KR20200131223A - Composition for anisotropic dye film formation, anisotropic dye film, and optical element - Google Patents

Abstract

The composition for forming an anisotropic dye film of the first aspect of the present invention contains a dye and a liquid crystal compound having a partial structure represented by formula (1). -Cy-X2-C≡CX-… (1) (In the formula, Cy represents a hydrocarbon cyclic 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 S-, or -SCH ₂ -is represented; -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 -, -CH ₂ S-, or -SCH ₂ -.)

Description

Composition for anisotropic dye film formation, anisotropic dye film, and optical element

The present invention is useful for anisotropic dye film formed by applying a liquid crystal composition, in particular, a light modulation element, a liquid crystal element (LCD), and a polarizing film provided in a display element of an organic electroluminescence element (OLED), and has high dichroic properties. It relates to a composition for forming an anisotropic dye film, an anisotropic dye film, and an optical element.

In LCD, a linear polarizing film and a circular polarizing film are used in order to control optical rotation and birefringence in display. Also in OLED, a circular polarizing film is used to prevent reflection of external light at a spot.

Conventionally, as such a polarizing film, it is known to include, for example, a polarizing film (iodine-PVA polarizing film) in which polyvinyl alcohol (PVA) is dyed with low concentration of iodine (Patent Document 1).

Further, 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 Laid-Open Patent Publication No. Hei 1-105204 Japanese Patent Publication No. 2004-535483

However, the iodine-PVA polarizing plate with such a low concentration has a problem that iodine sublimates or deteriorates depending on the use environment, and the color tone changes, and warpage occurs due to the relaxation of the stretching of PVA. .

In addition, in the case of a polarizing film formed by applying a liquid crystal composition containing a dye, there is a problem that high light absorption selectivity cannot be obtained, or if a high light absorption selectivity is to be obtained, difficulties in the process may occur. have.

Under such circumstances, a polarizing film having high light absorption selectivity even as a thin film is desired.

By the way, in the manufacturing process of the anisotropic dye film, in the orientation process performed as necessary after application and drying of the anisotropic dye film-forming composition to a substrate, heating to the isotropic appearance temperature or higher of the anisotropic dye film-forming composition Then, cooling is performed again so that it becomes a liquid crystal phase. Alternatively, cooling is performed after heating to a temperature at which a liquid crystal phase with high fluidity (for example, a nematic phase) is expressed. In this respect, the composition for forming an anisotropic dye film having a high isotropic appearance temperature requires a higher temperature in the above alignment process, and from the viewpoint of stability of the dye or liquid crystal compound, ease of handling of the process, energy consumption, etc. It becomes disadvantageous. Further, when the liquid crystal compound has a polymerizable group, unintended thermal polymerization may occur due to heating at a high temperature in the above-described rearrangement process. Further, depending on the heat-resistant temperature of the substrate, the degree of freedom for selection of the usable substrate is lowered.

On the other hand, in order to increase the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film, it is conceivable to increase the ratio of the long axis and the short axis of the core of the liquid crystal compound molecule contained in the composition for forming an anisotropic dye film.

However, when the core of the liquid crystal compound molecule is enlarged, the melting point of the liquid crystal compound (the phase transition point between the solid and the liquid) and the isotropic phase appearance temperature (the phase transition point between the liquid crystal and the liquid) tend to increase.

That is, if it is desired to lower the isotropic appearance temperature, it is conceivable to reduce the core of the liquid crystal compound molecule, while by reducing the core of the liquid crystal compound molecule, the ratio of the long axis and the short axis of the core of the liquid crystal compound molecule becomes small, As a result, the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film is lowered.

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

One aspect (first aspect) of the present invention aims to provide a composition for forming an anisotropic dye film capable of realizing a low isotropic appearance temperature while maintaining excellent optical performance, particularly a sufficient dichroic ratio.

In addition, one aspect (first aspect) of the present invention aims to provide an anisotropic dye film which can maintain excellent optical performance, particularly a sufficient dichroic ratio, and can be formed at a lower temperature.

In addition, one aspect (first aspect) of the present invention is to provide an optical element including an anisotropic dye film capable of maintaining excellent optical performance, particularly a sufficient dichroic ratio, and capable of being formed at a lower temperature. .

On the other hand, in order to increase the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film, the ratio of the long axis and the short axis of the core of the liquid crystal compound molecule contained in the composition for forming an anisotropic dye film is increased, and the liquid crystal molecules It is conceivable to orientate in the uniaxial direction.

However, when the core of the liquid crystal compound molecule is enlarged, the core is made of an aromatic ring such as a benzene ring or an alicyclic ring such as a cyclohexane ring, and therefore, with respect to the direction of the alignment regulating force obtained from the alignment film, etc. Molecules tend to be tilted and oriented.

That is, in order to align the liquid crystal compound molecules in the uniaxial direction, it is conceivable to reduce the core of the liquid crystal compound molecules, reduce the interaction between molecules, and reduce the inclination of the molecules. By making it small, the ratio of the long axis and the short axis of the core of the liquid crystal compound molecule becomes small, and as a result, the dichroism of the anisotropic dye film formed from the composition for anisotropic dye film formation is lowered.

Under such circumstances, the development of a liquid crystal compound molecule in which the anisotropic dye film exhibits high dichroism and a composition for forming an anisotropic dye film containing the same is desired.

Another aspect (second aspect) of the present invention aims to provide a composition for forming an anisotropic dye film capable of realizing excellent optical performance, particularly a sufficient dichroic ratio.

Further, another aspect (second aspect) of the present invention aims to provide an anisotropic dye film capable of realizing excellent optical performance, particularly a sufficient dichroic ratio.

Moreover, another aspect (second aspect) of the present invention aims to provide an optical element comprising an anisotropic dye film capable of realizing excellent optical performance, particularly a sufficient dichroic ratio.

The inventors of the present invention found that in the composition for forming an anisotropic dye film containing a dye and a liquid crystal compound, the above problem can be solved by using a liquid crystal compound having a specific structure.

That is, the 1st aspect of this invention makes the following a summary.

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

The said liquid crystal compound is a composition for anisotropic dye film formation containing a liquid crystal compound which has a partial structure represented by Formula (1).

-Cy-X2-C≡C-X- … (One)

(In the formula,

Cy represents a hydrocarbon cyclic 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 -, -CH ₂ S- or -SCH ₂ -is represented.)

[2] -X- is -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -phosphorus, as described in [1] A composition for forming an anisotropic dye film.

[3] The composition for forming an anisotropic dye film according to [1] or [2], wherein Cy is a hydrocarbon cyclic 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 formula (2).

R1-A1-Y1-A2-Y2-A3-R2 … (2)

(In the formula,

R1 and R2 each independently represent a chain organic group;

A1 and A3 each independently represent a partial structure represented by the above formula (1), a divalent organic group, or a single bond;

A2 represents a partial structure represented by the above formula (1) or a divalent organic group;

-Y1- and -Y2- are each independently 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 Represents O-, -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -;

One of A1 and A3 is a partial structure represented by the above formula (1) or a divalent organic group;

At least one of A1, A2, and A3 is a partial structure represented by the above formula (1).)

[5] One of A1, A2, and A3 is a partial structure represented by the above formula (1), Cy is a hydrocarbon cyclic group, and -X2- is a single bond; The composition for anisotropic dye film formation according to [4], wherein the other two are each independently a divalent organic group, and the divalent organic group is a hydrocarbon cyclic 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 each independently a single bond, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -, -X- is, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -phosphorus, [4 ] The composition for forming an anisotropic dye film according to any one of [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], in which one of A1 and A3 is a cyclohexane-1,4-diyl group.

[10] One of A1 and A3 is 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 using the composition for forming an anisotropic dye film according to any one of [1] to [10].

[12] An optical element comprising the anisotropic dye film according to [11].

Moreover, the 2nd aspect of this invention makes the following a summary.

As a composition for forming an anisotropic dye film containing a <1> dye and a liquid crystal compound,

The said liquid crystal compound is a composition for anisotropic dye film formation containing a liquid crystal compound which has a partial structure represented by Formula (B1).

-CyH-Z1-E1-C≡C-E2- … (B1)

(In the formula,

CyH represents a substituted or unsubstituted non-aromatic hydrocarbon cyclic group;

E1 and E2 each independently represent a hydrocarbon cyclic group or a heterocyclic group;

-Z1-silver, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC (=O)-, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH ₂ O-, -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -.)

<2> The composition for anisotropic dye film formation according to <1>, in which the liquid crystal compound is a liquid crystal compound represented by formula (B2).

T1-CyH-Z1-E1-C≡C-E2-Z2-E3-T2 … (B2)

(In the formula,

CyH, E1, E2, and -Z1- each have the same meaning as defined in the formula (B1);

T1 and T2 each independently represent a chain organic group;

E3 represents a divalent organic group or a single bond;

-Z2- 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≡C-, -C(=O)NH-, -NHC(=O)-, -CH ₂ O- , -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -.)

<3> -Z1- is, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -phosphorus, <1> or < The composition for forming an anisotropic dye film according to 2>.

The composition for anisotropic dye film formation in any one of <1>-<3> in which <4> E1 or E2 is a hydrocarbon cyclic group.

<5> The composition for anisotropic dye film formation according to <4>, in which the hydrocarbon cyclic group is a phenylene group or a cyclohexanediyl group.

The composition for anisotropic dye film formation in any one of <2>-<5> in which <6> E3 is a hydrocarbon cyclic group, a heterocyclic group, or a single bond.

The composition for anisotropic dye film formation as described in <6> in which <7> E3 is a phenylene group, a cyclohexanediyl group, or a single bond.

<8> -Z2- is a single bond, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -phosphorus, <2 The composition for forming an anisotropic dye film according to any one of> to <7>.

An anisotropic dye film formed using the composition for anisotropic dye film formation in any one of <9> <1>-<8>.

<10> An optical element containing the anisotropic dye film described in <9>.

The composition for anisotropic dye film formation of the first aspect of the present invention can achieve a low isotropic appearance temperature while maintaining excellent optical performance, particularly a sufficient dichroic ratio.

Since the anisotropic dye film of the first aspect of the present invention is formed 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 can be formed at a lower temperature.

Since the optical element of the first aspect of the present invention contains the anisotropic dye film of the present invention, excellent optical performance, particularly a sufficient dichroic ratio can be maintained, and an anisotropic dye film capable of being formed at a lower temperature can be included.

The composition for forming an anisotropic dye film of the second aspect of the present invention can achieve excellent optical performance, particularly a sufficient dichroic ratio.

Since the anisotropic dye film of the second aspect of the present invention is formed using the composition for forming an anisotropic dye film of the present invention, it is possible to realize excellent optical performance, particularly a sufficient dichroic ratio.

Since the optical element of the second aspect of the present invention contains the anisotropic dye film of the present invention, excellent optical performance, particularly sufficient dichroic ratio, can be realized.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is demonstrated concretely, this invention is not limited to the following embodiment, It can be implemented by making various changes within the scope of the summary.

The anisotropic dye film as used in the present invention is selected from three directions in total in the three-dimensional coordinate system in the thickness direction of the anisotropic dye film and in two directions in an arbitrary orthogonal plane, having anisotropy in electromagnetic properties in any two directions. It is a pigment film. Electromagnetic properties include, for example, optical properties such as absorption and refraction, and electrical properties such as resistance and capacity.

Examples of the film having optical anisotropy such as absorption and refraction include polarizing films such as a linear polarizing film and 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 for a polarizing film.

[Composition for anisotropic dye film formation]

The composition for forming an anisotropic dye film of the present invention contains a dye and a liquid crystal compound.

As long as the composition for forming an anisotropic dye film of the present invention does not cause phase separation, it may be a solution, may be a liquid crystal, or may be in a dispersed state. However, as the composition for forming an anisotropic dye film, from the viewpoint of easy application to a substrate, It is preferably a solution. On the other hand, it is preferable that the solid component component excluding the solvent from the composition for forming an anisotropic dye film is in a liquid crystal state at an arbitrary temperature from the viewpoint of aligning on the substrate as described later.

In addition, in the present invention, the state of the liquid crystal is specifically, as described on pages 1 to 16 of "Basics and Applications of Liquid Crystal" (Shoichi Matsumoto, Ichiro Tsunoda; 1991), It is a liquid crystal state that exhibits both or intermediate properties of a crystal, and is a nematic phase, a smectic phase, a cholesteric phase, or a discotic phase.

(Color)

In the present invention, the dye is a substance or compound that absorbs at least a part of the wavelength in the visible region (380 nm to 780 nm).

As a dye that can be used in the present invention, a dichroic dye can be mentioned. In addition, the dichroic dye refers to a dye having a property different from the absorbance in the long axis direction of the molecule and the absorbance in the short axis direction. Moreover, the dye may be a dye having liquid crystallinity or may not have liquid crystallinity. In addition, having liquid crystal property means expressing a liquid crystal phase at an arbitrary temperature.

As a dye contained in the composition for forming an anisotropic dye film of the present invention, an azo dye, a quinone dye (including a naphthoquinone dye, an anthraquinone dye, etc.), a stilbene dye, a cyanine dye, and a phthalocyanine dye Pigments, indigo pigments, condensed polycyclic pigments (perylene pigments, oxazine pigments, acridine pigments, etc.), and the like. Among these dyes, an azo dye is preferred because the molecular long-short ratio is large and a high molecular sequence can be obtained in the anisotropic dye film.

An azo-based 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, color tone, and ease of manufacture. In, 1 or more are preferable, 2 or more are more preferable, 6 or less are preferable, 4 or less are more preferable, and 3 or less are still more preferable.

As an azo dye, a compound represented by Formula (A) is mentioned, for example.

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

In formula (A),

D1, D2, and D3 each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent;

p represents the integer of 0-4;

When p is an integer of 2 or more, a plurality of D2 may be the same or different;

R11 and R12 represent the same or each different monovalent organic group.

D1, D2, and D3 each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent.

