JP6798600B2 - Anisotropic dye film forming composition, anisotropic dye film, and optical element - Google Patents

Description

The present invention is an anisotropic dye film formed by applying a liquid crystal composition, particularly a polarizing film provided in a display element of a dimming element, a liquid crystal element (LCD), and an organic electroluminescence element (OLED). The present invention relates to an anisotropic dye film forming composition and an anisotropic dye film exhibiting high bichromaticity, and an optical element, which are useful for the above.

In the LCD, a linear polarizing film and a circular polarizing film are used in order to control the optical rotation and birefringence in the display. Also in OLED, a circular polarizing film is used to prevent reflection of external light in a bright place.
Conventionally, as such a polarizing film, for example, a polarizing film obtained by dyeing polyvinyl alcohol (PVA) with a low concentration of iodine (iodine-PVA polarizing film) is known (Patent Document 1).
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).

Japanese Unexamined Patent Publication No. 1-105204 Special Table 2004-535483

However, the iodine-PVA polarizing plate having such a low concentration alleviates the problem that iodine sublimates or deteriorates depending on the usage environment and the color changes, and the stretching of PVA is alleviated. There is a problem that warpage occurs due to

Further, in a polarizing film formed by applying a liquid crystal composition containing a dye, high light absorption selection performance cannot be obtained, or if high light absorption selection performance is to be obtained, process difficulties occur. There is a problem that there are times.
Under such circumstances, a polarizing film having high light absorption selection performance even in a thin film is desired.

By the way, in the process of producing the anisotropic dye film, the composition for forming the anisotropic dye film is applied to the substrate, and in the orientation process performed as necessary after drying, the composition for forming the anisotropic dye film is formed. After heating to an isotropic phase appearance temperature or higher, cooling is performed so that the liquid crystal phase is formed again. Alternatively, cooling is performed after heating to a temperature at which a highly fluid liquid crystal phase (for example, a nematic phase) appears. From this, the composition for forming an anisotropic dye film having a high isotropic phase appearance temperature requires a higher temperature in the above-mentioned orientation process, and the stability of the dye and the liquid crystal compound, the ease of handling of the process, and the like. It is disadvantageous from the viewpoint of energy consumption. Furthermore, when the liquid crystal compound has a polymerizable group, unintended thermal polymerization may occur due to heating at a high temperature in the above reorientation process. Further, depending on the heat resistant temperature of the base material, the degree of freedom in selecting a base material that can be used is reduced.

On the other hand, in order to enhance the dichroism of the anisotropic dye film formed from the anisotropic dye film forming composition, the core of the liquid crystal compound molecule contained in the anisotropic dye film forming composition is used. It is conceivable to increase the ratio of the long axis to the short axis.
However, when the core of the liquid crystal compound molecule is enlarged, the melting point of the liquid crystal compound (phase transition point between solid and liquid) and the isotropic phase appearance temperature (phase transition point between liquid crystal and liquid) tend to increase.
That is, if it is attempted to lower the isotropic phase appearance temperature, it is conceivable to make the core of the liquid crystal compound molecule smaller, while by making the core of the liquid crystal compound molecule smaller, the major axis and the short axis of the core of the liquid crystal compound molecule The ratio of the axes becomes small, and as a result, the bipolarity of the anisotropic dye film formed from the composition for forming the anisotropic dye film is lowered.

Under such circumstances, the isotropic appearance temperature of the anisotropic dye film forming composition is adjusted while maintaining high dichroism of the anisotropic dye film formed from the anisotropic dye film forming composition. It is desired to lower it.

An object of the present invention is to provide a composition for forming an anisotropic dye film capable of achieving a low isotropic dye film appearance temperature while maintaining excellent optical performance, particularly a sufficient two-color ratio.
Another object of the present invention is to provide an anisotropic dye film that can maintain excellent optical performance, particularly a sufficient dichroic ratio, and can be formed at a lower temperature.
Another object of the present invention is to provide an optical element including an anisotropic dye film that can maintain excellent optical performance, particularly a sufficient bicolor ratio, and can be formed at a lower temperature.

The present inventors have found that the above-mentioned problems can be solved by using a liquid crystal compound having a specific structure in a composition for forming an anisotropic dye film containing a dye and a liquid crystal compound.
That is, the gist of the present invention is as follows.

[1] An anisotropic dye film forming composition containing a dye and a liquid crystal compound.
The liquid crystal compound is a composition for forming an anisotropic dye film containing a liquid crystal compound represented by the formula (2).
R1-A1-Y1-A2-Y2-A3-R2 ... (2)
(During the ceremony,
R1 and R2 each independently represent a chain organic group;
At least one chain organic group of R1 and _{R2, - (CH 2) n-} CH 2 - polymerizable group or a _{-O- (CH 2) n-CH} 2 - represents a polymerizable group, Here, n , An integer from 1 to 24;
A1 and A3 independently represent a partial structure represented by the formula (1), a divalent organic group, or a single bond;
A2 represents a partial structure or a divalent organic group represented by the above formula (1);
-Y1- and -Y2- are independently single-bonded, -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, respectively. -C (= O) S-, -SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ Represents O-, -OCH _2- , -CH ₂ S-, or -SCH _2- ;
One of A1 and A3 is a partial structure or a divalent organic group represented by the formula (1);
At least one of A1, A2, and A3 is a partial structure represented by the formula (1). )
-Cy-X2-C≡C-X-... (1)
(During the ceremony,
Cy represents a hydrocarbon ring group or a heterocyclic group;
-X- is -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 Represents S- or -SCH _2- ;
-X2- is 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- , Represents -CH ₂ S- or -SCH _2- . )
[2] In [1], -X- is -C (= O) O-, -OC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, or -OCH _2- . The composition for forming an anisotropic dye film according to the above.
[3] The composition for forming an anisotropic dye film according to [1] or [2], wherein Cy is a hydrocarbon ring group and -X2- is a single bond.

[4] The anisotropic dye film formation according to any one of [1] to [3], wherein one of A1, A2, and A3 is a partial structure represented by the above formula (1). Composition for.
[5] Cy is a hydrocarbon ring group and -X2- is a single bond; one of A1, A2, and A3 is a partial structure represented by the above formula (1), and the other. The composition for forming an anisotropic dye film according to any one of [1] to [4], wherein the two are each independently a hydrocarbon ring group.
[6] The anisotropic dye film forming according to any one of [1] to [5], wherein the hydrocarbon ring group is a 1,4-phenylene group or a cyclohexane-1,4-diyl group. Composition.
[7] -Y1- and -Y2- are independently single-bonded, -C (= O) O-, -OC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, or -OCH _2- , and -X- is -C (= O) O-, -OC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, or -OCH _2- . The composition for forming an anisotropic dye film according to any one of [1] to [6].
[8] The composition for forming an anisotropic dye film according to any one of [1] to [7], wherein Cy is a 1,4-phenylene group.
[9] The composition for forming an anisotropic dye film according to any one of [1] to [8], wherein one of A1 and A3 is a cyclohexane-1,4-diyl group.
[10] One of A1 and A3 has a partial structure represented by the above formula (1).
The composition for forming an anisotropic dye film according to any one of [1] to [9], wherein the other is a cyclohexane-1,4-diyl group.
[11] Any of [1] to [10], wherein the content of the dye is 0.01 to 30 parts by mass with respect to 100 parts by mass of the solid content of the anisotropic dye film forming composition. The composition for forming an anisotropic dye film according to item 1.
[12] The composition for forming an anisotropic dye film according to any one of [1] to [11], wherein the dye is an azo-based dichroic dye.

[13] An anisotropic dye film formed by using the composition for forming an anisotropic dye film according to any one of [1] to [12].
[14] An optical element including the anisotropic dye film according to [13].

The composition for forming an anisotropic dye film of the present invention can realize a low isotropic phase appearance temperature while maintaining excellent optical performance, particularly a sufficient two-color ratio.
Since the anisotropic dye film of the present invention is formed by using the composition for forming an anisotropic dye film of the present invention, excellent optical performance, particularly a sufficient dichroic ratio can be maintained, and the anisotropic dye film is formed at a lower temperature. It is possible to do.
Since the optical element of the present invention contains the anisotropic dye film of the present invention, an anisotropic dye film capable of maintaining excellent optical performance, particularly a sufficient dichroic ratio, and being formed at a lower temperature can be obtained. Can include.

Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

The anisotropic dye film referred to in the present invention has electromagnetic properties in any two directions selected from a total of three directions in a three-dimensional coordinate system in the thickness direction of the anisotropic dye film and two arbitrary in-plane directions. It is a dye film having anisotropy. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance.
Examples of the film having optical anisotropy such as absorption and refraction include a linear polarizing film, a polarizing film such as a circular polarizing film, a retardation film, and a conductive anisotropic dye film. The anisotropic dye film of the present invention is preferably used as a polarizing film or a conductive anisotropic dye film, and more preferably used as a polarizing film.

[Composition for forming an anisotropic dye film]
The composition for forming an anisotropic dye film of the present invention contains a dye and a liquid crystal compound.
The composition for forming an anisotropic dye film of the present invention may be a solution, a liquid crystal, or a dispersed state as long as it does not cause phase separation, but the anisotropic dye film may be in a dispersed state. The forming composition is preferably a solution from the viewpoint of easy application to a substrate. On the other hand, the solid content component obtained by removing the solvent from the composition for forming an anisotropic dye film is preferably in a liquid crystal phase state at an arbitrary temperature from the viewpoint of orientation on the substrate as described later.
In the present invention, the state of the liquid crystal phase is specifically described on pages 1 to 16 of "Basics and Applications of Liquid Crystals" (Shoichi Matsumoto, Ryo Kakuda; 1991). As described above, it is a liquid crystal state exhibiting both liquid and crystal properties or intermediate properties, and is a nematic phase, a smectic phase, a cholesteric phase, or a discotic phase.

(Dye)
In the present invention, the dye is a substance or compound that absorbs at least a part of wavelengths in the visible light region (380 nm to 780 nm).
Examples of the dye that can be used in the present invention include a dichroic dye. The dichroic dye refers to a dye having a property in which the absorbance in the major axis direction and the absorbance in the minor axis direction of the molecule are different. Further, the dye may be a dye having a liquid crystal property or may not have a liquid crystal property. In addition, having liquid crystal property means that the liquid crystal phase is expressed at an arbitrary temperature.

The dyes contained in the composition for forming an anisotropic dye film of the present invention include azo dyes, quinone dyes (including naphthoquinone dyes, anthraquinone dyes, etc.), stilben dyes, cyanine dyes, and phthalocyanines. Examples thereof include system dyes, indigo dyes, condensed polycyclic dyes (including perylene dyes, oxazine dyes, acrydin dyes, etc.) and the like. Among these dyes, azo dyes are preferable because they have a large molecular length-minor axis ratio and can have a high molecular arrangement in an anisotropic dye film.
The azo dye refers to a dye having at least one azo group (-N = N-), and the number of azo groups in one molecule is the solubility in a solvent, compatibility with a liquid crystal compound, and color tone. From the viewpoint of ease of production, 1 or more is preferable, 2 or more is more preferable, 6 or less is preferable, 4 or less is more preferable, and 3 or less is further preferable.

Examples of the azo dye include a compound represented by the formula (A).

R11-D1-N = N- (D2-N = N) _p- D3-R12 ... (A)

In formula (A),
D1, D2 and D3 are each independently a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocycle which may have a substituent. Represents a group;
p represents an integer from 0 to 4;
If p is an integer greater than or equal to 2, multiple D2s may be the same or different from each other;
R11 and R12 represent the same or different monovalent organic groups.

D1, D2 and D3 are each independently a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocycle which may have a substituent. Represents a group.
As the substitution position of the phenylene group, a 1,4-phenylene group is preferable because the linearity of the molecule is high.
As the substitution position of the naphthylene group, a 1,4-naphthylene group or a 2,6-naphthylene group is preferable because of the high linearity of the molecule.

As the divalent heterocyclic group, the number of carbon atoms forming the ring is preferably 3 or more and 14 or less, and more preferably 10 or less. In particular, monocyclic or bicyclic heterocyclic groups are preferable.
Examples of the atom other than carbon constituting the divalent heterocyclic group include at least one selected from nitrogen atom, sulfur atom and oxygen atom. When the heterocyclic group has a plurality of atoms constituting a ring other than carbon, they may be the same or different.
Specifically, a pyridinediyl group, a quinolinediyl group, an isoquinolindiyl group, a thiazolediyl group, a benzothiazolediyl group, a thienothiazolediyl group, a thienotiophendiyl group, a benzimidazolidinone diyl group, a benzofuranyl group, a phthalimidediyl group, Examples thereof include an oxazolediyl group and a benzoxazolediyl group.

The substituents optionally contained in the phenylene group, naphthylene group, and divalent heterocyclic group in D1, D2, and D3 are alkyl groups having 1 to 4 carbon atoms; and 1 carbon group such as methoxy group, ethoxy group, and butoxy group. Alkax groups of ~ 4; alkyl fluoride groups having 1 to 4 carbon atoms such as trifluoromethyl groups; cyano groups; nitro groups; hydroxyl groups; halogen atoms; amino groups, diethylamino groups, and pyrrolidino groups, etc. A group (a substituted amino group is an amino group having one or two alkyl groups having 1 to 4 carbon atoms, or two substituted alkyl groups are bonded to each other to form an alcandiyl group having 2 to 8 carbon atoms. refers to an amino group are. unsubstituted amino group is -NH _2. as the alkyl group having 1 to 4 carbon atoms,. 2-8 carbon atoms like methyl, ethyl and butyl groups As the alcandiyl group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1, 6-Diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like can be mentioned.)
From the point of high molecular linearity, when it is unsubstituted or substituted, it is substituted with a methyl group, a methoxy group, a hydroxyl group, a fluorine atom, a chlorine atom, a dimethylamino group, a pyrrolidinyl group, or a piperidinyl group. Is preferable.

p represents an integer from 0 to 4. From the viewpoints of solubility in a solvent, compatibility with a liquid crystal compound, color tone and ease of production, 1 or more is preferable, 4 or less is preferable, and 3 or less is more preferable.

R11 and R12 represent the same or different monovalent organic groups.
The monovalent organic group in R11 and R12 includes a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a branch; an alicyclic alkyl group having 1 to 20 carbon atoms; a methoxy group and an ethoxy group. And an alkoxy group having 1 to 20 carbon atoms which may have a branch such as a butoxy group; an alkyl fluoride group having 1 to 20 carbon atoms which may have a branch such as a trifluoromethyl group; a cyano group; Nitro group; hydroxyl group; halogen atom; substituted or unsubstituted amino group such as amino group, diethylamino group, and pyrrolidino group (Substituted amino group is an alkyl group having 1 to 20 carbon atoms which may have a branch. It means an amino group having one or two, or an amino group in which two substituted alkyl groups are bonded to each other to form an alcandiyl group having 2 to 20 carbon atoms. The unsubstituted amino group is -NH ₂ . Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group and a butyl group. Examples of the alcandiyl group having 2 to 20 carbon atoms include an ethylene group and a propane-1,3-diyl group. , Butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1, 8-Diyl group and the like can be mentioned.); Carboxy group; may have a branch such as a butoxycarbonyl group; an alkyloxycarbonyl group having 1 to 20 carbon atoms; may have a branch such as an ethenyl group. Alkenyl group having 1 to 20 carbon atoms; Alkylphenylalkenyl group such as 2- (4-butylphenyl) ethenyl group; Carbamoyl group; Alkylcarbamoyl having 1 to 20 carbon atoms which may have a branch such as a butylcarbamoyl group. Group; Sulfamoyl group; Alkyl sulfamoyl group having 1 to 20 carbon atoms which may have a branch such as a butyl sulfamoyl group; 1 to 1 carbon atoms which may have a branch such as a butylcarbonylamino group. An acylamino group of 20; an acyloxy group having 1 to 20 carbon atoms which may have a branch such as a butylcarbonyloxy group; a sulfanyl group; an alkylsulfanyl group having 1 to 20 carbon atoms such as a butylsulfanyl group; a liquid crystal described later. Examples thereof include a chain organic group having a polymerizable group of R1 and R2 in the compound.

R11 and R12 include hydrogen atoms, chain groups, aliphatic organic groups (“aliphatic organic groups” include chain and cyclic groups), and part of the carbon is nitrogen and / or oxygen. Substituted aliphatic organic groups (“Adioxyorganic groups in which a part of carbon is replaced with nitrogen and / or oxygen” includes chain-like and cyclic ones, and methyl of some of the aliphatic organic groups. A group in which the group is replaced with a hydroxyl group, an oxo group (= O), an amino group, an imino group, or the like is included.) In one embodiment, a hydrogen atom or a chain group is preferable, and in another embodiment, a hydrogen atom or a chain group is preferable. Is preferably a hydrogen atom or an aliphatic organic group, and in still another embodiment, a hydrogen atom or an aliphatic organic group in which a part of carbon is replaced with nitrogen and / or oxygen is preferable.

