adopting the above embodiment, the molecular orientation of the compound (12) tends to be good.

[0241] -X 20 , -Y 20 -X in the monovalent substituent 20 Preferred-R x 、-OR x 、-OC(=O)-R x 、-C(=O)-OR x 、-N(-R y )-R x 、-NH-R x , more preferably -R x 、-OR x 、-OC(=O)-R x 、-C(=O)-OR x , especially preferably -R x 、-OR x As -R x Specifically, it is preferably a cycloalkyl group having 5 to 8 carbon atoms constituting the ring which has no substituent or has an alkyl group having 1 to 10 carbon atoms as a substituent at the para position, more preferably a cyclohexyl group having no substituent or having an alkyl group having 1 to 10 carbon atoms as a substituent at the para position, and further preferably a cyclohexyl group having an alkyl group having 3 to 6 carbon atoms as a substituent at the para position. x , preferably -R x is an alkyl group having 3 to 12 carbon atoms and may have a branch or an unbranched chain, and -R x It is an alkyl group having 3 to 10 carbon atoms and may have a branch.

[0242] In addition, as -Y 20 , preferably -R x 、-OR x 、-OC(=O)-R x 、-C(=O)-OR x 、-N(-R y )-R x , more preferably -OR x 、-OC(=O)-R x 、-N(-R y )-R x , further preferably -OR x 、-N(-R y )-R x 、-NH-R x , particularly preferably a group represented by the following formula (12a).

[0243] -N-(Ry )-R x (12a)

[0244] (In formula (12a), -R x , -R y Each independently represents an alkyl group or an aryl group which may or may not have a branch, and the alkyl group or the aryl group may or may not have a substituent. x and -R y They may be combined with N to form a ring having 2 to 15 carbon atoms, and the ring may have a substituent.

[0245] Specific examples of the group represented by formula (12a) include dimethylamino, diethylamino, di-n-propylamino, ethylmethylamino, methylpropylamino, ethylpropylamino, methylbutylamino, ethylbutylamino, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, morpholinyl, piperazinyl and thiomorpholinyl, with diethylamino, pyrrolidinyl and piperidinyl being more preferred.

[0246] By adopting the above embodiment, the absorption transition moment of the compound (12) is aligned with the major axis direction of the compound, so that the dichroism tends to be improved.

[0247] When high solubility of the pigment is required, -R in formula (12a) x , -R y Preferably -R x and / or -R y The branched alkyl group is more preferably isopropyl or isobutyl.

[0248] When it is necessary to adjust the absorption wavelength of the pigment, -R in formula (12a) x , -R y It preferably has a substituent, and more preferably has -OH, -OR f 、-OC(=O)-R f 、-C(=O)-R f 、-C(=O)-OR f , a halogen atom as a substituent, and more preferably a fluorine atom. f It represents a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.

[0249] (m1)

[0250] m1 means 1 or 2.

[0251] m1 is preferably 2. By adopting the above embodiment, the dye association state tends to be optimal.

[0252] When m1 is 2, each -A21 - may be the same or different, but are preferably the same because they tend to provide an optimal pigment association state.

[0253] (n1)

[0254] n1 represents 0, 1, 2, or 3.

[0255] When n1 is 1 or 2, it tends to be an optimal dye association state, which is preferred, and when it is 1, it tends to further improve the molecular orientation of the compound (12), which is more preferred.

[0256] When n1 is 2 or 3, each -A 22 - may be the same or different, but are preferably the same because they tend to provide an optimal pigment association state.

[0257] The sum of m1 and n1 is not particularly limited as long as m1 and n1 are within the above ranges, but is preferably 2 or 3, and more preferably 3. By adopting the above embodiment, the molecular orientation of the compound (12) tends to be good.

[0258] (-N=N-)

[0259] From the viewpoint of improving the linearity of the compound (12), -N=N- in the formula (12) is preferably a trans form.

[0260] (Specific example of compound (12))

[0261] Specific examples of compound (12) include the following compounds, but are not limited to these.

[0262] [Chemistry 10]

[0263]

[0264] [Pigment in the Composition of the Present Invention]

[0265] The composition of the first invention contains compound (2). The composition of the first invention may also contain a pigment other than compound (2). Examples of pigments other than compound (2) contained in the composition of the first invention 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, oxazine pigments, acridine pigments, etc.) other than compound (2).

[0266] The composition of the first invention may contain only one kind of a dye other than the compound (2) alone, or may contain two or more kinds in any combination and ratio.

[0267] The composition of the second invention preferably contains compound (12) as the pigment of the second invention. The composition of the second invention may also contain pigments other than the pigment of the second invention. As pigments other than the pigment of the second invention contained in the composition of the second invention, there can be mentioned azo pigments, quinone pigments (including naphthoquinone pigments, anthraquinone pigments, etc.), stilbene pigments, anthocyanin pigments, phthalocyanine pigments, indigo pigments, condensed polycyclic pigments (including perylene pigments, oxazine pigments, acridine pigments, etc.) which do not satisfy the above-mentioned relationship (11).

[0268] As the dye other than compound (2) or the dye of the second invention contained in the composition of the present invention, that is, the composition of the first invention and the composition of the second invention, it is preferred that the wavelength showing the maximum value in the absorption curve in the wavelength range of 350 nm to 800 nm differs by 5 nm or more from the wavelength showing the maximum value in the absorption curve in the wavelength range of 350 nm to 800 nm of compound (2) or the dye of the second invention contained in the composition, and it is more preferred that the wavelength showing the maximum value in the absorption curve in the wavelength range of 350 nm to 800 nm differs by 10 nm or more from the wavelength showing the maximum value in the absorption curve in the wavelength range of 350 nm to 800 nm of compound (2) or the dye of the second invention contained in the composition. By adopting the above embodiment, when the anisotropic dye film is formed into a polarizing element for a display or the like using the composition of the present invention, polarization characteristics are exhibited in a wide range of the visible light region.

[0269] (Molecular weight of pigment)

[0270] The molecular weight of the pigment contained in the 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, 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 composition of the present invention is preferably 300 to 1500, more preferably 350 to 1200, and further preferably 380 to 1000. By being within the above range, the molecular length and volume of the pigment are appropriately obtained, so the molecular orientation of the pigment tends to be good. The molecular weight of the pigment is the sum of the atomic weights contained in the pigment molecule.

[0271] (Pigment content)

[0272] The content of the pigment in the composition of the present invention (when two or more pigments are used in combination, the sum of the respective contents) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, preferably 30 parts by mass or less, more preferably 10 parts by mass or less, for example, relative to the solid content (100 parts by mass) of the composition. Specifically, the content of the pigment in the composition is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, for example, relative to the solid content (100 parts by mass) of the composition.

[0273] If the content of the pigment is within the above range, there is a tendency to polymerize the polymerizable liquid crystal compound contained in the composition of the present invention without disturbing the orientation of the liquid crystal compound contained in the composition of the present invention. If the content of the pigment is above the above lower limit, sufficient light absorption can be obtained, and there is a tendency to obtain sufficient polarization performance. If the content of the pigment is below the above upper limit, there is a tendency to easily suppress the orientation obstruction of the liquid crystal molecules.

[0274] Here, the solid content of the composition corresponds to the total of all components in the composition except the solvent.

[0275] The composition of the present invention only needs to contain the compound (2) or the pigment of the second invention as an essential component, and may contain the above-mentioned other pigments together with the compound (2) or the pigment of the second invention. In the case where the composition of the present invention contains other pigments, from the viewpoint of more effectively obtaining the effect of the present invention brought about by using the compound (2) or the pigment of the second invention, the proportion of the compound (2) or the pigment of the second invention in the total amount of the pigment in the composition of the present invention (100% by mass) is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass to 100% by mass.

[0276] (Method for producing pigment)

[0277] The compound (2) contained in the composition of the present invention and the pigment of the second invention can be produced by combining known chemical reactions such as alkylation reaction, esterification reaction, amidation reaction, etherification reaction, in-situ substitution reaction, diazotization coupling reaction, and coupling reaction using a metal catalyst.

[0278] For example, compound (2), the pigment of the second invention, can be synthesized by the method described in the examples described later, "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).

[0279] [Polymerizable liquid crystal compound]

[0280] In the present invention, the liquid crystal compound refers to a substance that exhibits a liquid crystal state, and specifically refers to 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 on pages 1 to 28 of the "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2001).

[0281] The polymerizable liquid crystal compound contained in the composition of the present invention is a liquid crystal compound having a polymerizable group as described later.

[0282] In the polymerizable liquid crystal compound, the polymerizable group may be arranged at any position in the liquid crystal compound molecule. In the polymerizable liquid crystal compound, the polymerizable group is preferably substituted at the terminal of the liquid crystal compound molecule from the viewpoint of ease of polymerization.

[0283] 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 from the viewpoint of ease of polymerization.

[0284] 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 molecular mobility is high, and the intermolecular interaction between the liquid crystal molecules and the compounds having a π conjugated system such as the pigment molecules is strong, and the molecular orientation increases.

[0285] As the polymerizable liquid crystal compound contained in the composition of the present invention, any liquid crystal compound having a polymerizable group can be used without particular limitation.

[0286] For example, as the polymerizable liquid crystal compound contained in the composition of the present invention, there can be mentioned a compound represented by the following formula (3) (hereinafter sometimes referred to as “polymerizable liquid crystal compound (3)”).

[0287] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 (3)

[0288] (In formula (3),

[0289] -Q 1represents a hydrogen atom or a polymerizable group,

[0290] -Q 2 represents a polymerizable group,

[0291] -R 1 -and-R 2 - each independently represents a chain organic group,

[0292] -A 11 -and-A 13 - each independently represents a partial structure represented by the following formula (4), a divalent organic group, or a single bond,

[0293] -A 12 - represents a partial structure or a divalent organic group represented by the following formula (4),

[0294] -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 -,

[0295] -A 11 -and-A 13 - one of which is a partial structure or a divalent organic group represented by the following formula (4);

[0296] k is 1 or 2.

[0297] When k is 2, 2 -Y 2 -A 13 - can be the same or different from each other. )

[0298] -C y -X 2 -C≡CX 1 -(4)

[0299] (In formula (4),

[0300] -C y - represents a hydrocarbon ring group or a heterocyclic group,

[0301] -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 -,

[0302] -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 -. )

[0303] It should be noted that -A 11 - When the partial structure is represented by formula (4), formula (3) may be the following formula (3A) or the following formula (3B).

[0304] Q 1 -R 1 -C y -X 2 -C≡CX 1 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 (3A)

[0305] Q 1 -R 1 -X 1 -C≡CX 2 -C y -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 (3B)

[0306] In addition, -A 12When - is a partial structure represented by formula (4), formula (3) may be the following formula (3C) or the following formula (3D).

[0307] Q 1 -R 1 -A 11 -Y 1 -C y -X 2 -C≡CX 1 -(Y 2 -A 13 ) k -R 2 -Q 2 (3C)

[0308] Q 1 -R 1 -A 11 -Y 1 -X 1 -C≡CX 2 -C y -(Y 2 -A 13 ) k -R 2 -Q 2 (3D)

[0309] In addition, -A 13 When - is a partial structure represented by formula (4), formula (3) may be the following formula (3E) or the following formula (3F).

[0310] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -C y -X 2 -C≡CX 1 ) k -R 2 -Q 2 (3E)

[0311] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -X 1 -C≡CX 2 -C y ) k -R 2 -Q 2 (3F)

[0312] Similarly, in -A 11 -、-A 12 -and-A 13 -, when there are two or more partial structures represented by formula (4), the orientations of the partial structures represented by formula (4) can be reversed independently of each other.

[0313] As mentioned above, -A 11 -、-A 12 -and-A 13 - are each independently a partial structure represented by formula (4) or a divalent organic group. 11 -and-A 13 - can be a single bond, but -A 11 -and-A 13 -Not a single bond at the same time.

[0314] (-C y -)

[0315] -C y The hydrocarbon ring group in - includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.

[0316] The aromatic hydrocarbon ring group includes a non-bonded aromatic hydrocarbon ring group and a bonded aromatic hydrocarbon ring group.

[0317] The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and preferably has 6 to 20 carbon atoms because the molecular orientation is improved by an appropriate core size. The non-linked aromatic hydrocarbon ring group more preferably has 6 to 15 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.

[0318] 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 position on the atoms constituting the ring. For the reason that the molecular orientation is improved by the appropriate size of the core, it is preferred that the number of carbon atoms of the monocyclic or condensed ring is 6 to 20. The number of carbon atoms of the monocyclic or condensed ring is more preferably 6 to 15. As the connecting aromatic hydrocarbon ring group, for example, a monocyclic or condensed first aromatic hydrocarbon ring having 6 to 20 carbon atoms and a monocyclic or condensed second aromatic hydrocarbon ring having 6 to 20 carbon atoms are bonded by a single bond, and a first bonding position is provided on the atoms constituting the ring of the monocyclic or condensed first aromatic hydrocarbon ring having 6 to 20 carbon atoms, and a second bonding position is provided on the atoms 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, a specific example is biphenyl-4,4'-diyl.