As the substitution position of the phenylene group, a 1,4-phenylene group is preferable because the linearity of the molecule is high.

As a substitution position for a naphthylene group, a 1,4-naphthylene group or a 2,6-naphthylene group is preferable because the molecule has high linearity.

As a divalent heterocyclic group, the number of carbon atoms forming a ring is preferably 3 or more and 14 or less, and more preferably 10 or less. In particular, monocyclic or bicyclic heterocyclic groups are preferred.

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

Specifically, pyridindiyl group, quinolindiyl group, isoquinolindiyl group, thiazoldiyl group, benzothiazoldiyl group, thienothiazoldiyl group, thienothiophendiyl group, benzimidazolidinonediyl group, benzofurandiyl group , A phthalimidediyl group, an oxazoldiyl group, and a benzooxazoldiyl group.

Examples of the substituents which the phenylene group, naphthylene group, and divalent heterocyclic group in D1, D2 and D3 have optionally include an alkyl group having 1 to 4 carbon atoms; Alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group; C1-C4 fluorinated alkyl groups, such as a trifluoromethyl group; Cyano group; Nitro group; Hydroxyl group; Halogen atom; A substituted or unsubstituted amino group such as an amino group, diethylamino group, and pyrrolidino group (a substituted amino group means an amino group having 1 or 2 alkyl groups having 1 to 4 carbon atoms, or two substituted alkyl groups bonded to each other to have 2 to carbon atoms. It means an amino group forming an alkanediyl group of 8. The unsubstituted amino group is -NH _2. Further, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a butyl group, and the like. Examples of the alkanediyl group of 8 include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1 , 6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc. are mentioned.) is mentioned.

From the viewpoint of high molecular linearity, it is preferably unsubstituted or 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. .

p represents the integer of 0-4. 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 each different monovalent organic group.

Examples of the monovalent organic group for R11 and R12 include a hydrogen atom and an alkyl group having 1 to 20 carbon atoms which may have a branch; An alicyclic C1-C20 alkyl group; Alkoxy groups having 1 to 20 carbon atoms which may have branches such as a methoxy group, an ethoxy group and a butoxy group; A C1-C20 fluorinated alkyl group which may have branches such as a trifluoromethyl group; Cyano group; Nitro group; Hydroxyl group; Halogen atom; Substituted or unsubstituted amino groups such as an amino group, diethylamino group, and pyrrolidino group (a substituted amino group refers to an amino group having 1 or 2 alkyl groups having 1 to 20 carbon atoms which may have a branch, or two substituted alkyl groups It refers to an amino group which is bonded to form an alkanediyl group having 2 to 20 carbon atoms, and 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 alkanediyl group having 2 to 20 carbon atoms include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-di Diary, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, etc. are mentioned.); Carboxyl group; An alkyloxycarbonyl group having 1 to 20 carbon atoms which may have a branch such as a butoxycarbonyl group; Alkenyl groups having 1 to 20 carbon atoms which may have branches such as ethenyl groups; Alkylphenylalkenyl groups such as 2-(4-butylphenyl)ethenyl group; Carbamoyl group; An alkyl carbamoyl group having 1 to 20 carbon atoms which may have a branch such as a butyl carbamoyl group; Sulfamoyl group; C1-C20 alkyl sulfamoyl group which may have a branch, such as a butyl sulfamoyl group; An acylamino group having 1 to 20 carbon atoms which may have a branch such as a butylcarbonylamino group; An acyloxy group having 1 to 20 carbon atoms which may have a branch such as a butylcarbonyloxy group; Sulfanyl group; Alkylsulfanyl groups having 1 to 20 carbon atoms such as butylsulfanyl groups; The chain organic group which has a polymerizable group of R1 and R2 in a liquid crystal compound mentioned later is mentioned.

As R11 and R12, a hydrogen atom, a chain group, an aliphatic organic group ("aliphatic organic group" includes a chain type and a cyclic type), and an aliphatic oil in which a part of carbon is substituted with nitrogen and/or oxygen. Equipment ("aliphatic organic groups in which a part of carbon is substituted with nitrogen and/or oxygen" includes those of a chain and a cyclic type, and the methyl group of a part of the aliphatic organic group is a hydroxyl group, an oxo group (=O), And those each substituted with an amino group, an imino group, etc.) and the like. In one aspect, a hydrogen atom and a chain group are preferable, in another aspect, a hydrogen atom and an aliphatic organic group are preferable, and as another aspect, , A hydrogen atom, an aliphatic organic group in which a part of carbon is substituted with nitrogen and/or oxygen is preferred.

As the chain group, the above-described alkyl group having 1 to 20 carbon atoms which may have a branch; A C1-C20 alkoxy group which may have a branch; A C1-C20 fluorinated alkyl group which may have a branch; Substituted or unsubstituted amino group (The substituted amino group means an amino group having one or two alkyl groups having 1 to 20 carbon atoms which may have a branch. The unsubstituted amino group is -NH ₂ .); Carboxyl group; An alkyloxycarbonyl group having 1 to 20 carbon atoms which may have a branch; Carbamoyl group; A C1-C20 alkylcarbamoyl group which may have a branch; Sulfamoyl group; A C1-C20 alkylsulfamoyl group 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; Sulfanyl group; A C1-C20 alkylsulfanyl group, etc. are mentioned.

Examples of the aliphatic organic group include the aforementioned alkyl group having 1 to 20 carbon atoms which may have a branch, and an alicyclic alkyl group having 1 to 20 carbon atoms.

As the aliphatic organic group in which a part of carbon is substituted with nitrogen and/or oxygen, the above-described alkoxy group having 1 to 20 carbon atoms which may have a branch; Substituted or unsubstituted amino group (with a substituted amino group, an amino group having one or two alkyl groups having 1 to 20 carbon atoms which may have a branch, or two substituted alkyl groups are bonded to each other to form an alkanediyl 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, a butyl group, etc. As an alkanediyl group having 2 to 20 carbon atoms, 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, etc. are mentioned.); Carboxyl group; An alkyloxycarbonyl group having 1 to 20 carbon atoms which may have a branch; Carbamoyl group; A C1-C20 alkylcarbamoyl group which may have a branch; An acylamino group having 1 to 20 carbon atoms which may have a branch; A C1-C20 acyloxy group etc. which may have a branch are mentioned.

R11 and R12 each independently represent 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; It is preferably substituted with an alkoxy group having 1 to 10 carbon atoms such as a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group and an octyloxy group, a diethylamino group, a pyrrolidino group, and a piperidinyl group. In addition, preferred in a chain organic group having a polymerizable group of R1 and R2 in the liquid crystal compound of the first aspect, which will be described later, a chain having a polymerizable group of T1 and T2 in the liquid crystal compound of the second aspect. Also preferred in the organic group is preferred.

The dye contained in the composition for forming an anisotropic dye film of the present invention is not particularly limited, and a known dye may 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. 2014-095899 described above. And dichroic dyes).

Specifically, although the pigment|dye described below is mentioned, it is not limited to these.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

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

As the content occupied by the dye (dichroic dye) in the composition for forming an anisotropic dye film, for example, 0.01 parts by mass or more is preferable with respect to the solid content (100 parts by mass) of the composition for forming an anisotropic dye film, and 0.05 It is more preferably at least 30 parts by mass, more preferably at most 10 parts by mass. Specifically, as the content occupied by the dye (dichroic dye) in the composition for forming an anisotropic dye film, for example, 0.01 to 30 parts by mass with respect to the solid content (100 parts by mass) of the composition for forming an anisotropic dye film And preferably 0.05 to 10 parts by mass.

When the content occupied by the dye (dichroic dye) is within the above range, the compound contained in the composition for forming an anisotropic dye film of the present invention is not disturbed without disturbing 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 to polymerize. Moreover, when the content occupied by the dye (dichroic dye) is equal to or greater than the lower limit, sufficient light absorption tends to be obtained and sufficient polarization performance tends to be obtained. Moreover, when the content occupied by the dye (dichroic dye) is less than or equal to the above upper limit, there is a tendency that inhibition of alignment of the liquid crystal molecules is easily suppressed.

Depending on the purpose, the dye (dichroic dye) may be used alone or in combination of plural types.

(Liquid crystal compound)

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

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

-Cy-X2-C≡C-X- … (One)

In equation (1),

Cy represents a hydrocarbon cyclic 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 -, -CH ₂ S- or -SCH ₂ -is represented.

The hydrocarbon cyclic group for Cy includes an aromatic hydrocarbon cyclic group and a non-aromatic hydrocarbon cyclic group.

The aromatic hydrocarbon ring group includes an unlinked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.

The unlinked aromatic hydrocarbon ring group is a monocyclic or a divalent group of a condensed aromatic hydrocarbon ring, and the number of carbon atoms is preferably 6 to 20. As the aromatic hydrocarbon ring, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring And a fluorene ring.

The linked aromatic hydrocarbon cyclic group is a monocyclic or a divalent group having a bond hand on an atom constituting the ring by bonding a plurality of condensed aromatic hydrocarbon rings by a single bond. The number of carbon atoms in the monocyclic or condensed ring is preferably 6-20. 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 carbon number of 6 to 20 A second bond has a first bond on an atom constituting the ring of a monocyclic or condensed aromatic hydrocarbon ring, and a second bond on the atom constituting the ring of a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms. Having 2 is a group. Examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.

As the aromatic hydrocarbon ring group, an unlinked aromatic hydrocarbon ring group is preferable.

Among 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 cyclic group includes an unlinked non-aromatic hydrocarbon cyclic group and a linked non-aromatic hydrocarbon cyclic group.

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

The non-linked non-aromatic hydrocarbon ring group is an alicyclic hydrocarbon ring group that does not have an unsaturated bond as an interatomic bond constituting the ring of the non-aromatic hydrocarbon ring, and an unsaturated bond having an unsaturated bond as an inter-atomic bond constituting the ring of the non-aromatic hydrocarbon ring. And non-aromatic hydrocarbon cyclic groups. As the non-linked non-aromatic hydrocarbon cyclic group, an alicyclic hydrocarbon cyclic group is preferable.

The linked non-aromatic hydrocarbon cyclic group is a monocyclic or a divalent group having a bond hand on an atom constituting the ring, and a plurality of condensed non-aromatic hydrocarbon rings are bonded by a single bond; Alternatively, at least one ring selected from the group consisting of a monocyclic aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic nonaromatic hydrocarbon ring, and a condensed nonaromatic hydrocarbon ring, and a monocyclic or condensed nonaromatic hydrocarbon ring It is a divalent group bonded by a bond and having a bond hand on an 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 by a single bond, and the first carbon number is 3 to It has a first bond on an atom constituting the ring of a 20 monocyclic or condensed non-aromatic hydrocarbon ring, and is added on an atom constituting the ring of a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. It is a divalent group having 2 bonding hands, for example, a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, and Has a first bond on an atom constituting the ring of a 20 monocyclic or condensed aromatic hydrocarbon ring, and a second bond on an atom constituting the ring of a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms Having 2 is a group. 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 cyclic group, a non-linked non-aromatic hydrocarbon cyclic group is preferable.

Among these, as the non-aromatic hydrocarbon cyclic group, a divalent group of cyclohexane (cyclohexanediyl group) is preferable. As the cyclohexanediyl group, a cyclohexane-1,4-diyl group is preferable.

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

The aromatic heterocyclic group includes an unlinked aromatic heterocyclic group and a linked aromatic heterocyclic group.

The unlinked aromatic heterocyclic group is a monocyclic or a divalent group of a condensed aromatic heterocyclic ring, and the number of carbon atoms is preferably 4 to 20. As the aromatic heterocycle, a furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloymidazole ring , Pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzoisooxazole ring, benzoisothiazole ring , Benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinorine ring, quinoxaline ring, phenanthridine ring, benzoimidazole ring, pyri A midine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like.

The linked aromatic heterocyclic group is a monocyclic or a divalent group having a bond hand on an atom constituting the ring by bonding a plurality of condensed aromatic heterocyclic rings by a single bond. The number of carbon atoms in the monocyclic or condensed ring is preferably 4-20. For example, a first monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and the first carbon number of 4 to 20 A second bond has a first bond on an atom constituting the ring of a monocyclic or condensed aromatic heterocycle, and a second bond is formed on an atom constituting the ring of a second monocyclic or condensed aromatic heterocycle having 4 to 20 carbon atoms. Having 2 is a group.

The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.

The non-linked non-aromatic heterocyclic group is a monocyclic or a divalent group of a condensed non-aromatic heterocyclic ring, and the number of carbon atoms is preferably 4 to 20. A monocyclic or condensed non-aromatic heterocyclic divalent group having 4 to 20 carbon atoms, and examples of the non-aromatic heterocyclic ring include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, and a tetrahydrothiopyran. Ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetra Hydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzoimidazole ring, quinuclidine ring, etc. are mentioned.

The linked non-aromatic heterocyclic group is a divalent group having a monocyclic or condensed non-aromatic heterocycle bonded by a single bond and having a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4-20. For example, a first monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and the first carbon number is 4 to 20 It has a first bond on an atom constituting the ring of a 20 monocyclic or condensed non-aromatic heterocyclic ring, and is added on an atom constituting the ring of a second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms. It is a divalent group with two bond hands.

The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group for Cy are, respectively, RA, -OH, -O-RA, -OC(=O)-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, carboxyl group, sulfo group, cyano group, nitro group, and halogen It may be substituted with one or more groups selected from the group consisting of. 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 liquid crystal compounds having a partial structure represented by formula (1) associate with each other. From the viewpoint of easy and easy to express a liquid crystal state, each independently is unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, and more preferably unsubstituted.

The substituents of the aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be the same or different, and further, an aromatic hydrocarbon cyclic group, a non-aromatic hydrocarbon cyclic group, an aromatic heterocyclic group, All of the non-aromatic heterocyclic groups may be substituted, all may be unsubstituted, part may be substituted, and part may be unsubstituted.