As the chain group, the above-mentioned alkyl group having 1 to 20 carbon atoms which may have a branch; an alkoxy group having 1 to 20 carbon atoms which may have a branch; even if it has a branch. A good alkyl fluoride group having 1 to 20 carbon atoms; a substituted or unsubstituted amino group (a substituted amino group is an amino group having one or two alkyl groups having 1 to 20 carbon atoms which may have a branch. The substituent (unsubstituted amino group is -NH ₂ ); carboxy group; may have a branch alkyloxycarbonyl group having 1 to 20 carbon atoms; carbamoyl group; even if it has a branch. A good alkylcarbamoyl group having 1 to 20 carbon atoms; a sulfamoyl group; an alkylsulfamoyl group having 1 to 20 carbon atoms which may have a branch; an acylamino group having 1 to 20 carbon atoms which may have a branch. An acyloxy group having 1 to 20 carbon atoms which may have a branch; a sulfanyl group; an alkylsulfanyl group having 1 to 20 carbon atoms and the like can be mentioned.

Examples of the aliphatic organic group include the above-mentioned alkyl groups having 1 to 20 carbon atoms which may have a branch, and alicyclic alkyl groups having 1 to 20 carbon atoms.
As the aliphatic organic group in which a part of carbon is replaced with nitrogen and / or oxygen, the above-mentioned alkoxy group having 1 to 20 carbon atoms which may have a branch; a substituted or unsubstituted amino group (substituted amino) A group is an amino group having one or two alkyl groups having 1 to 20 carbon atoms which may have a branch, or an alkanediyl group having 2 to 20 carbon atoms in which two substituted alkyl groups are bonded to each other. The unsubstituted amino group is −NH ₂ , and examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group and a butyl group. Examples of the alkanediyl group having the number 2 to 20 include an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. Examples include hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc.); Carboxy group; 1 to 20 carbon atoms which may have a branch. Alkyloxycarbonyl group; carbamoyl group; may have a branched alkylcarbamoyl group having 1 to 20 carbon atoms; may have a branched acylamino group having 1 to 20 carbon atoms; even if it has a branch Examples thereof include an acyloxy group having 1 to 20 carbon atoms.

R11 and R12 are independent of each other because of their high molecular linearity, that is, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms such as a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group; a butoxy group. , Pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and other alkoxy groups having 1 to 10 carbon atoms, diethylamino group, pyrrolidino group and piperidinyl group are preferably substituted. Further, a chain organic group having a polymerizable group of R1 and R2 in the liquid crystal compound, which will be described later, is also preferable.

The dye contained in the composition for forming an anisotropic dye film of the present invention is not particularly limited, and a known dye can also be used.
Known dyes include, for example, the dyes described in Patent Document 1, Japanese Patent No. 5982762, Japanese Patent Application Publication No. 2017-025317, and Japanese Patent Application Publication No. 2014-09589. (Dichroic dye, dichroic dye) can be mentioned.

Specific examples thereof include, but are not limited to, the dyes described below.

The molecular weight of the dye contained in the composition for forming an anisotropic dye film of the present invention is preferably 300 or more, more preferably 350 or more, further preferably 380 or more, further preferably 1500 or less, and even more preferably 1200 or less. 1000 or less is more preferable. Specifically, the molecular weight of the dye contained in the composition for forming an anisotropic dye film of the present invention is preferably 300 to 1500, more preferably 350 to 1200, and even more preferably 380 to 1000.

The content of the dye (dichroic dye) in the anisotropic dye film forming composition is, for example, 0.01 with respect to the solid content (100 parts by mass) of the anisotropic dye film forming composition. It is preferably parts by mass or more, more preferably 0.05 parts by mass or more, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less. Specifically, the content of the dye (dichroic dye) in the anisotropic dye film forming composition is, for example, relative to the solid content (100 parts by mass) of the anisotropic dye film forming composition. It is 0.01 to 30 parts by mass, preferably 0.05 to 10 parts by mass. When the content occupied by the dye (dichroic dye) is within the above range, the anisotropic dye of the present invention does not disturb the orientation of the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention. There is a tendency that the compound contained in the film-forming composition can be polymerized. Further, when the content occupied by the dye (dichroic dye) is at least the above lower limit value, sufficient light absorption tends to be obtained and sufficient polarization performance tends to be obtained. Further, when the content occupied by the dye (dichroic dye) is not more than the above upper limit value, the inhibition of the orientation of the liquid crystal molecules tends to be suppressed easily.
Depending on the purpose, the dye (dichroic dye) may be used alone or in combination of two or more.

(Liquid crystal compound)
In the present invention, the liquid crystal compound refers to a substance indicating a liquid crystal state, and specifically, it is described on pages 1 to 28 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000). As described above, a compound that does not directly transfer from a crystal to a liquid but becomes a liquid through an intermediate state exhibiting the properties of both a crystal and a liquid.

The liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention includes a liquid crystal compound having a partial structure represented by the following formula (1).

-Cy-X2-C≡C-X-... (1)

In equation (1),
Cy represents a hydrocarbon ring group or a heterocyclic group;
-X- is -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 Represents S- or -SCH _2- ;
-X2- is 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- , Represents -CH ₂ S- or -SCH _2- .

Hydrocarbon ring groups in Cy include aromatic hydrocarbon ring groups and non-aromatic hydrocarbon ring groups.

The aromatic hydrocarbon ring group includes a non-linked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.
The unlinked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the number of carbon atoms is preferably 6 to 20. 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 benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. ..
A linked 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 bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 6 to 20. For example, a first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms are bonded by a single bond, and the first is A single ring having 6 to 20 carbon atoms or a condensed aromatic hydrocarbon ring having a first bond on the atom constituting the ring of the hydrocarbon ring, and a second monocyclic ring or condensed aromatic ring having 6 to 20 carbon atoms. It is a divalent group having a second bond on the atom constituting the ring of the group hydrocarbon ring. Examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.
As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferable.
Of these, as the aromatic hydrocarbon ring group, a divalent group of a benzene ring and a divalent group of a naphthalene ring are preferable, and a divalent group of a benzene ring (phenylene group) is more preferable. As the phenylene group, a 1,4-phenylene group is preferable.

The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.
The unlinked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and the number of carbon atoms is preferably 3 to 20. Examples of non-aromatic hydrocarbon rings include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, bornan ring, adamantane ring, tetrahydronaphthalene ring, and bicyclo [2]. .2.2] Octane ring and the like can be mentioned.
The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond constituting the ring of the non-aromatic hydrocarbon ring and a ring of the non-aromatic hydrocarbon ring. It contains an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting the above. As the unlinked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferable.
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 has a bond on the atom constituting the ring; or a monocyclic ring. One or more rings selected from the group consisting of an aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring, and a single ring or It is a divalent group that is bonded to the condensed non-aromatic hydrocarbon ring by a single bond and has a bond on the atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20. For example, a first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded in a single bond. , A first single bond having a first bond on an atom constituting a first monocyclic ring having 3 to 20 carbon atoms or a fused non-aromatic hydrocarbon ring, or a second monocyclic ring having 3 to 20 carbon atoms. It is a divalent group having a second bond on the atom constituting the ring of the fused non-aromatic hydrocarbon ring, and is, for example, a monocyclic ring having 3 to 20 carbon atoms or a fused aromatic hydrocarbon ring and the number of carbon atoms. The first on the atom constituting the ring of the monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms, which is bonded by a single bond with 3 to 20 monocyclic or condensed non-aromatic hydrocarbon rings. It is a divalent group having a bond and having a second bond on the atom constituting the ring of a monocyclic ring having 3 to 20 carbon atoms or a fused non-aromatic hydrocarbon ring. Examples of the linked non-aromatic hydrocarbon ring group include a bis (cyclohexane) -4,4'-diyl group and a 1-cyclohexylbenzene-4,4'-diyl group.
As the non-aromatic hydrocarbon ring group, a non-linked non-aromatic hydrocarbon ring group is preferable.
Of these, the divalent group of cyclohexane (cyclohexanediyl group) is preferable as the non-aromatic hydrocarbon ring group. As the cyclohexanediyl group, a cyclohexane-1,4-diyl group is preferable.

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

Aromatic heterocyclic groups include unlinked aromatic heterocyclic groups and linked aromatic heterocyclic groups.
The unlinked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocycle, and the number of carbon atoms is preferably 4 to 20. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyroloymidazole ring, a pyrrolopyrazole ring, and a pyrrolopyrrole. Ring, thienopyrrole ring, thienothiophene ring, flopyrol ring, flofuran ring, thienofuran ring, thienothiazole ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring , Kinolin ring, isoquinolin ring, sinoline ring, quinoxalin ring, phenanthridin ring, benzimidazole ring, pyrimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.
A linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocycles are bonded by a single bond and have a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a first monocyclic or condensed aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or condensed aromatic heterocycle having 4 to 20 carbon atoms are bonded by a single bond, and the first A monocyclic or fused aromatic heterocycle having a first bond on an atom constituting a monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or condensed aromatic heterocycle having 4 to 20 carbon atoms. It is a divalent group having a second bond on the atom constituting the ring of.

The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.
The unlinked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocycle, and the number of carbon atoms is preferably 4 to 20. It is a divalent group of a monocyclic or condensed non-aromatic heterocycle having 4 to 20 carbon atoms, and examples of the non-aromatic heterocycle include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydropyran ring, and a tetrahydropyran ring. Pyrrolidin ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzoimidazole ring, quinucrine ring, etc. Can be mentioned.
A linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocycles are bonded by a single bond and have a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a first monocyclic or condensed non-aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or condensed non-aromatic heterocycle having 4 to 20 carbon atoms are bonded in a single bond, and the first bond is formed. A single ring having 4 to 20 carbon atoms or a condensed non-aromatic heterocyclic ring having a first bond on an atom constituting a ring of a non-aromatic heterocyclic ring having 4 to 20 carbon atoms. It is a divalent group having a second bond on the atom constituting the ring of the aromatic heterocycle.

The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy are RA, -OH, -O-RA, and -OC (= O, respectively). ) -RA, -NH ₂ , -NH-RA, -N (RB) -RA, -C (= O) -RA, -C (= O) -O-RA, -C (= O) -NH ₂ , -C (= O) -NH-RA, -C (= O) -N (RB) -RA, -SH, -S-RA, trifluoromethyl group, sulfamoyl group, carboxy group, sulfo group, cyano group , Nitro groups, and one or more groups selected from the group consisting of halogens. Here, RA and RB each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.
The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy have high linearity in molecular structure and have a partial structure represented by the formula (1). From the viewpoint that the liquid compound compounds are easily associated with each other and easily develop a liquid crystal state, it is preferable that they are independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, and a bromine atom. It is more preferable that it is unsubstituted.
The substituents of the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group may be the same or different, and the aromatic hydrocarbon ring group, All of the non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be substituted, all may be unsubstituted, and some may be substituted and some may be substituted. It may be unsubstituted.

As Cy, a hydrocarbon ring group is preferable, and a phenylene group and a cyclohexanediyl group are more preferable. Further, since the linearity of the molecular structure of the liquid crystal compound can be increased, 1,4-phenylene group and cyclohexane-1,4-diyl group are more preferable as Cy, and 1,4-phenylene group is particularly preferable. ..

Since the liquid crystal compound tends to have linearity and rotational movement around the minor axis of the molecule, -X- has a small π-bonding property, -C (= O) O- and -OC (= O)-. , -C (= S) O-, -OC (= S)-, -C (= O) S-, -SC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -CH ₂ S-, -SCH _2- are preferable, -C (= O) O-, -OC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- Is more preferable. In one embodiment, -X- is -C (= O) O- or -OC (= O)-, and in another embodiment, -X- is -CH ₂ CH _2- , -CH ₂ O-. , Or -OCH _2- .

-Cy- and -C≡C- are groups with high linearity from the viewpoint of increasing the core of the liquid crystal compound and increasing the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film. It is preferable to connect the two. Specifically, as -X2-, -C (= O) O-, -OC (= O)-, -C (= S) O-, and -OC (=) having a single bond or π bond property. S)-, -C (= O) S-, -SC (= O)-, -CH = CH-, -C (= O) NH-, -NHC (= O)-are more preferable. A single bond is more preferable because of its high linearity.

Examples of the liquid crystal compound having a partial structure represented by the above formula (1) contained in the composition for forming an anisotropic dye film of the present invention include a liquid crystal compound represented by the following formula (2).

R1-A1-Y1-A2-Y2-A3-R2 ... (2)

In equation (2),
R1 and R2 each independently represent a chain organic group;
A1 and A3 independently represent a partial structure represented by the above formula (1), a divalent organic group, or a single bond;
A2 represents a partial structure or a divalent organic group represented by the above formula (1);
-Y1- and -Y2- are independently single-bonded, -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, respectively. -C (= O) S-, -SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ Represents O-, -OCH _2- , -CH ₂ S-, or -SCH _2- ;
One of A1 and A3 is a partial structure or a divalent organic group represented by the above formula (1);
At least one of A1, A2, and A3 is a partial structure represented by the above formula (1).

When A1 is a partial structure represented by the equation (1), the equation (2) is:
R1-Cy-X2-C≡C-X-Y1-A2-Y2-A3-R2 ... (2A) may be used.
R1-X-C≡C-X2-Cy-Y1-A2-Y2-A3-R2 ... (2B) may be used.
Further, when A2 is a partial structure represented by the equation (1), the equation (2) is:
R1-A1-Y1-Cy-X2-C≡C-X-Y2-A3-R2 ... (2C) may be used.
It may be R1-A1-Y1-X-C≡C-X2-Cy-Y2-A3-R2 ... (2D).
Further, when A3 is a partial structure represented by the equation (1), the equation (2) is:
R1-A1-Y1-A2-Y2-Cy-X2-C≡C-X-R2 ... (2E) may be used.
It may be R1-A1-Y1-A2-Y2-X-C≡C-X2-Cy-R2 ... (2F).

Similarly, when two or more of A1, A2, and A3 are substructures represented by the formula (1), the directions of the substructures represented by the formula (1) are independently reversed. You may.

Further, as described above, A1, A2, and A3 are each independently a partial structure or a divalent organic group represented by the formula (1); in addition, A1 and A3 are single bonds. However, A1 and A3 are not both single-bonded; at least one of A1, A2, and A3 represents a partial structure represented by the above formula (1).

The chain organic groups in R1 and R2 do not contain cyclic structures such as the above-mentioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic heterocycle (however, the chain in R1 and R2). When the organic group has a cyclic polymerizable group such as an oxylane ring, an oxetane ring, a vinylbenzene ring, etc., which will be described later, the portion excluding the polymerizable group does not include the above cyclic structure.) Monovalent It is an organic group.
Examples of such a chain organic group include- (alkyl group), -O- (alkyl group), -S- (alkyl group), -NH- (alkyl group), -N (alkyl group)-(alkyl group). ), -OC (= O)-(alkyl group), -C (= O) O- (alkyl group). As such a chain organic group, − (alkyl group) and −O− (alkyl group) are preferable. In one embodiment, such a chain organic group is − (alkyl group), and in another embodiment, such a chain organic group is −O− (alkyl group).

Examples of the alkyl group in these chain organic groups include a linear or branched alkyl group having 1 to 25 carbon atoms, and the carbon-carbon bond of the alkyl group is partially unsaturated. Also, one or more methylene groups contained in the alkyl group may be an ether oxygen atom, a thioether sulfur atom, an amine nitrogen atom (-NH-, -N (RA)-: here, RA represents a linear or branched alkyl group having 1 to 6 carbon atoms), a carbonyl group, an ester bond, an amide bond, -CHF-, -CF _2- , -CHCl-, -CCl _2- It may be a structure replaced by (displace).
Since the alkyl group in these chain organic groups has high molecular linearity, a part of the carbon of the alkyl group may be an unsaturated bond, and one or more of the alkyl groups are contained in the alkyl group. The methylene group is preferably a linear alkyl group having 1 to 25 carbon atoms, which may have a structure in which the above-mentioned group is substituted (displace).
Main chain in a chain organic group (meaning the longest chain portion in a chain organic group, and when the chain organic group is substituted with a polymerizable group described later, the most in the portion excluding the polymerizable group The number of atoms in (meaning a long chain portion) is preferably 3 to 25, more preferably 5 to 20, and even more preferably 6 to 20.