[0319] As the aromatic hydrocarbon ring group, a non-bonding aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction that acts between liquid crystal compounds and improves the molecular alignment.

[0320] Among these, 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. y - These groups tend to increase the linearity of liquid crystal molecules and improve the molecular orientation.

[0321] The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.

[0322] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and preferably has 3 to 20 carbon atoms because the molecular orientation is improved by an appropriate core size. The number of carbon atoms in the non-linked non-aromatic hydrocarbon ring group is more preferably 3 to 15. 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.

[0323] 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. As the non-linked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferred from the viewpoint of productivity.

[0324] 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 bonding positions on atoms constituting the ring; or a divalent group in which one or more rings selected from the group consisting of 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 bonding positions on atoms constituting the ring.

[0325] The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20 because the molecular orientation is improved by an appropriate core size.

[0326] Examples of the linked non-aromatic hydrocarbon ring group include 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 the first bonding position is on an atom constituting the monocyclic or condensed first non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and the second bonding position is on an atom constituting the monocyclic or condensed second non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. In addition, for example, a divalent group can be mentioned in which 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 each other by a single bond, and the first bonding position is on an atom constituting the monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms, and the second bonding position is on an atom constituting the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0327] Specific 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.

[0328] As the non-aromatic hydrocarbon ring group, a non-bonding non-aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction that acts between liquid crystal compounds and improves the molecular alignment.

[0329] As the non-linked non-aromatic hydrocarbon ring group, a divalent group of cyclohexane (cyclohexanediyl) is preferred. As the cyclohexanediyl group, cyclohexane-1,4-diyl is preferred. y - These groups tend to increase the linearity of liquid crystal molecules and improve the molecular orientation.

[0330] -C y The heterocyclic group in - includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

[0331] The aromatic heterocyclic group includes a non-bonded aromatic heterocyclic group and a bonded aromatic heterocyclic group.

[0332] The non-linked aromatic heterocyclic group is a monocyclic or condensed divalent aromatic heterocyclic group, and preferably has 4 to 20 carbon atoms, and more preferably has 4 to 15 carbon atoms, because the molecular orientation is improved by an appropriate core size.

[0333] 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, a thiazole ring, an isothiazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furanofuran ring, a thienofuran ring, a thienothiazole ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0334] 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 position on the atoms constituting the ring. For the reason that the molecular orientation is improved by an appropriate core size, the number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. The number of carbon atoms in the linked aromatic heterocyclic group is more preferably 4 to 15.

[0335] Examples of the linked aromatic heterocyclic group include a divalent group in which a monocyclic or condensed first aromatic heterocyclic ring having 4 to 20 carbon atoms and a monocyclic or condensed second aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded to each other by a single bond, wherein the first bonding position is on an atom constituting the first aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bonding position is on an atom constituting the second aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0336] The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.

[0337] The non-linked non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group, and preferably has 4 to 20 carbon atoms because molecular orientation is improved by an appropriate core size. The non-linked non-aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0338] Examples of the non-aromatic heterocyclic ring which is a monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms and which is a divalent group include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, a pyrrolidine ring, a piperidine ring, a dihydropyridine ring, a piperazine ring, a tetrahydrothiazole ring, a tetrahydrooxazole ring, an octahydroquinoline ring, a tetrahydroquinoline ring, an octahydroquinazoline ring, a tetrahydroquinazoline ring, a tetrahydroimidazole ring, a tetrahydrobenzimidazole ring, and a quinuclidine ring.

[0339] 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 position on the atoms constituting the ring. For the reason that the molecular orientation is improved by an appropriate core size, the number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. The number of carbon atoms in the linked non-aromatic heterocyclic group is more preferably 4 to 15.

[0340] Examples of the linked aromatic heterocyclic group include a divalent group in which a monocyclic or condensed first non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a monocyclic or condensed second non-aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded to each other by a single bond, wherein the first bonding position is on an atom constituting the monocyclic or condensed first non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bonding position is on an atom constituting the monocyclic or condensed second non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0341] -C y The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - are each optionally selected from -R k 、-OH、-OR k 、-OC(=O)-R k 、-NH 2 、-NH-R k 、-N(R k’ )-R k , -C(=O)-R k 、-C(=O)-OR k 、-C(=O)-NH 2 , -C(=O)-NH-R k 、-C(=O)-N(R k’ )-R k , -SH, -SR k , trifluoromethyl, sulfamoyl, carboxyl, sulfonyl, cyano, nitro, and halogen. k and -R k’ Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0342] From the viewpoint that the molecular structure has high linearity, the polymerizable liquid crystal compounds (3) are easily associated with each other and easily exhibit a liquid crystal state, -C y 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 are more preferably unsubstituted.

[0343] -C yThe substituents possessed by the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group in - may be the same or different. In addition, the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group may all be substituted or all be unsubstituted, or may be partially substituted and partially unsubstituted.

[0344] AS-C y -, from the viewpoint of improving the molecular orientation of the polymerizable liquid crystal compound (3), is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group. From the viewpoint of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (3), -C y -, 1,4-phenylene and cyclohexane-1,4-diyl are more preferred, and 1,4-phenylene is particularly preferred.

[0345] (-X 1 -)

[0346] -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 -. In view of the linearity of the polymerizable liquid crystal compound (3) and the tendency to easily perform rotational motion around the short axis of the molecule, -X 1 -, and examples thereof include -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, and -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -、-CH 2 S-、-SCH 2 -, etc. are preferred groups. Among them, -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -, more preferably -X 1 - is -C(=O)O- or -OC(=O)-. In another embodiment, -X 1 -Preferably -CH 2CH 2 -、-CH 2 O- or -OCH 2 -.

[0347] (-X 2 -)

[0348] -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 -.

[0349] From the viewpoint of increasing the size of the core of the polymerizable liquid crystal compound (3) and increasing the dichroism of the anisotropic dye film formed from the anisotropic dye film-forming composition, it is preferred to replace -C y - is connected with -C≡C-. Specifically, as -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.

[0350] (-Q 1 and-Q 2 )

[0351] -Q 1 and-Q 2 The polymerizable group in 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 required to ensure the polymerization function. From the viewpoint of production of anisotropic dye film, the polymerizable group is preferably a photopolymerizable group.

[0352] Examples of the polymerizable group include acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, vinyl, vinyloxy, ethynyl, ethynyloxy, 1,3-butadienyl, 1,3-butadienyloxy, oxiranyl, oxetanyl, glycidyl, glycidyloxy, styryl, and styryloxy groups; preferably acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, oxiranyl, glycidyl, and glycidyloxy groups; more preferably acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, glycidyl, and glycidyloxy groups; and further preferably acryloyloxy, methacryloyloxy, and glycidyloxy groups.

[0353] (-R 1 -and-R 2 -)

[0354] -R 1 -and-R 2 The chain organic group in - is a divalent organic group which does not contain a cyclic structure such as the above-mentioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic heterocycle, etc.

[0355] 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)-.

[0356] Examples of the alkylene groups 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 groups may be unsaturated bonds. One or more methylene groups contained in the alkylene groups may be replaced by -O-, -S-, -NH-, -N(R m )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -、-CHCl-、-CCl 2 -Structure formed by substitution (displace). m It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0357] 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. For the alkylene group, a part of the carbon atoms of the alkylene group may be an unsaturated bond, and one or more methylene groups contained in the alkylene group may be substituted (displaced) with the above-mentioned groups.

[0358] 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.

[0359] As the chain organic group, -(CH 2 ) r -CH 2 -、-O-(CH 2 ) r -CH 2 -、-(O) r1 -(CH 2 CH 2 O) r2 -(CH 2 ) r3 -、-(O) r1 -(CH 2 ) r2 -(CH 2 CH 2 O) r3 -. r 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, r1, r2, and r3 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.

[0360] -R 1 -and-R 2 - are each independently preferably -(alkylene)- or -O-(alkylene)-, and more preferably -(alkylene)- or -O-(alkylene)-. 1 -and-R 2 The chain organic group in - is -(alkylene)-, and in another embodiment, is -O-(alkylene)-.

[0361] As in the above formula (3B) and formula (3E), -X 1 -with-R 1 -or-X 1 -with-R 2-bonded together, in the above formula (3B) -A 13 - is a single bond or in the above formula (3E) -A 11 - is a single bond and -R 1 -or-R 2 -with-Y 1 -or-Y 2 -Bonded together with -X 1 -、-Y 1 -or-Y 2 -Direct Bonded-R 1 -or-R 2 - is preferably -(alkylene)-.

[0362] In addition to the above, do not use -X 1 -、-Y 1 -or-Y 2 -Direct Bonded-R 1 -or-R 2 - is preferably -O-(alkylene)-.

[0363] (-A 11 -、-A 12 -and-A 13 - divalent organic group)

[0364] -A 11 -、-A 12 -and-A 13 The divalent organic group in - is preferably a group represented by the following formula (5).

[0365] -Q 3 -(5)

[0366] (In formula (6), Q 3 represents a hydrocarbon ring group or a heterocyclic ring group. )

[0367] -Q 3 The hydrocarbon ring group in - includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.

[0368] The aromatic hydrocarbon ring group includes a non-bonded aromatic hydrocarbon ring group and a bonded aromatic hydrocarbon ring group.

[0369] The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and preferably has 6 to 20 carbon atoms because the molecular orientation is improved by an appropriate core size. The non-linked aromatic hydrocarbon ring group more preferably has 6 to 15 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.

[0370] 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 position on the atoms constituting the ring. For the reason that the orientation is improved by the appropriate size of the core, it is preferred that the number of carbon atoms of the monocyclic or condensed ring is 6 to 20. The number of carbon atoms of the connecting aromatic hydrocarbon ring group is more preferably 6 to 15. As the connecting aromatic hydrocarbon ring group, for example, a monocyclic or condensed first aromatic hydrocarbon ring with 6 to 20 carbon atoms and a monocyclic or condensed second aromatic hydrocarbon ring with 6 to 20 carbon atoms are bonded by a single bond, and a first bonding position is provided on the atoms constituting the ring of the monocyclic or condensed first aromatic hydrocarbon ring with 6 to 20 carbon atoms, and a second bonding position is provided on the atoms constituting the ring of the monocyclic or condensed second aromatic hydrocarbon ring with 6 to 20 carbon atoms. As the connecting aromatic hydrocarbon ring group, a specific example is biphenyl-4,4'-diyl.

[0371] As the aromatic hydrocarbon ring group, a non-bonding aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction that acts between liquid crystal compounds and improves the molecular alignment.

[0372] Among these, 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. 3 - These groups tend to increase the linearity of liquid crystal molecules and improve the molecular orientation.

[0373] The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.

[0374] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and preferably has 3 to 20 carbon atoms because the molecular orientation is improved by an appropriate core size. The number of carbon atoms in the non-linked non-aromatic hydrocarbon ring group is more preferably 3 to 15. 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.

[0375] 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. As the non-linked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferred from the viewpoint of productivity.

[0376] 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 bonding positions on atoms constituting the ring; or a divalent group in which one or more rings selected from the group consisting of 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 bonding positions on atoms constituting the ring.

[0377] The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20 because the molecular orientation is improved by an appropriate core size.

[0378] Examples of the linked non-aromatic hydrocarbon ring group include 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 the first bonding position is on an atom constituting the monocyclic or condensed first non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and the second bonding position is on an atom constituting the monocyclic or condensed second non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. In addition, for example, a divalent group can be mentioned in which 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 each other by a single bond, and the first bonding position is on an atom constituting the monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms, and the second bonding position is on an atom constituting the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0379] Specific 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.

[0380] As the non-aromatic hydrocarbon ring group, a non-bonding non-aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction that acts between liquid crystal compounds and improves the molecular alignment.

[0381] As the non-linked non-aromatic hydrocarbon ring group, a divalent group of cyclohexane (cyclohexanediyl group) is preferred. As the cyclohexanediyl group, a cyclohexane-1,4-diyl group is preferred.

[0382] -Q 3 The heterocyclic group in - includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

[0383] The aromatic heterocyclic group includes a non-bonded aromatic heterocyclic group and a bonded aromatic heterocyclic group.

[0384] The non-linked aromatic heterocyclic group is a monocyclic or condensed divalent aromatic heterocyclic group, and preferably has 4 to 20 carbon atoms, and more preferably has 4 to 15 carbon atoms, because the molecular orientation is improved by an appropriate core size.

[0385] 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, a thiazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furanofuran ring, a thienofuran ring, a thienothiazole ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0386] 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 position on the atoms constituting the ring. For the reason that the molecular orientation is improved by an appropriate core size, the number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. The number of carbon atoms in the linked aromatic heterocyclic group is more preferably 4 to 15.