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

Since the linearity of the liquid crystal compound and the tendency to rotate around the short axis of the molecule tend to be easy, -X- has a small π bond, -C(=O)O-, -OC(=O)-,- C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH _2- , -CH ₂ S-, -SCH ₂ -is preferred, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH _2- More preferable. In one aspect, -X- is, -C(=O)O- or -OC(=O)-, and in another aspect, -X- is -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -.

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 -Cy- and -C≡C- with a group having high linearity. Specifically, as -X2-, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S) having a single bond or π bonding -, -C(=O)S-, -SC(=O)-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, and more linearity It is more preferable that it is a single bond from a high point.

As a liquid crystal compound which has a partial structure represented by said formula (1) contained in the composition for anisotropic dye film formation of this invention, the liquid crystal compound represented by following formula (2) is mentioned.

R1-A1-Y1-A2-Y2-A3-R2 … (2)

In equation (2),

R1 and R2 each independently represent a chain organic group;

A1 and A3 each independently represent a partial structure represented by the above formula (1), a divalent organic group, or a single bond;

A2 represents a partial structure represented by the above formula (1) or a divalent organic group;

-Y1- and -Y2- are each independently 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 Represents O-, -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -;

One of A1 and A3 is a partial structure represented by the above formula (1) or a divalent organic group;

At least one of A1, A2, and A3 is a partial structure represented by the above formula (1).

In addition, when A1 is a partial structure represented by formula (1), formula (2) is,

R1-Cy-X2-C≡C-X-Y1-A2-Y2-A3-R2 … (2A)

Yes,

R1-X-C≡C-X2-Cy-Y1-A2-Y2-A3-R2 … (2B)

You can open it.

Moreover, when A2 is a partial structure represented by formula (1), formula (2) is,

R1-A1-Y1-Cy-X2-C≡C-X-Y2-A3-R2 … (2C)

Yes,

R1-A1-Y1-X-C≡C-X2-Cy-Y2-A3-R2 … (2D)

You can open it.

Moreover, when A3 is a partial structure represented by Formula (1), Formula (2) is,

R1-A1-Y1-A2-Y2-Cy-X2-C≡C-X-R2 … (2E)

Yes,

R1-A1-Y1-A2-Y2-X-C≡C-X2-Cy-R2 … (2F)

You can open it.

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

Moreover, as described above, A1, A2, and A3 are each independently a partial structure represented by formula (1) or a divalent organic group; Moreover, although A1 and A3 may be a single bond, neither A1 nor A3 is a single bond; At least one of A1, A2, and A3 represents a partial structure represented by the above formula (1).

The chain organic group for R1 and R2 does not contain a cyclic structure such as an aromatic hydrocarbon ring, a non-aromatic hydrocarbon ring, an aromatic heterocycle, and a non-aromatic heterocycle (however, the chain type in R1 and R2 When the organic group has a cyclic polymerizable group described later, such as an oxirane ring, an oxetane ring, and a vinylbenzene ring, the portion excluding the polymerizable group does not include the cyclic structure described above.) It is a device.

Examples of such a chain organic group include -(alkyl group), -O-(alkyl group), -S-(alkyl group), -NH-(alkyl group), -N(alkyl group)-(alkyl group), -O(C=O) )-(Alkyl group) and -C(=O)O-(alkyl group). As such a chain organic group, -(alkyl group) and -O-(alkyl group) are preferable. In one aspect, such a chain organic group is -(alkyl group), and in another aspect, 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 may be partially unsaturated bond, or the alkyl group One or more methylene groups to be included are an etheric oxygen atom, a thioether sulfur atom, and an amine nitrogen atom (-NH-, -N(RA)-: where RA is a linear chain having 1 to 6 carbon atoms) Or a branched alkyl group.), a carbonyl group, an ester bond, an amide bond, and a structure substituted by -CHF-, -CF ₂ -, -CHCl-, -CCl ₂ -.

As the alkyl group in these chain organic groups, since the molecular linearity is high, a part of the carbon of the alkyl group may be an unsaturated bond, and one or more methylene groups contained in the alkyl group may be formed by the above-described groups. It is preferable that it is a C1-C25 linear alkyl group which may have a substituted structure.

The main chain in the chain organic group (means the longest chain part in the chain organic group, and when the chain organic group is substituted with a polymerizable group described later, the longest chain in the part excluding the polymerizable group It means a mold part.) 3-25 are preferable, as for the number of atoms of, 5-20 are more preferable, and 6-20 are still more preferable.

Moreover, 1 to 3 polymerizable groups may be substituted for these alkyl groups. The polymerizable group is a group having a partial structure capable of polymerization by light, heat, and/or radiation, and is a functional group or atomic group necessary to secure the function of polymerization. The polymerizable group is preferably a photopolymerizable group from the viewpoint of production of an anisotropic dye film.

Examples of the polymerizable group include acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, vinyl group, vinyloxy group, ethynyl group, Ethynyloxy group, 1,3-butadienyl group, 1,3-butadienyloxy group, oxiranyl group, oxetanyl group, glycidyl group, glycidyloxy group, styryl group, styryloxy group, and the like. Acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, oxiranyl group, glycidyl group, glycidyloxy group are preferable, and acryloyl group , Methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, glycidyl group, glycidyloxy group are more preferable, acryloyloxy group, methacryloyl oxy group The timing and glycidyloxy group are more preferable.

When a polymerizable group is substituted with these alkyl groups, it is preferable that one polymerizable group is substituted, and it is more preferable that one polymerizable group is substituted at the end of the alkyl group.

As a chain organic group, -(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 -Polymerization The genitals are preferred. In addition, n in these formulas is an integer of 1 to 24, an integer of 2 to 24 is preferable, an integer of 4 to 19 is more preferable, and an integer of 5 to 19 is still more preferable. In addition, n1, n2, and n3 in these formulas each independently represent an integer, and the main chain in the chain organic group (means the longest chain portion in the chain organic group, and the chain organic group is When substituted, it means the longest chain-like moiety in the moiety excluding the polymerizable group.) The number of atoms of is preferably 3 to 25, more preferably 5 to 20, still more preferably 6 to It is properly adjusted to be 20.

R1 and R2 are each independently -(alkyl group) which may be substituted with a polymerizable group, preferably -O-(alkyl group) in which the alkyl group may be substituted with a polymerizable group, and -(alkyl group) substituted with a polymerizable group It is more preferable that the alkyl group is -O-(alkyl group) substituted with a polymerizable group.

When X and R1 or X and R2 are bonded like formula (2B) and formula (2E); For example, when R1 or R2 is bonded to Y1 or Y2, such as when A3 is a single bond in formula (2B) or A1 is a single bond in formula (2E); For example, R1 or R2 bonded to X or Y1 or Y2 is preferably -(alkyl group) which may be substituted with a polymerizable group, and more preferably -(alkyl group) substituted with a polymerizable group.

In addition, as other than the above, R1 or R2 not bonded to X or Y1 or Y2 is preferably -O-(alkyl group) which may be substituted with a polymerizable group, and -O-(alkyl group) substituted with a polymerizable group It is more preferable that it is.

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

-Q1- … (3)

In equation (3),

Q1 represents a hydrocarbon cyclic group or a heterocyclic group.

The hydrocarbon cyclic group for Q1 includes an aromatic hydrocarbon cyclic group and a non-aromatic hydrocarbon cyclic group.

The aromatic hydrocarbon ring group includes an unlinked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.

The unlinked aromatic hydrocarbon ring group is a monocyclic or a divalent group of a condensed aromatic hydrocarbon ring, and the number of carbon atoms is preferably 6 to 20. As the aromatic hydrocarbon ring, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring And a fluorene ring.

The linked aromatic hydrocarbon cyclic group is a monocyclic or a divalent group having a bond hand on an atom constituting the ring by bonding a plurality of condensed aromatic hydrocarbon rings by a single bond. The number of carbon atoms in the monocyclic or condensed ring is preferably 6-20. 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 carbon number of 6 to 20 A second bond has a first bond on an atom constituting the ring of a monocyclic or condensed aromatic hydrocarbon ring, and a second bond on the atom constituting the ring of a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms. Having 2 is a group. Examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.

As the aromatic hydrocarbon ring group, an unlinked aromatic hydrocarbon ring group is preferable.

Among 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 cyclic group includes a non-connected non-aromatic hydrocarbon cyclic group and a linked non-aromatic hydrocarbon cyclic group.

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

The non-linked non-aromatic hydrocarbon ring group is an alicyclic hydrocarbon ring group that does not have an unsaturated bond as an interatomic bond constituting the ring of the non-aromatic hydrocarbon ring, and an unsaturated bond having an unsaturated bond as an inter-atomic bond constituting the ring of the non-aromatic hydrocarbon ring. And non-aromatic hydrocarbon cyclic groups. As the non-linked non-aromatic hydrocarbon cyclic group, an alicyclic hydrocarbon cyclic group is preferable.

The linked non-aromatic hydrocarbon cyclic group is a monocyclic or a divalent group having a bond hand on an atom constituting the ring, and a plurality of condensed non-aromatic hydrocarbon rings are bonded by a single bond; Alternatively, at least one ring selected from the group consisting of a monocyclic aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic nonaromatic hydrocarbon ring, and a condensed nonaromatic hydrocarbon ring, and a monocyclic or condensed nonaromatic hydrocarbon ring It is a divalent group bonded by a bond and having a bond hand on an 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 by a single bond, and the first carbon number is 3 to It has a first bond on an atom constituting the ring of a 20 monocyclic or condensed non-aromatic hydrocarbon ring, and is added on an atom constituting the ring of a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. It is a divalent group having 2 bonding hands, for example, a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, and Has a first bond on an atom constituting the ring of a 20 monocyclic or condensed aromatic hydrocarbon ring, and a second bond on an atom constituting the ring of a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms Having 2 is a group. 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 cyclic group, a non-linked non-aromatic hydrocarbon cyclic group is preferable.

Among these, as the non-aromatic hydrocarbon cyclic group, a divalent group of cyclohexane (cyclohexanediyl group) is preferable. As the cyclohexanediyl group, a cyclohexane-1,4-diyl group is preferable.

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

The aromatic heterocyclic group includes an unlinked aromatic heterocyclic group and a linked aromatic heterocyclic group.

The unlinked aromatic heterocyclic group is a monocyclic or a divalent group of a condensed aromatic heterocyclic ring, and the number of carbon atoms is preferably 4 to 20. As the aromatic heterocycle, a furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloymidazole ring , Pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzoisooxazole ring, benzoisothiazole ring , Benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinorine ring, quinoxaline ring, phenanthridine ring, benzoimidazole ring, pyri A midine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like.

The linked aromatic heterocyclic group is a monocyclic or a divalent group having a bond hand on an atom constituting the ring by bonding a plurality of condensed aromatic heterocyclic rings by a single bond. The number of carbon atoms in the monocyclic or condensed ring is preferably 4-20. For example, a first monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and the first carbon number of 4 to 20 A second bond has a first bond on an atom constituting the ring of a monocyclic or condensed aromatic heterocycle, and a second bond is formed on an atom constituting the ring of a second monocyclic or condensed aromatic heterocycle having 4 to 20 carbon atoms. Having 2 is a group.

The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.

The non-linked non-aromatic heterocyclic group is a monocyclic or a divalent group of a condensed non-aromatic heterocyclic ring, and the number of carbon atoms is preferably 4 to 20. A monocyclic or condensed non-aromatic heterocyclic divalent group having 4 to 20 carbon atoms, and examples of the non-aromatic heterocyclic ring include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, and a tetrahydrothiopyran. Ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetra Hydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzoimidazole ring, quinuclidine ring, etc. are mentioned.

The linked non-aromatic heterocyclic group is a divalent group having a monocyclic or condensed non-aromatic heterocycle bonded by a single bond and having a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4-20. For example, a first monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and the first carbon number is 4 to 20 It has a first bond on an atom constituting the ring of a 20 monocyclic or condensed non-aromatic heterocyclic ring, and is added on an atom constituting the ring of a second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms. It is a divalent group with two bond hands.

The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Q1 are, respectively, RA, -OH, -O-RA, -OC(=O)-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, carboxyl group, sulfo group, cyano group, nitro group, and halogen It may be substituted with one or more groups selected from the group consisting of. Here, RA and RB each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.

The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Q1 have high linearity in molecular structure, and liquid crystal compounds having a partial structure represented by formula (1) associate with each other. From the viewpoint of easy and easy to express a liquid crystal state, each independently is unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, and more preferably unsubstituted.

The substituents of the aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be the same or different, and further, an aromatic hydrocarbon cyclic group, a non-aromatic hydrocarbon cyclic group, an aromatic heterocyclic group, All of the non-aromatic heterocyclic groups may be substituted, all may be unsubstituted, part may be substituted, and part may be unsubstituted.

In addition, 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 the divalent organic groups may be free. Substitution may be sufficient, part may be substituted, and some may be unsubstituted.

As Q1, a hydrocarbon cyclic group is preferable, and a phenylene group and a cyclohexanediyl group are more preferable. Moreover, since the linearity of the molecular structure of a liquid crystal compound can be made high, as Q1, a 1,4-phenylene group and a cyclohexane-1,4-diyl group are more preferable.

As the divalent organic group, it is preferable that Q1 is a hydrocarbon cyclic group, that is, a hydrocarbon cyclic group as the divalent organic group. Moreover, as a divalent organic group, a phenylene group and a cyclohexanediyl group are more preferable, and 1,4-phenylene group and a cyclohexane-1,4- from the point which can improve the linearity of the molecular structure of a liquid crystal compound. A diyl group is more preferred.

In formula (2), it is preferable that one of A1, A2, and A3 is a partial structure represented by formula (1), and the other two are each independently a divalent organic group, and A1, A2, and A3 Among them, it is preferable that Cy of the partial structure represented by formula (1) is a hydrocarbon cyclic group, and it is particularly preferable that the divalent organic group is a hydrocarbon cyclic group. Further, it is preferable that the hydrocarbon ring group is a 1,4-phenylene group or a cyclohexane-1,4-diyl group. Moreover, it is preferable that one of A1 and A3 is a cyclohexane-1,4-diyl group.