Further, these alkyl groups may be substituted with 1 to 3 polymerizable groups. A polymerizable group is a group having a partial structure capable of being polymerized by light, heat, and / or radiation, and is a functional group or atomic group necessary for ensuring the function of polymerization. The polymerizable group is preferably a photopolymerizable group from the viewpoint of producing an anisotropic dye film.
Examples of the polymerizable group include acryloyl group, metaacryloyl group, acryloyloxy group, metaacryloyloxy group, acryloylamino group, metaacryloylamino group, vinyl group, vinyloxy group, ethynyl group, ethynyloxy group, 1,3-. Examples include butazienyl group, 1,3-butadienyloxy group, oxylanyl group, oxetanyl group, glycidyl group, glycidyloxy group, styryl group, styryloxy group, etc., and include acryloyl group, metaacryloyl group, acryloyloxy group, metaacryloyl. Oxy group, acryloyl amino group, metaacryloylamino group, oxylanyl group, glycidyl group, glycidyloxy group are preferable, and acryloyl group, metaacryloyl group, acryloyloxy group, metaacryloyloxy group, acryloylamino group, metaacryloylamino group, glycidyl. Groups and glycidyloxy groups are more preferable, and acryloyloxy groups, metaacryloyloxy groups, and glycidyloxy groups are even more preferable.
When these alkyl groups are substituted with a polymerizable group, it is preferable that one polymerizable group is substituted, and more preferably one polymerizable group is substituted at the terminal of the alkyl group.

The chain organic groups include-(CH ₂ ) _n- CH ₃ ,-(CH ₂ ) _n- CH ₂ -polymerizable group, -O- (CH ₂ ) _n- CH ₃ , -O- (CH ₂ ). _n- CH ₂ -polymerizable group,-(O) _n1- (CH ₂ CH ₂ O) _n2- (CH ₂ ) _n3- CH ₃ ,-(O) _n1- (CH ₂ CH ₂ O) _n2- (CH ₂ ) _n3 -polymerizable group,-(O) _n1- (CH ₂ ) _n2- (CH ₂ CH ₂ O) _n3- CH ₃ ,-(O) _n1- (CH ₂ ) _n2- (CH ₂ CH ₂ O) ) _N3 -polymerizable groups are preferred. Note that n in these equations is an integer of 1 to 24, preferably an integer of 2 to 24, more preferably an integer of 4 to 19, and even more preferably an integer of 5 to 19. Further, n1, n2, and n3 in these formulas independently represent integers, and mean the main chain in the chain organic group (meaning the longest chain portion in the chain organic group, and the chain organic group is polymerized. When substituted with a sex group, it means the longest chain portion in the portion excluding the polymerizable group.) The number of atoms is preferably 3 to 25, more preferably 5 to 20, and even more preferably. Is appropriately adjusted to be 6 to 20.

It is preferable that R1 and R2 are independently substituted with a polymerizable group- (alkyl group) and the alkyl group may be substituted with a polymerizable group-O- (alkyl group). , -(Alkyl group) substituted with a polymerizable group, and -O- (alkyl group) in which the alkyl group is substituted with a polymerizable group are more preferable.
When X and R1 or X and R2 are bonded as in the formulas (2B) and (2E); for example, when A3 is a single bond in the formula (2B) or A1 in the formula (2E). When R1 or R2 is bonded to Y1 or Y2, as in the case where is a single bond; R1 or R2 bonded to X or Y1 or Y2 may be substituted with a polymerizable group. − (Alkyl group) is preferable, and − (alkyl group) substituted with a polymerizable group is more preferable.
Further, as described above, R1 or R2 which does not bond with X or Y1 or Y2 is preferably —O— (alkyl group) which may be substituted with a polymerizable group, and is substituted with a polymerizable group. It is more preferably -O- (alkyl group).

The divalent organic group in A1, A2, and A3 is preferably a group represented by the following formula (3).

−Q1- ・ ・ ・ (3)

In equation (3),
Q1 represents a hydrocarbon ring group or a heterocyclic group.

The hydrocarbon ring group in Q1 includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.

The aromatic hydrocarbon ring group includes a non-linked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.
The unlinked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the number of carbon atoms is preferably 6 to 20. 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 benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. ..
A linked 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 bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 6 to 20. For example, a first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms are bonded by a single bond, and the first is A single ring having 6 to 20 carbon atoms or a condensed aromatic hydrocarbon ring having a first bond on the atom constituting the ring of the hydrocarbon ring, and a second monocyclic ring or condensed aromatic ring having 6 to 20 carbon atoms. It is a divalent group having a second bond on the atom constituting the ring of the group hydrocarbon ring. Examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.
As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferable.
Of these, as the aromatic hydrocarbon ring group, a divalent group of a benzene ring and a divalent group of a naphthalene ring are preferable, and a divalent group of a benzene ring (phenylene group) is more preferable. As the phenylene group, a 1,4-phenylene group is preferable.

The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.
The unlinked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and the number of carbon atoms is preferably 3 to 20. Examples of non-aromatic hydrocarbon rings include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, bornan ring, adamantane ring, tetrahydronaphthalene ring, and bicyclo [2]. .2.2] Octane ring and the like can be mentioned.
The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond constituting the ring of the non-aromatic hydrocarbon ring and a ring of the non-aromatic hydrocarbon ring. It contains an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting the above. As the unlinked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferable.
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 has a bond on the atom constituting the ring; or a monocyclic ring. One or more rings selected from the group consisting of an aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring, and a single ring or It is a divalent group that is bonded to the condensed non-aromatic hydrocarbon ring by a single bond and has a bond on the atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20. For example, a first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded in a single bond. , A first single bond having a first bond on an atom constituting a first monocyclic ring having 3 to 20 carbon atoms or a fused non-aromatic hydrocarbon ring, or a second monocyclic ring having 3 to 20 carbon atoms. It is a divalent group having a second bond on the atom constituting the ring of the fused non-aromatic hydrocarbon ring, and is, for example, a monocyclic ring having 3 to 20 carbon atoms or a fused aromatic hydrocarbon ring and the number of carbon atoms. The first on the atom constituting the ring of the monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms, which is bonded by a single bond with 3 to 20 monocyclic or condensed non-aromatic hydrocarbon rings. It is a divalent group having a bond and having a second bond on the atom constituting the ring of a monocyclic ring having 3 to 20 carbon atoms or a fused non-aromatic hydrocarbon ring. Examples of the linked non-aromatic hydrocarbon ring group include a bis (cyclohexane) -4,4'-diyl group and a 1-cyclohexylbenzene-4,4'-diyl group.
As the non-aromatic hydrocarbon ring group, a non-linked non-aromatic hydrocarbon ring group is preferable.
Of these, the divalent group of cyclohexane (cyclohexanediyl group) is preferable as the non-aromatic hydrocarbon ring group. As the cyclohexanediyl group, a cyclohexane-1,4-diyl group is preferable.

The heterocyclic group in Q1 includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

Aromatic heterocyclic groups include unlinked aromatic heterocyclic groups and linked aromatic heterocyclic groups.
The unlinked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocycle, and the number of carbon atoms is preferably 4 to 20. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyroloymidazole ring, a pyrrolopyrazole ring, and a pyrrolopyrrole. Ring, thienopyrrole ring, thienothiophene ring, flopyrol ring, flofuran ring, thienofuran ring, thienothiazole ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring , Kinolin ring, isoquinolin ring, sinoline ring, quinoxalin ring, phenanthridin ring, benzimidazole ring, pyrimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.
A linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocycles are bonded by a single bond and have a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a first monocyclic or condensed aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or condensed aromatic heterocycle having 4 to 20 carbon atoms are bonded by a single bond, and the first A monocyclic or fused aromatic heterocycle having a first bond on an atom constituting a monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or condensed aromatic heterocycle having 4 to 20 carbon atoms. It is a divalent group having a second bond on the atom constituting the ring of.

The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.
The unlinked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocycle, and the number of carbon atoms is preferably 4 to 20. It is a divalent group of a monocyclic or condensed non-aromatic heterocycle having 4 to 20 carbon atoms, and examples of the non-aromatic heterocycle include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydropyran ring, and a tetrahydropyran ring. Pyrrolidin ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzoimidazole ring, quinucrine ring, etc. Can be mentioned.
A linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocycles are bonded by a single bond and have a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a first monocyclic or condensed non-aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or condensed non-aromatic heterocycle having 4 to 20 carbon atoms are bonded in a single bond, and the first bond is formed. A single ring having 4 to 20 carbon atoms or a condensed non-aromatic heterocyclic ring having a first bond on an atom constituting a ring of a non-aromatic heterocyclic ring having 4 to 20 carbon atoms. It is a divalent group having a second bond on the atom constituting the ring of the aromatic heterocycle.

The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Q1 are RA, -OH, -O-RA, and -OC (= O, respectively). ) -RA, -NH ₂ , -NH-RA, -N (RB) -RA, -C (= O) -RA, -C (= O) -O-RA, -C (= O) -NH ₂ , -C (= O) -NH-RA, -C (= O) -N (RB) -RA, -SH, -S-RA, trifluoromethyl group, sulfamoyl group, carboxy group, sulfo group, cyano group , Nitro groups, and one or more groups selected from the group consisting of halogens. Here, RA and RB each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.
The aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group in Q1 have high linearity in molecular structure, and have a partial structure represented by the formula (1). From the viewpoint that the liquid compound compounds are easily associated with each other and easily develop a liquid crystal state, it is preferable that they are independently unsubstituted or substituted with methyl group, methoxy group, fluorine atom, chlorine atom and bromine atom. It is more preferable that it is unsubstituted.
The substituents of the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group may be the same or different, and the aromatic hydrocarbon ring group, All of the non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be substituted, all may be unsubstituted, and some may be substituted and some may be substituted. It may be unsubstituted.
Further, the substituents of the divalent organic groups in A1, A2, and A3 may be the same or different, and all of the divalent organic groups in A1, A2, and A3 may be substituted, and all of them may be substituted. It may be unsubstituted or partially substituted and partially unsubstituted.

As Q1, a hydrocarbon ring group is preferable, and a phenylene group and a cyclohexanediyl group are more preferable. Further, as Q1, 1,4-phenylene group and cyclohexane-1,4-diyl group are more preferable because the linearity of the molecular structure of the liquid crystal compound can be increased.

As the divalent organic group, it is preferable that Q1 is a hydrocarbon ring group, that is, the divalent organic group is a hydrocarbon ring group. Further, as the divalent organic group, a phenylene group and a cyclohexanediyl group are more preferable, and since the linearity of the molecular structure of the liquid crystal compound can be increased, a 1,4-phenylene group and a cyclohexane-1,4-diyl group can be obtained. Is even more preferable.

In formula (2), one of A1, A2, and A3 is a partial structure represented by formula (1), and the other two are independently divalent organic groups. Of the A1, A2, and A3, the Cy of the partial structure represented by the formula (1) is preferably a hydrocarbon ring group, and the divalent organic group is particularly preferably a hydrocarbon ring group. Further, the hydrocarbon ring group is preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group. Further, it is preferable that one of A1 and A3 is a cyclohexane-1,4-diyl group.
Further, it is more preferable that one of A1 and A3 has a partial structure represented by the formula (1), and the other one and A2 are divalent organic groups. In this case, one of A1 and A3 which is a divalent organic group is preferably a cyclohexane-1,4-diyl group, and A2 is particularly preferably a 1,4-phenylene group.

Since the linearity of the liquid crystal compound and the rotational movement around the minor axis of the molecule tend to be easy, the -Y1- and -Y2- are independent of each other and have a small π bond, a single bond and -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- Preferably, a single bond, −C (= O) O−, −OC (= O) −, −CH ₂ CH ₂ −, −CH ₂ O−, −OCH ₂₋ is more preferable.

When X and Y1 or X and Y2 are bonded as in the formula (2A), the formula (2C), the formula (2D), and the formula (2F), the Y1 that binds to X or the Y2 that binds to X Is preferably a single bond; the other of -X- and -Y1- and -Y2- is preferably -C (= O) O- or -OC (= O)-.
Further, when X is not bound to either Y1 or Y2 as in the formulas (2B) and (2E), -X- is -CH ₂ CH _2- , -CH ₂ O-, or -OCH _2- preferably; both -Y1- and -Y2- are preferably -C (= O) O- or -OC (= O)-.

As the formula (2), the above formula (2A), the above formula (2B), the above (2E), and the above (2F) are preferable.

Specifically, the following compounds can be mentioned as the formula (2), but the present invention is not limited thereto.

The liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention preferably comprises a liquid crystal compound having a partial structure represented by the above formula (1). Here, the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention may be one kind of a liquid crystal compound having a partial structure represented by the above formula (1), and two or more kinds may be used in combination. You may. Further, a liquid crystal compound other than the liquid crystal compound having a partial structure represented by the formula (1) may be used in combination.

From the viewpoint of the process, the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention preferably has an isotropic phase appearance temperature of generally less than 200 ° C and less than 160 ° C. , Less than 140 ° C., more preferably less than 115 ° C., even more preferably less than 110 ° C., and particularly preferably less than 105 ° C.
Here, the isotropic phase appearance temperature means the phase transition temperature from the liquid crystal to the liquid and the phase transition temperature from the liquid to the liquid crystal. In the present invention, at least one of these phase transition temperatures is preferably in the above range, and more preferably both of these phase transition temperatures are in the above range.

The liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention includes an alkylation reaction, an esterification reaction, an amidation reaction, an etherification reaction, an ipso substitution reaction, a coupling reaction using a metal catalyst, and the like. It can be produced by combining known chemical reactions.
For example, the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention includes the method described in Examples and 449 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000). It can be synthesized according to the method described on page 468.

(solvent)
The composition for forming an anisotropic dye film of the present invention may contain a solvent, if necessary.
The solvent that can be used is not particularly limited as long as it can sufficiently disperse or dissolve the dye or other additives in the liquid crystal compound, and for example, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene. Alcohol solvents such as 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; acetone, methyl ethyl ketone, Ketone solvents such as cyclopentanone, cyclohexanone, 2-heptanone, methylisobutylketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; tetrahydrofuran, Ether solvents such as dimethoxyethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether; fluorine-containing solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, hexafluoro-2-propanol; and chloroform, dichloromethane, chlorobenzene, di A chlorine-containing solvent such as chlorobenzene; can be mentioned.
Only one type of these solvents may be used, or two or more types may be used in combination.

The solvent is preferably a solvent capable of dissolving the liquid crystal compound and the dye, and more preferably a solvent in which the liquid crystal compound and the dye are completely dissolved. When the liquid crystal compound is a polymerizable compound, it is preferably a solvent that is inert to the polymerization reaction. Further, from the viewpoint of applying the composition for forming an anisotropic dye film of the present invention described later, a solvent having a boiling point in the range of 50 to 200 ° C. is preferable.

When the composition for forming an anisotropic dye film of the present invention contains a solvent, the content ratio of the solvent in the composition for forming an anisotropic dye film is the total amount (100% by mass) of the composition of the present invention. Therefore, 50 to 98% by mass is preferable. In other words, the solid content in the composition for forming an anisotropic dye film of the present invention is preferably 2 to 50% by mass.
When the solid content in the anisotropic dye film forming composition is not more than the above upper limit value, the viscosity of the anisotropic dye film forming composition does not become too high, and the thickness of the obtained polarizing film becomes uniform. , The polarizing film tends to be less likely to be uneven.
The solid content can be determined in consideration of the thickness of the polarizing film to be produced.
The viscosity of the composition for an anisotropic dye film of the present invention is not particularly limited as long as a uniform film having no uneven thickness is produced by the coating method described later, but the thickness uniformity over a large area, the coating speed, etc. From the viewpoint of obtaining in-plane uniformity of productivity and optical characteristics, 0.1 mPa · s or more is preferable, 500 mPa · s or less is preferable, 100 mPa · s or less is more preferable, and 50 mPa · s or less is further preferable.

(Other additives)
The composition for forming an anisotropic dye film of the present invention is a polymerizable liquid crystal compound other than the liquid crystal compound having a partial structure represented by the above formula (1), further represented by the above formula (1), if necessary. Non-polymerizable liquid crystal compounds other than liquid crystal compounds having a partial structure, polymerization initiators, 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 may be contained. By containing an additive, the coatability and stability of the anisotropic dye film forming composition can be improved, and the stability of the anisotropic dye film formed from the anisotropic dye film forming composition can be improved. May be improved.

[Method for Producing Composition for Anisotropic Dye Film Formation]
The method for producing the composition for an anisotropic dye film of the present invention is not particularly limited. For example, a dye, a liquid crystal compound, a solvent, other additives and the like are mixed, and the dye is dissolved by stirring and shaking at 0 to 80 ° C. In the case of poor solubility, a homogenizer, a bead mill disperser, or the like may be used.
As a method for producing the composition for an anisotropic dye film of the present invention, a filtration step may be provided for the purpose of removing foreign substances and the like in the composition.
In the composition for forming an anisotropic dye film of the present invention, the composition obtained by removing the solvent from the composition for forming an anisotropic dye film may or may not be a liquid crystal at an arbitrary temperature, but at an arbitrary temperature. It is preferable to show liquid crystallinity. The composition obtained by removing the solvent from the composition for forming an anisotropic dye film has an isotropic phase appearance temperature of generally less than 200 ° C. and less than 160 ° C. from the viewpoint of the coating process described below. It is preferably less than 140 ° C, more preferably less than 115 ° C, even more preferably less than 110 ° C, and particularly preferably less than 105 ° C.