[0387] Examples of the linked aromatic heterocyclic group include a divalent group in which a monocyclic or condensed first aromatic heterocyclic ring having 4 to 20 carbon atoms and a monocyclic or condensed second aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded to each other by a single bond, wherein the first bonding position is on an atom constituting the first aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bonding position is on an atom constituting the second aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0388] The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.

[0389] The non-linked non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group, and preferably has 4 to 20 carbon atoms because molecular orientation is improved by an appropriate core size. The non-linked non-aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0390] Examples of the non-aromatic heterocyclic ring which is a monocyclic or condensed non-aromatic heterocyclic divalent group having 4 to 20 carbon atoms include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, a pyrrolidine ring, a piperidine ring, a dihydropyridine ring, a piperazine ring, a tetrahydrothiazole ring, a tetrahydrooxazole ring, an octahydroquinoline ring, a tetrahydroquinoline ring, an octahydroquinazoline ring, a tetrahydroquinazoline ring, a tetrahydroimidazole ring, a tetrahydrobenzimidazole ring and a quinuclidine ring.

[0391] 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 position on the atoms constituting the ring. For the reason that the molecular orientation is improved by an appropriate core size, the number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. The number of carbon atoms in the linked non-aromatic heterocyclic group is more preferably 4 to 15.

[0392] Examples of the linked aromatic heterocyclic group include a divalent group in which a monocyclic or condensed first non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a monocyclic or condensed second non-aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded to each other by a single bond, wherein the first bonding position is on an atom constituting the monocyclic or condensed first non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bonding position is on an atom constituting the monocyclic or condensed second non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0393] -Q 3 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - are each optionally selected from -R n 、-OH、-OR n 、-OC(=O)-R n 、-NH 2 、-NH-R n 、-N(R n’ )-R n , -C(=O)-R n 、-C(=O)-OR n 、-C(=O)-NH 2 , -C(=O)-NH-R n 、-C(=O)-N(R n’ )-R n , -SH, -SR n , trifluoromethyl, sulfamoyl, carboxyl, sulfonyl, cyano, nitro, and halogen. n and -R n’ Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0394] From the viewpoint that the molecular structure has high linearity, the polymerizable liquid crystal compounds (3) are easily associated with each other and easily exhibit a liquid crystal state, -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 are more preferably unsubstituted.

[0395] -Q 3The substituents possessed by the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group in - may be the same or different. In addition, the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group may all be substituted or all be unsubstituted, or may be partially substituted and partially unsubstituted.

[0396] -A 11 -、-A 12 -and-A 13 The substituents of the divalent organic group in - 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.

[0397] AS-Q 3 - is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group. From the viewpoint of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (3), Q 3 -, and more preferably 1,4-phenylene and cyclohexane-1,4-diyl.

[0398] AS-A 11 -、-A 12 -and-A 13 -a divalent organic group, preferably -Q 3 - is a hydrocarbon ring group, that is, preferably a hydrocarbon ring group as a divalent organic group. As the 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 polymerizable liquid crystal compound (3), a 1,4-phenylene group or a cyclohexane-1,4-diyl group is further preferred.

[0399] As the polymerizable liquid crystal compound (3), in -A 11 -、-A 12 -and-A 13 -, preferably one of them is a partial structure represented by formula (4), and the other two are each independently a divalent organic group. 11 -、-A 12 -and-A 13 - is more preferably -C y - 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 - is cyclohexane-1,4-diyl.

[0400] In-A 11 -and-A 13 -, it is more preferred that one of them is a partial structure represented by formula (4), and the other one and -A 12 - is a divalent organic group. In this case, 11 -and-A 13 -, one of the divalent organic groups is preferably cyclohexane-1,4-diyl, and -A is particularly preferred. 12 - is 1,4-phenylene.

[0401] (-Y 1 -and-Y 2 -)

[0402] -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 From the viewpoint of the linearity of the polymerizable liquid crystal compound (3) 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 having a small π-bonding property, -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 -.

[0403] In the above formula (3A), formula (3C), formula (3D), formula (3F), -X 1 -with-Y 1 -or-X1 -with-Y 2 -Bonded together with -X 1 -Bonded-Y 1 -or with -X 1 -Bonded-Y 2 - is preferably a single bond. -X 1 -with-Y 1 -and-Y 2 The other of - is preferably -C(=O)O- or -OC(=O)-.

[0404] In the above formula (3B) and formula (3E), -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 - are preferably -C(=O)O- or -OC(=O)-.

[0405] (k)

[0406] k is 1 or 2. In one embodiment, k is preferably 1. In another embodiment, k is preferably 2.

[0407] When k is 2, each -Y 2 - can be the same or different from each other, each -A 13 - can be the same or different from each other.

[0408] (Preferred structure)

[0409] As the polymerizable liquid crystal compound (3), the compound represented by the above formula (3A), (3B), (3E) or (3F) is preferred because the intermolecular interaction between the liquid crystal compounds is optimal and the core size and molecular orientation are good.

[0410] In addition, the polymerizable liquid crystal compound used in the present invention is preferably a low-molecular polymerizable liquid crystal compound, and particularly preferably a low-molecular polymerizable liquid crystal compound having no copolymer structure, because of a tendency to obtain good molecular orientation.

[0411] The molecular weight of the low molecular weight polymerizable liquid crystal compound is preferably 2000 or less, more preferably 1500 or less, and further preferably 1000 or less. The lower limit is not particularly limited, but is preferably 400 or more, and more preferably 500 or more. As a molecular weight range, it is preferably 400 to 2000, more preferably 400 to 1500, and particularly preferably 500 to 1000. The molecular weight of the polymerizable liquid crystal compound is the sum of the atomic weights contained in the polymerizable liquid crystal compound molecule.

[0412] (Specific examples of polymerizable liquid crystal compounds)

[0413] As the polymerizable liquid crystal compound contained in the composition of the present invention, specifically, the polymerizable liquid crystal compounds described below can be cited, but are not limited to these. In the following exemplary formula, C 6 H 13 refers to n-hexyl, C 5 H 11 It refers to n-pentyl.

[0414] [Chemistry 11]

[0415]

[0416] [Chemistry 12]

[0417]

[0418] [Chemistry 13]

[0419]

[0420] [Chemistry 14]

[0421] [Chemistry 15]

[0422]

[0423] [Chemistry 16]

[0424]

[0425] [Chemistry 17]

[0426]

[0427] [Chemistry 18]

[0428]

[0429] [Chemistry 19]

[0430]

[0431] [Chemistry 20]

[0432]

[0433] [Chemistry 21]

[0434]

[0435] [Chemistry 22]

[0436]

[0437] [Chemistry 23]

[0438]

[0439] (Content of Liquid Crystalline Compound)

[0440] The liquid crystal compound contained in the composition of the present invention is preferably composed of a polymerizable liquid crystal compound (3). The composition of the present invention may contain only one polymerizable liquid crystal compound alone, or may contain two or more polymerizable liquid crystal compounds in any combination and ratio.

[0441] The content of the liquid crystal compound in the composition of the present invention (when two or more liquid crystal compounds are used in combination, the sum of the contents of each) is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, preferably 99 parts by mass or less, more preferably 98 parts by mass or less relative to the solid content (100 parts by mass) of the composition. If the content of the liquid crystal compound in the composition is above the lower limit and below the upper limit, there is a tendency for the orientation of the liquid crystal molecules to increase.

[0442] The composition of the present invention may contain one or more polymerizable or non-polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (3). From the viewpoint of more effectively obtaining the effect of the present invention brought about by the use of the polymerizable liquid crystal compound (3), the proportion of the polymerizable liquid crystal compound (3) in the total amount (100% by mass) of the liquid crystal compounds contained in the composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass to 100% by mass.

[0443] (Isotropic phase appearance temperature)

[0444] From a process point of view, the isotropic phase appearance temperature of the polymerizable liquid crystal compound contained in the composition of the present invention is 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.

[0445] Here, the isotropic phase appearance temperature 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, it is preferred that at least one of these phase transition temperatures is below the above upper limit, and it is more preferred that both of these phase transition temperatures are below the above upper limit.

[0446] (Method for producing polymerizable liquid crystal compound)

[0447] The polymerizable liquid crystal compound contained in the 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 substitution reaction, and coupling reaction using a metal catalyst.

[0448] For example, the polymerizable liquid crystal compound contained in the composition of the present invention can be synthesized by the method described in the examples described below or by the method described in “Liquid Crystal Handbook” (Maruzen Co., Ltd., published on October 30, 2001, pp. 449 to 468).

[0449] (Relationship between polymerizable liquid crystal compounds and pigments)

[0450] From the viewpoint of easily improving the orientation of the anisotropic dye film formed using the composition of the present invention, in the composition of the present invention, the smaller the difference between the molecular length of the polymerizable 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.

[0451] Therefore, in the composition of the present invention, the number of ring structures (r n1 ) and the number of ring structures possessed by the pigment contained in the composition (r n2 ) ratio (r n1 / r n2 ) is preferably 0.6 to 1.5.

[0452] In addition, a fused ring in which two or more rings are fused is counted as one ring structure.

[0453] Here, the number of ring structures (r n2 ) refers to B in the formula 1 , B 2 , B 3 and B 4 Specifically, when n is 0, r n2 is 4; when n is 1, r n2 is 5; when n is 2, r n2 is 6.

[0454] It should be noted that even if N(-RB 1 )RB 2 It is a cyclic functional group such as pyrrolidinyl or piperidinyl, N(-RB 1 )RB 2 The ring structure contained in is also not included in the number of ring structures (r) possessed by the compound (2) represented by formula (2) n2 )middle.

[0455] More specifically, when n is 0, r n2 is 4, so r n1 is 3, 4, 5 or 6; when n is 1, r n2 is 5, so if r n1 If 4, 5, 6 or 7 is included in the anisotropic dye film-forming composition, the number of ring structures (r n1 ) and the number of ring structures (r n2 ) ratio (r n1 / r n2 ) is 0.6 to 1.5, so it is preferred.

[0456] In addition, the number of ring structures (r n2 ) refers to A in the formula 21 , A 22 , A 23 and -X 20 Specifically, when n1 is 1 and m1 is 1, r n2 is 3; when n1 is 1 and m1 is 2, r n2 is 4; when n1 is 2 and m1 is 1, r n2 is 4; when n1 is 2 and m1 is 2, r n2 is 5; when n1 is 3 and m1 is 1, r n2 is 5.

[0457] It should be noted that even if -Y 20 is a cyclic functional group such as pyrrolidinyl or piperidinyl, -Y 20 The number of ring structures (r) contained in the compound (12) represented by the formula (12) is not included in the ring structure contained in the compound (12) represented by the formula (12). n2 )middle.

[0458] More specifically, when n1 is 1 and m1 is 1, r n2 is 3, so r n1 is 2, 3, or 4; when n1 is 1 and m1 is 2, r n2is 4, so r n1 is 3, 4, 5, or 6; when n1 is 2 and m1 is 1, r n2 is 4, so r n1 is 3, 4, 5, or 6; when n1 is 2 and m1 is 2, r n2 is 5, so r n1 is 3, 4, 5, 6, or 7; when n1 is 3 and m1 is 1, r n2 is 5, so if r n1 If 3, 4, 5, 6, or 7 is included, the number of ring structures (r n1 ) and the number of ring structures (r n2 ) ratio (r n1 / r n2 ) is 0.6 to 1.5, so it is preferred.

[0459] The number of ring structures (r n1 ) does not include a ring structure (such as an oxirane ring, an oxetane ring, etc.) contained in the polymerizable group in the polymerizable liquid crystal compound.

[0460] [Polymerization initiator]

[0461] The composition of the present invention may contain a polymerization initiator as needed.

[0462] 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.

[0463] Usable polymerization initiators include, for example, titanocene derivatives; biimidazole derivatives; halomethyl oxadiazole derivatives; halomethyl s-triazine derivatives; alkyl phenone derivatives; oxime ester derivatives; benzoin; benzophenone derivatives; acylphosphine oxide derivatives; iodonium salts; sulfonium salts; anthraquinone derivatives; acetophenone derivatives; thioxanthone derivatives; benzoate derivatives; acridine derivatives; phenazine derivatives; and anthrone derivatives.

[0464] Among these photopolymerization initiators, alkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferred.

[0465] 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 [2,6-difluoro-3-(pyrrol-1-yl)-phenyl-1-yl]titanium.

[0466] 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.

[0467] Examples of the halomethylated 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'-benzofuranyl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

[0468] 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.

[0469] 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.

[0470] 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, and oxime ester derivatives described in JP-A-2000-80068, JP-A-2006-36750, and International Publication No. 2009 / 131189.

[0471] Examples of the benzoins include benzoin, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.

[0472] 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.