Moreover, it is more preferable that one of A1 and A3 is a partial structure represented by the formula (1), and one other and A2 are a divalent organic group. In this case, among A1 and A3, one of the divalent organic groups is preferably a cyclohexane-1,4-diyl group, and particularly preferably A2 is a 1,4-phenylene group.

Since the linearity of the liquid crystal compound and the tendency to easily rotate around the short axis of the molecule, -Y1- and -Y2- are each independently a single bond, -C(=O)O, which has a small π bond. -, -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 -is preferred, A single bond, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -are more preferable.

When X and Y1 or X and Y2 are bonded as in formula (2A), formula (2C), formula (2D), and formula (2F), Y1 bonded to X or Y2 bonded to X is provided It is preferable that it is a bond; The other of -X- and -Y1- and -Y2- is preferably -C(=O)O- or -OC(=O)-.

In addition, as in formulas (2B) and (2E), when X is not bonded to any of Y1 and Y2, -X- is -CH ₂ CH ₂ -, -CH ₂ O-, or- It is preferably OCH ₂ -; It is preferable that both -Y1- and -Y2- are -C(=O)O- or -OC(=O)-.

As formula (2), said formula (2A), said formula (2B), said formula (2E), said formula (2F) is preferable.

Specifically, although the following compounds are mentioned as formula (2), it is not limited to these.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

The liquid crystal compound of the first aspect contained in the composition for forming an anisotropic dye film of the first aspect of the present invention is preferably made of a liquid crystal compound having a partial structure represented by the above formula (1). Here, the liquid crystal compound of the first aspect contained in the composition for forming an anisotropic dye film of the first aspect of the present invention may be one type of liquid crystal compound having a partial structure represented by the above formula (1), and two or more types are used in combination. May be. Moreover, liquid crystal compounds other than the liquid crystal compound which has a partial structure represented by said formula (1) may be used together.

The liquid crystal compound of the second aspect contained in the composition for forming an anisotropic dye film of the second aspect of the present invention contains a liquid crystal compound having a partial structure represented by the following formula (B1).

-CyH-Z1-E1-C≡C-E2- … (B1)

In equation (1),

CyH represents a substituted or unsubstituted non-aromatic hydrocarbon cyclic group;

E1 and E2 each independently represent a hydrocarbon cyclic group or a heterocyclic group;

-Z1-silver, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC (=O)-, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH ₂ O-, -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -.

The non-aromatic hydrocarbon cyclic group in CyH contains a non-connected non-aromatic hydrocarbon cyclic group and a connected non-aromatic hydrocarbon cyclic group, and relates to the liquid crystal compound of the first aspect of the composition for forming an anisotropic dye film of the first aspect of the present invention. It has the same meaning as the non-aromatic hydrocarbon cyclic group for Cy in (1).

In addition, the permissible substituent for the non-aromatic hydrocarbon cyclic group in CyH is the ratio in Cy in formula (1) related to the liquid crystal compound of the first aspect of the composition for forming an anisotropic dye film of the first aspect of the present invention. It is the same as the substituent allowed in the aromatic hydrocarbon ring group.

As the non-aromatic hydrocarbon cyclic group for CyH, a divalent group of cyclohexane (cyclohexanediyl group) is preferable. As a cyclohexanediyl group, it is preferable that it is a substituted or unsubstituted cyclohexane-1,4-diyl group because linearity of the molecular structure of a liquid crystal compound can be improved.

In addition, the substituted or unsubstituted non-aromatic hydrocarbon cyclic group in CyH has high linearity in the molecular structure, the liquid crystal compounds having a partial structure represented by formula (B1) are easily associated with each other, and the liquid crystal state is easily expressed. In this, it is preferably unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom or a bromine atom, and more preferably an unsubstituted one.

The hydrocarbon cyclic group and the heterocyclic group in E1 and E2 each independently represent the liquid crystal compound of the first aspect of the composition for forming an anisotropic dye film of the first aspect of the present invention, in Cy in formula (1). It has the same meaning as a hydrocarbon cyclic group and a heterocyclic group.

In addition, the substituents allowed for the hydrocarbon cyclic group and the heterocyclic group in E1 and E2 are each independently, the formula (()) relating to the liquid crystal compound of the first aspect of the composition for forming an anisotropic dye film of the first aspect of the present invention. It is the same as the substituents allowed for the hydrocarbon cyclic group and the heterocyclic group for Cy in 1).

In addition, the preferred embodiments of the hydrocarbon cyclic group and the heterocyclic group in E1 and E2 are each independently of the formula (1), which relates to the liquid crystal compound of the first aspect of the composition for forming an anisotropic dye film of the first aspect of the present invention. It is the same as the preferred aspect for the hydrocarbon cyclic group and heterocyclic group for Cy in 1).

Since the linearity of the liquid crystal compound and the tendency to rotate around the short axis of the molecule tend to be easy, -Z1- is -C≡C-, or -C(=O)O-, -OC (=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -CH ₂ S-, -SCH ₂ -are preferred, and -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O -, -OCH ₂ -is more preferable. In one aspect, -Z1- is, -C(=O)O- or -OC(=O)-, and in another aspect, -Z1-is, -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -.

As the liquid crystal compound having a partial structure represented by the formula (B1) contained in the composition for forming an anisotropic dye film of the present invention, a liquid crystal compound represented by the following formula (B2) may be mentioned.

T1-CyH-Z1-E1-C≡C-E2-Z2-E3-T2 … (B2)

In formula (B2),

CyH, E1, E2, and -Z1- each have the same meaning as defined in the formula (B1);

T1 and T2 each independently represent a chain organic group;

E3 represents a divalent organic group or a single bond;

-Z2- 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≡C-, -C(=O)NH-, -NHC(=O)-, -CH ₂ O- , -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -.

The chain organic groups in T1 and T2 are each independently a chain in R1 and R2 in formula (2) related to the liquid crystal compound of the first aspect of the composition for forming an anisotropic dye film of the first aspect of the present invention. It has the same meaning as the type organic group.

T1 and T2 are each independently -(alkyl group) which may be substituted with a polymerizable group, preferably -O-(alkyl group) in which the alkyl group may be substituted with a polymerizable group, and -(alkyl group) substituted with a polymerizable group It is more preferable that the alkyl group is -O-(alkyl group) substituted with a polymerizable group.

T1 is preferably -O-(alkyl group) in which the alkyl group may be substituted with a polymerizable group, and more preferably -O-(alkyl group) in which the alkyl group is substituted with a polymerizable group.

-Z2- is a single bond and E3 is a single bond; When E3 is a divalent organic group; For T2, it is preferable that it is -O-(alkyl group) in which an alkyl group may be substituted with a polymeric group, and it is more preferable that it is -O-(alkyl group) where an alkyl group is substituted with a polymeric group.

When -Z2- is other than a single bond and E3 is a single bond, T2 is preferably -(alkyl group) which may be substituted with a polymerizable group, and more preferably -(alkyl group) substituted with a polymerizable group.

It is preferable that the divalent organic group in E3 is a group represented by the following formula (B3) or a single bond.

-Q1- … (B3)

The group represented by the formula (B3) is a divalent organic group in A1, A2, and A3 in the formula (2) related to the liquid crystal compound of the first aspect of the composition for forming an anisotropic dye film of the first aspect of the present invention. , It has the same meaning as the group represented by formula (3).

E3 is preferably a phenylene group, a cyclohexanediyl group, or a single bond, and more preferably a 1,4-phenylene group, a cyclohexane-1,4-diyl group, or a single bond.

Since the linearity of the liquid crystal compound and the tendency to rotate around the short axis of the molecule tend to be easy, -Z2- is -C≡C-, or a single bond, -C(=O)O-, which has a small π bond. , -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 -is preferred, provided that Bonds, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -are more preferable.

Specifically, although the following compounds are mentioned as formula (B2), it is not limited to these.

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

The liquid crystal compound of the second aspect contained in the composition for forming an anisotropic dye film of the second aspect of the present invention is preferably made of a liquid crystal compound having a partial structure represented by the above formula (B1). Here, the liquid crystal compound of the second aspect contained in the composition for forming an anisotropic dye film of the second aspect of the present invention may be one type of liquid crystal compound having a partial structure represented by the formula (B1), and two or more types are used in combination. May be. Moreover, liquid crystal compounds other than the liquid crystal compound which has a partial structure represented by said formula (B1) may be used together.

The liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention has an isotropic appearance temperature of generally less than 200°C, preferably less than 160°C, and more preferably less than 140°C from the viewpoint of the process. , Less than 115°C is more preferable, less than 110°C is still more preferable, and less than 105°C is particularly preferable.

In addition, the isotropic appearance temperature here means a phase transition temperature from a liquid crystal to a liquid and a phase transition temperature from a liquid to a liquid crystal. In the present invention, it is preferable that at least one of these phase transition temperatures is in the above range, and it is more preferable that 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 is a combination of known chemical reactions such as alkylation reaction, esterification reaction, amidation reaction, etherification reaction, mouth substitution reaction, and coupling reaction using a metal catalyst. It can be manufactured by doing.

For example, the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention is the method described in Examples or pages 449 to 468 of the "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000). It can be synthesized according to the described method.

(solvent)

The composition for forming an anisotropic dye film of the present invention may contain a solvent as necessary.

The solvent that can be used is not particularly limited as long as it can sufficiently disperse or dissolve a dye or other additive in the liquid crystal compound, but examples include methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl Alcohol solvents such as ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; Aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; Fluorine-containing solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, and hexafluoro-2-propanol; And chlorine-containing solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene; Can be mentioned.

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

The solvent is preferably a solvent capable of dissolving a liquid crystal compound and a dye, and more preferably a solvent in which the liquid crystal compound and a dye are completely dissolved. Moreover, when a liquid crystal compound is a polymeric compound, it is preferable that it is a solvent inert to a 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.

In the case where 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 50 to 98 with respect to the total amount (100 mass%) of the composition of the present invention. The 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 composition for forming an anisotropic dye film is less than or equal to the above upper limit, the viscosity of the composition for forming an anisotropic dye film is not too high, the thickness of the obtained polarizing film becomes uniform, and there is a tendency that unevenness does not easily occur in the polarizing film. have.

Such solid content may be determined in consideration of the thickness of the polarizing film to be manufactured.

The viscosity of the composition for an anisotropic dye film of the present invention is particularly irrelevant as long as a uniform film without thickness unevenness is produced by the coating method described later, but thickness uniformity in a large area, productivity such as coating speed, and optical properties From the viewpoint of obtaining uniformity, 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 still more preferable.

(Other additives)

The composition for forming an anisotropic dye film of the present invention is further, if necessary, a polymerizable liquid crystal compound other than a liquid crystal compound having a partial structure represented by the formula (1), and a liquid crystal compound having a partial structure represented by the formula (1) Non-polymerizable liquid crystal compounds, 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, and other additives such as metal oxides may be contained. By containing an additive, it is sometimes possible to improve the coating properties or stability of the composition for forming an anisotropic dye film, or to improve the stability of the anisotropic dye film formed from the composition for forming an anisotropic dye film.

[Method of manufacturing 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, etc. are mixed as needed, and the dye is dissolved by stirring and shaking at 0 to 80°C. In the case of poorly soluble, 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 excluding the solvent from the composition for forming an anisotropic dye film may not be a liquid crystal at an arbitrary temperature, but it is preferable to exhibit liquid crystallinity at an arbitrary temperature. The composition in which the solvent is excluded from the composition for forming an anisotropic dye film has an isotropic appearance temperature of generally less than 200°C, preferably less than 160°C, and more preferably less than 140°C from the viewpoint of the coating process described below. And, less than 115 degreeC is more preferable, less than 110 degreeC is still more preferable, and less than 105 degreeC is especially preferable.

[Anisotropic pigment 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, when the liquid crystal compound having a partial structure represented by the formula (1) is a polymerizable compound, And one or both of a liquid crystal compound having a partial structure represented by the formula (1) and a polymer having a unit based on a liquid crystal compound having a partial structure represented by the formula (1).)

The anisotropic dye film of the present invention is a polymerizable liquid crystal compound other than a 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, a polymerizable non-liquid crystal compound, and a non-polymerizable Non-liquid crystal compounds, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, organic/inorganic fillers, organic/inorganic nanosheets, organic/inorganic nanofibers, metal oxides, and the like may be included.

The anisotropic dye film of the present invention can be formed 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 for obtaining linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption, as well as the film formation process and the substrate or organic compound (color or transparent By selecting the composition containing the material), functionalization can be performed 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 a liquid crystal display or an antireflection film for OLEDs, the orientation characteristic of the anisotropic dye film can be expressed using a dichroic ratio. If the dichroic ratio is 8 or more, it functions as a polarizing element, but 15 or more are preferable, 20 or more are more preferable, 25 or more are more preferable, 30 or more are especially preferable, and 40 or more are especially preferable. Moreover, the higher the dichroic ratio, the more preferable. Since the dichroic ratio is more than the above lower limit, it is useful as an optical element described later, particularly a polarizing element.

When used as a polarizing element of an antireflection film for 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 properties as an antireflection film are improved. Therefore, when the performance of the polarizing element is high, it is easy to simplify the layer configuration, and it is easy to express sufficient functions even in a thin film configuration, and it can be suitably used for applications such as folding and bending. Moreover, it becomes possible to keep the cost low.

The dichroic ratio (D) in the present invention is represented by the following formula when the dye is evenly oriented.

D = Az/Ay

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

Each absorbance is not particularly limited as long as the same wavelength is used, and any wavelength may be selected according to the purpose. However, in the case of indicating the degree of orientation of the anisotropic dye film, the luminous sensitivity in a specific wavelength range of 380 nm to 780 nm of the anisotropic dye film It is preferable to use a value corrected by, or a value in the maximum absorption wavelength in the visible region.

