JP2018053167A - Dichroic dye compound, coloring composition, light absorption anisotropic film, laminate and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dichroic dye compound from which a light absorption anisotropic film having a high dichroic ratio in a wavelength region of 390-550 nm can be produced; and a coloring composition, a light absorption anisotropic film, a laminate and an image display device using the same.SOLUTION: A dichroic dye compound has a structure represented by formula (I). In formula (I), Xand Xeach independently represents a substituent; and m and n each independently represent an integer of 0-2. Arand Areach independently represents an aromatic hydrocarbon ring or a heteroaromatic ring, and Arrepresents a heteroaromatic ring in which two hetero 5-membered rings that may have a substituent are ring-condensed. At least one of Land Lrepresents any one connection group selected from the group consisting of -CH=CH-, -CH=N- and -N=CH-.SELECTED DRAWING: None

Description

  The present invention relates to a dichroic dye compound, a coloring composition, a light absorption anisotropic film, a laminate, and an image display device.

Conventionally, when an attenuation function, a polarization function, a scattering function, a light shielding function, etc. of irradiation light including laser light and natural light are required, an apparatus that operates according to a different principle for each function has been used. For this reason, products corresponding to the above functions are also manufactured by different manufacturing processes for each function.
For example, in a liquid crystal display (LCD), a linearly polarizing plate and a circularly polarizing plate are used to control optical rotation and birefringence in display. An organic light emitting diode (OLED) also uses a circularly polarizing plate to prevent reflection of external light.

In these polarizing plates (polarizing elements), iodine has been widely used as a dichroic substance, but a polarizing element using an organic dye as a dichroic substance instead of iodine has been studied.
For example, Patent Document 1 describes a polarizing film formed from a composition containing a predetermined azo dye and a polymerizable liquid crystal compound ([Claim 1]).

JP, 2006-006502, A

  The inventors of the present invention have studied the organic dye described in Patent Document 1, and have described a compound that functions as a dichroic dye having a maximum absorption in the wavelength region of 390 to 550 nm. It is clear that a coating film formed using a composition containing a chromatic dye compound and a liquid crystal compound has a poor surface condition, and as a result, the dichroic ratio of the light-absorbing anisotropic film is low. It was.

  Therefore, the present invention provides a dichroic dye compound capable of producing a light-absorbing anisotropic film having a high dichroic ratio in a wavelength region of 390 to 550 nm, a colored composition using the same, and a light-absorbing anisotropic material It is an object to provide a conductive film, a laminate, and an image display device.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have used a dichroic dye compound having a specific structure, so that a light absorption anisotropic film having a high dichroic ratio in a wavelength region of 390 to 550 nm. The present invention has been completed.
That is, it has been found that the above-described problem can be achieved by the following configuration.

[1] A dichroic dye compound having a structure represented by the following formula (I).
Here, in formula (I),
X ¹ and X ² each independently represent a substituent, m and n each independently represent an integer of 0 to 2, and when m is 2, a plurality of X ¹ may be the same It may be different, and when n is 2, the plurality of X ² may be the same or different.
Ar ¹ and Ar ³ each independently represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and Ar ² represents an aromatic group in which two hetero 5-membered rings optionally having a substituent are condensed. Represents a family heterocycle.
L ¹ and L ² are each independently a single bond, —N═N—, —CH═CH—, —CH═N—, —N═CH—, —C≡C—, and a carbon atom. Represents an linking group selected from the group consisting of an alkylene group optionally substituted with an oxygen atom or a sulfur atom, and at least one of L ¹ and L ² is —CH═CH—, —CH═ It represents any linking group selected from the group consisting of N- and -N = CH-.
[2] formula (I) L ² in the, -CH = CH -, - CH = represents one of linking group selected from the N- and the group consisting of -N = CH-, according to [1] A dichroic dye compound.
[3] The dichroic dye compound according to [1] or [2], wherein Ar ¹ and Ar ^{3 in} formula (I) are both benzene rings.
[4] formula (I) is L ¹ in a single bond, represents one of linking group selected from -N = N-and the group consisting of -CH = CH-, [1] to [3] The dichroic dye compound according to any one of the above.
[5] X ¹ and X ^{2 in} Formula (I) each independently represent any substituent selected from the group consisting of an alkyl group, an alkoxy group, an ester group, an amide group, and an amino group, The dichroic dye compound according to any one of [1] to [4].