[Anisotropic dye film]
The anisotropic dye film of the present invention contains a dye and a liquid crystal compound having a partial structure represented by the formula (1) (however, the liquid crystal compound having a partial structure represented by the formula (1) is polymerized. In the case of a sex compound, one of a dye and a polymer having a unit based on the liquid crystal compound having a partial structure represented by the formula (1) and the liquid crystal compound having a partial structure represented by the formula (1). Or both.).
The anisotropic dye film of the present invention comprises a polymerizable liquid crystal compound other than the liquid crystal compound having a partial structure represented by the above formula (1), a non-polymerizable liquid crystal compound, a polymerization initiator, a polymerization inhibitor, a polymerization aid, and the like. Polymerizable non-liquid compound, non-polymerizable non-liquid compound, surfactant, leveling agent, coupling agent, pH adjuster, dispersant, antioxidant, organic / inorganic filler, organic / inorganic nanosheet, organic / inorganic nanofiber , Metal oxides and the like may be included.

The anisotropic dye film of the present invention can be formed by using the composition for forming an anisotropic dye film of the present invention.

The anisotropic dye film in the present invention can function as a polarizing film that obtains linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption, and also has a film forming process and a substrate or an organic compound (dye). By selecting a composition containing (or transparent material), it is possible to function as various anisotropic dye films such as refractive anisotropy and conduction anisotropy.

When the anisotropic dye film of the present invention is used as a polarizing element for an antireflection film for a liquid crystal display or an OLED, the orientation characteristic of the anisotropic dye film can be expressed by using a two-color ratio. When the two-color ratio is 8 or more, it functions as a polarizing element, but 15 or more is preferable, 20 or more is more preferable, 25 or more is further preferable, 30 or more is particularly preferable, and 40 or more is particularly preferable. Further, the higher the two-color ratio, the more preferable. When the two-color ratio is at least the above lower limit value, it is useful as an optical element described later, particularly a polarizing element.
When used as a polarizing element for an antireflection film for an OLED, even if the performance of a peripheral material such as a retardation film is low, if the performance of the polarizing element is high, the characteristics as an antireflection film are improved. Therefore, if the performance of the polarizing element is high, the layer structure can be easily simplified, and even a thin film structure can easily exhibit a sufficient function, and the polarizing element can be suitably used for applications including folding and bending. In addition, the cost can be kept low.

The two-color ratio (D) referred to in the present invention is expressed by the following formula when the dyes are uniformly oriented. D = Az / Ay
Here, Az is the absorbance observed when the polarization direction of the light incident on the anisotropic dye film is parallel to the orientation direction of the anisotropic dye, and Ay is the polarization of the light incident on the anisotropic dye film. Absorbance observed when the direction is perpendicular.
The absorbance of each of them is not particularly limited as long as it has the same wavelength, and any wavelength may be selected depending on the purpose. However, when expressing the degree of orientation of the anisotropic dye film, it is 380 nm of the anisotropic dye film. It is preferable to use a value corrected by luminosity factor in a specific wavelength range of about 780 nm or a value in the maximum absorption wavelength in the visible range.

The transmittance of the anisotropic dye film of the present invention in the visible light wavelength region is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more. Further, the transmittance may be an upper limit according to the application. For example, when the degree of polarization is increased, the transmittance is preferably 50% or less. Having a transmittance in the above range, it is useful as an optical element described later, and particularly as an optical element for a liquid crystal display used for color display or an antireflection film in which an anisotropic dye film and a retardation film are combined. It is useful.

The 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 as a dry film thickness. On the other hand, it is preferably 30 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, and particularly preferably 3 μm or less. When the thickness of the anisotropic dye film is within the above range, it tends to be possible to obtain a uniform orientation and a uniform film thickness of the dye in the film.

[Manufacturing method of anisotropic dye film]
The anisotropic dye film of the present invention is preferably produced by a wet film forming method using the composition for forming an anisotropic dye film of the present invention.
The wet film forming method referred to in the present invention is a method of applying and orienting an anisotropic dye film composition on a substrate by some method. Therefore, the composition for an anisotropic dye film may or may not contain a solvent as long as it has fluidity. From the viewpoint of viscosity and film uniformity at the time of coating, it is more preferable to contain a solvent.
The orientation of the liquid crystal or the dye in the anisotropic dye film may be oriented by shearing or the like in the coating process, or may be oriented in the process of drying the solvent. Further, the liquid crystal, the dye and the like may be oriented and laminated on the substrate through a process of reorienting the liquid crystal and the dye by heating after coating and drying. In the wet film formation method, when the composition for an anisotropic dye film is applied onto a substrate, it is already in the composition for an anisotropic dye film, in the process of drying the solvent, or after the solvent is completely removed. Then, the dye or the liquid crystal compound undergoes self-association (molecular association state such as liquid crystal state), so that orientation occurs in a minute area. By giving an external field to this state, it is possible to obtain an anisotropic dye film having desired performance by orienting in a certain direction in a macro region. In this respect, it is different from the method in which a polyvinyl alcohol (PVA) film or the like is dyed with a solution containing a dye, stretched, and the dye is oriented only by a stretching step. Here, the external field includes the influence of the alignment treatment layer previously applied on the substrate, shearing force, magnetic field, electric field, heat, etc., and these may be used alone or in combination of two or more. Good. If necessary, a heating step may be performed.

The process of applying the composition for an anisotropic dye film on the substrate to form a film, the process of applying an external field to align the composition, and the process of drying the solvent may be performed sequentially or simultaneously.

Examples of the method of applying the anisotropic dye film forming composition on the substrate in the wet film forming method include a coating method, a dip coating method, an LB film forming method, and a known printing method. There is also a method of transferring the anisotropic dye film thus obtained to another substrate.

Among these, it is preferable to apply the composition for forming an anisotropic dye film onto the substrate by using a coating method.
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 is, for example, the transmission axis (polarization axis) or absorption axis of polarized light in the case of a polarizing film, and the phase advance axis in the case of a retardation film. Or it is the slow axis.

The method for applying the composition for an anisotropic dye film to obtain an anisotropic dye film is not particularly limited, but for example, "Coating Engineering" by Yuji Harasaki (Asakura Shoten Co., Ltd., published on March 20, 1971). ), Pages 253 to 277, "Creation and application of molecular coordinating materials" supervised by Kunihiro Ichimura (CMC Publishing Co., Ltd., published March 3, 1998), methods described on pages 118 to 149, steps. Slot die coating method, spin coating method, spray coating method, bar coating method, roll coating method, blade coating method, curtain coating method, fountain method, dip method, etc. on a substrate having a structure (orientation treatment may be performed in advance). The method of applying with is mentioned. Of these, the slot die coating method and the bar coating method are preferable because an anisotropic dye film having high uniformity can be obtained.

The die coater used in the slot die coating method generally includes a coating machine that discharges a coating liquid, a so-called slit die. Slit dies are used, for example, in Japanese Patent Application Laid-Open No. 2-164480, Japanese Patent Application Laid-Open No. 6-154678, Japanese Patent Application Laid-Open No. 9-131559, "Basics and Applications of Dispersion / Coating / Drying" (2014). , Technosystem Co., Ltd., ISBN97849274728707 C 305), "Wet coating technology in display and optical components" (2007, Information Organization, ISBN9784901677752), "Precision coating and drying technology in the electronics field" (2007, Technical Information Association, ISBN9784861041389) ) Etc. are disclosed. These known slit dies can be applied even to a flexible member such as a film or tape or a hard member such as a glass substrate.

As the substrate used for forming the anisotropic dye film of the present invention, glass, triacetate, acrylic, polyester, polyimide, polyetherimide, polyetheretherketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetyl Examples thereof include cellulose or urethane films. Further, on the surface of this substrate, in order to control the orientation direction of the dye, a known method (rubbing) described on pages 226 to 239 of "LCD Handbook" (Maruzen Co., Ltd., published on October 30, 2000). Method, method of forming a groove (fine groove structure) on the surface of the alignment film, method of using polarized ultraviolet light / polarized laser (photoalignment method), orientation method by LB film formation, orientation method by diagonal deposition of inorganic substances, etc.) Therefore, the alignment treatment (alignment film) may be applied. In particular, orientation treatment by a rubbing method or a photo-alignment method can be preferably mentioned. Examples of the material used in the rubbing method include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, acrylic resin and the like. Examples of the material used in the photoalignment method include polycinnamate type, polyamic acid / polyimide type, and azobenzene type. When the alignment treatment layer is provided, it is considered that the liquid crystal compound and the dye are oriented due to the influence of the alignment treatment of the alignment treatment layer and the shearing force applied to the composition for the anisotropic dye film at the time of coating.

When the composition for the anisotropic dye film is applied, the supply method and the supply interval of the composition for the anisotropic dye film are not particularly limited. Since the coating liquid supply operation may become complicated or the coating film thickness may fluctuate at the start and stop of the coating liquid, it is continuously anisotropic when the thickness of the anisotropic dye film is thin. It is desirable to apply the composition for a sex dye film while supplying it.

The speed at which the composition for an anisotropic dye film is applied is usually 0.001 m / min or more, preferably 0.01 m / min or more, more preferably 0.1 m / min or more, still more preferable. Is 1.0 m / min or more, and particularly preferably 5.0 m / min or more. Further, it 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. When the coating rate is in the above range, the anisotropy of the anisotropic dye film can be obtained, and the coating tends to be uniform.
The coating temperature of the composition for an anisotropic dye film is usually 0 ° C. or higher and 100 ° C. or lower, preferably 80 ° C. or lower, and more preferably 60 ° C. or lower.
The humidity at the time of coating the composition for an anisotropic dye film is preferably 10% RH or more, and preferably 80 RH or less.

The anisotropic dye film may be insolubilized. The insolubilization means a treatment of controlling the elution of the compound from the anisotropic dye film by reducing the solubility of the compound in the anisotropic dye film and enhancing the stability of the film.
Specifically, film polymerization and overcoating are preferable from the viewpoints of ease of post-process, durability of anisotropic dye film, and the like.

When polymerizing a film, the film in which liquid crystal molecules and dye molecules are oriented is polymerized using light, heat, and / or radiation.

When the polymerization is carried out using light or radiation, it is preferable to irradiate with active energy rays having a wavelength in the range of 190 to 450 nm.
The light source of the active energy ray having a wavelength of 190 to 450 nm is not particularly limited, but for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and carbon. Lamp light sources such as arcs and fluorescent lamps; laser light sources such as argon ion lasers, YAG lasers, excima lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers can be mentioned. An optical filter can also be used when irradiating light of a specific wavelength for use. The exposure amount of the active energy ray is preferably 1 to 100,000 J / m ² , more preferably 10 to 10,000 J / m ² .

When the polymerization is carried out using heat, it is preferably carried out in the range of 50 to 200 ° C., and more preferably carried out in the range of 60 to 150 ° C.
Polymerization may be carried out using light, heat, and / or radiation, but it is preferable to use photopolymerization or to use photopolymerization and thermal polymerization in combination because the film forming process takes a short time and the apparatus is simple. Is preferable.

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

The optical element in the present invention has functions such as a polarizing element that obtains linearly polarized light, circularly polarized light, and elliptically polarized light, a retardation element, and refractive anisotropy and conduction anisotropy by utilizing the anisotropy of light absorption. Represents an element. These functions can be appropriately adjusted by the anisotropic dye film forming process and the selection of a composition containing a substrate or an organic compound (dye or transparent material).

The optical element of the present invention is most preferably used as a polarizing element.
The optical element of the present invention can be suitably used for applications such as flexible displays because a polarizing element can be obtained by forming an anisotropic dye film on a substrate by coating or the like.

The optical element may be provided with another layer in order to maintain and improve the function of the anisotropic dye film. For example, a layer having a function of blocking a specific wavelength or a layer having a function of blocking a specific substance (oxygen blocking film, steam blocking film) used to improve durability such as light resistance, heat resistance, and water resistance. Barrier film, etc.); A wavelength cut filter or a layer containing a material that absorbs a specific wavelength, which is used for changing the color range or improving the optical characteristics; and the like.

[Polarizing element]
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.
Further, the polarizing element is not limited to an anisotropic dye film, but is an overcoat layer having functions such as improving polarization performance and mechanical strength; an adhesive layer or an antireflection layer; an alignment film; as a retardation film. It may be used in combination with a layer having optical functions such as a function as a brightness improving film, a function as a reflection or antireflection film, a function as a transflective reflective film, and a function as a diffusion film; .. Specifically, the above-mentioned layers having various functions may be laminated and formed by coating, bonding, or the like, and used as a laminated body.
These layers can be appropriately provided according to the manufacturing process, characteristics, and functions, and the position and order of lamination thereof are not particularly limited. For example, the position where each layer is formed may be formed on the anisotropic dye film or may be formed on the opposite surface of the substrate provided with the anisotropic dye film. Further, the order of forming each layer may be before or after forming the anisotropic dye film.

The layer having these optical functions can be formed by the following method.

The layer having a function as a retardation film can be formed by applying or bonding the retardation film to other layers constituting the polarizing element. The retardation film is, for example, subjected to the stretching treatment described in Japanese Patent Application Laid-Open No. 2-59703, Japanese Patent Application Laid-Open No. 4-230704, etc., or described in Japanese Patent Application Laid-Open No. 7-230007. It can be formed by subjecting it to treatment.

The layer having a function as the brightness improving film can be formed by applying or bonding the brightness improving film to other layers constituting the polarizing element. The brightness-improving film has, for example, formed micropores by a method as described in Japanese Patent Application Laid-Open No. 2002-1690.25 and Japanese Patent Application Laid-Open No. 2003-29030, or has a center wavelength of selective reflection. It can be formed by superimposing two or more different cholesteric liquid crystal layers.

The layer having a function as a reflective film or a transflective reflective film is formed by, for example, applying or bonding a metal thin film obtained by vapor deposition or sputtering to another layer constituting a polarizing element. Can be done.
The layer having a function as a diffusion film can be formed, for example, by coating another layer constituting the polarizing element with a resin solution containing fine particles.

The layer having a function as a retardation film or an optical compensation film is composed of 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, and another layer constituting the polarizing element. It can be formed by applying it to and orienting it. At that time, an alignment film may be provided on the substrate, and a retardation film or an optical compensation film may be formed on the surface of the alignment film.

When the anisotropic dye film of the present invention is used as an anisotropic dye film or the like for various display elements such as LCDs and OLEDs, the present invention is directly applied to the surface of the electrode substrate or the like constituting these display elements. An anisotropic dye film may be formed, or a substrate on which the anisotropic dye film of the present invention is formed may be used as a constituent member of these display elements.

The present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
In the following description, "part" means "part by weight".

[Method for identifying liquid crystal phase]
The liquid crystallinity of the obtained anisotropic dye film forming composition is as follows: differential scanning calorimetry (Seiko Instruments Co., Ltd. "DSC220CU"), X-ray structural analysis (Rigaku Co., Ltd. "NANO-Viewer"), hot stage (Co., Ltd.) Observe with a polarizing microscope (Nikon Instec Co., Ltd. "ECLIPSE LV100N POL") attached to Toyo Technica "HCS302-LN190"), and see "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000) 9 The liquid crystal was identified according to the method described on pages 117 to 176 and the like.

[Measurement of transmittance and two-color ratio for polarized light in the absorption axis / polarization axis direction of the anisotropic dye film]
The transmittance of the obtained anisotropic dye film with respect to polarized light in the absorption axis / polarization axis direction was determined using a spectrophotometer equipped with a Gran Thomson polarizer (manufactured by Otsuka Electronics Co., Ltd., product name "RETS-100"). It was measured.
The measurement light of linearly polarized light is incident on the anisotropic dye film, and the transmittance of the anisotropic dye film for polarization in the absorption axis direction and the transmittance of the anisotropic dye film for polarization in the polarization axis direction are measured. The two-color ratio (D) was calculated as described above.
D = Az / Ay
(During the ceremony,
Ay = -log (Ty);
Az = -log (Tz);
Tz is the transmittance of the anisotropic dye film for polarization in the absorption axis direction;
Ty is the transmittance of the anisotropic dye film with respect to polarized light in the polarization axis direction. )

Specifically, a sandwich cell (cell gap: 8.0 μm, 10.0 μm, 12.0 μm, film formation) in which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems) is formed on glass as a base material. The anisotropic dye film is formed by injecting the composition for an anisotropic dye film into an isotropic phase and cooling the mixture to 80 ° C at 5 ° C / min. The two-color ratio was measured at each temperature while further cooling to 0 ° C. at 5 ° C./min. Among them, the two-color ratio at the temperature and wavelength showing the maximum two-color ratio was determined as the two-color ratio of the anisotropic dye film.
Further, the anisotropic dye film having a two-color ratio of 40 or more was evaluated as A, 20 or more and less than 40 was evaluated as B, 8 or more and less than 20 was evaluated as C, and one less than 8 was evaluated as D.

[Synthesis of liquid crystal compounds]
<Liquid crystal compound (I-1)>
The liquid crystal compound (I-1) was synthesized according to the synthesis method described below.