Further, the transmittance of the anisotropic dye film of the present invention in the visible wavelength region is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more. In addition, the transmittance may be an upper limit according to the application. For example, when making the polarization degree high, it is preferable that the transmittance is 50% or less. Since the transmittance is within the above range, it is useful as an optical element to be described later, and is particularly useful 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.

The film thickness of the anisotropic dye film is a dry film thickness, preferably 10 nm or more, more preferably 100 nm or more, and still more preferably 500 nm or more. 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 film thickness of the anisotropic dye film is in the above range, there is a tendency that a uniform orientation and a uniform film thickness of the dye within the film can be obtained.

[Method for producing anisotropic dye film]

It is preferable to produce the anisotropic dye film of this invention by the wet film forming method using the composition for anisotropic dye film formation of this invention.

The wet film forming method in the present invention is a method of applying and aligning the composition for anisotropic dye films on a substrate by any method. Therefore, the composition for anisotropic dye films may have fluidity, and may or may not contain a solvent. From the viewpoint of viscosity and film uniformity at the time of application, it is more preferable to contain a solvent.

The alignment of the liquid crystal or the dye in the anisotropic dye film may be oriented by shearing or the like in the application process, or may be oriented in the process of drying the solvent. Further, after coating and drying, it may be heated and then subjected to a process of re-orienting liquid crystals or dyes, etc. to align and laminate liquid crystals or dyes on the substrate. In the wet film formation method, when the composition for anisotropic dye film is applied on a substrate, the dye or liquid crystal compound is self-associated (liquid crystal state) already in the composition for anisotropic dye film, in the process of drying the solvent, or after the solvent is completely removed. Orientation in a small area occurs by taking the molecular association state). By giving an exterior to this state, it is oriented in a fixed direction in a macro area, and an anisotropic dye film having a desired performance can be obtained. In this respect, it differs from a method in which a polyvinyl alcohol (PVA) film or the like is dyed and stretched with a solution containing a dye, and the dye is oriented only in the stretching step. In addition, the exterior here includes the influence of the orientation treatment layer formed on the substrate in advance, shear force, magnetic field, electric field, heat, and the like, and these may be used alone or in combination of a plurality of them. If necessary, you may go through a heating process.

The process of applying the composition for anisotropic dye films on the substrate and forming a film, the process of giving an exterior to be oriented, and the process of drying the solvent may be performed sequentially or simultaneously.

As a method of applying the composition for forming an anisotropic dye film on the substrate in the wet film forming method, for example, a coating method, a dip coating method, an LB film forming method, a known printing method, and the like can be mentioned. In addition, 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 on the substrate using a coating method.

The orientation direction of the anisotropic dye film may be different from the application direction. In addition, in the present invention, the orientation direction of the anisotropic dye film refers to a transmission axis (polarization axis) or absorption axis of polarized light if it is a polarizing film, and refers to a fast axis or a slow axis if it is a retardation film.

Although it does not specifically limit as a method of applying the composition for anisotropic dye films and obtaining anisotropic dye films, for example, 253-277 of "Coating Engineering" by Yuji Harazaki (Asakura Bookstore, issued on March 20, 1971) The method described on the page, the method described on pages 118 to 149 of ``Creation and Application of Molecular Cooperation Materials'', supervised by Kunihiro Ichimura (published by Siemshi Co., Ltd., issued on March 3, 1998), a substrate having a step structure (pre-orientation treatment) May be performed), a slot die coating method, a spin coating method, a spray coating method, a bar coating method, a roll coating method, a blade coating method, a curtain coating method, a fountain method, a dip method, or the like. Among them, the use of the slot die coating method or the bar coating method is preferable because an anisotropic dye film with high uniformity can be obtained.

The die coater used for the slot die coating method is generally equipped with an applicator for discharging a coating liquid, a so-called slit die. The slit die is, for example, Japanese Patent Application Laid-Open No. Hei 2-164480, Japanese Patent Application Laid-Open No. 6-154687, Japanese Patent Application Laid-Open No. Hei 9-131559, ``Basic and application of dispersion, application and drying'' ( 2014, Techno-Siste Co., Ltd., ISBN9784924728707 C 305), ``Wet coating technology in display and optical members'' (2007, information equipment, ISBN9784901677752), ``Precision coating and drying technology in the field of electronics'' (2007) , Technical Information Association, ISBN9784861041389). These known slit dies can be applied even if they are members having flexibility, such as films and tapes, or rigid members such as glass substrates.

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 Cellulose or urethane-based films, etc. are mentioned. In addition, on the surface of this substrate, in order to control the orientation direction of the dye, a known method described in pages 226 to 239 of the "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000) (rubbing method, Orientation by a method of forming a groove (fine groove structure) in, a method of using a polarized ultraviolet light/polarized laser (a photo-alignment method), an alignment method by forming an LB film, an alignment method by oblique deposition of an inorganic substance, etc.) Treatment (orientation film) may be performed. In particular, orientation treatment by a rubbing method and a photoalignment method are preferably mentioned. Examples of the material used in the rubbing method include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, and acrylic resin. Examples of the material used in the photoalignment method include polycinnamate-based, polyamic acid-polyimide-based, and azobenzene-based materials. When the alignment treatment layer is formed, it is considered that the liquid crystal compound and the dye are aligned by the influence of the alignment treatment of the alignment treatment layer and the shear force applied to the composition for anisotropic dye films at the time of application.

When applying the composition for anisotropic dye films, the supply method and the supply interval of the composition for anisotropic dye films are not particularly limited. Since the supply operation of the coating liquid is complicated, or fluctuations in the coating film thickness may occur at the start and stop of the coating liquid, when the film thickness of the anisotropic dye film is thin, a composition for anisotropic dye film is continuously used. It is preferable to apply while supplying.

The rate at which the composition for 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 preferably 1.0 m/min or more. , Particularly preferably 5.0 m/min or more. Moreover, it is usually 400 m/min or less, preferably 200 m/min or less, more preferably 100 m/min or less, and still more preferably 50 m/min or less. When the coating speed is within the above range, the anisotropy of the anisotropic dye film is obtained, and there is a tendency that it can be uniformly applied.

The application temperature of the composition for an anisotropic dye film is usually 0°C or more and 100°C or less, preferably 80°C or less, and more preferably 60°C or less.

The humidity at the time of application of the composition for anisotropic dye films is preferably 10% RH or more, and preferably 80 RH% or less.

The anisotropic dye film may be subjected to an insolubilization treatment. By insolubilization, the solubility of the compound in the anisotropic dye film is lowered, thereby controlling the elution of the compound from the anisotropic dye film and increasing the stability of the film.

Specifically, film polymerization or overcoat is preferable from the viewpoint of easiness of post-processing and durability of an anisotropic dye film.

When the film is polymerized, the film in which the liquid crystal molecules and the dye molecules are aligned is subjected to polymerization using light, heat, and/or radiation.

In the case of performing polymerization 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 an 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 ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, Lamp light sources such as fluorescent lamps; And laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. When using by irradiating light of a specific wavelength, an optical filter can also be used. The exposure amount of the active energy ray is preferably from 1 to 100,000 J/m 2, and more preferably from 10 to 10,000 J/m 2.

In the case of performing polymerization 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.

The 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 time of the film formation process is short and the device is also simple. .

[Optical element]

The optical element of the present invention contains the anisotropic dye film of the present invention.

The optical element in the present invention refers to a polarizing element for obtaining linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing anisotropy of light absorption, a retardation element, and an element having functions such as refractive anisotropy and conduction anisotropy. These functions can be appropriately adjusted by the anisotropic dye film formation process and selection of a substrate or a composition containing an organic compound (color or transparent material).

It is most preferable to use the optical element of this invention as a polarizing element.

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

In the optical element, another layer may be formed in order to maintain and improve the function of the anisotropic dye film. For example, a layer having a function of blocking specific wavelengths or a layer having a function of blocking specific substances used to improve durability such as light resistance, heat resistance, and water resistance (barrier films such as oxygen blocking film and water vapor blocking film Etc) ; A layer containing a wavelength cut filter or a material absorbing a specific wavelength, which is used to change a color gamut or improve optical properties; And the like.

[Polarization 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 manufacture by forming an alignment film on a board|substrate, and forming an anisotropic dye film of this invention on the surface of an alignment film.

Moreover, the polarizing element is not limited only to an anisotropic dye film, It is an overcoat layer which has functions, such as improving polarization performance and improving mechanical strength; Adhesive layer or antireflection layer; Alignment film; A layer having optical functions such as a function as a retardation film, a function as a luminance enhancing film, a function as a reflection or antireflection film, a function as a transflective film, and a function as a diffusion film; You may use it in combination with etc. Specifically, layers having various functions described above may be laminated by coating or bonding, and may be used as a laminate.

These layers can be appropriately formed according to the manufacturing process, characteristics, and functions, and the position and order of the stacking 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 on which the anisotropic dye film is formed. Moreover, the order of forming each layer may be before or after formation of the anisotropic dye film.

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

A layer having a function as a retardation film can be formed by applying a retardation film to another layer constituting a polarizing element, bonding, or the like. The retardation film is, for example, subjected to a stretching treatment described in JP-A No. Hei 2-59703, JP-A No. 4-230704, or the like, or subjected to a treatment described in JP-A No. 7-230007 or the like. It can be formed by doing.

The layer having a function as a brightness improving film can be formed by applying or bonding a brightness improving film to another layer constituting a polarizing element. The brightness enhancing film is, for example, by forming fine pores in the same manner as described in JP 2002-169025 A and JP 2003-29030 A, or by two or more layers having different central wavelengths of selective reflection. It can be formed by superimposing a cholesteric liquid crystal layer.

The layer having a function as a reflective film or a semi-transmissive reflective film can be formed, for example, by applying or bonding a metal thin film obtained by vapor deposition or sputtering to another layer constituting a polarizing element.

A layer having a function as a diffusion film can be formed, for example, by coating another layer constituting a polarizing element with a resin solution containing fine particles.

The layer having a function as a retardation film or an optical compensation film includes liquid crystal compounds such as a discotic liquid crystal compound, a nematic liquid crystal compound, a smectic liquid crystal compound, and a cholesteric liquid crystal compound. It can be formed by applying to a layer and orienting it. In that case, an alignment film may be formed on a 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 in various display elements such as LCD or OLED, the anisotropic dye film of the present invention may be formed directly on the surface of electrode substrates constituting these display elements, The substrate on which the anisotropic dye film of the present invention is formed may be used as a constituent member of these display elements.

Example

Although the present invention will be described more specifically by way of examples, the present invention is not limited to the following examples, unless departing from the gist of the present invention.

In the following description, "part" means "part by weight".

[How to identify liquid crystal phase]

The liquid crystal properties of the obtained composition for forming anisotropic dye films were measured by differential scanning calorimetry (“DSC220CU”, manufactured by Seiko Instruments), X-ray structure analysis (“NANO-Viewer”, Inc.), and hot stage (“HCS302-LN190” by Toyo Technica Co., Ltd.) ), observed with a polarizing microscope (Nikon Instech Co., Ltd. ``ECLIPSE LV100N POL''), and described on pages 9 to 50 and pages 117 to 176 of the ``Liquid Crystal Handbook'' (Maruzen Co., Ltd., issued on October 30, 2000). According to the method, the liquid crystal was identified.

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

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

Measurement light of linearly polarized light is incident on the anisotropic dye film, the transmittance of the polarized light in the direction of the absorption axis of the anisotropic dye film and the transmittance of the polarized light in the direction of the polarization axis of the anisotropic dye film are measured, and the dichroic ratio (D) is calculated by the following equation. I did.

D = Az/Ay

(In the formula,

Ay = -log(Ty);

Az = -log(Tz);

Tz is the transmittance of the anisotropic dye film with respect to polarized light in the direction of the absorption axis;

Ty is the transmittance of the anisotropic dye film with respect to the polarization in the polarization axis direction.)

Specifically, a sandwich cell (cell gap: 8.0 µm, 10.0 µm, 12.0 µm) in which an alignment film of polyimide (LX1400, manufactured by Hitachi Chemicals DuPont Microsystems) was formed on glass as a substrate, and rubbed with a cloth in advance on the formed polyimide. Treatment), the composition for anisotropic dye film was injected isotropically, and cooled to 80[deg.] C. at 5[deg.] C./min to obtain an anisotropic dye film, further cooled to 0[deg.] C. at 5[deg.] C./min. The ratio was measured. Among them, the dichroic ratio in the temperature and wavelength showing the maximum dichroic ratio was determined as the dichroic ratio of the anisotropic dye film.

Further, the dichroic ratio of the anisotropic dye film is 40 or more as A, 20 or more and less than 40 as B, 8 or more and less than 20 as C, or less than 8 as D, or dichroic ratio of 30 or more as ``++'', 20 or more What was less than 30 was evaluated as "+", what was 8 or more and less than 20 was evaluated as "-", and what was less than 8 was evaluated as "-".

Hereinafter, the first aspect of the present invention will be described using a specific example.

[Synthesis A of liquid crystal compounds]

<Liquid Crystal Compound (I-1)>

Liquid crystal compound (I-1) was synthesized according to the synthesis method described below.

[Formula 21]

Synthesis of (I-1-a):

To a N,N-dimethylformamide solution (150 mL) of p-iodophenol (11.0 g, 50 mmol), ethyl propiolate (9.7 g, 99 mmol) and copper (I) oxide (7.5 g, 94 mmol) were added. It added, stirred at 110 degreeC for 9 hours, and stood to cool to room temperature. After separating the precipitate by filtration, ethyl acetate was added, followed by washing with water and saturated brine. It purified by silica gel column chromatography (hexane/ethyl acetate), and 7.3g of brown crystals (I-1-a) were obtained.

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) were mixed and stirred at 80°C for 4 hours. After separating the precipitate by filtration, diethyl ether was added, followed by washing with water and saturated brine. It purified by silica gel column chromatography (hexane/ethyl acetate), and 5.5g of orange solid (I-1-b) was obtained.