[6] The dichroic dye compound according to any one of [1] to [5], wherein Ar ² in the formula (I) is an aromatic heterocyclic ring represented by the following formula (II).
Here, in formula (II), * 1 represents a bonding position with L ¹ , * 2 represents a bonding position with L ^2, and X ³ represents a hydrogen atom or a substituent.
[7] The dichroic dye compound according to [6], wherein L ¹ in formula (I) is a single bond.
[8] The dichroic dye compound according to [6] or [7], wherein L ² in formula (I) is —CH═CH—.
[9] The dichroic dye according to any one of [6] to [8], wherein X ¹ in formula (I) is an alkyl group, and X ² in formula (I) is an amino group. Compound.

[10] A colored composition comprising the dichroic dye compound according to any one of [1] to [9] and a liquid crystalline compound.
[11] The colored composition according to [10], further comprising a horizontal alignment agent.
[12] A light absorption anisotropic film formed using the colored composition according to [10] or [11].
[13] A laminate having a base material and the light absorption anisotropic film according to [12] provided on the base material.
[14] The laminate according to [13], further including a λ / 4 plate provided on the light absorption anisotropic film.
[15] An image display device comprising the light absorption anisotropic film according to [12] or the laminate according to [13] or [14].

  According to the present invention, a dichroic dye compound capable of producing a light-absorbing anisotropic film having a high dichroic ratio in a wavelength region of 390 to 550 nm, a colored composition using the same, and a light-absorbing anisotropic material Film, laminate, and image display device can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Dichroic dye compound]
The dichroic dye compound of the present invention is a compound having a structure represented by the following formula (I).
In the present invention, as described above, by using a dichroic dye compound having a structure represented by the following formula (I), a light absorption anisotropic film having a high dichroic ratio in a wavelength region of 390 to 550 nm is obtained. Can be produced.
Although the details of the reason have not yet been clarified, the present inventors presume that the reason is as follows.
That is, as shown in the following formula (I), an aromatic heterocycle in which two hetero 5-membered rings represented by Ar ² are condensed (for example, a thienothiazole ring) [hereinafter referred to as “aromatic heterocondensed ring” in this paragraph] Abbreviated. As the predetermined linking group bonded to the linking group, at least one linking group is any linking group selected from the group consisting of -CH = CH-, -CH = N-, and -N = CH-, It has absorption on the shorter wavelength side than the polyazo structure known as a conventionally known aromatic heterocyclic ring linking group, and rotation of peripheral molecules of the aromatic heterocyclic ring is promoted, so that the crystallinity It is considered that a high dichroic ratio could be achieved in the wavelength region of 390 to 550 nm.
In general, when the crystallinity of the compound is reduced, the degree of orientation order also tends to be reduced. As a result of the study by the present inventors, the aromatic heterocyclic ring having a linking group described above is Surprisingly, it has been clarified that the dichroic ratio is hardly lost even when the property is lowered.

Here, in formula (I), X ¹ and X ² each independently represent a substituent, m and n each independently represent an integer of 0 to 2, and a plurality of Xs when m is 2 ¹ may be the same or different, and the plurality of X ² when n is 2 may be the same or different.
Ar ¹ and Ar ³ each independently represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and Ar ² represents an aromatic group in which two hetero 5-membered rings optionally having a substituent are condensed. Represents a family heterocycle.
L ¹ and L ² are each independently a single bond, —N═N—, —CH═CH—, —CH═N—, —N═CH—, —C≡C—, and a carbon atom. Represents an linking group selected from the group consisting of an alkylene group optionally substituted with an oxygen atom or a sulfur atom, and at least one of L ¹ and L ² is —CH═CH—, —CH═ It represents any linking group selected from the group consisting of N- and -N = CH-.

The “substituent” represented by X ¹ and X ^{2 in the} above formula (I) will be described.
Examples of the substituent include any substituent selected from the group consisting of an alkyl group, an alkoxy group, an ester group, an amide group, and an amino group.

  Here, examples of the alkyl group as a substituent include a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms). Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, methoxyethyl group, ethoxycarbonylethyl group, cyanoethyl group, Examples include a diethylaminoethyl group, a hydroxyethyl group, a chloroethyl group, an acetoxyethyl group, a trifluoromethyl group.