Synthesis of (I-1-a):
Ethyl propiolic acid (9.7 g, 99 mmol) and copper (I) oxide (7.5 g, 94 mmol) were added to an N, N-dimethylformamide solution (150 mL) of p-iodophenol (11.0 g, 50 mmol). , Stirred at 110 ° C. for 9 hours and allowed to cool to room temperature. The precipitate was filtered off, ethyl acetate was added, and the mixture was washed with water and then saturated brine. Purification by silica gel column chromatography (hexane / ethyl acetate) gave 7.3 g of brown crystals (I-1-a).

Synthesis of (I-1-b):
(I-1-a) (4.20 g, 22.1 mmol), 11-bromo-1-undecanol (5.55 g, 22.1 mmol), potassium carbonate (6.10 g, 44.2 mmol), N, N- Dimethylformamide (30 mL) was mixed and stirred at 80 ° C. for 4 hours. The precipitate was filtered off, diethyl ether was added, and the mixture was washed with water and then saturated brine. Purification by silica gel column chromatography (hexane / ethyl acetate) gave 5.5 g of an orange solid (I-1-b).

Synthesis of (I-1-c):
(I-1-b) (3.6 g, 10 mmol), potassium hydroxide (1.7 g, 30 mmol) and water (20 mL) were mixed and stirred at 100 ° C. for 2 hours. Water (20 mL) was added, acidified with concentrated hydrochloric acid, and then the precipitated precipitate was filtered off. The obtained precipitate was washed with acetonitrile to obtain 3.2 g of a milky white solid (I-1-c).

Synthesis of (I-1-d):
(I-1-c) (2.33 g, 7.0 mmol), tetrahydrofuran (20 mL) was mixed, followed by N, N-dimethylaniline (1.02 g, 8.4 mmol), 2,5-di-t. -Butylphenol (54 mg) was added. After cooling in an ice bath, acryloyl chloride (0.76 g, 8.4 mmol) was slowly added. After stirring under an ice bath for 6 hours, methylene chloride was added, and the mixture was washed in the order of 1 mol / L hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and saturated brine. Purification by silica gel column chromatography (chloroform / methanol) gave 2.0 g of a white solid (I-1-d).

Synthesis of (I-1-e):
(I-1-e) was synthesized by the synthesis method described in Japanese Patent Application Laid-Open No. 2014-262884.

Synthesis of (I-1-f):
(I-1-d) (2.00 g, 5.17 mmol), (I-1-e) (1.01 g, 5.17 mmol), N, N-dimethylamino-4-pyridine (0.13 g, 1) .03 mmol), 2,5-di-t-butylphenol (58 mg), methylene chloride (30 mL) are mixed, cooled in an ice bath, and then 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride ( 1.09 g, 5.69 mmol) was added. After leaving it to stand overnight, it was washed with saturated aqueous ammonium chloride solution and then saturated brine. Purification by silica gel column chromatography (hexane / ethyl acetate) gave 1.9 g of a white solid (I-1-f).

Synthesis of (I-1-g):
(I-1-f) (2.6 g, 4.62 mmol), p-toluenesulfonic acid pyridinium salt (0.23 g, 0.92 mmol), 2,5-di-t-butylphenol (44 mg), ethanol (20 mL) ) Was mixed and stirred at 50 ° C. for 2 hours. The reaction solution was discharged into water, and the precipitated precipitate was filtered off and dried to obtain 2.0 g of a white solid (I-1-g).

Synthesis of (I-1-h):
Compound (I-1-h) was synthesized according to the synthesis method described below.

Lub et al. , Recl. Trav. ChIm. (I-1-i) was synthesized by a method according to the compound described in Pays-Bas, 115, 321-328 (1996). Next, (I-1-i) (trans form only) (42.9 g, 107.6 mmol), p-toluenesulfonic acid pyridinium salt (2.6 g, 10.8 mmol), and ethanol (430 mL) were mixed. The mixture was stirred at 78 ° C. for 2 hours. The solvent was distilled off, it was dissolved in ethyl acetate (150 mL), hexane (750 mL) was added, and the mixture was cooled. The precipitated precipitate was separated by filtration, washed with hexane, and dried to obtain 29.2 g of a white solid (I-1-j).
(I-1-j) (37.2 g, 118.3 mmol), N, N-dimethylaniline (21.5 g, 177.5 mmol), 2,5-di-t-butylphenol (0.24 g), tetrahydrofuran ( 380 mL) was mixed. After cooling in an ice bath, acryloyl chloride (16.1 g, 177.5 mmol) was slowly added. After the dropwise addition, the mixture was stirred at 50 ° C. for 2 hours, the solvent was distilled off until the liquid volume reached 190 mL, and the mixture was released into 1 mol / L hydrochloric acid under ice-cooling. The precipitated precipitate was separated by filtration and washed with water and hexane. Purification by silica gel column chromatography (hexane / ethyl acetate) gave 39.4 g of a white solid (I-1-h).

Synthesis of (I-1):
(I-1-g) (494 mg, 1.03 mmol), (I-1-h) (400 mg, 1.09 mmol), N, N-dimethylamino-4-pyridine (27 mg, 0.22 mmol), 2, 5-di-t-butylphenol (2 mg) and methylene chloride (10 mL) are mixed, cooled in an ice bath, and then 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (230 mg, 1.19 mmol). Was added. After stirring under an ice bath for 4 hours, the mixture was washed with saturated aqueous ammonium chloride solution and then saturated brine. Purification by silica gel column chromatography (hexane / ethyl acetate) gave 530 mg of liquid crystal compound (I-1) as a white solid.

The results of liquid chromatograph-mass spectrometry of this compound are shown below.
LC-MS (APCI) m / z 851.5 (M + Na ⁺ )
In addition, the structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ1.20-1.70 (m, 38H), 1.74-1.85 (m, 2H), 2.05-2.25 (m, 4H), 2. 49-2.57 (m, 1H), 3.21-3.29 (m, 1H), 3.46 (t, 2H, J = 6.8Hz), 3.99 (t, 2H, J = 6) .8Hz), 4.15 (t, 4H, J = 6.8Hz), 5.80 (d, 2H, J = 10.4Hz), 6.12 (dd, 2H, J = 17.2, 10. 4Hz), 6.39 (d, 2H, J = 17.2Hz), 6.89 (d, 2H, J = 6.8Hz), 7.10 (d, 2H, J = 6.8Hz), 7. 19 (d, 2H, J = 6.8Hz), 7.55 (d, 2H, J = 6.8Hz)

<Liquid crystal compound (I-2)>
The liquid crystal compound (I-2) was synthesized according to the synthesis method described below.

Synthesis of (I-2-a):
Ethyl 4-iodobenzoate (8.20 g, 29.7 mmol), dichlorobis (triphenylphosphine) palladium (II) (626 mg, 0.89 mmol), copper (I) iodide (170 mg, 0.89 mmol), triethylamine ( 200 mL) was mixed and 10-undecine-1-ol (5.0 g, 29.7 mmol) was added. After heating at room temperature for 4 hours and further at 40 ° C. for 1 hour, the mixture was allowed to cool to room temperature. After water-ether extraction, the mixture was further washed with 1 mol / L hydrochloric acid, separated and concentrated to obtain a crudely purified brown oily compound (I-2-a).

Synthesis of (I-2-b):
A 50 mL aqueous solution of crudely purified (I-2-a) and potassium hydroxide (5.0 g, 90 mmol) obtained by the above operation was mixed and heated at 100 ° C. for 5 hours. After allowing to cool to room temperature, 20 mL of water was added under an ice bath, and then concentrated hydrochloric acid was added until pH = 1. The precipitated white solid was filtered off and recrystallized from hot acetonitrile to obtain 7.5 g of a milky white solid (I-2-b).

Synthesis of (I-2-c):
(I-2-b) (7.4 g, 25.7 mmol), tetrahydrofuran (50 mL), N, N-dimethylaniline (3.78 g, 31.2 mmol), p-methoxyphenol (89 mg) are mixed and bathed in water. Below, after confirming that the internal temperature was 15 ° C. or lower, acryloyl chloride (2.82 g, 31.2 mmol) was slowly added. After 30 minutes, the water bath was removed and the mixture was further stirred for 2 hours. The reaction mixture was discharged into 100 mL of water, concentrated hydrochloric acid (0.8 mL) was added, and the mixture was extracted with ethyl acetate. Half of the brown powder obtained by concentration was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 3.0 g of milky white powder (I-2-c).

Synthesis of (I-2-d):
(I-2-c) (2.95 g, 8.6 mmol), (I-1-e) (1.70 g, 8.8 mmol), N, N-dimethylaminopyridine (0.21 g, 1.75 mmol) , Dichloromethane (13 mL) was mixed, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (1.84 g, 9.6 mmol) was added under an ice bath. After stirring for 30 minutes under an ice bath, the mixture was further stirred at room temperature for 1 hour. The reaction mixture was extracted with saturated aqueous ammonium chloride solution and then saturated aqueous saline, and then purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 4.4 g of (I-2-d) as a white solid.

Synthesis of (I-2-e):
(I-2-d) (4.1 g, 7.9 mmol), ethanol (20 mL) and p-toluenesulfonic acid pyridinium salt (0.40 g, 1.58 mmol) were mixed and heated at 60 ° C. for 1 hour. After allowing to cool to room temperature, it was discharged into water (100 mL), and the obtained solid was filtered off. The obtained solid was recrystallized (ethanol-water) and filtered to obtain 3.3 g of (I-2-e) as a solid.

Synthesis of (I-2-f):
(I-2-e) (435 mg, 1.0 mmol), (I-1-i) (mixture of trans / cis = 67: 33) (438 mg, 1.1 mmol), N, N-dimethylaminopyridine (24 mg) , 0.2 mmol) and dichloromethane (10 mL) were added, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (211 mg, 1.1 mmol) was added under an ice bath. After stirring for 30 minutes under an ice bath, the mixture was further stirred at room temperature for 2 hours. The reaction mixture was washed with saturated aqueous ammonium chloride solution and then saturated brine, and then purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 0.46 g of trans form (I-2-f).

Synthesis of (I-2-g):
(I-2-f) (0.46 g, 0.56 mmol), ethanol (10 mL) and p-toluenesulfonic acid pyridinium salt (28 mg, 0.11 mmol) were mixed and heated at 60 ° C. for 2 hours. After allowing to cool to room temperature, water (20 mL) was added and the obtained solid was filtered off. The obtained solid was recrystallized (ethanol-water) to obtain 0.36 g of (I-2-g) as a solid.

Synthesis of (I-2):
(I-2-g) (0.36 g, 0.49 mmol), tetrahydrofuran (10 mL), N, N-dimethylaniline (72 mg, 0.59 mmol), p-methoxyphenol (3.6 mg) are mixed and bathed in water. Below, acryloyl chloride (53 mg, 0.59 mmol) was added slowly. After stirring in a water bath for 30 minutes, the mixture was further stirred for 2 hours. The reaction mixture was discharged into water (20 mL), concentrated hydrochloric acid (0.2 mL) was added, and the mixture was extracted with ethyl acetate. Half of the brown powder obtained by concentration was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 183 mg of liquid crystal compound (I-2) as a white powder.

<Liquid crystal compound (I-3)>
The liquid crystal compound (I-3) was synthesized according to the synthesis method described below.

Synthesis of (I-3-a):
p-acetoxybenzoic acid (3.60 g, 20.0 mmol), (I-1-e) (3.88 g, 20.0 mmol), N, N-dimethylaminopyridine (489 mg, 4.0 mmol), dichloromethane (50 mL) ) Was mixed and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (4.22 g, 22.0 mmol) was added at 2 ° C. After stirring at 2 ° C. for 30 minutes, the mixture was further stirred at room temperature for 17 hours. The reaction mixture was washed with saturated aqueous ammonium chloride solution and then saturated brine, and then purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 3.63 g of (I-3-a) as a white solid.

Synthesis of (I-3-b):
(I-3-a) (0.95 g, 2.7 mmol), ethanol (20 mL) and p-toluenesulfonic acid pyridinium salt (134 mg, 0.53 mmol) were mixed and heated at 78 ° C. for 3 hours. After allowing to cool to room temperature, water (60 mL) was added, and the obtained solid was filtered off and dried at 50 ° C. under reduced pressure to obtain 0.31 g of a white solid (I-3-b).

Synthesis of (I-3-c):
(I-3-b) (230 mg, 1.0 mmol), (I-1-i) (trans form only) (810 mg, 2.0 mmol), N, N-dimethylaminopyridine (58 mg, 0.48 mmol), Dichloromethane (6 mL) was mixed and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (428 mg, 2.2 mmol) was added at 2 ° C. After stirring at 2 ° C. for 30 minutes, the mixture was further stirred at room temperature for 20 hours. The reaction mixture was washed with saturated aqueous ammonium chloride solution and then saturated brine, and then purified by silica gel column chromatography (methylene chloride / ethyl acetate) to obtain 662 mg of (I-3-c) as a white solid.

Synthesis of (I-3-d):
(I-3-c) (662 mg, 0.67 mmol), ethanol (15 mL) and p-toluenesulfonic acid pyridinium salt (69 mg, 0.27 mmol) were mixed and heated at 78 ° C. for 1 hour. After allowing to cool to room temperature, water (70 mL) was added, and the obtained solid was filtered off and dried at 50 ° C. under reduced pressure to obtain 555 mg of a white solid (I-3-d).

Synthesis of (I-3):
(I-3-d) (555 mg, 0.67 mmol), methylene chloride (12 mL), N, N-dimethylaniline (225 mg, 1.85 mmol) were mixed and acryloyl chloride (169 mg, 1.87 mmol) was mixed at 2 ° C. ) Was added slowly. After stirring at 2 ° C. for 30 minutes, the mixture was further stirred at room temperature for 18 hours. The reaction mixture was washed with saturated aqueous ammonium chloride solution and then saturated brine, and purified by silica gel column chromatography (toluene / ethyl acetate) to obtain 424 mg of liquid crystal compound (I-3) as a white solid.

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ8.21 (d, 2H, J = 9.2 Hz), 7.21 (d, 4H, J = 9.2 Hz), 7.12 (d, 2H, J = 9) .2Hz), 6.40 (dd, 2H, J = 17.2,1.6Hz), 6.12 (dd, 2H, J = 17.2, 10.4Hz), 5.81 (dd, 2H, J = 10.4, 1.6Hz), 4.15 (t, 4H, J = 7.2Hz), 3.47 (t, 4H, J = 6.8Hz), 3.32-3.21 (m) , 2H), 2.62-2.49 (m, 2H), 2.25-2.10 (m, 8H), 1.71-1.52 (m, 16H), 1.42-1.25 (M, 28H)

<Liquid crystal compound (I-4)>
The liquid crystal compound (I-4) was synthesized according to the synthesis method described below.

Synthesis of (I-4-b):
(I-4-b) was synthesized by the synthesis method described in Japanese Patent Application Laid-Open No. 2015-896.

Synthesis of (I-4-c):
(I-4-b) (50.3 g, 162 mmol), tetrahydrofuran (320 mL), N, N-dimethylaniline (23.6 mg, 195 mmol), 4-methoxyphenol (307 mg) were mixed and acryloyl at 15 ° C. Chloride (17.6 g, 195 mmol) was added over 40 minutes. After stirring at room temperature for 18 hours, the reaction solution was discharged into water (940 mL), the pH was adjusted to 1.2 with concentrated hydrochloric acid, and the precipitated solid was collected by filtration. The obtained solid was washed with water and dried at 50 ° C. under reduced pressure to obtain 58.5 g of a white solid (I-4-c).

Synthesis of (I-4-d):
(I-4-c) (35.8 g, 98.7 mmol), (I-1-e) (19.2 g, 98.7 mmol), N, N-dimethylaminopyridine (2.41 g, 19.7 mmol) , 4-methoxyphenol (47 mg) and dichloromethane (150 mL) were mixed, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (16.9 g, 109 mmol) was added at 3 ° C. After stirring for 30 minutes under an ice bath, the mixture was further stirred at room temperature for 21 hours. The reaction solution was washed with saturated aqueous ammonium chloride solution, followed by water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off to obtain a light brown solid. This light brown solid is dissolved in ethanol (220 mL) at 60 ° C., allowed to stand at 0 ° C. for 15 hours, the resulting solid is collected by filtration, dried under reduced pressure at 50 ° C., and the white solid (I-4-). 39.1 g of d) was obtained.

Synthesis of (I-4-e):
(I-4-d) (39.0 g, 72.4 mmol), ethanol (180 mL) and p-toluenesulfonic acid pyridinium salt (3.71 g, 14.8 mmol) were mixed and heated at 60 ° C. for 1 hour. After allowing to cool to room temperature, the solid was released into water (490 mL), and the obtained solid was filtered and dried at 50 ° C. under reduced pressure to obtain 32.8 g of a white solid (I-4-e).