[0473] 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.

[0474] Examples of the iodonium salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4-nonylphenyl)iodonium hexafluorophosphate.

[0475] Examples of the 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, 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.

[0476] Examples of the anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone.

[0477] Examples of the 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.

[0478] Examples of the thioxanthone derivatives include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0479] Examples of the benzoic acid ester derivatives include ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

[0480] Examples of the acridine derivatives include 9-phenylacridine and 9-(p-methoxyphenyl)acridine.

[0481] Examples of phenazine derivatives include 9,10-dimethylbenzophenazine.

[0482] Examples of the anthrone derivatives include benzanthrone and the like.

[0483] The polymerization initiator may be used alone or in combination of two or more.

[0484] As the polymerization initiator, a commercially available product may be used.

[0485] Commercially available products include, for example, 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); SEIKUOL (registered trademark) BZ, Z, and BEE (manufactured by Seiko Chemical Co., Ltd.); Kayacure (registered trademark) BP100 and UVI-6992 (manufactured by Dow Chemical Co., Ltd.); ADEKA Optimer SP-152 and SP-170 (manufactured by ADEKA Corporation); 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.).

[0486] 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 usually 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.

[0487] In addition, 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 N,N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole and other heterocyclic mercapto compounds; and mercapto compounds such as aliphatic multifunctional mercapto compounds.

[0488] The polymerization accelerator may be used alone or in combination of two or more.

[0489] 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-based dyes described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756; coumarin-based dyes with heterocyclic rings described in Japanese Patent Laid-Open No. 3-239703 and Japanese Patent Laid-Open No. 5-289335; 3-coumarin keto-based dyes described in Japanese Patent Laid-Open No. 3-239703 and Japanese Patent Laid-Open No. 5-289335; pyrromethene-based dyes described in Japanese Patent Laid-Open No. 6-19240; pyrromethene-based dyes described in Japanese Patent Laid-Open No. 47-2528 and Japanese Patent Laid-Open No. 5-289335. 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.

[0490] The sensitizing dye may be used alone or in combination of two or more.

[0491] [Solvent]

[0492] The composition of the present invention may contain a solvent as necessary.

[0493] The solvent that can be used in the composition of the present invention is not particularly limited as long as it can sufficiently disperse or dissolve the pigment or other additives in the polymerizable liquid crystal compound. Examples include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-pentanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; fluorine-containing solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, and hexafluoro-2-propanol; and chlorine-containing solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene.

[0494] These solvents may be used alone or in combination of two or more.

[0495] 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, the solvent is preferably a solvent inactive to the polymerization reaction of the polymerizable liquid crystal compound. In addition, from the viewpoint of applying the composition of the present invention described later, the solvent is preferably a solvent having a boiling point in the range of 50°C to 200°C.

[0496] When the composition of the present invention contains a solvent, the content ratio of the solvent in the composition of the present invention 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 composition of the present invention is preferably 2% to 50% by mass.

[0497] When the solid content in the composition of the present invention is below the upper limit, the viscosity of the composition of the present invention 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.

[0498] The solid content of the composition of the present invention can be determined in consideration of the thickness of the polarizing film to be produced.

[0499] The viscosity of the 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 uniform thickness over a large area, productivity such as coating speed, and in-plane uniformity of optical properties, the viscosity of the composition of the present invention is preferably 0.1 mPa·s or more, preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and further preferably 50 mPa·s or less.

[0500] [Other additives]

[0501] In addition to the above-mentioned polymerization initiator, the composition of the present invention may further contain 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, metal oxides and other additives as components other than the pigment and polymerizable liquid crystal compound as needed. By containing these additives, the coating properties and stability of the composition of the present invention can sometimes be improved, and the stability of the anisotropic pigment film formed by the composition of the present invention can be improved.

[0502] [Method for producing composition]

[0503] The method for manufacturing the composition of the present invention is not particularly limited. For example, a pigment containing compound (2) or the pigment of the second invention, a polymerizable liquid crystal compound, a solvent as required, other additives, etc. are mixed, stirred and shaken at 0 to 80° C. to dissolve the pigment. In the case where they are poorly soluble, a homogenizer, a bead mill disperser, etc. can be used.

[0504] The method for producing the composition of the present invention may include a filtration step in order to remove foreign matter and the like in the composition.

[0505] The composition of the present invention may or may not be liquid crystal at any temperature after the solvent is removed from the composition, but preferably exhibits liquid crystal properties at any temperature.

[0506] From the viewpoint of the coating process described below, the isotropic phase appearance temperature of the composition after removing the solvent from the composition of the present invention is preferably lower than 160°C, more preferably lower than 140°C, further preferably lower than 115°C, further preferably lower than 110°C, and particularly preferably lower than 105°C.

[0507] [Anisotropic pigment film]

[0508] The anisotropic dye film of the present invention is formed using the composition of the present invention.

[0509] Therefore, the anisotropic dye film of the first invention includes a dye and one or both of a polymerizable liquid crystal compound and a polymer having units based on the polymerizable liquid crystal compound, and the dye includes the compound (2).

[0510] Furthermore, the anisotropic dye film of the second invention includes a dye and one or both of a polymerizable liquid crystal compound and a polymer having units based on the polymerizable liquid crystal compound, and the dye includes the dye of the second invention.

[0511] Hereinafter, the “anisotropic dye film of the first invention” and the “anisotropic dye film of the second invention” are collectively referred to as “anisotropic dye film of the present invention”.

[0512] In addition, the composition of the present invention for forming the anisotropic dye film of the present invention may be referred to as an "anisotropic dye film-forming composition".

[0513] 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. as other ingredients.

[0514] The anisotropic dye film of 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).

[0515] When the anisotropic dye film of the present invention is used as a polarizing element for liquid crystal displays or an antireflection film for OLEDs, the orientation characteristics of the anisotropic dye film can be expressed using a dichroic ratio.

[0516] If the dichroic ratio is 8 or more, the polarizing element functions. However, in the first invention, the dichroic ratio is preferably 23 or more, more preferably 25 or more, further preferably 30 or more, and particularly preferably 40 or more.

[0517] In the second invention, the two-color ratio is preferably 13 or more, more preferably 20 or more.

[0518] The higher the dichroic ratio of the anisotropic dye film, the more preferable it is.

[0519] When the dichroic ratio is equal to or greater than the above lower limit, the optical element described below, particularly a polarizing element, is useful.

[0520] When used as a polarizing element for 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.

[0521] The dichroic ratio (D) in the present invention is represented by the following formula when the dyes are uniformly oriented.

[0522] D=Az / Ay

[0523] Here, Az 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 film, and Ay is the absorbance observed when the polarization direction of light incident on the anisotropic dye film is perpendicular to the orientation direction of the anisotropic dye film.

[0524] Each absorbance (Az, Ay) is not particularly limited as long as it uses absorbance at the same wavelength, and any wavelength can be selected according to the purpose. When indicating the degree of orientation of an anisotropic dye film, it is preferred to use a value corrected by visibility in a specific wavelength range of 350nm to 800nm ​​of the anisotropic dye film, or a value at the maximum absorption wavelength in the visible light region.

[0525] At the target wavelength used, 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. When the anisotropic dye film of the present invention is used as a dye film having anisotropy in the entire visible light wavelength range, the transmittance of the anisotropic dye film in the visible light wavelength range is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more. The upper limit of the transmittance of the anisotropic dye film of the present invention 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 setting the transmittance in the above range, it is useful as an optical element described later, especially as an optical element for liquid crystal displays used for color displays and an anti-reflection film composed of a combination of an anisotropic dye film and a phase difference film.

[0526] 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. The film thickness of the anisotropic dye film 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 setting the film thickness of the anisotropic dye film to the above range, there is a tendency to obtain uniform orientation of the dye and uniform film thickness in the film.

[0527] [Method for producing anisotropic dye film]

[0528] The anisotropic dye film of the present invention is preferably produced by a wet film-forming method using the composition of the present invention.

[0529] 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.

[0530] The orientation of the liquid crystal and the pigment in the anisotropic dye film can be oriented by shearing during the coating process, or can be oriented during 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, if the anisotropic dye film composition is given on the substrate, the pigment and the liquid crystal compound will produce a small area orientation due to self-association (molecular association state such as liquid crystal state) in the anisotropic dye film composition, or in the process of solvent drying, or after the solvent is completely removed. 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. Here, the external field can cite the influence of the orientation treatment layer applied on the substrate in advance, shear force, magnetic field, electric field, heat, etc. They can be used alone or in combination. If necessary, it can also be heated.

[0531] 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.

[0532] 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. There is also a method of transferring the anisotropic dye film thus obtained to another substrate.

[0533] Among these, it is preferable to apply the anisotropic dye film-forming composition to the substrate by a coating method.

[0534] The orientation direction of the anisotropic dye film may be different from the coating direction. 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. In the case of a retardation film, the orientation direction refers to the fast axis or the slow axis.

[0535] 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 on pages 253 to 277 of "Coating Engineering" by Yuji Harasaki (published by Asakura Shoten Co., Ltd. on March 20, 1971), the method described on pages 118 to 149 of "Creation and Application of Molecular Coordination Materials" edited by Kunihiro Ichimura (published by CMC Corporation on March 3, 1998), and a method of applying the composition on a substrate having a height difference structure (optionally subjected to an orientation treatment in advance) 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.

[0536] 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, Technosystem, ISBN 9784924728707C305), "Wet Coating Technology for Displays / Optical Components" (2007, Information Agency, ISBN 9784901677752), and "Precision Coating / Drying Technology in the Electronic Field" (2007, Technical Information Association, ISBN 9784861041389). These known slot dies can apply coating even to flexible members such as films and tapes, and hard members such as glass substrates.

[0537] Examples of the substrate used for forming the anisotropic dye film of the present invention include glass, triacetyl cellulose, acrylic, polyester, polyimide, polyetherimide, polyetheretherketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetyl cellulose, and urethane films.

[0538] For the substrate surface, in order to control the orientation direction of the pigment, the known methods described in pages 226 to 239 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2001) (rubbing method, method of forming grooves (fine groove structure) on the surface of the orientation film, method of using polarized ultraviolet light / polarized laser (photo-orientation method), orientation method based on LB film formation, orientation method based on inclined evaporation of inorganic substances, etc.) can be used to implement orientation treatment (orientation film). Particularly preferred are orientation treatments based on friction method and photo-orientation method. As materials used in the friction method, polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, and acrylic resin can be cited. As materials used in the photo-orientation method, polycinnamate system, polyamic acid / polyimide system, azobenzene system, etc. can be cited. In the case of providing an orientation treatment layer, it is believed that the liquid crystal compound and the pigment are oriented by the influence of the orientation treatment of the orientation treatment layer and the shear force applied to the anisotropic pigment film composition during coating.

[0539] The supply method and supply interval of the anisotropic dye film composition when applying 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.

[0540] The speed of applying 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. The speed of applying the anisotropic dye film composition 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 making the coating speed within the above range, the anisotropy of the anisotropic dye film can be obtained, and there is a tendency to be able to apply uniformly.

[0541] The coating temperature of the anisotropic dye film composition is usually 0°C to 100°C, preferably 80°C or less, and more preferably 60°C or less.

[0542] The humidity during application of the anisotropic dye film composition is preferably 10% RH or more and preferably 80 RH% or less.

[0543] 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.

[0544] Specifically, from the viewpoint of easiness of post-processing, durability of the anisotropic dye film, etc., film polymerization, surface coating, etc. are preferred.

[0545] 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.

[0546] 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 nm to 450 nm.

[0547] The light source of the active energy ray with a wavelength of 190 nm to 450 nm is not particularly limited. Examples thereof include lamp light sources such as 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 laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers. When used by irradiating light of a specific wavelength, a filter may also be used.

[0548] The exposure dose of active energy rays is preferably 10 J / m 2 ~10,000J / m 2 .

[0549] When the polymerization is performed using heat, it is preferably performed at a temperature in the range of 50°C to 200°C, and more preferably in the range of 60°C to 150°C.

[0550] 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.

[0551] [Optical components]

[0552] The optical element of the present invention includes the anisotropic dye film of the present invention.

[0553] 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).

[0554] The optical element of the present invention is most preferably used as a polarizing element.

[0555] 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.

[0556] In order to maintain and improve the function of the anisotropic pigment film, the optical element may be provided with other layers. Examples of other layers include layers having a function of shielding specific wavelengths used to improve durability such as light resistance, heat resistance, and water resistance, layers having a function of blocking specific substances (barrier films such as oxygen barrier films and water vapor barrier films, etc.); wavelength cutoff filters used to change the color gamut and improve optical properties, and layers containing materials that absorb specific wavelengths; etc.

[0557] [Polarizing element]

[0558] A polarizing element (hereinafter sometimes referred to as “polarizing element of the present invention”) can be produced using the anisotropic dye film of the present invention.