  Moreover, as an alkoxy group as a substituent, a C1-C18 (preferably C1-C8) substituted or unsubstituted alkoxy group is mentioned, for example, Specifically, a methoxy group, an ethoxy group, Examples include n-butoxy group and methoxyethoxy group.

Further, an ester group as a ^{substituent, R 1 -C (= O)} O-R 2 -, ^{and, R 1 -OC (= O)} -R 2 - is a group represented by the R ¹ is For example, a C1-C10 alkyl group is mentioned, As R < ² >, a single bond or a C1-C6 alkylene group is mentioned.
Specific examples of the alkyl group having 1 to 10 carbon atoms include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- A pentyl group, 1-ethylpentyl group, n-hexyl group, n-heptyl group, octyl group, 3-methyl-7-methyloctyl group, n-nonyl group and the like can be mentioned.
Specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a pentylene group, and a hexylene group.

The amide group as a substituent is a group represented by R ³ —C (═O) N (R ⁴ ) — and —C (═O) N (R ⁴ ) (R ⁵ ), Examples of R ^{3 to} R ⁵ include an alkyl group having 1 to 6 carbon atoms.
Specific examples of the alkyl group having 1 to 6 carbon atoms include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- Examples include a pentyl group and an n-hexyl group.

  Moreover, as an amino group as a substituent, an unsubstituted amino group or a C1-C18 (preferably C1-C8) substituted amino group is mentioned, for example, Specifically, a methylamino group, Dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino, methylcarbamoyl Amino group, phenylcarbamoylamino group, ethylthiocarbamoylamino group, methylsulfamoylamino group, phenylsulfamoylamino group, acetylamino group, ethylcarbonylamino group, ethylthiocarbonylamino group, cyclohexylcarbonylamino , Benzoylamino group, chloroacetyl group, methanesulfonylamino group, etc. benzenesulfonylamino group.

In the present invention, the surface state of the coating film of the coloring composition containing the dichroic dye compound is improved, and the dichroic ratio in the wavelength region of 390 to 550 nm is higher, so that in the above formula (I) X ¹ is preferably an alkyl group, and X ² in the above formula (I) is preferably an amino group.

  Moreover, in this invention, it is preferable that m and n in the said formula (I) which shows the number of the substituents mentioned above are respectively independently 1 or 2, and it is more preferable that all are 1.

Next, the “aromatic hydrocarbon ring or aromatic heterocycle” represented by Ar ¹ and Ar ³ in the above formula (I) will be described.
Specific examples of the aromatic hydrocarbon ring include a benzene ring (for example, 1,4-phenylene group and the like when m in the above formula (I) is 1, a naphthalene ring, an anthracene ring, etc.). Can be mentioned.
Specific examples of the aromatic heterocycle include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, an oxazole ring, a benzothiazole ring, a thienothiazole ring, and a phenanthroline ring.

In the present invention, it is preferable that both Ar ¹ and Ar ³ in the above formula (I) are benzene rings because the dichroic ratio in the wavelength region of 390 to 550 nm becomes higher.

Next, the “aromatic heterocycle in which two hetero 5-membered rings optionally having a substituent are condensed” represented by Ar ² in the above formula (I) will be described.
Here, examples of the aromatic heterocycle in which two hetero 5-membered rings are condensed include, for example, two hetero 5-membered rings selected from the group consisting of a furan ring, a pyrrole ring, a thiophene ring, a thiazole ring, and an oxazole ring. Can be mentioned.
In addition, examples of the substituent that the aromatic heterocycle in which two hetero 5-membered rings are condensed may have the same substituent as the “substituent” represented by X ¹ and X ² described above.

In the present invention, Ar ² in the above formula (I) is an aromatic heterocyclic ring represented by the following formula (II) because the dichroic ratio in the wavelength region of 390 to 550 nm becomes higher. preferable.

In the above formula (II), * 1 represents a bonding position with L ¹ , * 2 represents a bonding position with L ^2, and X ³ represents a hydrogen atom or a substituent.
Examples of the substituent represented by X ³ include the same substituents as the “substituent” represented by X ¹ and X ² described above.