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. After water (20 ml) was added and acidified with concentrated hydrochloric acid, the precipitated precipitate was separated by filtration. 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) and tetrahydrofuran (20 mL) were mixed, followed by N,N-dimethylaniline (1.02 g, 8.4 mmol), 2,5-di-t- Butylphenol (54 mg) was added. After cooling with an ice bath, acryloyl chloride (0.76 g, 8.4 mmol) was slowly added. After stirring for 6 hours in an ice bath, methylene chloride was added, followed by washing with 1 mol/L hydrochloric acid, saturated sodium hydrogen carbonate solution, and saturated brine in that order. It purified by silica gel column chromatography (chloroform/methanol) to obtain 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 JP 2014-262884 A.

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) and methylene chloride (30 ml) were mixed, cooled with an ice bath, and then 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (1.09 g, 5.69 mmol) was added. After leaving to stand overnight, it was washed with a saturated aqueous ammonium chloride solution and then with a saturated saline solution. It purified by silica gel column chromatography (hexane/ethyl acetate), and 1.9g of white solid (I-1-f) was obtained.

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) And stirred at 50° C. for 2 hours. The reaction solution was discharged into water, and the precipitated precipitate was separated by filtration 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.

[Formula 22]

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) (transform only) (42.9 g, 107.6 mmol), p-toluenesulfonic acid pyridinium salt (2.6 g, 10.8 mmol) and ethanol (430 mL) were mixed, and at 78°C Stir for 2 hours. The solvent was distilled off, dissolved in ethyl acetate (150 mL), hexane (750 mL) was added, and 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 ) Were mixed. After cooling with an ice bath, acryloyl chloride (16.1 g, 177.5 mmol) was slowly added. After dripping, after stirring at 50 degreeC for 2 hours, the solvent was distilled off until the liquid volume became 190 ml, and it discharge|released to 1 mol/L hydrochloric acid under ice cooling. The precipitated precipitate was separated by filtration and washed with water and hexane. It purified by silica gel column chromatography (hexane/ethyl acetate), and 39.4g of white solids (I-1-h) were obtained.

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) were mixed, cooled with 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 a saturated aqueous ammonium chloride solution and then saturated brine. It purified by silica gel column chromatography (hexane/ethyl acetate), and 530 mg of liquid crystal compounds (I-1) were obtained as a white solid.

The results of liquid chromatography mass spectrometry of this compound are shown below.

LC-MS(APCI)m/z 851.5 (M+Na ⁺ )

Further, the structure was confirmed by NMR. The results are shown below.

<Liquid Crystal Compound (I-2)>

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

[Formula 23]

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) were mixed, and 10-undecin-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, it was left to cool to room temperature. After water-ether extraction, it wash|cleaned further with 1 mol/L hydrochloric acid, it liquid-separated and concentrated, and obtained the multicolor oily compound (I-2-a) of a regulator (粗精製).

Synthesis of (I-2-b):

A 50 ml aqueous solution of (I-2-a) and potassium hydroxide (5.0 g, 90 mmol) obtained by the above operation were mixed, and heated at 100°C for 5 hours. After standing 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 separated by filtration, and recrystallized with hot acetonitrile to obtain 7.5 g of 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) and p-methoxyphenol (89 mg) were mixed, In a water bath, after confirming that the internal temperature became 15° C. or less, acryloyl chloride (2.82 g, 31.2 mmol) was slowly added. After the lapse of 30 minutes, the water bath was removed and further stirred for 2 hours. The reaction solution was discharged into 100 ml of water, concentrated hydrochloric acid (0.8 ml) was added, followed by extraction with ethyl acetate. Half the amount of 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 stirred for an additional hour at room temperature. After the reaction solution was extracted with a saturated aqueous ammonium chloride solution and then saturated brine, it was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 4.4 g of a white solid (I-2-d).

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 standing to cool to room temperature, it discharged into water (100 ml), and the obtained solid was separated by filtration. 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) (trans/cis = 67:33 mixture) (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 stirred for 2 hours at room temperature. The reaction solution was washed with a 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 (I-2-f) of the trans form.

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 standing to cool to room temperature, water (20 ml) was added, and the obtained solid was separated by filtration. 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), and p-methoxyphenol (3.6 mg) were mixed, Under a water bath, acryloyl chloride (53 mg, 0.59 mmol) was slowly added. After stirring for 30 minutes in a water bath, it was stirred for an additional 2 hours. The reaction solution was discharged into water (20 ml), concentrated hydrochloric acid (0.2 ml) was added, followed by extraction with ethyl acetate. Half amount of the brown powder obtained by concentration was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 183 mg of a liquid crystal compound (I-2) as a white powder.

<Liquid Crystal Compound (I-3)>

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

[Formula 24]

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), and dichloromethane (50 mL) After mixing, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (4.22 g, 22.0 mmol) was added at 2°C. After stirring at 2 degreeC for 30 minutes, it stirred at room temperature for 17 hours. The reaction solution was washed with a saturated ammonium chloride aqueous solution and then saturated brine, and then purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 3.63 g of a white solid (I-3-a).

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 standing to cool to room temperature, water (60 ml) was added, and the obtained solid was separated by filtration and dried at 50 degreeC under reduced pressure, and 0.31 g of white solid (I-3-b) was obtained.

Synthesis of (I-3-c):

(I-3-b) (230 mg, 1.0 mmol), (I-1-i) (trans 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 degreeC for 30 minutes, it stirred at room temperature for further 20 hours. The reaction solution was washed with an aqueous saturated ammonium chloride solution and then saturated brine, and then purified by silica gel column chromatography (methylene chloride/ethyl acetate) to obtain 662 mg of white solid (I-3-c).

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 standing to cool to room temperature, water (70 mL) was added, and the obtained solid was separated by filtration and dried at 50 degreeC under reduced pressure, and 555 mg of white solid (I-3-d) was obtained.

Synthesis of (I-3):

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

The structure was confirmed by NMR. The results are shown below.

<Liquid Crystal Compound (I-4)>

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

[Formula 25]

Synthesis of (I-4-b):

(I-4-b) was synthesized by the synthesis method described in Japanese Unexamined Patent Application Publication 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), and 4-methoxyphenol (307 mg) were mixed, At 15° C., acryloyl 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 under reduced pressure at 50°C 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, it was stirred at room temperature for additional 21 hours. The reaction solution was washed with a saturated aqueous solution of ammonium chloride, followed by water and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off to obtain a light brown solid. After dissolving this light brown solid in ethanol (220 ml) at 60°C, it was allowed to stand at 0°C for 15 hours, and the resulting solid was collected by filtration and dried under reduced pressure at 50°C, and the white solid (I-4-d ) Was obtained 39.1 g.

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, followed by heating at 60°C for 1 hour. After standing to cool to room temperature, it discharged into water (490 ml), and the obtained solid was separated by filtration and dried at 50 degreeC under reduced pressure, and 32.8g of white solids (I-4-e) were obtained.

Synthesis of (I-4-f):

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

[Formula 26]

Trans-4-hydroxycyclohexanecarboxylic acid (4.33 g, 30.0 mmol), dichloromethane (100 mL), and p-toluenesulfonic acid pyridinium salt (1.51 g, 6.0 mmol) were 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 (I-4-i) as a transparent liquid. 8.47 g was obtained.

(I-4-i) (8.14 g, 26.0 mmol) obtained above was mixed with 10 wt% potassium hydroxide aqueous solution (73 g), and stirred at 100 degreeC for 5 hours. After standing to cool to room temperature, a 33 wt% aqueous citric acid solution (75 g) was added, and after stirring, extraction was performed 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 degreeC for 30 minutes, it stirred at room temperature for further 16 hours. The reaction solution was washed with a saturated ammonium chloride aqueous solution and then saturated brine, and then purified by silica gel column chromatography (toluene/ethyl acetate) to obtain 1.68 g of a white solid (I-4-g).

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 standing to cool to room temperature, water (40 ml) was added, and the obtained solid was filtered off and dried at 50 degreeC under reduced pressure, and 1.42 g of white solid (I-4-h) was obtained.

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, it was stirred at room temperature for further 6 hours. The reaction solution was washed with a 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 a liquid crystal compound (I-4) as a white solid.

The structure was confirmed by NMR. The results are shown below.

<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.

<Liquid Crystal Compound (I-6)>

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

[Formula 27]

Synthesis of (I-6-a):

4-iodophenol (25 g, 114 mmol), 4-dihydro-2H-pyran (13.4 g, 160 mmol), and a dichloromethane solution (125 ml) were mixed, and p-toluenesulfonic acid pyridinium salt (PPTS) ( 2.85 g, 11.4 mmol) was added, and after stirring at room temperature for 5 hours, saturated aqueous sodium hydrogen carbonate solution (200 ml) was added, followed by extraction with methylene chloride. The obtained organic layer was washed with a saturated aqueous sodium hydrogencarbonate solution and a saturated saline solution, dried by adding sodium sulfate, and then concentrated by filtration to obtain a crude body. The obtained crude body 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), trimethylsilylacetylene (11.6 g, 118.3 mmol) in tetrahydrofuran (370 mL), triethylamine (31.6 mL, 225.8 mmol), copper iodide (I) (2.03 g, 10.7 mmol) was added and 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 and ethyl acetate. The organic layer was washed with saturated brine, sodium sulfate was added and dried, followed by filtration and concentration to obtain a crude body. The obtained crude body 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 with an ice bath. A solution of tetra-n-butylammonium fluoride tetrahydrofuran (1 mol/L, 133.8 ml) was added, followed by stirring at room temperature for 1 hour. After extraction with water-ethyl acetate, the organic layer was washed with saturated brine, dried by adding 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) obtained by the above operation, 4-iodophenol (26.4 g, 102.2 mmol), and tetrahydrofuran (300 mL) were mixed, and triethylamine (23 mL, 229.5 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, followed by stirring at room temperature for 4 hours. After the reaction solution was filtered through Celite, the filtrate was concentrated under reduced pressure. 22.1 g of (I-6-d) was obtained by washing the obtained crude body with methylene chloride.

Synthesis of (I-6-e):

(I-6-d) (11.0 g, 37.4 mmol) and N,N-dimethylformamide (22 mL) were mixed, and 11-bromo-1-undecanol (9.39 g, 37.4 mmol), potassium carbonate ( 25.8 g, 187 mmol) was added, followed by stirring at 90°C for 1 hour. After standing to cool, it was added to ice water, and the precipitated solid was collected by filtration and washed with hexane to obtain a crude body. After dissolving the obtained crude body in ethyl acetate, sodium sulfate was added and dried, and Celite filtration was carried out, and 17.0 g of (I-6-e) was obtained by performing the solvent distillation.

Synthesis of (I-6-f):

(I-6-e) (4.0 g, 8.61 mmol), tetrahydrofuran (40 mL), triethylamine (2.4 mL, 17.2 mmol) were mixed, cooled with an ice bath, and acryloyl chloride (1.04 mL, 12.9 mmol) was added and stirred for 10 minutes. After the reaction solution was added to ice water, extraction was performed with ethyl acetate, and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. Sodium sulfate was added to the obtained organic layer, dried, and concentrated by filtration to obtain 4.44 g of (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, followed by stirring at 50°C for 1 hour. After standing to cool, after concentrating under reduced pressure, the crude product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 3.36 g of (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) was mixed, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (0.57 g, 3.0 mmol) was added at 0°C, followed by stirring at room temperature for 2 hours. After pouring the obtained reaction solution into ice water (20 ml), extraction was performed 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 body. The obtained crude body was purified by silica gel column chromatography (hexane/methylene chloride/ethyl acetate), and 0.98 g of (I-6) was obtained.

The structure was confirmed by NMR. The results are shown below.

<Liquid Crystal Compound (I-7)>

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

[Formula 28]

Synthesis of (I-7):

(I-7-a) (2 g, 4.0 mmol) synthesized in the same manner as (I-1-g) except for using 12-bromo-1-dodecanol as a starting material, 12-bro as a starting material (I-7-b) (1.68 g, 4.4 mmol) synthesized in the same manner as (I-1-h), except that mo-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, followed by stirring 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, and the obtained organic layer was washed with saturated brine, dried by adding magnesium sulfate, and concentrated by filtration. 2.17 g of (I-7) was obtained by purifying the obtained crude product by silica gel column chromatography (hexane/methylene chloride/ethyl acetate).

The structure was confirmed by NMR. The results are shown below.

<Liquid Crystal Compound (I-8)>

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

[Chemical Formula 29]

Synthesis of (I-8-a):

To a DMF solution (100 mL) of trans-4-hydroxycyclohexylphenol (10.0 g, 52.0 mmol) and potassium carbonate (28.8 g, 208 mmol) was added chloromethylmethyl ether (6.30 g, 78.0 mmol) for 6 hours. Stirred. After adding water (100 ml) to the reaction solution, extraction was performed three times with diisopropyl ether (100 ml). After washing the obtained organic layer with saturated brine, magnesium sulfate was added and stirred. After performing filtration and concentration, 5.79 g of (I-8-a) was obtained by performing silica gel column chromatography (methylene chloride/ethyl acetate).

The structure was confirmed by NMR. The results are shown below.

Synthesis of (I-8-b):

(I-8-a) (5.30 g, 22.0 mmol) was dissolved in DMF (30 mL), and dodecane iodide (13.0 g, 44.0 mmol) and sodium hydride (oily 50-70%, 2.0 g) were added. It was stirred at room temperature for 8 hours. After water was added to the reaction solution and extracted with diisopropyl ether, the organic layer was washed with saturated brine. Further magnesium sulfate was added and dried, followed by filtration and concentration to obtain a crude product. By performing purification by silica gel column chromatography (hexane/ethyl acetate), 4.58 g of (I-8-b) was obtained.

The structure was confirmed by NMR. The results are shown below.

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, followed by stirring at 40°C for 2 hours and at room temperature for 24 hours. After filtering the generated precipitate, it was washed with water to obtain 3.93 g of (I-8-c).