Synthesis of (I-4-f):
Compound (I-4-f) was synthesized according to the synthesis method described below.

Trans-4-hydroxycyclohexanecarboxylic acid (4.33 g, 30.0 mmol), dichloromethane (100 mL), p-toluenesulfonic acid pyridinium salt (1.51 g, 6.0 mmol) are mixed and 3,4- at 15 ° C. Dihydro-2H-pyran (5.05 g, 60 mmol) was added dropwise over 10 minutes. After stirring at room temperature for 15 hours, the reaction solution was washed with 7.5 wt% aqueous sodium hydrogen carbonate solution, water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a transparent liquid (I-4-i). ) Was obtained in an amount of 8.47 g.
The (I-4-i) (8.14 g, 26.0 mmol) obtained above was mixed with a 10 wt% potassium hydroxide aqueous solution (73 g) and stirred at 100 ° C. for 5 hours. After allowing to cool to room temperature, a 33 wt% citric acid aqueous solution (75 g) was added, and the mixture was stirred, extracted with methylene chloride (200 mL), and washed with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the obtained solid was purified by silica gel column chromatography (chloroform / ethyl acetate) to obtain 4.35 g of a white solid (I-4-f).

Synthesis of (I-4-g):
(I-4-e) (1.39 g, 3.1 mmol), (I-4-f) (700 mg, 3.1 mmol), N, N-dimethylaminopyridine (75 mg, 0.61 mmol), dichloromethane (7) .5 mL) was mixed and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (647 mg, 3.4 mmol) was added at 2 ° C. After stirring at 2 ° C. for 30 minutes, the mixture was further stirred at room temperature for 16 hours. The reaction mixture was washed with saturated aqueous ammonium chloride solution and then saturated brine, and then purified by silica gel column chromatography (toluene / ethyl acetate) to obtain 1.68 g of (I-4-g) as a white solid.

Synthesis of (I-4-h):
(I-4-g) (1.68 g, 2.53 mmol), ethanol (20 mL) and p-toluenesulfonic acid pyridinium salt (64 mg, 0.25 mmol) were mixed and heated at 60 ° C. for 1 hour. After allowing to cool to room temperature, water (40 mL) was added, and the obtained solid was filtered off and dried at 50 ° C. under reduced pressure to obtain 1.42 g of a white solid (I-4-h).

Synthesis of (I-4):
(I-4-h) (1.39 g, 2.4 mmol), (I-1-h) (888 mg, 2.4 mmol), N, N-dimethylaminopyridine (58 mg, 0.48 mmol), dichloromethane (7) .5 mL) was mixed and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (523 mg, 2.7 mmol) was added at 2 ° C. After stirring at 2 ° C. for 1 hour, the mixture was further stirred at room temperature for 6 hours. The reaction mixture was washed with saturated aqueous ammonium chloride solution and then saturated brine, and then purified by silica gel column chromatography (toluene / ethyl acetate) to obtain 1.13 g of liquid crystal compound (I-4) as a white solid.

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ8.12 (d, 2H, J = 8.8 Hz), 7.21 (d, 2H, J = 8.8 Hz), 7.11 (d, 2H, J = 8) .8Hz), 6.96 (d, 2H, J = 9.2Hz), 6.40 (dd, 2H, J = 17.2, 1.2Hz), 6.12 (dd, 2H, J = 17. 2,10.4Hz), 5.81 (dd, 2H, J = 10.4, 1.2Hz), 4.81-4.68 (m, 1H), 4.15 (t, 4H, J = 6) .8Hz), 4.04 (t, 2H, J = 6.8Hz), 3.44 (t, 2H, J = 6.8Hz), 3.25-3.25 (m, 1H), 2.62 -2.48 (m, 1H), 2.30-1.96 (m, 9H), 1.86-1.20 (m, 44H)

<Liquid crystal compound (I-5)>
The liquid crystal compound (I-5) is described in Lub et al. , Recl. Trav. Chim. It was synthesized using a method according to the compound described in Pays-Bas, 115, 321-328 (1996).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ1.23-1.72 (m, 38H), 1.76-1.86 (m, 2H), 2.11-2.23 (m, 4H), 2. 48-2.60 (m, 1H), 3.20-3.30 (m, 1H), 3.47 (t, 2H, J = 6.8Hz), 4.04 (t, 2H, J = 6) .8Hz), 4.15 (t, 2H, J = 6.8Hz) 5.82 (d, 2H, J = 10.4Hz), 6.12 (dd, 2H, J = 10.4, 17.4Hz) ), 6.40 (d, 2H, J = 17.4Hz), 6.97 (d, 2H, J = 9.2Hz), 7.11 (d, 2H, J = 9.2Hz), 7.21 (D, 2H, J = 9.0Hz), 8.13 (d, 2H, J = 9.0Hz)

<Liquid crystal compound (I-6)>
The liquid crystal compound (I-6) was synthesized according to the synthesis method described below.

Synthesis of (I-6-a):
4-Iodophenol (25 g, 114 mmol), 4-dihydro-2H-pyran (13.4 g, 160 mmol), and dichloromethane solution (125 mL) were mixed, and p-toluenesulfonate pyridinium salt (PPTS) (2.85 g, 11) was mixed. .4 mmol) was added, and the mixture was stirred at room temperature for 5 hours, saturated aqueous sodium hydrogen carbonate solution (200 mL) was added, and extraction was performed with methylene chloride. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over sodium sulfate, and concentrated by filtration to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 32.7 g of a white solid (I-6-a).

Synthesis of (I-6-b):
(I-6-a) (32.7 g, 107.5 mmol), tetrahydrofuran (370 mL), trimethylsilylacetylene (11.6 g, 118.3 mmol), triethylamine (31.6 mL, 225.8 mmol), copper iodide (I) ) (2.03 g, 10.7 mmol) was added, and the mixture was stirred. Then, dichlorobis (triphenylphosphine) palladium (II) (3.8 g, 5.38 mmol) was added. After stirring at room temperature for 12 hours, extraction was performed with water-ethyl acetate. The organic layer was washed with saturated brine, sodium sulfate was added, dried, and then filtered and concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 30.6 g of a white solid (I-6-b).

Synthesis of (I-6-c):
(I-6-b) (30.6 g, 111.5 mmol) and tetrahydrofuran (250 mL) were mixed and cooled in an ice bath. A solution of tetra-n-butylammonium fluoride in tetrahydrofuran (1 mol / L, 133.8 mL) was added, and the mixture was stirred at room temperature for 1 hour. The mixture was extracted with water-ethyl acetate, the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated by filtration to obtain 22.1 g of (I-6-c).

Synthesis of (I-6-d):
(I-6-c) (22.1 g, 109.3 mmol), 4-iodophenol (26.4 g, 102.2 mmol) and tetrahydrofuran (300 mL) obtained by the above operation were mixed, and triethylamine (23 mL, 229) was mixed. .5 mmol) was added. Copper (I) iodide (2.1 g, 10.9 mmol) and tetrakistriphenylphosphine palladium (0) (3.8 g, 5.5 mmol) were added to the reaction solution, and the mixture was stirred at room temperature for 4 hours. The reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure. The obtained crude product was washed with methylene chloride to obtain 22.1 g (I-6-d).

Synthesis of (I-6-e):
(I-6-d) (11.0 g, 37.4 mmol), N, N-dimethylformamide (22 mL) were mixed, 11-bromo-1-undecanol (9.39 g, 37.4 mmol), potassium carbonate (. 25.8 g, 187 mmol) was added, and the mixture was stirred at 90 ° C. for 1 hour. After allowing to cool, the mixture was added to ice water, and the precipitated solid was collected by filtration and washed with hexane to obtain a crude product. The obtained crude product was dissolved in ethyl acetate, sodium sulfate was added, dried, filtered through Celite, and the solvent was distilled off to obtain 17.0 g of (I-6-e).

Synthesis of (I-6-f):
(I-6-e) (4.0 g, 8.61 mmol), tetrahydrofuran (40 mL), triethylamine (2.4 mL, 17.2 mmol) are mixed, cooled in an ice bath, and then acryloyl chloride (1.04 mL, 12). .9 mmol) was added and the mixture was stirred for 10 minutes. The reaction mixture was added to ice water, extracted with ethyl acetate, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine. Sodium sulfate was added to the obtained organic layer, dried, and then filtered and concentrated to obtain 4.44 g (I-6-f).

Synthesis of (I-6-g):
(I-6-f) (4.44 g, 8.56 mmol) and ethanol (45 mL) were mixed, PPTS (215 mg, 0.856 mmol) was added, and the mixture was stirred at 50 ° C. for 1 hour. After allowing to cool, the mixture was concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 3.36 g (I-6-g).

Synthesis of (I-6):
(I-6-g) (1.0 g, 2.3 mmol), (I-1-i) (0.85 g, 2.3 mmol), N, N-dimethylamino-4-pyridine (56 mg, 0.46 mmol) ), Methylene chloride (10 mL), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) (0.57 g, 3.0 mmol) was added at 0 ° C., and the mixture was stirred at room temperature for 2 hours. did. The obtained reaction solution was poured into ice water (20 mL) and then extracted with methylene chloride. The obtained organic layer was washed with saturated brine, sodium sulfate was added, dried, and then filtered and concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (hexane / methylene chloride / ethyl acetate) to obtain 0.98 g of (I-6).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.50 (d, 2H, J = 6.8 Hz), 7.44 (d, 2H, J = 6.8 Hz), 7.04 (d, 2H, J = 6) .8Hz), 6.86 (d, 2H, J = 6.8Hz), 6.39 (d, 2H, J = 17.2Hz), 6.12 (dd, 2H, J = 17.2, 10. 4Hz), 5.82 (d, 2H, J = 10.4Hz), 4.15 (t, 4H, J = 6.8Hz), 3.99 (t, 2H, J = 6.8Hz), 3. 47 (t, 2H, J = 6.8Hz), 3.29-3.21 (m, 1H), 2.57-2.49 (m, 1H), 2.25-2.10 (m, 4H) ), 1.88-1.70 (m, 2H), 1.70-1.24 (m, 38H)

<Liquid crystal compound (I-7)>
The liquid crystal compound (I-7) was synthesized according to the synthesis method described below.

Synthesis of (I-7):
It was synthesized in the same manner as (I-1-g) except that 12-bromo-1-dodecanol was used as a starting material (I-7-a) (2 g, 4.0 mmol), and 12-bromo as a starting material. (I-7-b) (1.68 g, 4.4 mmol) synthesized in the same manner as in (I-1-h) except that -1-dodecanol was used, N, N-dimethyl-4-aminopyridine. (97.7 mg, 0.8 mmol) was mixed with methylene chloride (30 mL), EDC (0.92 g, 4.8 mmol) was added at 0 ° C., and the mixture was stirred at room temperature for 12 hours. After adding a saturated aqueous sodium hydrogen carbonate solution to the reaction solution, extraction was performed with methylene chloride, the obtained organic layer was washed with saturated brine, magnesium sulfate was added, and the mixture was dried and concentrated by filtration. The obtained crude product was purified by silica gel column chromatography (hexane / methylene chloride / ethyl acetate) to obtain 2.17 g of (I-7).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.55 (d, 2H), 7.19 (d, 2H), 7.11 (d, 2H), 6.89 (d, 2H), 6.39 (dd) , 2H), 6.12 (dd, 2H), 5.81 (dd, 2H), 4.15 (t, 4H), 3.99 (t, 2H), 3.46 (t, 2H), 3 .21-3.29 (m, 1H), 2.49-2.57 (m, 1H), 2.15 (m4H), 1.79 (m, 2H), 1.52-1.72 (m) , 12H), 1.24-1.49 (m, 42H)

<Liquid crystal compound (I-8)>
The liquid crystal compound (I-8) was synthesized according to the synthesis method described below.

Synthesis of (I-8-a):
Add chloromethyl methyl ether (6.30 g, 78.0 mmol) to a DMF solution (100 mL) of trans-4-hydroxycyclohexylphenol (10.0 g, 52.0 mmol) and potassium carbonate (28.8 g, 208 mmol) 6 Stirred for hours. After adding water (100 mL) to the reaction solution, extraction was performed 3 times with diisopropyl ether (100 mL). The obtained organic layer was washed with saturated brine, magnesium sulfate was added, and the mixture was stirred. After filtration and concentration, silica gel column chromatography (methylene chloride / ethyl acetate) was performed to obtain 5.79 g of (I-8-a).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.12 (d, 2H), 6.96 (d, 2H), 5.15 (s, 2H), 3.6-3.7 (m, 1H), 3 .47 (d, 3H), 2.6-2.7 (m, 1H), 2.0-2.1 (m, 2H), 1.85-1.95 (m, 2H), 1.3 -1.6 (m, 6H)

Synthesis of (I-8-b):
(I-8-a) (5.30 g, 22.0 mmol) was dissolved in DMF (30 mL), dodecane iodide (13.0 g, 44.0 mmol), sodium hydride (oil-based 50-70%, 2. 0 g) was added, and the mixture was stirred at room temperature for 8 hours. After adding water to the reaction solution and extracting with diisopropyl ether, the organic layer was washed with saturated brine. Further, magnesium sulfate was added, dried, and then filtered and concentrated to obtain a crude product. Purification by silica gel column chromatography (hexane / ethyl acetate) gave 4.58 g of (I-8-b).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.11 (d, 2H), 6.96 (d, 2H), 5.14 (s, 2H), 3.47 (m, 5H), 3.2-3 .3 (m, 1H), 2.4-2.5 (m, 1H), 2.1-2.2 (m, 2H), 1.9-2.0 (m, 2H), 1.2 -1.6 (m, 20H), 0.88 (t, 3H)

Synthesis of (I-8-c):
(I-8-b) (4.58 g, 11.7 mmol) was dissolved in methanol (60 mL), concentrated hydrochloric acid (18 mL) was added thereto, and the mixture was stirred at 40 ° C. for 2 hours and at room temperature for 24 hours. The precipitate formed was filtered and then washed with water to obtain 3.93 g of (I-8-c).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ 7.07 (d, 2H), 6.75 (d, 2H), 3.49 (t, 2H), 3.2-3.3 (m, 1H), 2 .4-2.5 (m, 1H), 2.1-2.2 (m, 2H), 1.9-2.0 (m, 2H), 1.2-1.6 (m, 20H) , 0.88 (t, 3H)

Synthesis of (I-8):
(I-8-c) (438 mg, 1.26 mmol), (I-1-d) (465 mg, 1.20 mmol), N, N-dimethyl-4-aminopyridine (29.3 mg, 0.24 mmol) It was dissolved in methylene chloride (30 mL), EDC (276 mg, 1.44 mmol) was added at 0 ° C., and the mixture was stirred at room temperature for 4 hours. After adding a saturated aqueous solution of sodium hydrogen carbonate to the reaction solution, extraction was performed with methylene chloride, the obtained organic layer was washed with saturated brine, magnesium sulfate was added, and the mixture was dried and concentrated by filtration. The obtained crude product was subjected to column purification by silica gel column chromatography (hexane / ethyl acetate) to obtain 447 mg of (I-8).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.6 (d, 2H), 6.95 (d, 2H), 3.47 (t, 2H), 3.2-3.3 (m, 1H), 2 .4-2.5 (m, 1H), 2.1-2.2 (m, 2H), 1.8-1.9 (m, 1H), 1.2-1.6 (m, 20H) , 0.88 (t, 3H)

<Liquid crystal compound (I-9)>
The liquid crystal compound (I-9) was synthesized according to the synthesis method described below.