Next, the linking group represented by L ¹ and L ² in the above formula (I) will be described.
L ¹ and L ² in the above formula (I) are each independently a single bond, —N═N—, —CH═CH—, —CH═N—, —N═CH—, —C≡C— And a linking group selected from the group consisting of an alkylene group in which the carbon atom may be substituted with an oxygen atom or a sulfur atom, and at least one of L ¹ and L ² is —CH It represents any linking group selected from the group consisting of ═CH—, —CH═N—, and —N═CH—.
Here, as an alkylene group which L < ¹ > and L < ² > show, a C1-C6 alkylene group is mentioned, for example, A methylene group, ethylene group, pentylene group, hexylene group etc. are mentioned specifically ,. In addition, regarding this alkylene group, “a carbon atom may be substituted with an oxygen atom or a sulfur atom” means that one or more of —CH ₂ — constituting the alkylene group is, for example, —O—, -S -, - C (= O ) -, - OC (= O) -, - C (= O) O -, - OC (= O) O -, - N (R 6) C (= O) - , -C (= O) N ( R 7) -, - OC (= O) N (R 8) -, - N (R 9) C (= O) O -, - SC (= O) - or - It represents that it may be substituted with C (= O) S-.

In the present invention, as described above, at least one of L ¹ and L ² is any linking group selected from the group consisting of —CH═CH—, —CH═N— and —N═CH—. Thus, a light absorption anisotropic film having a high dichroic ratio in a wavelength region of 390 to 550 nm can be produced.

In the present invention, L ¹ in the above formula (I) is a group consisting of a single bond, —N═N— and —CH═CH— because the absorption wavelength is given in the wavelength region of 390 to 550 nm. It represents any linking group selected from, L ² in the formula (I) is, -CH = CH -, - CH = of any one selected from the N- and the group consisting of -N = CH- It preferably represents a linking group.

Furthermore, in the present invention, when Ar ² in the above formula (I) is an aromatic heterocyclic ring represented by the above formula (II), the surface of the coating film of the colored composition containing the dichroic dye compound For the reason that the shape becomes good and the dichroic ratio in the wavelength region of 390 to 550 nm becomes higher, L ¹ in the formula (I) is a single bond, and L ² in the formula (I) is —CH═. CH- is preferred.

Specific examples of the dichroic dye compound having the structure represented by the formula (I) include compounds represented by the following formulas (1) to (11). In the following description, the compound represented by the following formula (1) is represented as “compound (1)”, and the compounds represented by the following formulas (2) to (11) are also represented by the same method. To do.

[Coloring composition]
The coloring composition of the present invention is a composition containing the above-described dichroic dye compound of the present invention and a liquid crystal compound.
By containing the liquid crystalline compound, the colored composition of the present invention can align the dichroic dye compound with a high degree of orientation while suppressing the precipitation of the dichroic dye compound.

[Liquid crystal compound]
As the liquid crystalline compound contained in the colored composition of the present invention, both a low molecular liquid crystalline compound and a high molecular liquid crystalline compound can be used.
Here, the “low molecular weight liquid crystalline compound” refers to a liquid crystalline compound having no repeating unit in the chemical structure.
The “polymer liquid crystalline compound” refers to a liquid crystalline compound having a repeating unit in its chemical structure.
Examples of the low-molecular liquid crystalline compound include those described in JP2013-228706A.
Examples of the polymer liquid crystalline compound include thermotropic liquid crystalline polymers described in JP2011-237513A. The polymer liquid crystalline compound may have a crosslinkable group (for example, an acryloyl group and a methacryloyl group) at the terminal.

(Horizontal alignment agent)
The coloring composition of the present invention preferably contains a horizontal alignment agent.
Examples of the horizontal alignment agent include compounds represented by general formulas (1) to (3) described in paragraphs [0253] to [0292] of Patent Document 1 (Japanese Patent Application Laid-Open No. 2011-237513). The contents of which are incorporated herein by reference.
By adding a horizontal alignment agent, it is possible to suppress the occurrence of alignment defects and irregularities at the light absorption anisotropic film / air interface, and it is possible to further improve the surface uniformity. The term “horizontal alignment” means that the major axis direction of the dichroic dye compound is parallel to the horizontal plane of the light-absorbing anisotropic film, but does not require that it be strictly parallel. In the present specification, an orientation in which the inclination angle formed between the major axis direction and the horizontal plane is less than 10 degrees is meant. The inclination angle is preferably 5 degrees or less, more preferably 3 degrees or less, still more preferably 2 degrees or less, and most preferably 1 degree or less.

  In this invention, 0.01-20 mass% is preferable with respect to the mass of the dichroic dye compound of this invention, and, when containing the said horizontal aligning agent, 0.05-10 mass% is more. Preferably, 0.1-5 mass% is especially preferable. In addition, a horizontal alignment agent may be used independently and may use 2 or more types together.