[0559] 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.

[0560] 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 such as improving polarization performance and mechanical strength; 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, laminating, etc., so as to be used as a laminate.

[0561] These layers can be appropriately arranged according to the manufacturing process, characteristics and functions, and the position and order of their lamination are not particularly limited. For example, the position of forming each layer can be on the anisotropic pigment film, or it can be the opposite side of the substrate provided with the anisotropic pigment film. In addition, the order of forming each layer can be before forming the anisotropic pigment film, or it can be after forming the anisotropic pigment film.

[0562] The layers having these optical functions can be formed by the following various methods.

[0563] 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 performing a treatment described in Japanese Patent Laid-Open No. 7-230007, etc.

[0564] 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 Nos. 2002-169025 and 2003-29030, or by overlapping two or more cholesteric liquid crystal layers having different central wavelengths for selective reflection.

[0565] 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.

[0566] 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.

[0567] 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.

[0568] 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.

[0569] Example

[0570] The present invention will be described in more detail below by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

[0571] In the following description, "parts" means "parts by mass".

[0572] [Method for Identifying Liquid Crystal Phase]

[0573] The liquid crystal properties of the obtained composition were observed by differential scanning calorimetry (DSC220CU manufactured by Seiko Instruments), X-ray structural analysis (NANO-Viewer manufactured by Rigaku Corporation), and a polarizing microscope (ECLIPSE LV100N POL manufactured by Nikon Instech Corporation) attached to a heating stage (HCS302-LN190 manufactured by TOYO Corporation). The liquid crystals were identified according to the methods described in pages 9 to 50 and 117 to 176 of the Liquid Crystal Handbook (manufactured by Maruzen Co., Ltd., published on October 30, 2001).

[0574] [Measurement of transmittance of anisotropic dye film for polarized light in the absorption axis / polarization axis direction and calculation of dichroic ratio]

[0575] 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.

[0576] Linearly polarized measurement light is 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. The dichroic ratio (D) is calculated by the following formula.

[0577] D=Az / Ay

[0578] (Where,

[0579] Ay=-log(Ty);

[0580] Az = -log(Tz);

[0581] Tz is the transmittance of the anisotropic pigment film for polarized light in the absorption axis direction;

[0582] Ty is the transmittance of the anisotropic dye film for polarized light in the direction of the polarization axis.)

[0583] Specifically, the composition was injected in an isotropic phase into a sandwich cell (cell gap: 8.0 μm or 10.0 μm, the formed polyimide film was previously rubbed with cloth) having an oriented film of polyimide (LX1400, manufactured by Hitachi Chemical DuPont Microsystems) formed on a glass substrate, and then cooled to 80°C at 10°C / min to obtain an anisotropic dye film. The dichroic ratio was measured at each temperature while further cooling to 40°C at 10°C / min. The dichroic ratio at the temperature and wavelength at which the maximum dichroic ratio was obtained was determined as the dichroic ratio of the anisotropic dye film.

[0584] In the first invention, the dichroic ratio of the anisotropic dye film measured above is preferably 23 or more.

[0585] In the second invention, the dichroic ratio of the anisotropic dye film measured above is preferably 13 or more, and more preferably 20 or more.

[0586] [Light resistance evaluation]

[0587] The light resistance was evaluated from the maximum Az maintenance rate (maximum Az after light resistance test / maximum Az before light resistance test×100) based on the maximum Az of the anisotropic dye film at 0 hours (before light resistance test) measured as follows.

[0588] Specifically, the composition was injected into the sandwich unit in an isotropic phase, cooled to 40°C at a rate of 10°C / min, and then heated by a high-pressure mercury lamp (500 mJ / cm 2 ) was photopolymerized to obtain a polymerized anisotropic dye film, and Tz was measured at 5 nm intervals within a wavelength range of 400 nm to 800 nm using the above-mentioned spectrophotometer to obtain Az before the light resistance test. Furthermore, the film was placed in a weather resistance tester (Atlas Weather-Ometer CI4000, product name: Atlas Weather-Ometer CI4000, blackboard temperature: 58.0°C, test tank temperature: 33.0°C, relative humidity: 50%, irradiance: 0.55 W / m 2 (340nm), total exposure 79.2kJ / m 2 ) for 40 hours, and then a light resistance test was performed. After the light resistance test, Tz was measured using the above-mentioned spectrophotometer, and Az after the light resistance test was measured.

[0589] It should be noted that Az and Tz are as described above.

[0590] (Evaluation criteria for light resistance evaluation)

[0591] ○: Maximum Az maintenance rate is 80% or more

[0592] ×: Maximum Az maintenance rate is less than 80%

[0593] [Synthesis of polymerizable liquid crystal compounds]

[0594] <Polymerizable Liquid Crystal Compound (I-1)>

[0595] According to the description of Japanese Patent Application Publication No. 2020-042305, a polymerizable liquid crystal compound (I-1) represented by the following structural formula was synthesized. 11 H 22 This means that 11 methylene chains are bonded in a straight chain.

[0596] [Chemistry 24]

[0597]

[0598] For the polymerizable liquid crystal compound (I-1), 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. In the differential scanning calorimetry, 0.2 parts by mass of 4-methoxyphenol as a polymerization inhibitor was added to 100 parts by mass of the polymerizable liquid crystal compound (I-1).

[0599] The phase transition temperature of the polymerizable liquid crystal compound (I-1) from liquid crystal to liquid was 111.0°C, and the phase transition temperature from liquid to liquid crystal was 109.4°C.

[0600] It should be noted that this temperature was confirmed to be the isotropic phase appearance temperature by polarizing microscope observation and X-ray structural analysis.

[0601] [Synthesis of pigments]

[0602] <Pigment (II-1)>

[0603] The dye (II-1) was synthesized by the synthesis method described below: Compound (II-1-a) was synthesized by the method described in JP-A-2010-155924.

[0604] [Chemistry 25]

[0605]

[0606] In a reactor, under a nitrogen atmosphere and at room temperature, compound (II-1-a) (1.61 g, 5.0 mmol) was dissolved in N-methylpyrrolidone (30 mL), and concentrated hydrochloric acid (2.1 mL, 4.2 eq.) was added, and the internal temperature was cooled to 5°C. A sodium nitrite aqueous solution (40% by mass, 0.40 g, 1.2 eq.) was added, and the mixture was stirred at an internal temperature of 0 to 5°C for 1.5 hours to obtain a diazonium salt solution. In another reactor, under a nitrogen atmosphere and at room temperature, diethylaniline (1.49 g, 2.0 eq.) was dissolved in N-methylpyrrolidone (10 mL), and the internal temperature was cooled to 0°C. The previous diazonium salt solution was added thereto at an internal temperature of 0 to 5°C, and sodium acetate (5.0 g, 12 eq.) was added, and the mixture was stirred for 1 hour while returning to room temperature. Drip pure water (40mL), suction filtration is carried out to precipitation, wash with pure water (20mL), obtain brown wet solid.This crude product is separated and purified with silica gel column chromatography (hexane / dichloromethane) and concentrated.Obtained yellow solid is dispersed among the methyl alcohol (40mL), at room temperature stirred after 1 hour, leaching solid component and obtain pigment (II-1) 2.05g.

[0607] The structure of the dye (II-1) was confirmed by nuclear magnetic resonance (NMR) spectrum measurement. The results are shown below.

[0608] 1 H-NMR (CDCl 3 , 400MHz) δ0.93 (t, 3H, J = 7.1Hz), δ1.10-1.18 (m, 2H), δ1.22-1.38 (m, 15H), δ1.46-1.56 (m, 2H), δ1.87-2.02 (m, 4H), δ2.50-2.60 (m, 1H), δ3.50(q,4H,J=6.6Hz), δ6.77(d,2H,J=8.7Hz) δ7.33(d,2H,J=8.7Hz), δ7.61(d,2H,J=8.4Hz), δ7.71(d,2H,J=8.4Hz), δ7.87-7.97(m,4H)

[0609] <Pigment (II-2)>

[0610] The dye (II-2) was synthesized according to the synthesis method described below.

[0611] [Chemistry 26]

[0612]

[0613] In a reactor, compound (II-1-a) (0.64 g, 2.0 mmol) was dissolved in N-methylpyrrolidone (10 mL), and concentrated hydrochloric acid (0.84 mL, 5.0 eq.) was added, and the internal temperature was cooled to 5°C. Then, sodium nitrite (0.145 g, 1.05 eq.) was dissolved in a small amount of water and added, and stirred at an internal temperature of 0 to 5°C for 1.5 hours to obtain a diazonium salt solution. In another reactor, 1-phenylpyrrolidine (0.59 g, 2.0 eq.) was dissolved in methanol (10 mL), and the internal temperature was cooled to 0°C. After adding the previous diazonium salt solution at an internal temperature of 0 to 5°C, sodium acetate (2.0 g, 12 eq.) was added, and stirring was continued for 1 hour while returning to room temperature. Purified water was added dropwise, and the precipitate was suction filtered and washed with purified water to obtain a brown wet solid. The crude product was separated and purified by silica gel column chromatography (toluene) and concentrated. The obtained yellow solid was dispersed in methanol, and the mixture was stirred at room temperature for 1 hour, and then the solid content was collected by filtration to obtain 0.49 g of a dye (II-2).

[0614] <Pigment (II-3)>

[0615] The dye (II-3) was synthesized according to the synthesis method described below.

[0616] [Chemistry 27]

[0617]

[0618] In a reactor, under a nitrogen atmosphere and at room temperature, compound (II-1-a) (0.64 g, 2.0 mmol) was dissolved in N-methylpyrrolidone (10 mL), and concentrated hydrochloric acid (0.99 mL, 5.0 eq.) was added, and the internal temperature was cooled to 5°C. Sodium nitrite aqueous solution (40% by mass, 0.145 g, 1.05 eq.) was added, and the mixture was stirred at an internal temperature of 0 to 5°C for 1.5 hours, and then sulfamic acid (10% by mass, 0.3 mL) was added to obtain a diazonium salt solution. In another reactor, under a nitrogen atmosphere and at room temperature, N-phenylpiperidine (0.645 g, 2.0 eq.) was dissolved in methanol (10 mL), and the internal temperature was cooled to 0°C. The previous diazonium salt solution was added thereto at an internal temperature of 0 to 5°C, and then sodium acetate (2.0 g, 12 eq.) was added, and stirring was continued for 1 hour while returning to room temperature. Drip pure water (40mL), suction filtration is carried out to precipitation, wash with pure water (20mL), obtain brown wet solid.This crude product is separated and purified with silica gel column chromatography (hexane / dichloromethane) and concentrated.Obtained yellow solid is dispersed in methyl alcohol (40mL), after at room temperature stirring 1 hour, filter solid component and obtain pigment (II-3) 0.25g.

[0619] <Pigment (II-4)>

[0620] The dye (II-4) was synthesized according to the synthesis method described below.

[0621] [Chemistry 28]

[0622]

[0623] Synthesis of compound (II-4-a):

[0624] Under nitrogen flow, acetic acid (500 mL) was added to compound (II-1-a) (15.0 g, 0.0467 mol) at room temperature, and the mixture was stirred and dissolved at 35°C. 1-nitroso-4-nitrobenzene (7.8 g, 1.1 eq.) was added in batches, and stirring was continued overnight at room temperature. The reaction solution was injected into 200 mL of pure water, stirred at room temperature for a period of time, and then filtered, and washed with pure water (200 mL) and methanol (200 mL) to obtain 15.9 g of compound (II-4-a).

[0625] Synthesis of compound (II-4-b):

[0626] Under nitrogen flow, compound (II-4-a) (15.9 g, 0.0348 mol) and 400 mL of ethanol were added at room temperature and stirred to dissolve. 2 O (11.1 g, 1.9 eq.), stirred at 78°C for 2 hours. The reaction solution was poured into purified water (110 mL), stirred at room temperature for a while, and then filtered, washed with purified water (150 mL) and methanol (200 mL) to obtain 13.8 g of compound (II-4-b).

[0627] Synthesis of Pigment (II-4):

[0628] In a reactor, compound (II-4-b) (2.0 g, 4.70 mmol) was dissolved in N-methylpyrrolidone (50 mL) at room temperature, and concentrated hydrochloric acid (1.37 mL, 3.8 eq.) was added, and the internal temperature was cooled to 5°C. Sodium nitrite (0.356 g, 1.1 eq.) was dissolved in a small amount of water and added dropwise, and stirred at an internal temperature of 0 to 5°C for 1 hour to obtain a diazonium salt solution. In another reactor, diethylaniline (1.05 g, 1.5 eq.) and aminosulfonic acid (0.138 g, 1.4 mmol) were dissolved in methanol (50 mL) under a nitrogen atmosphere at room temperature, and the internal temperature was cooled to 5°C. The previous diazonium salt solution was added thereto at an internal temperature of 0 to 5°C, and stirring was continued for 1 hour while returning the internal temperature to room temperature over 4 hours at an internal temperature of 0 to 5°C. Sodium acetate (0.85 g, 14 mmol) was added, and stirred at room temperature for 1 hour. Purified water (100 mL) was added dropwise, and the precipitate was filtered by suction and washed with purified water (100 mL) to obtain a brown wet solid. The crude product was separated and purified by silica gel column chromatography (hexane / dichloromethane) to obtain 0.55 g of pigment (II-4).