The structure was confirmed by NMR. The results are shown below.

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) in methylene chloride It dissolved in (30 mL), EDC (276 mg, 1.44 mmol) was added at 0 degreeC, and it stirred at room temperature for 4 hours. After adding a saturated aqueous solution of sodium hydrogencarbonate to the reaction solution, extraction was performed with methylene chloride, and the obtained organic layer was washed with saturated brine, dried by adding magnesium sulfate, 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.

<Liquid Crystal Compound (I-9)>

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

[Formula 30]

Synthesis of (I-9-a):

Sodium hydride (oily 50-70%, 1.03 g) was added to a DMF solution (20 mL) synthesized below (I-10-b) (3.25 g, 10.7 mmol), followed by stirring for 1 hour. Then, 1-bromoundecane (7.80 g, 31.4 mmol) was added, and it stirred at room temperature for 4 hours. A saturated aqueous ammonium chloride 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, 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.

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) were mixed, propionic acid (785 mg, 8.0 mmol) was added, and nitrogen It heated and stirred at 110 degreeC for 10.5 hours under airflow. After cooling to room temperature, water (100 ml) was added and extraction was carried out 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.

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, followed by heating and stirring at 100°C for 1 hour, After cooling to room temperature, 2 mol/L of 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.

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, EDC (364 mg, 1.9 mmol) was added under a nitrogen stream at 0°C, and then the temperature was raised to room temperature and stirred for 6 hours. A saturated aqueous sodium hydrogen carbonate solution was added, followed by extraction 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.

<Liquid Crystal Compound (I-10)>

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

[Formula 31]

Synthesis of (I-10-a):

4-cyclohexylphenyl (36.8 g, 211 mmol), 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octanebis(tetrafluoroborate) (30.0 g, 84.0 mmol ) And acetonitrile (800 ml) were mixed, iodine (21.3 g, 84.0 mmol) was added, and heating and stirring was performed at 60°C for 3 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution (400 ml) was added, followed by extraction three times with diisopropyl ether (200 ml). After washing the obtained organic layer with saturated brine (200 ml), magnesium sulfate was added, dried, and then 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.

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) were mixed, and sodium borohydride (4.40 g, 107 mmol) was added at 40°C. After addition, it heated up to 74 degreeC, and heated and stirred for 1 hour. After cooling to room temperature, saturated aqueous ammonium chloride solution (20 ml) was added and stirred. Then, after adding water (200 ml), extraction was performed using 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. 8.93 g of (I-10-b) was obtained by washing the obtained crude product with acetone.

The structure was confirmed by NMR. The results are shown below.

Synthesis of (I-10-c):

(I-10-b) (8.93 g, 29.6 mmol) and DMF (60 ml) were mixed, sodium hydride (oily 50%, 3.40 g) was added, and under a nitrogen stream, until the occurrence of bubbles disappeared Stirred. Then, 2-(11-bromoundecoxy)oxane (29.5 g, 88.0 mmol) was added, followed by stirring 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, after washing with saturated brine, magnesium sulfate was added and dried, followed by filtration and concentration 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.

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 (I) iodide (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, followed by stirring 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, magnesium sulfate was added, dried, filtered, and concentrated under reduced pressure. 1.78 g of (I-10-d) was obtained by purifying the obtained crude product by silica gel column chromatography (developing liquid: hexane/ethyl acetate).

The structure was confirmed by NMR. The results are shown below.

Synthesis of (I-10-e):

THF (5 mL) and ethanol (2.5 mL) were added to (I-10-d) (602 mg, 1.1 mmol) and completely dissolved, then potassium hydroxide (188 mg, 3.3 mmol) was added to water (5 mL). The dissolved solution was added and stirred at room temperature for 1 hour. After adding 2 mol/L hydrochloric acid (20 ml), the mixture was stirred at room temperature for further 10 minutes. Diisopropyl ether was added to the solution for extraction, and the organic layer was washed with saturated brine, then magnesium sulfate was added and dried, followed by filtration and concentration 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. After the solvent was concentrated, 435 mg was obtained by washing with water (I-10-e).

The structure was confirmed by NMR. The results are shown below.

Synthesis of (I-10-f):

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

The structure was confirmed by NMR. The results are shown below.

Synthesis of (I-10-g):

According to the synthesis method described below, compound (I-10-g) was synthesized.

[Formula 32]

Synthesis of (1-10-h):

(I-1-e) (31.1 g, 160 mmol), 11-bromo-1-undecanol (44.2 g, 176 mmol), potassium carbonate (44.2 g, 320 mmol) were mixed with DMF (125 mL) And stirred at 100°C for 1.5 hours. After stirring, after cooling to room temperature, it was added to water (2 L), and the solid material was collected by filtration and washed with water. Then, the solid was dissolved in dichloromethane, washed with water and saturated brine, dried by adding 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 of (I-10-h).

The structure was confirmed by NMR. The results are shown below.

Synthesis of (1-10-i):

(I-10-h) (47.6 g, 131 mmol) and THF (480 mL) were mixed, and N,N-dimethylaniline (31.6 g, 261 mmol) and acryloyl chloride (17.7 g, 196 mmol) were mixed. It was added and stirred at room temperature for 2 hours. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed sequentially with 1 mol/L hydrochloric acid and saturated brine, dried by adding 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.

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, followed by heating and refluxing 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 of (I-10-g).

The structure was confirmed by NMR. The results are shown below.

Synthesis of (I-10):

(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) was mixed with methylene chloride (20 ml), and after adding EDC (403 mg, 2.1 mmol) at 0°C under a nitrogen stream, the temperature was raised to room temperature and stirred for 3 hours. A saturated aqueous sodium hydrogen carbonate solution was added, followed by extraction 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.

<Liquid Crystal Compound (I-11)>

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

[Formula 33]

Synthesis of (I-11-a):

(I-8-a) (7.20 g, 30.5 mmol) and DMF (35 mL) were mixed, sodium hydride (oily: content 50%, 3.6 g, 91.4 mmol) was added, and bubbles were generated under a nitrogen stream. Stir until disappeared. Then, 2-(11-bromoundecoxy)oxane (19.3 g, 54.5 mmol) was added, followed by heating and stirring for 6 hours. After cooling to room temperature, water (100 ml) was added and extraction was carried out using ethyl acetate. After repeating 3 times, after washing with saturated brine, sodium sulfate was added and dried, followed by filtration and concentration 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.

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 using 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.

Synthesis of (I-11-c):

Under a nitrogen stream, (I-11-b) (1.2 g, 3.0 mmol) and THF (12 mL) were mixed, N,N-dimethylaniline (0.56 mL, 4.5 mmol) was added, followed by ice-cooling with acryl chloride. One (0.29 mL, 3.6 mmol) was added and stirred at room temperature for 3 hours. The reaction solution was added to a mixture of 2 mol/L hydrochloric acid (2.3 ml) and ice water (10 ml), and the pH was set to 1, followed by extraction three times with ethyl acetate. The organic layer was washed with water and saturated brine, dried by adding sodium sulfate, filtered, and then concentrated under reduced pressure to obtain 1.36 g of (I-11-c).

The structure was confirmed by NMR. The results are shown below.

Synthesis of (I-11-d):

(I-11-c) (0.05 g, 0.11 mmol) was mixed with methanol (1 ml), after cooling with ice, chlorotrimethylsilane (19 µL, 0.11 mmol) was added, followed by stirring at room temperature for 4 hours. After concentration under reduced pressure, it was purified by silica gel chromatography (hexane/ethyl acetate) to obtain 35 mg of (I-11-d).

The structure was confirmed by NMR. The results are shown below.

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 It mixed with (50 ml), EDC (1.77 g, 9.24 mmol) was added at 0 degreeC, and it 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, and the obtained organic layer was washed with saturated brine, dried by adding magnesium sulfate, 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.

<Liquid Crystal Compound (I-12)>

A liquid crystal compound (I-12) was synthesized according to the synthesis method described below.

[Formula 34]

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, followed by stirring 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, and the obtained organic layer was washed with saturated brine, dried by adding magnesium sulfate, 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.

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 addition, in the formula, C ₁₁ H ₂₂ means that ₁₁ methylene chains are linearly bonded, C ₉ H ₁₈ means that ₉ methylene chains are linearly bonded, C ₁₂ H ₂₄ means that ₁₂ methylene chains are linearly bonded.

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

[Chemical Formula 46]

[Chemical Formula 47]

[Formula 48]

With respect to the liquid crystal compound (I-1) to the liquid crystal compound (I-12), an isotropic phase appearance temperature (a phase transition temperature from a liquid crystal to a liquid and a phase transition temperature from a liquid to a liquid crystal) was determined by differential scanning calorimetry. For differential scanning calorimetry, the sample amount is 0.5 mg to 10 mg, an aluminum pan is used, the heating process and the cooling process are 5°C/min or 10°C/min, and heating from -50°C to an arbitrary temperature and Cooling was repeatedly measured 3 times, and the third measurement was taken as the phase transition temperature.

In addition, in the measurement of differential scanning calorimetry, for the liquid crystal compound (I-1) to the liquid crystal compound (I-8) and (I-12), 4-methoxyphenol was used as a polymerization inhibitor based on 100 parts by weight of the liquid crystal compound. What added 0.2 parts by weight was used. About the liquid crystal compound (I-9), the composition 11 for anisotropic dye film formation mentioned later was used. About the liquid crystal compound (I-10), the composition 12 for anisotropic dye film formation mentioned later was used. About the liquid crystal compound (I-11), the composition 13 for anisotropic dye film formation mentioned later was used.

The results are shown in Table 1.

In addition, that this temperature is the isotropic appearance temperature was confirmed by observation with a polarization microscope and X-ray structure analysis.

A liquid crystal compound (I-1), a liquid crystal compound (I-2), a liquid crystal compound (I-7), a liquid crystal compound (I-8), a liquid crystal compound (a liquid crystal compound having a partial structure represented by the formula (1)) ( 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 (I), which are liquid crystal compounds that do not have a partial structure represented by the formula (1). -3), compared with the liquid crystal compound (I-4), and the liquid crystal compound (I-5), the isotropic appearance temperature is low, the ease of handling of the process, the viewpoint of energy consumption, a reorientation process that heats in an isotropic phase , It is clear that the degree of freedom of selection of the substrate is excellent.

Example A1

To 79.80 parts of chloroform, 20.00 parts of a liquid crystal compound (I-1), 0.12 parts of an azo dye of formula (II-1) (manufactured by Hayashibara Co., Ltd.), an azo dye of formula (II-2) (manufactured by Showa Chemical Industries, Ltd.) After adding and mixing 0.08 part of the mixture, the solvent was removed to obtain a composition A1 for forming an anisotropic dye film.

Using the obtained composition A1 for anisotropic dye film formation, in order to determine the dichroic ratio by the method described above, an anisotropic dye film A1 was produced, and the dichroic ratio of the anisotropic dye film A1 was determined.

The results are shown in Table 2. In addition, the dichroic ratio of the anisotropic dye film A1 was 46.34 in 40.0°C and 570 nm.

Example A2

In place of the liquid crystal compound (I-1), the composition A2 for anisotropic dye film formation and the anisotropic dye film A2 were obtained in the same manner as in Example A1 except that the liquid crystal compound (I-2) was used. With respect to the anisotropic dye film A2, the dichroic ratio of the anisotropic dye film A2 was determined.

The results are shown in Table 2.

Example A3

In place of the liquid crystal compound (I-1), the composition A9 for anisotropic dye film formation and the anisotropic dye film A9 were obtained in the same manner as in Example A1 except that the liquid crystal compound (I-7) was used. With respect to the anisotropic dye film A9, the dichroic ratio of the anisotropic dye film A9 was determined.

The results are shown in Table 2.

Example A4

In place of the liquid crystal compound (I-1), the composition A10 for anisotropic dye film formation and the anisotropic dye film A10 were obtained in the same manner as in Example A1 except that the liquid crystal compound (I-8) was used. With respect to the anisotropic dye film A10, the dichroic ratio of the anisotropic dye film A10 was determined.

The results are shown in Table 2.

Example A5

To 79.80 parts of chloroform, 8.00 parts of liquid crystal compound (I-1), 12.00 parts of liquid crystal compound (I-9), 0.12 parts of azo dye of formula (II-1) (manufactured by Hayashibara Co., Ltd.), formula (II-2) ) Of the azo dye (manufactured by Showa Chemical Co., Ltd.) was added, stirred and mixed, and then the solvent was removed to obtain a composition A11 for anisotropic dye film formation.

In order to determine the dichroic ratio by the method described above using the obtained composition A11 for anisotropic dye film formation, the anisotropic dye film A11 was produced, and the dichroic ratio of the anisotropic dye film A11 was determined.

The results are shown in Table 2.

Example A6

In place of the liquid crystal compound (I-9), the composition A12 for anisotropic dye film formation and the anisotropic dye film A12 were obtained in the same manner as in Example A5 except that the liquid crystal compound (I-10) was used. With respect to the anisotropic dye film A12, the dichroic ratio of the anisotropic dye film A12 was determined.

The results are shown in Table 2.

Example A7

In place of the liquid crystal compound (I-9), the composition A13 for anisotropic dye film formation and the anisotropic dye film A13 were obtained in the same manner as in Example A5 except that the liquid crystal compound (I-11) was used. With respect to the anisotropic dye film A13, the dichroic ratio of the anisotropic dye film A13 was determined.

The results are shown in Table 2.

Comparative Example A1

In place of the liquid crystal compound (I-1), the composition A3 for anisotropic dye film formation and the anisotropic dye film A3 were obtained in the same manner as in Example A1 except that the liquid crystal compound (I-3) was used. With respect to the anisotropic dye film A3, the dichroic ratio of the anisotropic dye film A3 was determined.

The results are shown in Table 2.

Comparative Example A2

In place of the liquid crystal compound (I-1), except having used the liquid crystal compound (I-4), it carried out similarly to Example A1, and obtained the composition A4 for anisotropic dye film formation and the anisotropic dye film A4. With respect to the anisotropic dye film A4, the dichroic ratio of the anisotropic dye film A4 was determined.