(Polymerization initiator)
The coloring composition of the present invention may contain a polymerization initiator.
Although there is no restriction | limiting in particular as a polymerization initiator, It is preferable that it is a compound which has photosensitivity, ie, a photoinitiator.
As the photopolymerization initiator, various compounds can be used without particular limitation. Examples of photopolymerization initiators include α-carbonyl compounds (U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (U.S. Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin. Compound (US Pat. No. 2,722,512), polynuclear quinone compound (US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) ), Acridine and phenazine compounds (JP-A-60-105667 and US Pat. No. 4,239,850), oxadiazole compounds (US Pat. No. 4,221,970), and acylphosphine oxide compounds (Japanese Patent Publication) 63-40799 gazette, special No. 5-29234, JP-A-10-95788 and JP-A-10-29997).
Commercially available products can be used as such photopolymerization initiators, and examples include Irgacure 184, Irgacure 907, Irgacure 369, Irgacure 651, Irgacure 819, and Irgacure OXE-01 manufactured by BASF.
When the coloring composition of this invention contains a polymerization initiator, content of a polymerization initiator is 0.00 with respect to a total of 100 mass parts of the said dichroic dye compound and the said liquid crystalline compound in a coloring composition. 01-30 mass parts is preferable and 0.1-15 mass parts is preferable. When the content of the polymerization initiator is 0.01 parts by mass or more, the curability of the light absorption anisotropic film becomes good, and when it is 30 parts by mass or less, the orientation of the light absorption anisotropic film is good. It becomes.

〔solvent〕
The colored composition of the present invention preferably contains a solvent from the viewpoint of workability and the like.
Examples of the solvent include ketones (for example, acetone, 2-butanone, methyl isobutyl ketone, cyclopettanone, cyclohexanone, etc.), ethers (for example, dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (for example, hexane, etc.) ), Alicyclic hydrocarbons (eg, cyclohexane, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, trimethylbenzene, etc.), halogenated carbons (eg, dichloromethane, trichloromethane, dichloroethane, dichlorobenzene) , Chlorotoluene, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (eg, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (eg, methyl cellosol) , Ethyl cellosolve, 1,2-dimethoxyethane, etc.), cellosolve acetates, sulfoxides (eg dimethyl sulfoxide etc.), amides (eg dimethylformamide, dimethylacetamide etc.), and heterocyclic compounds (eg pyridine etc.) ) And the like, and water. These solvents may be used alone or in combination of two or more.
Of these solvents, organic solvents are preferably used, and halogenated carbons or ketones are more preferably used.
When the coloring composition of this invention contains a solvent, it is preferable that content of a solvent is 80-99 mass% with respect to the total mass of a coloring composition, and it is 83-97 mass%. More preferably, it is still more preferably 85 to 95% by mass.

[Other ingredients]
The colored composition of the present invention may contain a dichroic dye compound other than the dichroic dye compound of the present invention (hereinafter abbreviated as “other dichroic dye compound”).
Other dichroic dye compounds are not particularly limited, and examples thereof include paragraphs [0008] to [0026] in JP2013-227532A and [0012] to [0029] in JP2013-109090A. Examples include dichroic dye compounds described in paragraphs and the like.

[Light absorption anisotropic film]
The light absorption anisotropic film of the present invention is a light absorption anisotropic film formed using the above-described colored composition of the present invention.
As an example of the manufacturing method of the light absorption anisotropic film of this invention, the process (henceforth a "coating film formation process") of apply | coating the said coloring composition on a base material, and forming a coating film, And a step of aligning liquid crystalline components contained in the coating film (hereinafter also referred to as “alignment step”) in this order.
The liquid crystalline component is a component including not only the above-described liquid crystalline compound but also the dichroic dye compound having liquid crystallinity when the above-described dichroic dye compound has liquid crystallinity.

[Coating film forming process]
A coating film formation process is a process of apply | coating the said coloring composition on a base material, and forming a coating film.
It is easy to apply the colored composition on the substrate by using the above-described colored composition containing the solvent, or by using the colored composition that has been made into a liquid such as a melt by heating. Become.
Specific examples of the method for applying the coloring composition include a roll coating method, a gravure printing method, a spin coating method, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method. , Known methods such as a spray method and an ink jet method.
In this embodiment, an example in which the colored composition is applied on the base material has been described. However, the present invention is not limited to this. For example, the colored composition may be applied on an alignment film provided on the base material. . Details of the alignment film will be described later.