[0629] The maximum absorption wavelength (λ max1 ) is 495nm.

[0630] The structure of the dye (II-4) was confirmed by NMR spectrum measurement. The results are shown below.

[0631] 1 H-NMR (CDCl 3 ,400MHz)δ0.91(t,3H,J=6.9Hz),δ1.01-1.16(m,2H),δ1.24-1.35(m,14H ), δ1.44-1.51(m,2H), δ1.89-1.96(m,4H), δ2.50-2.60(m,1H), δ3.45-3. 52(m,4H), δ6.73-6.75(m,2H), δ7.33(d,2H,J=8.2Hz), δ7.61(d,2H,J=8. 2Hz), δ7.77(d,2H,J=8.8Hz), δ7.90(d,2H,J=8.8Hz), δ7.90-8.10(m,6H)

[0632] <Pigment (II-5)>

[0633] The dye (II-5) was synthesized according to the synthesis method described below.

[0634] [Chemistry 29]

[0635]

[0636] Synthesis of compound (II-5-a):

[0637] N-ethylaniline (130.0 g, 1073 mmol), 2-iodopropane (200 g, 1080 mmol), potassium carbonate (297 g, 2146 mmol), and acetonitrile (520 mL) were mixed and heated and stirred under reflux for 16 hours. After cooling to 25°C, the reaction solution was filtered and the filtrate was concentrated. The obtained yellow oily crude product was purified by silica gel chromatography (hexane / dichloromethane) to obtain 100 g of compound (II-5-a).

[0638] Synthesis of Pigment (II-5):

[0639] In a reactor, under a nitrogen atmosphere at room temperature, compound (II-4-b) (1.1 g, 2.58 mmol) was dissolved in N-methylpyrrolidone (20 mL), and concentrated hydrochloric acid (0.75 g, 3.5 eq.) was added, and the internal temperature was cooled to 5°C. Sodium nitrite (0.20 mg, 1.1 eq.) was added dropwise, and the mixture was stirred at an internal temperature of 0 to 5°C for 1 hour to obtain a diazonium salt solution. In another reactor, under a nitrogen atmosphere at room temperature, compound (II-5-a) (0.842 g, 2.0 eq.) and aminosulfonic acid (1.0 g, 10.5 mmol) were dissolved in methanol (12 mL) and tetrahydrofuran (2 mL), and the internal temperature was cooled to 0°C. The previous diazonium salt solution was added thereto over 20 minutes at an internal temperature of 0 to 5°C, and the mixture was returned to room temperature over 4 hours at an internal temperature of 0 to 5°C, and stirring was continued for 1 hour. Add sodium acetate (0.85g, 14mmol), at room temperature stir 1 hour.Drop pure water (20mL), precipitate is carried out suction filtration, wash with pure water (20mL), obtain brown wet solid.This crude product is separated and purified with silica gel column chromatography (hexane / dichloromethane), obtain pigment (II-5) 0.30g.

[0640] The maximum absorption wavelength (λ max1 ) is 497nm.

[0641] The structure of the dye (II-5) was confirmed by NMR spectrum measurement. The results are shown below.

[0642] 1 H-NMR (CDCl 3,400MHz)δ0.90-0.96(m,3H),δ1.02-1.17(m,2H),δ1.18-1.42(m,17H) , δ1.46-1.59(m,1H), δ1.88-2.02(m,4H), δ2.52-2.59(m,1H), δ3.40-3. 45(m,2H),δ4.21-4.35(m,1H),δ6.83-6.86(m,2H),δ7.35(d,2H,J=8.2 Hz), δ7.64(d,2H,J=8.2Hz), δ7.77(d,2H,J=8.8Hz), δ7.90-8.10(m,8H)

[0643] <Pigment (II-6)>

[0644] The dye (II-6) was synthesized according to the synthesis method described below.

[0645] [Chemistry 30]

[0646]

[0647] Synthesis of compound (II-6-a):

[0648] In a reactor, under a nitrogen atmosphere and at room temperature, N-methylaniline (50 g, 0.47 mol) was dissolved in acetonitrile (200 mL), and 2-iodopropane (87 g, 1.1 eq) and potassium carbonate (129 g, 2.0 eq) were added, and stirred for 14 hours under heating reflux at an external temperature of 80°C. After cooling to 25°C, the reaction solution was filtered and the filtrate was concentrated. The obtained yellow oily crude product was purified by silica gel chromatography (hexane / dichloromethane) to obtain 39 g of compound (II-6-a).

[0649] Synthesis of Pigment (II-6):

[0650] In a reactor, under a nitrogen atmosphere and at room temperature, compound (II-4-b) (433 mg, 2 mmol) was dissolved in N-methylpyrrolidone (8 mL), and concentrated hydrochloric acid (319 mg, 3.0 eq.) was added, and the internal temperature was cooled to 5°C. A sodium nitrite aqueous solution (20% by mass, 397 mg, 1.2 eq.) was added dropwise, and the mixture was stirred at an internal temperature of 0 to 5°C for 1 hour to obtain a diazonium salt solution. In another reactor, under a nitrogen atmosphere and at room temperature, compound (II-6-a) (314 mg, 2.0 eq.) was dissolved in methanol (8 mL) and tetrahydrofuran (1 mL), and the internal temperature was cooled to 0°C. The previous diazonium salt solution was added thereto over 20 minutes at an internal temperature of 0 to 5°C, and the mixture was returned to room temperature over 4 hours at an internal temperature of 0 to 5°C, and stirring was continued for 1 hour. Purified water (5 mL) was added dropwise, and the precipitate was filtered by suction and washed with purified water (5 mL) to obtain a brown wet solid. The crude product was separated and purified by silica gel column chromatography (hexane / dichloromethane) to obtain 101 mg of pigment (II-6).

[0651] The maximum absorption wavelength (λ max1 ) is 491nm.

[0652] The structure of the dye (II-6) was confirmed by NMR spectrum measurement. The results are shown below.

[0653] 1 H-NMR (CDCl 3 , 400MHz) δ0.93 (t, 3H, J = 6.9Hz), δ1.02-1.17 (m, 2H), δ1.18-1.42 (m, 16H), δ1.46-1.59 (m, 1H), δ1.88-2.02 (m, 4H), δ2.50-2.60 (m, 1H), δ2.9 2(s,3H), δ4.21-4.35(m,1H), δ6.83-6.95(m,2H), δ7.35(d,2H,J=8.2Hz), δ7.64(d,2H,J=8.2Hz), δ7.77(d,2H,J=8.8Hz), δ7.90-8.10(m,8H)

[0654] <Pigment (II-7)>

[0655] The dye (II-7) was synthesized according to the synthesis method described below.

[0656] [Chemistry 31]

[0657]

[0658] Synthesis of compound (II-7-a):

[0659] In a reactor, under a nitrogen atmosphere and at room temperature, N-isopropylaniline (19.0 g, 0.140 mol) was dissolved in N,N-dimethylformamide (76 mL), and 1-fluoro-2-iodoethane (24.4 g, 1.1 eq) and potassium carbonate (38.8 g, 2.0 eq) were added, and stirred for 15 hours under heating reflux at an external temperature of 95°C. After cooling to 25°C, the reaction solution was filtered and the filtrate was concentrated. The obtained yellow oily crude product was purified by silica gel chromatography (hexane / dichloromethane) to obtain 7.91 g of compound (II-7-a).

[0660] Synthesis of Pigment (II-7):

[0661] In a reactor, under a nitrogen atmosphere and at room temperature, compound (II-4-b) (1.74 mg, 2.35 mmol) was dissolved in N-methylpyrrolidone (100 mL), and concentrated hydrochloric acid (1.18 mL, 3.5 eq.) was added, and the internal temperature was cooled to 5°C. Sodium nitrite (0.31 g, 1.1 eq.) was dissolved in a small amount of water, and then added dropwise, and stirred at an internal temperature of 0 to 5°C for 1 hour to obtain a diazonium salt solution. In another reactor, under a nitrogen atmosphere and at room temperature, compound (II-7-a) (1.48 g, 2.0 eq.) was dissolved in methanol (17 mL), and the internal temperature was cooled to 0°C. The previous diazonium salt solution was added thereto at an internal temperature of 0 to 5°C, and stirred at an internal temperature of 0 to 5°C for 1 hour, and then sodium acetate (0.75 g) was added, and stirring was continued for 1 hour while returning to room temperature. Purified water (20 mL) was added dropwise, the precipitate was filtered by suction, and washed with purified water (50 mL) and methanol (200 mL) to obtain a brown wet solid. The crude product was separated and purified by silica gel column chromatography (hexane / dichloromethane) to obtain 0.274 g of pigment (II-7).

[0662] The maximum absorption wavelength (λ max1 ) is 470nm.

[0663] The structure of the dye (II-7) was confirmed by NMR spectrum measurement. The results are shown below.

[0664] 1 H-NMR (CDCl 3,400MHz)δ0.90-0.95(m,3H),δ1.02-1.17(m,2H),δ1.18-1.42(m,14H),δ1. 46-1.59(m,1H),δ1.88-2.02(m,4H),δ2.52-2.59(m,1H),δ3.65-3.75(m,2H) ,δ4.21-4.30(m,1H),δ6.54-6.60(m,1H),δ6.66-6.70(m,1H),δ7.35(d,2H,J =8.2Hz), δ7.64(d,2H,J=8.2Hz), δ7.77(d,2H,J=8.8Hz), δ7.90-8.10(m,8H)

[0665] <Pigment (II-8)>

[0666] The dye (II-8) was synthesized according to the synthesis method described below.

[0667] [Chemistry 32]

[0668]

[0669] Synthesis of compound (II-8-a):

[0670] 3,5,5-triethyl-1-hexanol (76.8 g, 532 mmol), 47% aqueous hydrogen bromide (HBr) solution (100.8 g, 586 mmol), and concentrated sulfuric acid (16.6 g, 185 mmol) were mixed and stirred at 120°C for 5 hours. After cooling to 25°C, the mixture was added to hexane (1200 mL) and washed with purified water (2400 mL × 3 times). After concentrating the organic layer, it was purified by silica gel chromatography (hexane) to obtain 71.0 g of compound (II-8-a).

[0671] Synthesis of compound (II-8-b):

[0672] Under nitrogen flow, 4-nitrophenol (65.0 g, 467 mmol), compound (II-8-a) (116.2 g, 560 mmol), dimethylformamide (520 mL), potassium carbonate (129.1 g, 934 mmol) were mixed and stirred at 90°C for 6 hours. Purified water (1000 mL) was added thereto, and the mixture was extracted with a 1 / 4 mixture of ethyl acetate / hexane, and the oil layer was concentrated. Purification was performed by silica gel chromatography (ethyl acetate / hexane) to obtain 113.5 g of compound (II-8-b).

[0673] Synthesis of compound (II-8-c):

[0674] Under argon flow, compound (II-8-b) (113.5 g, 427.7 mmol) and ethyl acetate (1100 mL) were mixed, palladium carbon (5% Pd / C, water content 55% by mass, 11.4 g) was added, and stirred at 25 ° C for 60 hours under a hydrogen atmosphere. After the container was replaced with argon, the catalyst was filtered out. The catalyst was extracted with dichloromethane, the organic layers were combined and concentrated, and purified by silica gel chromatography (dichloromethane) to obtain 99.5 g of compound (II-8-c).

[0675] Synthesis of compound (II-8-d):

[0676] Under nitrogen flow, compound (II-8-c) (43.3 g, 0.184 mol) and acetic acid (1.3 L) were added at room temperature, stirred and dissolved, and 1-nitroso-4-nitrobenzene (28.0 g, 1.0 eq.) was added in batches. After stirring for 4 hours, 1-nitroso-4-nitrobenzene (8.4 g, 0.3 eq.) was added, and stirring was continued overnight at room temperature. Dichloromethane (3.9 L) and purified water (1.3 L) were injected, and after stirring for a period of time, oil-water separation was performed. After the aqueous layer was extracted with dichloromethane (1.3 L), it was combined with the original organic layer, washed with purified water (1.3 L), saturated sodium bicarbonate water (1.3 L), and saturated brine (500 mL) in sequence, dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated to obtain a reddish brown solid. The crude product was purified by silica gel column chromatography (hexane / dichloromethane=3 / 1) to obtain 52.08 g of compound (II-8-d).