Synthesis of (I-9-a):
Sodium hydride (oil-based 50-70%, 1.03 g) was added to a DMF solution (20 mL) of (I-10-b) (3.25 g, 10.7 mmol) synthesized below, and the mixture was stirred for 1 hour. Then, 1-bromoundecane (7.80 g, 31.4 mmol) was added, and the mixture was further stirred at room temperature for 4 hours. Saturated ammonium chloride aqueous solution (50 mL) and water (50 mL) were added to the reaction solution, and extraction was performed using diisopropyl ether. The organic layer was washed with saturated brine, magnesium sulfate was added, the mixture was dried, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solution: hexane) and then washed with methanol to obtain 3.61 g of (I-9-a).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.6 (d, 2H), 6.95 (d, 2H), 3.47 (t, 2H), 3.2-3.3 (m, 1H), 2 .4-2.5 (m, 1H), 2.1-2.2 (m, 2H), 1.8-1.9 (m, 1H), 1.2-1.6 (m, 20H) , 0.88 (t, 3H)

Synthesis of (I-9-b):
(I-9-a) (1.88 g, 4.0 mmol), copper (I) oxide (858 mg, 6.0 mmol), DMF (10 mL) are mixed, and propionic acid (785 mg, 8.0 mmol) is added. , The mixture was heated and stirred at 110 ° C. for 10.5 hours under a nitrogen stream. After cooling to room temperature, water (100 mL) was added, and extraction was performed with diisopropyl ether. Magnesium sulfate was added to the organic layer, dried, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solution: hexane / ethyl acetate) to obtain 791 mg of (I-9-b).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.5 (d, 2H), 7.2 (d, 2H), 4.28 (q, 2H), 3.47 (t, 2H), 3.2-3 .3 (m, 1H), 2.4-2.5 (m, 1H), 2.1-2.2 (m, 2H), 1.8-1.9 (m, 1H), 1.2 -1.6 (m, 20H), 0.88 (t, 3H)

Synthesis of (I-9-c):
(I-9-b) (420 mg, 0.95 mmol), potassium hydroxide (104 mg, 2.0 mmol), methylene chloride (4 mL) and water (10 mL) were added, and the mixture was heated and stirred at 100 ° C. for 1 hour, and then at room temperature. The mixture was cooled to (I-9-c), 2 mol / L hydrochloric acid was added, and the resulting precipitate was washed with ethanol to obtain 237 mg (I-9-c).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.5 (d, 2H), 7.2 (d, 2H), 3.47 (t, 2H), 3.2-3.3 (m, 1H), 2 .4-2.5 (m, 1H), 2.1-2.2 (m, 2H), 1.8-1.9 (m, 1H), 1.2-1.6 (m, 20H) , 0.88 (t, 3H)

Synthesis of (I-9):
(I-9-c) (697 mg, 1.6 mmol), (I-10-g) (602 mg, 1.8 mmol), N, N-dimethyl-4-aminopyridine (39.0 mg, 0.32 mmol), Methylene chloride (30 mL) was mixed, and EDC (364 mg, 1.9 mmol) was added at 0 ° C. under a nitrogen stream, the temperature was raised to room temperature, and the mixture was stirred for 6 hours. A saturated aqueous sodium hydrogen carbonate solution was added and the mixture was extracted with a methylene chloride solution, and the obtained organic layer was washed with saturated brine. Then, magnesium sulfate was added, dried, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 774 mg of (I-9).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.54 (d, 2H), 7.23 (d, 2H), 7.08 (d, 2H), 6.89 (d, 2H), 6.39 (d) , 1H), 6.12 (dd, 1H), 5.8 (d, 1H), 4.15 (t, 2H), 3.94 (t, 2H), 3.48 (t, 2H), 3 .2-3.3 (m, 1H), 2.4-2.5 (m, 1H), 2.1-2.2 (m, 2H), 1.9-2.0 (m, 1H) , 1.7-1.8 (m, 2H), 1.6-1.7 (m, 2H), 1.2-1.6 (m, 34H), 0.88 (t, 3H)

<Liquid crystal compound (I-10)>
The liquid crystal compound (I-10) was synthesized according to the synthesis method described below.

Synthesis of (I-10-a):
4-Cyclohexylphenyl (36.8 g, 211 mmol), 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2.2.2] octambis (tetrafluoroborate) (30.0 g, 84.0 mmol) ) And acetonitrile (800 mL) were mixed, iodine (21.3 g, 84.0 mmol) was added, and the mixture was heated and stirred at 60 ° C. for 3 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution (400 mL) was added, and then extraction was performed 3 times with diisopropyl ether (200 mL). The obtained organic layer was washed with saturated brine (200 mL), magnesium sulfate was added, the mixture was dried, and the mixture was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solution: hexane / ethyl acetate) to obtain 28.0 g of (I-10-a).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.64 (d, 2H), 6.99 (d, 2H), 2.94-3.01 (m, 1H), 2.48-2.51 (m, 4H), 2.04-2.16 (m, 2H), 1.56-1.85 (m, 2H)

Synthesis of (I-10-b):
(I-10-a) (17.6 g, 58.6 mmol), sodium hydrogen carbonate (1.62 g, 11.7 mmol) and acetonitrile (330 mL) are mixed to add sodium borohydride (4.40 g, 107 mmol). After adding at 40 ° C., the temperature was raised to 74 ° C., and heating and stirring were performed for 1 hour. The mixture was cooled to room temperature, saturated aqueous ammonium chloride solution (20 mL) was added, and the mixture was stirred. Then, water (200 mL) was added, and the mixture was extracted with diisopropyl ether (200 mL), and the organic layer was washed with saturated brine. Magnesium sulfate was added to the obtained organic layer, dried, filtered, and concentrated under reduced pressure. The obtained crude product was washed with acetone to obtain 8.93 g (I-10-b).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.6 (d, 2H), 6.95 (d, 2H), 3.6-3.7 (m, 2H), 2.4-2.5 (m, 1H), 2.1-2.2 (m, 2H), 1.9-2.0 (m, 2H), 1.39-1.51 (m, 4H)

Synthesis of (I-10-c):
(I-10-b) (8.93 g, 29.6 mmol) and DMF (60 mL) are mixed, sodium hydride (oil-based 50%, 3.40 g) is added, and the generation of bubbles disappears under a nitrogen stream. Stirred to. Then, 2- (11-bromoundecoxy) oxane (29.5 g, 88.0 mmol) was added, and the mixture was stirred at 60 ° C. for 5 hours. After cooling to room temperature, water (100 mL) was added, diisopropyl ether (200 mL) was added, and extraction was performed. After repeating twice, the mixture was washed with saturated brine, dried by adding magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solution: hexane / ethyl acetate) to obtain 13.8 g of (I-10-c).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.59 (d, 2H), 6.95 (d, 2H), 4.5-4.6 (m, 1H), 3.83-3.9 (m, 1H), 3.69-3.74 (m, 1H), 3.2-3.5 (m, 5H), 2.4-2.5 (m, 1H), 2.13-2.18 ( m, 2H), 1.2-1.92 (m, 22H)

Synthesis of (I-10-d):
(I-10-c) (2.22 g, 4.0 mmol), bis (triphenylphosphine) palladium (II) dichloride (84.0 mg, 0.12 mmol), copper iodide (I) (44.0 mg, 0) .24 mmol), sodium carbonate (1.66 g, 12.0 mmol) and DMF (20 mL) were mixed, ethyl propionate (588 mg, 6.0 mmol) was added under a nitrogen stream, and the mixture was stirred at 70 ° C. for 5 hours. After cooling to room temperature, water (100 mL) was added, and extraction was performed with diisopropyl ether. The obtained organic layer was washed with saturated brine, added with magnesium sulfate, dried, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solution: hexane / ethyl acetate) to obtain 1.78 g of (I-10-d).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.59 (d, 2H), 7.19 (d, 2H), 4.5-4.6 (m, 1H), 4.29 (q, 2H), 3 .83-3.9 (m, 1H), 3.69-3.74 (m, 1H), 3.2-3.5 (m, 5H), 2.4-2.5 (m, 1H) , 2.13-2.18 (m, 2H), 1.2-1.92 (m, 25H)

Synthesis of (I-10-e):
(I-10-d) (602 mg, 1.1 mmol) was added with THF (5 mL) and ethanol (2.5 mL) to completely dissolve the mixture, and then potassium hydroxide (188 mg, 3.3 mmol) was added to water (5 mL). ) Was added, and the mixture was stirred at room temperature for 1 hour. After adding 2 mol / L hydrochloric acid (20 mL), the mixture was further stirred at room temperature for 10 minutes. Diisopropyl ether was added to the solution for extraction, the organic layer was washed with saturated brine, magnesium sulfate was added and dried, and the mixture was filtered and concentrated under reduced pressure. The obtained crude product, ethanol (20 mL) and PPTS (30 mg, 0.12 mmol) were mixed and stirred at 50 ° C. for 1 hour. The solvent was concentrated and then washed with water to obtain 435 mg (I-10-e).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CD ₃ OD, 400 MHz) δ7.52 (d, 2H), 7.30 (d, 2H), 3.52-3.57 (m, 4H), 3.32-3.36 (m) , 1H), 2.4-2.5 (m, 1H), 2.13-2.18 (m, 2H), 1.34-1.59 (m, 22H)

Synthesis of (I-10-f):
(I-10-e) (1.20 g, 3.0 mmol), N, N-dimethylaniline (909 mg, 7.5 mmol) and THF (30 mL) were mixed, and acryloyl chloride (452 mg, 5.0 mmol) was added to 0. The mixture was added at ° C. and stirred at 50 ° C. for 2.5 hours. Then, the reaction solution was added to ice-cooled 2 mol / L hydrochloric acid (50 mL), stirred, and then extracted with diisopropyl ether. The organic layer was washed with saturated brine, magnesium sulfate was added and dried, and the mixture was filtered and concentrated under reduced pressure. Hexane was added to the obtained crude product, and the mixture was filtered and washed to obtain 691 mg (I-10-f).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.53 (d, 2H), 7.23 (d, 2H), 6.39 (d, 1H), 6.11 (dd, 1H), 5.81 (d) , 1H), 4.15 (t, 2H), 3.48 (t, 2H), 3.32-3.36 (m, 1H), 2.45-2.5 (m, 1H), 2. 13-2.18 (m, 2H), 1.28-1.69 (m, 22H)

Synthesis of (I-10-g):
Compound (I-10-g) was synthesized according to the synthesis method described below.

Synthesis of (1-10-h):
(I-1-e) (31.1 g, 160 mmol), 11-bromo-1-undecanol (44.2 g, 176 mmol) and potassium carbonate (44.2 g, 320 mmol) were mixed with DMF (125 mL) and 100 ° C. Was stirred for 1.5 hours. After stirring, the mixture was cooled to room temperature, added to water (2 L), and the solid matter was collected by filtration and washed with water. Then, the solid was dissolved in dichloromethane, washed with water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. After concentration, isopropanol was added and suspended, and the solid was collected by filtration to obtain 47.6 g (I-10-h).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ 6.96 (d, 2H), 6.92 (d, 2H), 5.28 (m, 1H), 3.38-3.94 (m, 3H), 3 .3-3.6 (m, 3H), 1.14-2.0 (m, 22H)

Synthesis of (1-10-i):
(I-10-h) (47.6 g, 131 mmol) and THF (480 mL) were mixed, N, N-dimethylaniline (31.6 g, 261 mmol) and acryloyl chloride (17.7 g, 196 mmol) were added, and room temperature was reached. Was stirred for 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed successively with 1 mol / L hydrochloric acid and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 48.6 g of (I-10-i).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ 6.96 (d, 2H), 6.92 (d, 2H), 6.3 (d, 1H), 6.15 (dd, 1H), 5.8 (d) , 1H), 5.28 (m, 1H), 4.15 (t, 2H), 3.8-4.0 (m, 3H), 3.5-3.6 (m, 1H), 1. 2-2.1 (m, 24H)

Synthesis of (1-10-g):
(I-10-i) (48.6 g, 116 mmol) was mixed with ethanol (260 mL), PPTS (2.9 g, 11.6 mmol) was added, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / methylene chloride / ethyl acetate) to obtain 25.9 g (I-10-g).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ6.7-6.8 (m, 4H), 6.37 (d, 2H), 6.14 (d, 1H), 6.80 (dd, 1H), 5 0.8 (d, 1H), 4.15 (t, 2H), 3.75 (t, 2H), 1.2-2.1 (m, 18H)

Synthesis of (I-10):
Methylene chloride (20 mL) with (I-10-f) (829 mg, 1.77 mmol), (I-10-g) (669 mg, 2 mmol), N, N-dimethyl-4-aminopyridine (43 mg, 0.35 mmol). ), EDC (403 mg, 2.1 mmol) was added at 0 ° C. under a nitrogen stream, the temperature was raised to room temperature, and the mixture was stirred for 3 hours. A saturated aqueous sodium hydrogen carbonate solution was added and the mixture was extracted with a methylene chloride solution, and the obtained organic layer was washed with saturated brine. Then, magnesium sulfate was added, dried, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 740 mg of (I-10).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.53 (d, 2H), 7.23 (d, 2H), 7.07 (d, 2H), 6.90 (d, 2H), 6.39 (d) , 2H), 6.11 (dd, 2H), 5.81 (d, 4H), 4.15 (t, 2H), 3.94 (t, 2H), 3.48 (t, 2H), 3 .24-3.27 (m, 1H), 2.45-2.5 (m, 1H), 2.13-2.18 (m, 2H), 1.92-1.95 (m, 2H) , 1.2-1.8 (m, 40H)

<Liquid crystal compound (I-11)>
The liquid crystal compound (I-11) was synthesized according to the synthesis method described below.

Synthesis of (I-11-a):
(I-8-a) (7.20 g, 30.5 mmol) and DMF (35 mL) are mixed, sodium hydride (oiliness: content 50%, 3.6 g, 91.4 mmol) is added, and a nitrogen stream is used. The mixture was stirred until no bubbles were generated. Then, 2- (11-bromoundecoxy) oxane (19.3 g, 54.5 mmol) was added, and the mixture was heated and stirred for 6 hours. After cooling to room temperature, water (100 mL) was added, and extraction was performed using ethyl acetate. After repeating 3 times, the mixture was washed with saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (developing solution: hexane / ethyl acetate) to obtain 12.4 g of (I-11-a).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.12 (d, 2H), 6.97 (d, 2H), 5.15 (s, 2H), 4.56-4.58 (m, 1H), 3 .85-3.9 (m, 1H), 3.7-3.75 (m, 1H), 3.41-3.52 (m, 6H), 3.35-3.39 (m, 1H) , 3.22-3.35 (m, 1H), 2.4-2.5 (m, 1H), 2.1-2.2 (m, 2H), 1.8-1.93 (m, 3H), 1.68-1.75 (m, 1H), 1.2-1.6 (m, 29H)

Synthesis of (I-11-b):
Under a nitrogen stream, (I-11-a) (18.6 g, 37.9 mmol) and PPTS (1.0 g, 3.8 mmol) were mixed with ethanol (200 mL) and stirred at 40 ° C. After distilling the solvent under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solution: hexane: ethyl acetate) to obtain 10.5 g of (I-11-b).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.12 (d, 2H), 6.96 (d, 2H), 5.15 (s, 2H), 3.65 (t, 2H), 3.48 (t) , 3H), 3.23-3.28 (m, 1H), 2.4-2.5 (m, 1H), 2.1-2.2 (m, 2H), 1.89-1.93 (M, 2H), 1.2-1.6 (m, 19H)

Synthesis of (I-11-c):
Mix (I-11-b) (1.2 g, 3.0 mmol) and THF (12 mL) under a nitrogen stream, add N, N-dimethylaniline (0.56 mL, 4.5 mmol), and cool with ice. Acryloyl chloride (0.29 mL, 3.6 mmol) was added while stirring at room temperature for 3 hours. The reaction solution was added to a mixed solution of 2 mol / L hydrochloric acid (2.3 mL) and ice water (10 mL) to set the pH to 1, and then extracted with ethyl acetate three times. The organic layer was washed with water and saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 1.36 g (I-11-c).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.12 (d, 2H), 6.96 (d, 2H), 6.39 (d, 1H), 6.12 (dd, 1H), 5.81 (d) , 1H), 5.15 (s, 2H), 4.12 (t, 2H), 3.46 (t, 2H), 3.23-3.28 (m, 1H), 2.4-2. 5 (m, 1H), 2.1-2.2 (m, 2H), 1.89-1.93 (m, 2H), 1.2-1.6 (m, 19H)

Synthesis of (I-11-d):
(I-11-c) (0.05 g, 0.11 mmol) was mixed with methanol (1 mL), ice-cooled, chlorotrimethylsilane (19 μL, 0.11 mmol) was added, and the mixture was stirred at room temperature for 4 hours. The mixture was concentrated under reduced pressure and then purified by silica gel chromatography (hexane / ethyl acetate) to give 35 mg of (I-11-d).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.08 (d, 2H), 6.77 (d, 2H), 6.39 (d, 1H), 6.12 (dd, 1H), 5.81 (d) , 1H), 4.8 (s, 1H), 4.15 (t, 2H), 3.48 (t, 2H), 3.22-3.3 (m, 1H), 2.4-2. 47 (m, 1H), 2.1-2.2 (m, 2H), 1.89-1.93 (m, 2H), 1.2-1.6 (m, 19H)

Synthesis of (I-11):
(I-11-d) (3.55 g, 8.5 mmol), (I-1-d) (3.05 g, 7.7 mmol), N, N-dimethyl-4-aminopyridine (188 mg, 1.54 mmol) ), Was mixed with methylene chloride (50 mL), EDC (1.77 g, 9.24 mmol) was added at 0 ° C., and the mixture was stirred at room temperature for 4 hours. After adding a saturated solution of sodium hydrogen carbonate to the reaction solution, extraction was performed with methylene chloride, the obtained organic layer was washed with saturated brine, magnesium sulfate was added, and the mixture was dried and concentrated by filtration. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 1.60 g of (I-11).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.54 (d, 2H), 7.22 (d, 2H), 7.09 (d, 2H), 6.88 (d, 2H), 6.39 (d) , 2H), 6.12 (dd, 2H), 5.81 (d, 1H), 4.15 (t, 4H), 3.98 (t, 2H), 3.48 (t, 2H), 3 .22-3.3 (m, 1H), 2.4-2.47 (m, 1H), 2.1-2.2 (m, 2H), 1.89-1.93 (m, 2H) , 1.75-1.81 (m, 2H), 1.2-1.6 (m, 38H)

<Liquid crystal compound (I-12)>
The liquid crystal compound (I-12) was synthesized according to the synthesis method described below.