The results are shown in Table 2.

Comparative Example A3

In place of the liquid crystal compound (I-1), the composition A5 for anisotropic dye film formation and the anisotropic dye film A5 were obtained in the same manner as in Example A1 except that the liquid crystal compound (I-5) was used. With respect to the anisotropic dye film A5, the dichroic ratio of the anisotropic dye film A5 was determined.

The results are shown in Table 2.

Reference Example A1

In place of the liquid crystal compound (I-1), the composition A8 for anisotropic dye film formation and the anisotropic dye film A8 were obtained in the same manner as in Example A1 except that the liquid crystal compound (I-6) was used. With respect to the anisotropic dye film A8, the dichroic ratio of the anisotropic dye film A8 was determined.

The results are shown in Table 2.

Example A8

To 69.99 parts of cyclopentanone, 28.57 parts of liquid crystal compound (I-1), 0.43 parts of azo dye of formula (II-1), 0.29 parts of azo dye of formula (II-2), IRGACURE (registered trademark) 369 A syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE 13045, diameter 0.45 µm) after adding 0.29 part of (BASF) and 0.43 part of BYK-361N (manufactured by BYK-Chemie) and stirring at 80°C The composition A6 for anisotropic dye film formation was obtained by filtering using.

Composition A6 for anisotropic dye films was formed on a substrate on which an alignment film of polyimide (LX1400, manufactured by DuPont Microsystems, Hitachi Chemical Co., Ltd., an alignment film was produced by the rubbing method) formed on glass by a spin coating method, and heated at 120° C. for 2 minutes After drying, it cooled to a liquid crystal phase, and it superposed|polymerized at the exposure amount 500 mj/cm<2> (365 nm standard), and obtained the anisotropic dye film A6. It was confirmed that the obtained anisotropic dye film A6 was covered on a commercially available polarizing plate and turned into light and dark, and exhibited good performance that can be used as a polarizing film.

Example A9

The substrate used was the same as in Example A8, except that a substrate having an alignment film of polyimide (LX1400, manufactured by DuPont Microsystems, Hitachi Chemical Co., Ltd., an alignment film was produced by a rubbing method) on a polyimide film (film thickness of 100 μm) was used. Then, an anisotropic dye film A7 was obtained from the composition A6 for anisotropic dye films. It was confirmed that the obtained anisotropic dye film A7 was covered on a commercially available polarizing plate and turned into light and dark, and exhibited good performance that can be used as a polarizing film.

From the above, it is clear that the film produced 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), can sufficiently function as a polarizing film. Became.

Hereinafter, a second aspect of the present invention will be described using specific examples.

[Synthesis B of liquid crystal compounds]

<Liquid Crystal Compound (III-1)>

Liquid crystal compound (III-1) was synthesized according to the synthesis method described below.

[Chemical Formula 49]

Synthesis of (III-1-a):

Lub et al., Recl. Trav. Chim. (III-1-a) was synthesized by a method according to the compound described in Pays-Bas, 115, 321-328 (1996).

Synthesis of (III-1-b):

4-iodophenol (3.62 g, 16.5 mmol), (III-1-a) (6.43 g, 16.1 mmol), N,N-dimethylamino-4-pyridine (0.39 g, 3.20 mmol), methylene chloride (80 mL ) Was mixed, and after cooling with an ice bath, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) (3.39 g, 17.7 mmol) was added, followed by stirring for 5 minutes. Then, it stirred at room temperature for 2 hours, and it wash|cleaned with saturated aqueous ammonium chloride aqueous solution and then saturated brine. The solution was concentrated and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 8.49 g of a white solid (III-1-b).

Synthesis of (III-1-c):

After (III-1-b) (5.00 g, 8.33 mmol) was added to diisopropylamine (70 mL) and completely dissolved, dichlorobis (triphenylphosphine) palladium (II) (58 mg, 0.08 mmol), iodide Copper (I) (48 mg, 0.25 mmol) was mixed, and trimethylsilylacetylene (0.98 g, 9.99 mmol) was added. After stirring at room temperature for 30 minutes, extraction was performed with water-ethyl acetate, and washed with saturated brine. The solution was concentrated and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 4.30 g of a white solid (III-1-c).

Synthesis of (III-1-d):

(III-1-c) (4.30 g, 7.53 mmol) and chloroform (100 mL) were mixed, cooled with an ice bath, and then tetra-n-butylammonium fluoride (TBAF) tetrahydrofuran solution (1 mol/L, 9 ml) was added. After stirring for 20 minutes, it was extracted with water-chloroform and washed with saturated brine. The solution was concentrated and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 3.80 g of a white solid (III-1-d).

Synthesis of (III-1-e):

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

Synthesis of (III-1-f):

After (III-1-e) and tetrahydrofuran (60 ml) obtained by the above operation were mixed and completely dissolved at 50°C, ethanol (60 ml) was added. P-toluenesulfonic acid pyridinium salt (PPTS) (0.54 g, 2.13 mmol) was added to this slurry solution, and after heating at 60° C. for 2 hours, it was left to stand overnight. The next day, the mixture was heated again to 60° C. and completely dissolved, and then the reaction solution was added to ice water. After extraction with chloroform and concentration of the solution, the obtained solid was washed with hexane to obtain 4.02 g of a white solid (III-1-f).

Synthesis of (III-1):

(III-1-f) (4.00 g, 4.98 mmol), acrylic acid (0.72 g, 9.96 mmol, N,N-dimethyl-4-aminopyridine (0.12 g, 0.10 mmol) and dichloromethane (100 mL) were mixed , After cooling with an ice bath, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (2.10 g, 11.0 mmol) was added After stirring for 2 hours, acrylic acid (0.36 g, 4.98) mmol) and EDC (1.05 g, 5.5 mmol) were added, and after 18 hours, acrylic acid (0.36 g, 4.98 mmol) and EDC (1.05 g, 5.5 mmol) were further added, followed by stirring for 5 hours. It washed with a saturated aqueous solution and then saturated brine, and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 2.30 g of a white solid (III-1).

The structure was confirmed by NMR. The results are shown below.

Compound (III-1) exhibits liquid crystal properties, with respect to 100 parts by weight of the liquid crystal compound, in which 0.2 parts by weight of 4-methoxyphenol was added as a polymerization inhibitor, and with a polarization microscope attached with a hot stage, 70 It was confirmed by observing birefringence at °C.

<Liquid Crystal Compound (III-2)>

The liquid crystal compound (III-2) of the same compound as the liquid crystal compound (I-6) was synthesized by the same synthesis method as in the above <liquid crystal compound (I-6)>.

Compound (III-2) exhibits liquid crystal properties, with respect to 100 parts by weight of the liquid crystal compound, in which 0.2 parts by weight of 4-methoxyphenol was added as a polymerization inhibitor, and with a polarizing microscope attached with a hot stage, 40 It was confirmed by observing birefringence at °C.

The chemical structural formulas of the liquid crystal compounds synthesized above and the dyes used in the following examples are shown below. In addition, in the formula, C ₁₁ H ₂₂ means that ₁₁ methylene chains are linearly bonded.

[Formula 50]

[Formula 51]

[Formula 52]

[Formula 53]

Example B1

To 79.80 parts of chloroform, 20.00 parts of a liquid crystal compound (III-1), 0.12 parts of an azo dye of formula (II-1) (manufactured by Hayashibara Co., Ltd.), an azo dye of formula (II-2) (manufactured by Showa Chemical Industries, Ltd.) After adding and mixing 0.08 parts of the mixture by stirring and removing the solvent, the composition B1 for forming an anisotropic dye film was obtained.

It was confirmed that the composition B1 for anisotropic dye film formation exhibits liquid crystallinity by observing birefringence at 70°C with a polarizing microscope equipped with a hot stage.

Using the obtained composition B1 for anisotropic dye film formation, in order to determine the dichroic ratio by the method described above, the anisotropic dye film B1 was produced, and the dichroic ratio of the anisotropic dye film B1 was determined.

The results are shown in Table 3.

Example B2

To 69.99 parts of cyclopentanone, 28.57 parts of the liquid crystal compound (III-1), 0.43 parts of the azo dye of the formula (II-1), 0.29 parts of the azo dye of the formula (II-2), IRGACURE (registered trademark) 369 A syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE 13045, diameter 0.45 µm) after adding 0.29 part of (BASF) and 0.43 part of BYK-361N (manufactured by BYK-Chemie) and stirring at 80°C By filtration using, the composition B2 for anisotropic dye films was obtained.

Composition B2 for anisotropic dye films was formed on a substrate on which an alignment film of polyimide (LX1400, manufactured by DuPont Microsystems, Hitachi Chemical Co., Ltd., an alignment film was formed by a rubbing method) was formed on glass by spin coating, and heated at 120° C. for 2 minutes After drying, it cooled to a liquid crystal phase, and it superposed|polymerized at an exposure amount of 500 mj/cm<2> (365 nm standard), and obtained the anisotropic dye film B2. It was confirmed that the obtained anisotropic dye film B2 was covered on a commercially available polarizing plate and turned into light and dark when rotated, and exhibited good performance that can be used as a polarizing film.

From the above, it became clear that the film produced using the liquid crystal compound (III-1), which is a liquid crystal compound having a partial structure represented by the formula (B1), can sufficiently function as a polarizing film.

Example B3

In place of the liquid crystal compound (III-1), except having used the liquid crystal compound (III-2), it carried out similarly to Example B1, and obtained the composition B3 for anisotropic dye film formation and the anisotropic dye film B3.

It was confirmed that the composition B3 for anisotropic dye film formation exhibits liquid crystallinity by observing birefringence at 40°C with a polarizing microscope equipped with a hot stage.

With respect to the anisotropic dye film B3, the dichroic ratio of the anisotropic dye film B3 was determined.

The results are shown in Table 3.

From the above, it is clear that a film produced using a liquid crystal compound (III-1) or a liquid crystal compound (III-2), which is a liquid crystal compound having a partial structure represented by the formula (B1), can sufficiently function as a polarizing film. Became.

The composition for forming an anisotropic dye film of the present invention can realize excellent optical performance, particularly a sufficient dichroic ratio.

Since the anisotropic dye film of the present invention is formed using the composition for forming an anisotropic dye film of the present invention, excellent optical performance, particularly sufficient dichroic ratio, can be realized.

Since the optical element of the present invention contains the anisotropic dye film of the present invention, excellent optical performance, particularly sufficient dichroic ratio, can be realized.

Industrial availability

The composition for forming an anisotropic dye film of the present invention can achieve a low isotropic appearance temperature while maintaining excellent optical performance, particularly a sufficient dichroic ratio.

Since the anisotropic dye film of the present invention is formed 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 can be formed at a lower temperature.

Since the optical element of the present invention contains the anisotropic dye film of the present invention, excellent optical performance, particularly a sufficient dichroic ratio can be maintained, and may contain an anisotropic dye film which can be formed at a lower temperature.

The composition for forming an anisotropic dye film of the present invention can realize excellent optical performance, particularly a sufficient dichroic ratio.

Since the anisotropic dye film of the present invention is formed using the composition for forming an anisotropic dye film of the present invention, excellent optical performance, particularly sufficient dichroic ratio, can be realized.

Since the optical element of the present invention contains the anisotropic dye film of the present invention, excellent optical performance, particularly sufficient dichroic ratio, can be realized.

Claims (12)

A composition for forming an anisotropic dye film containing a dye and a liquid crystal compound,
The said liquid crystal compound is a composition for anisotropic dye film formation containing a liquid crystal compound which has a partial structure represented by Formula (1).
-Cy-X2-C≡CX-… (One)
(In the formula,
Cy represents a hydrocarbon cyclic 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 -, -CH ₂ S- or -SCH ₂ -is represented.) The method of claim 1,
-X- is, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -phosphorus, a composition for forming an anisotropic dye film. The method according to claim 1 or 2,
Cy is a hydrocarbon cyclic group, -X2- is a single bond, anisotropic dye film-forming composition. The method according to any one of claims 1 to 3,
The composition for forming an anisotropic dye film, wherein the liquid crystal compound is a liquid crystal compound represented by Formula (2).
R1-A1-Y1-A2-Y2-A3-R2… (2)
(In the formula,
R1 and R2 each independently represent a chain organic group;
A1 and A3 each independently represent a partial structure represented by the above formula (1), a divalent organic group, or a single bond;
A2 represents a partial structure represented by the above formula (1) or a divalent organic group;
-Y1- and -Y2- are each independently 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 Represents O-, -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -;
One of A1 and A3 is a partial structure represented by the above formula (1) or a divalent organic group;
At least one of A1, A2, and A3 is a partial structure represented by the above formula (1).) The method of claim 4,
One of A1, A2, and A3 is a partial structure represented by the above formula (1), Cy is a hydrocarbon cyclic group, and -X2- is a single bond; The other two are each independently a divalent organic group, and the divalent organic group is a hydrocarbon cyclic group, the composition for anisotropic dye film formation. The method of claim 5,
The composition for forming an anisotropic dye film, wherein the hydrocarbon ring group is a 1,4-phenylene group or a cyclohexane-1,4-diyl group. The method according to any one of claims 4 to 6,
-Y1- and -Y2- are each independently a single bond, -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 -phosphorus, for forming anisotropic dye film Composition. The method according to any one of claims 4 to 7,
Cy is a 1,4-phenylene group, the composition for forming an anisotropic dye film. The method according to any one of claims 4 to 8,
One of A1 and A3 is a cyclohexane-1,4-diyl group, the composition for forming an anisotropic dye film. The method according to any one of claims 4 to 9,
One of A1 and A3 is a partial structure represented by the above formula (1),
The other is a cyclohexane-1,4-diyl group, the composition for anisotropic dye film formation. An anisotropic dye film formed using the composition for forming an anisotropic dye film according to any one of claims 1 to 10. An optical element comprising the anisotropic dye film according to claim 11.