[0677] Synthesis of compound (II-8-e):

[0678] Compound (II-8-d) (52.0 g, 0.141 mol) and ethanol (520 mL), purified water (52 mL) and sodium sulfide pentahydrate (Na 2 S.5H 2 O) (47.4 g, 2.0 eq.), stirred at an external temperature of 80°C for 6 hours. After naturally cooling to room temperature, the reaction solution was injected into pure water (500 mL), stirred for a period of time, filtered, and rinsed with pure water (250 mL). The obtained solid was purified by silica gel column chromatography (dichloromethane) to obtain 34.40 g of compound (II-8-e).

[0679] Synthesis of compound (II-8-f):

[0680] Under nitrogen flow, compound (II-8-e) (34.4 g, 0.101 mol) and acetic acid (1.0 L) were added at room temperature, stirred to dissolve, and 1-nitroso-4-nitrobenzene (20.0 g, 1.3 eq.) was added in batches, and stirring was continued overnight at room temperature. The reaction solution was injected into pure water, stirred at room temperature for a period of time, filtered, and rinsed with pure water. The solid was purified by silica gel column chromatography (chloroform) to obtain 38.6 g of compound (II-8-f).

[0681] Synthesis of compound (II-8-g):

[0682] Under nitrogen atmosphere, compound (II-8-f) (38.6 g, 81.5 mmol), ethanol (386 mL), purified water (39 mL) and Na 2 S.5H 2 O (27.4 g, 2.0 eq.), stirred at an external temperature of 80°C for 6 hours. After cooling naturally to room temperature, the reaction solution was injected into pure water (400 mL), stirred for a period of time, filtered, and rinsed with pure water (200 mL). The obtained solid was purified by silica gel column chromatography (hexane / dichloromethane = 1 / 1) to obtain 30.20 g of compound (II-8-g).

[0683] Synthesis of Pigment (II-8):

[0684] Compound (II-8-g) (1.5 g, 3.38 mmol) and HCl (1.4 mL) were dissolved in N-methyl-2-pyrrolidone (NMP) (20 mL), and the internal temperature was cooled to 0°C. Sodium nitrate (0.256 g, 3.718 mmol) was dissolved in 5 mL of purified water, and added dropwise to the previous solution at an internal temperature of 0 to 3°C, and stirred at an internal temperature of 0 to 2°C for 1 hour. In another reactor, 2-[ethyl(phenyl)amino]acetic acid (1.05 g, 1.5 eq.) was dissolved in methanol (10 mL) under a nitrogen atmosphere at room temperature, and sodium acetate (1.44 g) was added, and the internal temperature was cooled to 0°C. The previous diazonium salt solution was added thereto over 30 minutes at an internal temperature of 0 to 5°C, and stirred for 2 hours while returning to room temperature at an internal temperature of 0 to 5°C over 1 hour. Purified water was added, and the mixture was filtered and washed with methanol. The obtained crude product was purified by silica gel column chromatography (toluene / dichloromethane=1 / 3) to obtain 0.24 g of a dye (II-8).

[0685] The maximum absorption wavelength (λ max1 ) is 491nm.

[0686] In addition, the structure was confirmed by NMR spectrum measurement. The results are shown below.

[0687] 1 H-NMR (CDCl 3 , 400MHz) δ0.92 (s, 9H), δ1.02 (d, 3H, J = 6.8Hz), δ1.12-1.34 (m, 5H), δ1.66-1.85 (m, 3H), δ3.54 (q, 2H, J = 6.8Hz), δ3.698 (q, 2H, J=8.8Hz), δ4.09(t,2H,J=6.8Hz), δ4.31(t,2H,J=6.8Hz), δ6.83(d,2H,J=9.2Hz), δ7.03(d,2H,J=9.2Hz), δ7.92-8.10(m,12H)

[0688] <Pigment (III-1)>

[0689] The dye (III-1) was synthesized according to the synthesis method described below.

[0690] [Chemistry 33]

[0691]

[0692] Synthesis of compound (III-1-a):

[0693] After cooling a mixed solution of 4-iodoaniline (10 mmol, 2.2 g) in 2N HCl aqueous solution (15 mL) and ethanol (30 mL) to 0°C, an aqueous solution (10 mL) of sodium nitrite (11 mmol, 0.76 g) was added dropwise little by little, and the mixture was stirred at 0°C for 10 minutes. Then, aminosulfonic acid (0.2 mmol) was added to the reaction solution, and the mixture was further stirred at 0°C for 10 minutes to obtain a diazonium salt solution. On the other hand, a mixed solution of ethanol (200 mL) and water (100 mL) to which N,N-diethylaniline (10 mmol, 1.49 g) and sodium acetate (20 mmol, 1.7 g) were added was cooled to 0°C, and the previous diazonium salt solution was added little by little, and the mixture was stirred while warming to room temperature. NaOH was added to the obtained reaction solution to adjust the pH to 10-12. The crude product was filtered, washed with water, dried, and recrystallized from methanol to obtain 2.78 g of compound (III-1-a).

[0694] Synthesis of pigment (III-1):

[0695] Under nitrogen atmosphere, triethylamine (30 mL), 4-butylphenylacetylene (2.5 mmol, 332 mg), PdCl 2 (PPh 3 )2 (0.1mmol, 70mg) was added and heated under reflux for 6 hours. After filtering the precipitate, it was concentrated under reduced pressure. The obtained crude product was suspended and washed with methanol and purified by silica gel chromatography (developing solution (hexane: ethyl acetate = 9: 1 (volume ratio)) to obtain 836mg of pigment (III-1).

[0696] The chemical structures of the above-synthesized polymerizable liquid crystal compound (I-1) and pigments (II-1), (II-2), (II-3), (II-4), (II-5), (II-6), (II-7) and (II-8) and pigments (III-1) and (III-2) for comparison are shown below.

[0697] The maximum absorption wavelength (λ max1 ) is 454nm.

[0698] [Chemistry 34]

[0699]

[0700] [Table 1]

[0701]

[0702] [Examples and Comparative Examples of the First Invention]

[0703] [Example 1]

[0704] 20.05 parts of the polymerizable liquid crystal compound (I-1) and 0.40 parts of the pigment (II-1) were added to 4016.05 parts of chloroform, stirred to dissolve them, and then the solvent was removed to obtain a composition 1A. n1 / r n2 is 0.75.

[0705] The fact that Composition 1A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0706] In order to determine the dichroic ratio by the above method using the obtained composition 1A, an anisotropic dye film 1A was produced using a sandwich cell with a cell gap of 8.0 μm, and the dichroic ratio of the anisotropic dye film 1A was determined.

[0707] In addition, 24.15 parts of the polymerizable liquid crystal compound (I-1), 0.48 parts of the pigment (II-1), 0.48 parts of a polymerization initiator (IGM Resins BV Irgacure 369), and 0.36 parts of a surfactant (BYK-361N manufactured by BYK) were added to 6013.38 parts of chloroform, stirred to dissolve, and then the solvent was removed to obtain a composition 1B.

[0708] In order to determine the light resistance of the obtained composition 1B by the above method, an anisotropic dye film 1B was produced using a sandwich cell having a cell gap of 8.0 μm, and the light resistance of the anisotropic dye film 1B was determined.

[0709] Table 1 shows the evaluation results of the dichroic ratio and light resistance.

[0710] [Example 2]

[0711] Composition 2A and anisotropic dye film 2A were obtained in the same manner as composition 1A and anisotropic dye film 1A of Example 1 except that 0.39 parts of dye (II-2) was added instead of 0.40 parts of dye (II-1). n1 / r n2 is 0.75.

[0712] The fact that Composition 2A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0713] In addition, the dichroic ratio of the anisotropic dye film 2A is determined.

[0714] Composition 2B and anisotropic dye film 2B were obtained in the same manner as composition 1B and anisotropic dye film 1B of Example 1, except that 0.48 parts of dye (II-2) was added instead of 0.48 parts of dye (II-1).

[0715] In addition, the light resistance of the anisotropic dye film 2B was determined.

[0716] Table 1 shows the evaluation results of the dichroic ratio and light resistance.

[0717] [Example 3]

[0718] Composition 3A and anisotropic dye film 3A were obtained in the same manner as composition 1A and anisotropic dye film 1A of Example 1 except that 0.50 parts of dye (II-3) was added instead of 0.40 parts of dye (II-1). n1 / r n2 is 0.75.

[0719] The fact that Composition 3A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0720] In addition, the dichroic ratio of the anisotropic dye film 3A is determined.

[0721] Composition 3B and anisotropic dye film 3B were obtained in the same manner as composition 1B and anisotropic dye film 1B of Example 1, except that 0.61 parts of dye (II-3) was added instead of 0.48 parts of dye (II-1).

[0722] By the same method as in Example 1, the light resistance of the anisotropic dye film 3B was determined.

[0723] Table 1 shows the evaluation results of the dichroic ratio and light resistance.

[0724] [Example 4]

[0725] Composition 4 and anisotropic dye film 4A were obtained in the same manner as composition 1A and anisotropic dye film 1A of Example 1 except that 0.39 parts of dye (II-4) was added instead of 0.40 parts of dye (II-1). n1 / r n2 is 0.6.

[0726] The fact that Composition 4A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0727] In addition, the dichroic ratio of the anisotropic dye film 4A is determined.

[0728] Composition 4B and anisotropic dye film 4B were obtained in the same manner as composition 1B and anisotropic dye film 1B of Example 1, except that 0.47 parts of dye (II-4) was added instead of 0.48 parts of dye (II-1).

[0729] In addition, the light resistance of the anisotropic dye film 4B was determined.

[0730] Table 1 shows the evaluation results of the dichroic ratio and light resistance.

[0731] [Example 5]

[0732] Composition 5A and anisotropic dye film 5A were obtained in the same manner as composition 1A and anisotropic dye film 1A of Example 1 except that 0.39 parts of dye (II-5) was added instead of 0.40 parts of dye (II-1). n1 / r n2 is 0.6.

[0733] The fact that Composition 5A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0734] In addition, the dichroic ratio of the anisotropic dye film 5A is determined.

[0735] Composition 5B and anisotropic dye film 5B were obtained in the same manner as composition 1B and anisotropic dye film 1B of Example 1, except that 0.48 parts of dye (II-5) was added instead of 0.48 parts of dye (II-1).

[0736] In addition, the light resistance of the anisotropic dye film 5B was determined.

[0737] Table 1 shows the evaluation results of the dichroic ratio and light resistance.

[0738] [Example 6]

[0739] Composition 6A and anisotropic dye film 6A were obtained in the same manner as composition 1A and anisotropic dye film 1A of Example 1 except that 0.40 parts of dye (II-6) was added instead of 0.40 parts of dye (II-1). n1 / r n2 is 0.6.

[0740] The fact that Composition 6A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0741] In addition, the dichroic ratio of the anisotropic dye film 6A is determined.

[0742] Composition 6B and anisotropic dye film 6B were obtained in the same manner as composition 1B and anisotropic dye film 1B of Example 1, except that 0.48 parts of dye (II-6) was added instead of 0.48 parts of dye (II-1).

[0743] In addition, the light resistance of the anisotropic dye film 6B was determined.

[0744] Table 1 shows the evaluation results of the dichroic ratio and light resistance.

[0745] [Example 7]

[0746] Composition 7A and anisotropic dye film 7A were obtained in the same manner as composition 1A and anisotropic dye film 1A of Example 1 except that 0.42 parts of dye (II-7) was added instead of 0.40 parts of dye (II-1). n1 / r n2 is 0.6.

[0747] The fact that Composition 7A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0748] In addition, the dichroic ratio of the anisotropic dye film 7A is determined.

[0749] Composition 7B and anisotropic dye film 7B were obtained in the same manner as composition 1B and anisotropic dye film 1B of Example 1, except that 0.52 parts of dye (II-7) was added instead of 0.48 parts of dye (II-1).

[0750] In addition, the light resistance of the anisotropic dye film 7B was determined.

[0751] Table 1 shows the evaluation results of the dichroic ratio and light resistance.

[0752] [Comparative Example 1]

[0753] Composition 8A and anisotropic dye film 8A were obtained in the same manner as composition 1A and anisotropic dye film 1A of Example 1 except that 0.35 parts of dye (III-1) was used instead of 0.40 parts of dye (II-1). n1 / r n2 is 1.

[0754] The fact that Composition 8A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0755] In addition, the dichroic ratio of anisotropic dye film 8A is determined.

[0756] Composition 8B and anisotropic dye film 8B were obtained in the same manner as composition 1B and anisotropic dye film 1B of Example 1, except that 0.42 parts of dye (III-1) was added instead of 0.48 parts of dye (II-1).

[0757] In addition, the light resistance of the anisotropic dye film 8B was determined.

[0758] Table 1 shows the evaluation results of the dichroic ratio and light resistance.