Synthesis of (1-12):
(I-1-g) (1.44 g, 3.0 mmol), (I-7-b) (1.26 g, 3.3 mmol), N, N-dimethyl-4-aminopyridine (80 mg, 0.60 mmol) ) Was mixed with methylene chloride (30 mL), EDC (632 mg, 3.3 mmol) was added at 0 ° C., and the mixture was stirred at room temperature for 17 hours. After adding a saturated aqueous sodium hydrogen carbonate solution to the reaction solution, extraction was performed with methylene chloride, the obtained organic layer was washed with saturated brine, magnesium sulfate was added, and the mixture was dried and concentrated by filtration. The obtained crude product was purified by silica gel column chromatography (hexane / methylene chloride / ethyl acetate) to obtain 1.26 g of (I-12).

The structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ7.55 (d, 2H), 7.19 (d, 2H), 7.11 (d, 2H), 6.89 (d, 2H), 6.39 (dd) , 2H), 6.12 (dd, 2H), 5.81 (dd, 2H), 4.15 (t, 4H), 3.99 (t, 2H), 3.46 (t, 2H), 3 .21-3.29 (m, 1H), 2.49-2.57 (m, 1H), 2.15 (m4H), 1.79 (m, 2H), 1.52-1.72 (m) , 12H), 1.24-1.49 (m, 40H)

The chemical structural formulas of the liquid crystal compounds synthesized above and the dyes used in the following Examples or Comparative Examples are shown below. In the formula, C ₁₁ H ₂₂ means that ₁₁ methylene chains are linearly bonded, and C ₉ H ₁₈ means that ₉ methylene chains are linearly bonded. Meaning, C ₁₂ H ₂₄ means that ₁₂ methylene chains are linearly bonded.

For the liquid crystal compounds (I-1) to the liquid crystal compound (I-12), 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. For differential scanning calorimetry, the sample volume is 0.5 mg to 10 mg, an aluminum pan is used, the heating and cooling processes are 5 ° C / min or 10 ° C / min, and heating from -50 ° C to any temperature is performed. Cooling was repeatedly measured three times, and the third measured value was taken as the phase transition temperature.
For differential scanning calorimetry, for liquid crystal compounds (I-1) to liquid crystal compounds (I-8) and (I-12), 4-methoxyphenol was used as a polymerization inhibitor with respect to 100 parts by weight of the liquid crystal compound. Was added in an amount of 0.2 parts by weight. As for the liquid crystal compound (I-9), the composition 11 for forming an anisotropic dye film described later was used. As for the liquid crystal compound (I-10), the composition 12 for forming an anisotropic dye film described later was used. As for the liquid crystal compound (I-11), the composition 13 for forming an anisotropic dye film described later was used.
The results are shown in Table 1.
It was confirmed by polarization microscope observation and X-ray structure analysis that this temperature was the isotropic phase appearance temperature.

Liquid crystal compound (I-1), liquid crystal compound (I-2), liquid crystal compound (I-7), liquid crystal compound (I-8), which are liquid crystal compounds having a partial structure represented by the formula (1). The liquid crystal compound (I-9), the liquid crystal compound (I-10), the liquid crystal compound (I-11) and the liquid crystal compound (I-12) are liquid crystal compounds having no partial structure represented by the above formula (1). The isotropic phase appearance temperature is lower than that of the liquid crystal compound (I-3), the liquid crystal compound (I-4), and the liquid crystal compound (I-5), and the process is easy to handle and energy consumption. It is clear that the reorientation process of heating to an isotropic phase and the degree of freedom in selecting the base material are excellent.

Example 1
79.80 parts of chloroform, 20.00 parts of liquid crystal compound (I-1), 0.12 part of azo dye of formula (II-1) (manufactured by Hayashihara Co., Ltd.), azo dye of formula (II-2) 0.08 part of (Showa Kako Co., Ltd.) was added, and the mixture was stirred and compatible with each other, and then the solvent was removed to obtain an anisotropic dye film forming composition 1.
In order to determine the two-color ratio by the above method using the obtained anisotropic dye film forming composition 1, an anisotropic dye film 1 is prepared and the two-color ratio of the anisotropic dye film 1 is determined. Were determined.
The results are shown in Table 2. The two-color ratio of the anisotropic dye film 1 was 46.34 at 40.0 ° C. and 570 nm.

Example 2
An anisotropic dye film forming composition 2 and an anisotropic dye film 2 were obtained in the same manner as in Example 1 except that the liquid crystal compound (I-2) was used instead of the liquid crystal compound (I-1). It was. For the anisotropic dye film 2, the two-color ratio of the anisotropic dye film 2 was determined.
The results are shown in Table 2.

Example 3
An anisotropic dye film forming composition 9 and an anisotropic dye film 9 were obtained in the same manner as in Example 1 except that the liquid crystal compound (I-7) was used instead of the liquid crystal compound (I-1). It was. For the anisotropic dye film 9, the two-color ratio of the anisotropic dye film 9 was determined.
The results are shown in Table 2.

Example 4
An anisotropic dye film forming composition 10 and an anisotropic dye film 10 were obtained in the same manner as in Example 1 except that the liquid crystal compound (I-8) was used instead of the liquid crystal compound (I-1). It was. For the anisotropic dye film 10, the two-color ratio of the anisotropic dye film 10 was determined.
The results are shown in Table 2.

Example 5
In 79.80 parts of chloroform, 8.00 part of the liquid crystal compound (I-1), 12.00 parts of the liquid crystal compound (I-9), and 0 of the azo dye of the formula (II-1) (manufactured by Hayashihara Co., Ltd.). .12 parts, 0.08 part of the azo dye of formula (II-2) (manufactured by Showa Kako Co., Ltd.) was added, stirred and compatible, and then the solvent was removed to form an anisotropic dye film. Composition 11 for use was obtained.
In order to determine the two-color ratio by the above-mentioned method using the obtained anisotropic dye film forming composition 11, an anisotropic dye film 11 is prepared and the two-color ratio of the anisotropic dye film 11 is determined. Were determined.
The results are shown in Table 2.

Example 6
An anisotropic dye film forming composition 12 and an anisotropic dye film 12 were obtained in the same manner as in Example 5 except that the liquid crystal compound (I-10) was used instead of the liquid crystal compound (I-9). It was. For the anisotropic dye film 12, the two-color ratio of the anisotropic dye film 12 was determined.
The results are shown in Table 2.

Example 7
An anisotropic dye film forming composition 13 and an anisotropic dye film 13 were obtained in the same manner as in Example 5 except that the liquid crystal compound (I-11) was used instead of the liquid crystal compound (I-9). It was. For the anisotropic dye film 13, the two-color ratio of the anisotropic dye film 13 was determined.
The results are shown in Table 2.

Comparative Example 1
An anisotropic dye film forming composition 3 and an anisotropic dye film 3 were obtained in the same manner as in Example 1 except that the liquid crystal compound (I-3) was used instead of the liquid crystal compound (I-1). It was. For the anisotropic dye film 3, the two-color ratio of the anisotropic dye film 3 was determined.
The results are shown in Table 2.

Comparative Example 2
An anisotropic dye film forming composition 4 and an anisotropic dye film 4 were obtained in the same manner as in Example 1 except that the liquid crystal compound (I-4) was used instead of the liquid crystal compound (I-1). It was. For the anisotropic dye film 4, the two-color ratio of the anisotropic dye film 4 was determined.
The results are shown in Table 2.

Comparative Example 3
An anisotropic dye film forming composition 5 and an anisotropic dye film 5 were obtained in the same manner as in Example 1 except that the liquid crystal compound (I-5) was used instead of the liquid crystal compound (I-1). It was. For the anisotropic dye film 5, the two-color ratio of the anisotropic dye film 5 was determined.
The results are shown in Table 2.

Reference example 1
An anisotropic dye film forming composition 8 and an anisotropic dye film 8 were obtained in the same manner as in Example 1 except that the liquid crystal compound (I-6) was used instead of the liquid crystal compound (I-1). It was. For the anisotropic dye film 8, the two-color ratio of the anisotropic dye film 8 was determined.
The results are shown in Table 2.

Example 8
69.99 parts of cyclopentanone, 28.57 parts of liquid crystal compound (I-1), 0.43 parts of azo dye of formula (II-1), 0. of azo dye of formula (II-2). 29 parts, 0.29 part of IRGACURE (registered trademark) 369 (BASF product), 0.43 part of BYK-361N (manufactured by BYK-Chemie) are added, and after heating and stirring at 80 ° C. The composition 6 for an anisotropic dye film was obtained by filtering using a syringe equipped with PTFE 13045 manufactured by the same company and having a diameter of 0.45 μm).
The composition 6 for an anisotropic dye film is formed on a substrate on which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems, manufactured by a rubbing method) is formed on a glass by a spin coating method. After heating and drying at 120 ° C. for 2 minutes, the film was cooled to the liquid crystal phase and polymerized at an exposure of 500 mj / cm ² (365 nm standard) to obtain an anisotropic dye film 6. When the obtained anisotropic dye film 6 was held over a commercially available polarizing plate and rotated, it became bright and dark, and it was confirmed that it showed good performance that could be used as a polarizing film.

Example 9
Example 8 except that the substrate used was a substrate on which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems, manufactured by the rubbing method) was formed on a polyimide film (thickness 100 μm). In the same manner as above, the anisotropic dye film 7 was obtained from the composition 6 for the anisotropic dye film. It was confirmed that when the obtained anisotropic dye film 7 was held over a commercially available polarizing plate and rotated, it became bright and dark, and exhibited good performance that could be used as a polarizing film.

From the above, a film prepared by using the liquid crystal compound (I-1) or the liquid crystal compound (I-2), which is a liquid crystal compound having a partial structure represented by the formula (1), sufficiently functions as a polarizing film. It became clear that it could be done.

The composition for forming an anisotropic dye film of the present invention can realize a low isotropic phase appearance temperature while maintaining excellent optical performance, particularly a sufficient two-color ratio.
Since the anisotropic dye film of the present invention is formed by using the composition for forming an anisotropic dye film of the present invention, excellent optical performance, particularly a sufficient dichroic ratio can be maintained, and the anisotropic dye film is formed at a lower temperature. It is possible to do.
Since the optical element of the present invention contains the anisotropic dye film of the present invention, an anisotropic dye film capable of maintaining excellent optical performance, particularly a sufficient dichroic ratio, and being formed at a lower temperature can be obtained. Can include.

Another aspect of the present invention is as follows.
[1] An anisotropic dye film forming composition containing a dye and a liquid crystal compound.
The liquid crystal compound is a composition for forming an anisotropic dye film containing a liquid crystal compound having a partial structure represented by the formula (1).
-Cy-X2-C≡C-X-... (1)
(During the ceremony,
Cy represents a hydrocarbon ring group or a heterocyclic group;
-X- is -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 Represents S- or -SCH _2- ;
-X2- is 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- , Represents -CH ₂ S- or -SCH _2- . )
[2] In [1], -X- is -C (= O) O-, -OC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, or -OCH _2- . The composition for forming an anisotropic dye film according to the above.
[3] The composition for forming an anisotropic dye film according to [1] or [2], wherein Cy is a hydrocarbon ring group and -X2- is a single bond.
[4] The composition for forming an anisotropic dye film according to any one of [1] to [3], wherein the liquid crystal compound is a liquid crystal compound represented by the formula (2).
R1-A1-Y1-A2-Y2-A3-R2 ... (2)
(During the ceremony,
R1 and R2 each independently represent a chain organic group;
A1 and A3 independently represent a partial structure represented by the above formula (1), a divalent organic group, or a single bond;
A2 represents a partial structure or a divalent organic group represented by the above formula (1);
-Y1- and -Y2- are independently single-bonded, -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, respectively. -C (= O) S-, -SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ Represents O-, -OCH _2- , -CH ₂ S-, or -SCH _2- ;
One of A1 and A3 is a partial structure or a divalent organic group represented by the above formula (1); at least one of A1, A2, and A3 is a portion represented by the above formula (1). It is a structure. )
[5] One of A1, A2, and A3 is a partial structure represented by the above formula (1), Cy is a hydrocarbon ring group, and -X2- is a single bond; the other The composition for forming an anisotropic dye film according to [4], wherein the two are independently divalent organic groups, and the divalent organic group is a hydrocarbon ring group.
[6] The composition for forming an anisotropic dye film according to [5], wherein the hydrocarbon ring group is a 1,4-phenylene group or a cyclohexane-1,4-diyl group.
[7] -Y1- and -Y2- are independently single-bonded, -C (= O) O-, -OC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, or -OCH _2- , and -X- is -C (= O) O-, -OC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, or -OCH _2- . The composition for forming an anisotropic dye film according to any one of [4] to [6].
[8] The composition for forming an anisotropic dye film according to any one of [4] to [7], wherein Cy is a 1,4-phenylene group.
[9] The composition for forming an anisotropic dye film according to any one of [4] to [8], wherein one of A1 and A3 is a cyclohexane-1,4-diyl group.
[10] One of A1 and A3 has a partial structure represented by the above formula (1).
The composition for forming an anisotropic dye film according to any one of [4] to [9], wherein the other is a cyclohexane-1,4-diyl group.
[11] An anisotropic dye film formed by using the composition for forming an anisotropic dye film according to any one of [1] to [10].
[12] An optical element including the anisotropic dye film according to [11].

Claims (13)

An anisotropic dye film forming composition containing a dye and a liquid crystal compound.
The liquid crystal compound is a composition for forming an anisotropic dye film containing a liquid crystal compound represented by the formula (2).
R1-A1-Y1-A2-Y2-A3-R2 ... (2)
(During the ceremony,
R1 and R2 each independently represent a chain organic group;
At least one chain organic group of R1 and _{R2, - (CH 2) n-} CH 2 - polymerizable group or a _{-O- (CH 2) n-CH} 2 - represents a polymerizable group, Here, n , An integer from 1 to 24;
A1 and A3 independently represent a partial structure represented by the formula (1), a divalent organic group, or a single bond;
A2 represents a partial structure or a divalent organic group represented by the formula (1);
-Y1- and -Y2- are independently single-bonded, -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, respectively. -C (= O) S-, -SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH
Represents ₂ O-, -OCH _2- , -CH ₂ S-, or -SCH _2- ;
One of A1 and A3 is a cyclohexane-1,4-diyl group;
At least one of A1, A2, and A3 is a partial structure represented by the formula (1). )
-Cy-X2-C≡C-X-... (1)
(During the ceremony,
Cy represents a hydrocarbon ring group or a heterocyclic group;
-X- is -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, -C (= O) S-, -SC (= O)- ,- CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ O-, -OCH _2- , -CH ₂ S-, or -SCH ₂ Represents-;
-X2- is 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- , Represents -CH ₂ S- or -SCH _2- . ) The composition for forming an anisotropic dye film according to claim 1, wherein −X− is −C (= O) O−, −OC (= O) − , −CH ₂ O−, or −OCH _2−. Stuff. The composition for forming an anisotropic dye film according to claim 1 or 2, wherein Cy is a hydrocarbon ring group and -X2- is a single bond. The composition for forming an anisotropic dye film according to any one of claims 1 to 3, wherein one of A1, A2, and A3 is a partial structure represented by the above formula (1). Cy is a hydrocarbon ring group and -X2- is a single bond; one of A1, A2, and A3 is a partial structure represented by the above formula (1), and the other two are The composition for forming an anisotropic dye film according to any one of claims 1 to 4, which is independently a hydrocarbon ring group. The composition for forming an anisotropic dye film according to any one of claims 1 to 5, wherein the hydrocarbon ring group is a 1,4-phenylene group or a cyclohexane-1,4-diyl group. -Y1- and -Y2- are independently single-bonded, -C (= O) O-, -OC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, or -OCH _{2 respectively.} -, Whichever of claims 1 to 6, where -X- is -C (= O) O-, -OC (= O)- , -CH ₂ O-, or -OCH _2-. The composition for forming an anisotropic dye film according to. The composition for forming an anisotropic dye film according to any one of claims 1 to 7, wherein Cy is a 1,4-phenylene group. One of A1 and A3 is a cyclohexane-1,4-diyl group.
The composition for forming an anisotropic dye film according to any one of claims 1 to 8, wherein the other is a partial structure represented by the formula (1). The invention according to any one of claims 1 to 9, wherein the content of the dye is 0.01 to 30 parts by mass with respect to 100 parts by mass of the solid content of the composition for forming an anisotropic dye film. Composition for forming an anisotropic dye film. The composition for forming an anisotropic dye film according to any one of claims 1 to 10, wherein the dye is an azo-based dichroic dye. An anisotropic dye film formed by using the composition for forming an anisotropic dye film according to any one of claims 1 to 11. An optical element comprising the anisotropic dye film according to claim 12.