[0759] [Table 2]

[0760]

[0761] As is apparent from Table 2, in Examples 1 to 7 using the compounds of the first invention, the maximum dichroic ratio showed a high value and the light resistance was also good.

[0762] On the other hand, in Comparative Example 1, the dichroic ratio and the light resistance were lower than those of the Examples.

[0763] [Examples and Comparative Examples of the Second Invention]

[0764] [Example 8]

[0765] 20.05 parts of the polymerizable liquid crystal compound (I-1) and 0.39 parts of the pigment (II-4) were added to 4016.05 parts of chloroform, stirred to dissolve them, and then the solvent was removed to obtain a composition 9A. n1 / r n2 is 0.6.

[0766] The fact that Composition 9A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0767] In order to determine the dichroic ratio using the obtained composition 9A by the above method, an anisotropic dye film 9A was prepared using a sandwich cell with a cell gap of 8.0 μm, and the dichroic ratio and the wavelength (λ) at which the orthogonal absorbance of the anisotropic dye film 8A reached a maximum were determined. max2 ).

[0768] In addition, 24.15 parts of the polymerizable liquid crystal compound (I-1), 0.47 parts of the pigment (II-4), 0.48 parts of a polymerization initiator (Irgacure 369 manufactured by IGM Resins BV), and 0.36 parts of a surfactant (BYK-361N manufactured by BYK) were added to 6013.38 parts of chloroform, stirred to dissolve, and then the solvent was removed to obtain a composition 9B.

[0769] In order to determine the light resistance of the obtained composition 9B by the above method, an anisotropic dye film 9B was produced using a sandwich cell having a cell gap of 8.0 μm, and the light resistance of the anisotropic dye film 9B was determined.

[0770] The evaluation results of the dichroic ratio and light resistance were compared with the λ max1 , max2 and λ max2 -λ max1 The values ​​are shown in Table 3.

[0771] [Example 9]

[0772] Composition 10A and anisotropic dye film 10A were obtained in the same manner as composition 9A and anisotropic dye film 9A of Example 8 except that 0.39 parts of dye (II-5) was added instead of 0.39 parts of dye (II-4). n1 / r n2 is 0.6.

[0773] The fact that the composition 10A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0774] In addition, the wavelength (λ) at which the dichroic ratio and the orthogonal absorbance of the anisotropic dye film 10A reach a maximum is determined. max2 ).

[0775] Composition 10B and anisotropic dye film 10B were obtained in the same manner as composition 9B and anisotropic dye film 9B of Example 8 except that 0.48 parts of dye (II-5) was added instead of 0.48 parts of dye (II-4), and the light resistance of anisotropic dye film 10B was determined.

[0776] The evaluation results of the dichroic ratio and light resistance were compared with the λ max1 , max2 and λ max2 -λ max1 The values ​​are shown in Table 3.

[0777] [Example 10]

[0778] Composition 11A and anisotropic dye film 11A were obtained in the same manner as composition 9A and anisotropic dye film 9A of Example 8 except that 0.40 parts of dye (II-6) was added instead of 0.39 parts of dye (II-4). n1 / r n2 is 0.6.

[0779] The fact that the composition 11A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0780] In addition, the wavelength (λ) at which the dichroic ratio and the orthogonal absorbance of the anisotropic pigment film 11A reach a maximum is determined. max2 ).

[0781] Composition 11B and anisotropic dye film 11B were obtained in the same manner as composition 9B and anisotropic dye film 9B of Example 8 except that 0.48 parts of dye (II-6) was added instead of 0.48 parts of dye (II-4), and the light resistance of anisotropic dye film 11B was determined.

[0782] The evaluation results of the dichroic ratio and light resistance were compared with the λ max1 , max2 and λ max2 -λ max1 The values ​​are shown in Table 3.

[0783] [Example 11]

[0784] Composition 12A and anisotropic dye film 12A were obtained in the same manner as composition 9A and anisotropic dye film 9A in Example 8 except that 0.42 parts of dye (II-7) was added instead of 0.39 parts of dye (II-4). n1 / r n2 is 0.6.

[0785] The fact that the composition 12A exhibited liquid crystallinity was confirmed by observing the birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0786] In addition, the wavelength (λ) at which the dichroic ratio and the orthogonal absorbance of the anisotropic pigment film 12A reach a maximum is determined. max2 ).

[0787] Composition 12B and anisotropic dye film 12B were obtained in the same manner as composition 9B and anisotropic dye film 9B of Example 8 except that 0.52 parts of dye (II-7) was added instead of 0.48 parts of dye (II-4), and the light resistance of anisotropic dye film 12B was determined.

[0788] The evaluation results of the dichroic ratio and light resistance were compared with the λ max1 , max2 and λ max2 -λ max1 The values ​​are shown in Table 3.

[0789] [Example 12]

[0790] Composition 13A and anisotropic dye film 13A were obtained in the same manner as composition 9A and anisotropic dye film 9A in Example 8 except that 0.27 parts of dye (II-8) was added instead of 0.39 parts of dye (II-4). n1 / r n2 is 0.75.

[0791] The fact that Composition 13A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0792] In addition, the wavelength (λ) at which the anisotropic pigment film 13A and the orthogonal absorbance reach a maximum is determined. max2 )'s two-color ratio.

[0793] Composition 13B and anisotropic dye film 13B were obtained in the same manner as composition 9B and anisotropic dye film 9B of Example 8 except that 0.39 parts of dye (II-8) was added instead of 0.48 parts of dye (II-4), and the light resistance of anisotropic dye film 13B was determined.

[0794] The evaluation results of the dichroic ratio and light resistance were compared with the λ max1 , max2 and λ max2 -λ max1 The values ​​are shown in Table 3.

[0795] [Comparative Example 2]

[0796] Composition 14A and anisotropic dye film 14A were obtained in the same manner as composition 9A and anisotropic dye film 9A in Example 8, except that 0.55 parts of dye (III-2) was used instead of 0.39 parts of dye (II-4). n1 / r n2 is 0.6.

[0797] The fact that Composition 14A exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a heating stage.

[0798] In addition, the wavelength (λ) at which the dichroic ratio and the orthogonal absorbance of the anisotropic pigment film 14A reach a maximum is determined. max2 ).

[0799] Composition 14B and anisotropic dye film 14B were obtained in the same manner as composition 9B and anisotropic dye film 9B of Example 8 except that 0.66 parts of dye (III-2) was added instead of 0.48 parts of dye (II-4), and the light resistance of anisotropic dye film 14B was determined.

[0800] The evaluation results of the dichroic ratio and light resistance were compared with the λ max1 , max2 and λ max2 -λ max1 The values ​​are shown in Table 3.

[0801] [Table 3]

[0802]

[0803] According to Table 3, the pigments of the compositions used in Examples 8 to 12 satisfy λ max2 -λ max1 <0, the maximum dichroic ratio of the anisotropic dye film showed a high value, and the light resistance was also good. On the other hand, the dye of the composition used in Comparative Example 2 did not satisfy λ max2 -λ max1 <0, indicating that the maximum dichroic ratio and light resistance of the anisotropic pigment film are lower than those of the example.

[0804] Although the present invention has been described in detail using specific embodiments, it is apparent to one skilled in the art that various modifications can be made within the scope of achieving the effects of the invention.

[0805] This application is based on Japanese Patent Application No. 2022-160390 and Japanese Patent Application No. 2022-160391 filed on October 4, 2022, the entire contents of which are incorporated herein by reference.

Claims

1. A compound represented by the following formula (1): [Chemistry 1] In formula (1), -XA represents a monovalent organic group; -RA 1 and-RA 2 Each independently represents an alkyl group which may have a substituent; -RA 1 and-RA 2 Optionally, they can be combined to form a ring, but -RA 1 and-RA 2 The formed ring -RA 1 and-RA 2 Some are formed only of hydrocarbon chains; -A 1 -、-A 2 -、-A 3 -and-A 4 - each independently represents a 1,4-phenylene group which may be substituted; n represents 0, 1 or 2; When n is 2, multiple -A 3 - can be the same or different from each other.

2. The compound according to claim 1, wherein -XA in the formula (1) is a hydrogen atom, -Ra, -O-Ra, -NH-Ra, -C(=O)-Ra, -C(=O)-O-Ra, -C(=O)-NH-Ra, -C(=O)-N(-Rb)-Ra, -OC(=O)-Ra, -NH-C(=O)-Ra, -N(-Rb)-C(=O)-Ra, or -S-Ra, wherein -Ra and -Rb each independently represent an alkyl group having 1 to 15 carbon atoms which may or may not have a branch, a cycloalkyl group having 5 to 14 atoms constituting the ring, or an aryl group having 5 to 14 atoms constituting the ring, and the alkyl group, cycloalkyl group and aryl group may or may not have a substituent; furthermore, -Ra and -Rb may be combined to form a ring having 2 to 15 carbon atoms, and the ring may or may not have a substituent.

3. The compound according to claim 1 or 2, wherein -RA in the formula (1) 1 and-RA 2 Each is independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.

4. A composition comprising a compound represented by the following formula (2) and a polymerizable liquid crystal compound, [Chemistry 2] In formula (2), -XB represents a monovalent organic group; -RB 1 and-RB 2 Each independently represents an alkyl group which may have a substituent; -RB 1 and-RB 2 Optionally become one to form a ring; -B 1 -and-B 2 - each independently represents a 1,4-phenylene group which may be substituted; -B 3 -and-B 4 - each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent; n represents 0, 1 or 2; When n is 2, multiple -B 3 - can be the same or different from each other.

5. The composition according to claim 4, wherein In the formula (2), -B 4 - is 1,4-phenylene which may have a substituent.

6. The composition according to claim 4, wherein In the formula (2), -B 3 - is 1,4-phenylene which may have a substituent.

7. The composition according to claim 4, wherein -XB in the formula (2) is a hydrogen atom, -Ra, -O-Ra, -NH-Ra, -C(=O)-Ra, -C(=O)-O-Ra, -C(=O)-NH-Ra, -C(=O)-N(-Rb)-Ra, -OC(=O)-Ra, -NH-C(=O)-Ra, -N(-Rb)-C(=O)-Ra, or -S-Ra, wherein -Ra and -Rb each independently represent an alkyl group having 1 to 15 carbon atoms which may or may not have a branch, a cycloalkyl group having 5 to 14 atoms constituting the ring, or an aryl group having 5 to 14 atoms constituting the ring, and the alkyl group, cycloalkyl group and aryl group may or may not have a substituent. In addition, -Ra and -Rb may be combined to form a ring having 2 to 15 carbon atoms, and the ring may or may not have a substituent.

8. The composition according to claim 4, wherein -RB in the formula (2) 1 and-RB 2 Each is independently an alkyl group having 1 to 10 carbon atoms which may have a substituent. 9 . An anisotropic dye film formed using the composition according to claim 4 . 10 . An optical element comprising the anisotropic dye film according to claim 9 .

11. A composition comprising a polymerizable liquid crystal compound and a pigment, wherein: The maximum absorption wavelength of the pigment satisfies the following relational expression (11): l max2 -l max1 <0 (11) In formula (11), λ max1 represents the maximum absorption wavelength of the pigment in the solvent, λ max2 It indicates the maximum absorption wavelength of the pigment in the pigment film formed using the composition.

12. The composition according to claim 11, wherein The pigment is an azo pigment.

13. The composition according to claim 12, wherein The pigment is a compound represented by the following formula (12): X 20 (-A 21 ) m1 (-N=N-A 22 ) n1 -N=N-A 23 -Y 20 (12) In formula (12), -A 21 -、-A 22 -、-A 23 - each independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocyclic ring which may have a substituent, -X 20 , -Y 20 Each independently represents a monovalent arbitrary substituent, m1 means 1 or 2, n1 means 0, 1, 2 or 3; When m1 is 2, -A 21 - can be the same or different from each other; When n1 is 2 or 3, -A 22 - can be the same or different from each other.

14. The composition according to claim 13, wherein In the formula (12), -A 21 -、-A 23 - are each independently a divalent group of an aromatic hydrocarbon ring which may have a substituent.

15. The composition according to claim 13, wherein In the formula (12), -A 22 - is a divalent group of an aromatic hydrocarbon ring which may have a substituent.

16. The composition according to claim 13, wherein In the formula (12), -Y 20 It is represented by the following formula (12a), -N-(R y )-R x (12a) In formula (12a), -R x , -R y Each independently represents an alkyl group or an aryl group which may or may not have a branch, and the alkyl group or the aryl group may or may not have a substituent; -R x and -R y They may be combined with N to form a ring having 2 to 15 carbon atoms, and the ring may have a substituent.

17. The composition according to claim 11, wherein The polymerizable liquid crystal compound is a low-molecular polymerizable liquid crystal compound having no copolymerization structure. 18 . An anisotropic dye film formed using the composition according to claim 11 . 19 . An optical element comprising the anisotropic dye film according to claim 18 .

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