(Orientation process)
The alignment step is a step of aligning liquid crystalline components contained in the coating film. Thereby, a light absorption anisotropic film is obtained.
The alignment step may have a drying process. Components such as a solvent can be removed from the coating film by the drying treatment. The drying treatment may be performed by a method of leaving the coating film at room temperature for a predetermined time (for example, natural drying) or by a method of heating and / or blowing.
Here, the liquid crystalline component contained in the coloring composition may be aligned by the coating film forming process or the drying process described above. For example, in an embodiment in which the coloring composition is prepared as a coating solution containing a solvent, the coating film is dried, and the solvent is removed from the coating film, whereby a coating film having light absorption anisotropy (that is, light absorption) An anisotropic film) is obtained.
When the drying treatment is performed at a temperature equal to or higher than the transition temperature of the liquid crystalline component contained in the coating film to the liquid crystal phase, the heat treatment described below may not be performed.

  The transition temperature of the liquid crystalline component contained in the coating film to the liquid crystal phase is preferably 10 to 250 ° C., more preferably 25 to 190 ° C. from the viewpoint of production suitability and the like. It is preferable that the transition temperature is 10 ° C. or higher because a cooling treatment or the like for lowering the temperature to a temperature range exhibiting a liquid crystal phase is not necessary. In addition, when the transition temperature is 250 ° C. or lower, a high temperature is not required even when the isotropic liquid state is once higher than the temperature range in which the liquid crystal phase is exhibited. This is preferable because deformation and alteration can be reduced.

The alignment step preferably includes heat treatment. Thereby, since the liquid crystalline component contained in the coating film can be aligned, the coating film after the heat treatment can be suitably used as the light absorption anisotropic film.
The heat treatment is preferably 10 to 250 ° C, more preferably 25 to 190 ° C from the viewpoint of production suitability and the like. Further, the heating time is preferably 1 to 300 seconds, and more preferably 1 to 60 seconds.

The alignment process may have a cooling process performed after the heat treatment. A cooling process is a process which cools the coating film after a heating to about room temperature (20-25 degreeC). Thereby, the orientation of the liquid crystalline component contained in the coating film can be fixed. The cooling means is not particularly limited and can be carried out by a known method.
The light absorption anisotropic film can be obtained by the above steps.
In this embodiment, examples of the method for aligning the liquid crystalline component contained in the coating film include a drying process and a heating process. However, the present invention is not limited thereto, and can be performed by a known alignment process.

[Other processes]
The method for producing a light absorption anisotropic film may include a step of curing the light absorption anisotropic film (hereinafter also referred to as “curing step”) after the alignment step. Thereby, the light absorption anisotropic film-forming excellent in durability and sclerosis | hardenability is obtained.
For example, when the light absorption anisotropic film has a crosslinkable group (polymerizable group), the curing step is performed by heating and / or light irradiation (exposure). Among these, it is preferable that a hardening process is implemented by light irradiation.
As a light source used for curing, various light sources such as infrared rays, visible light, and ultraviolet rays can be used, but ultraviolet rays are preferable. Moreover, you may irradiate an ultraviolet-ray while heating at the time of hardening, and may irradiate an ultraviolet-ray through the filter which permeate | transmits only a specific wavelength.
When the exposure is performed while heating, the heating temperature at the time of exposure is preferably 25 to 140 ° C., although it depends on the transition temperature of the liquid crystalline component contained in the light absorption anisotropic film to the liquid crystal phase.
The exposure may be performed under a nitrogen atmosphere. In the case where curing of the light-absorbing anisotropic film proceeds by radical polymerization, exposure in a nitrogen atmosphere is preferable because inhibition of polymerization by oxygen is reduced.

  The thickness of the light absorption anisotropic film is preferably 0.1 to 5.0 μm, and more preferably 0.3 to 1.5 μm. Depending on the concentration of the dichroic dye compound in the coloring composition, when the film thickness is 0.1 μm or more, a light-absorbing anisotropic film having excellent absorbance is obtained, and the film thickness is 5.0 μm or less. Thus, a light-absorbing anisotropic film having excellent transmittance can be obtained.

[Laminate]
The laminate of the present invention is a laminate having a substrate and the above-described light absorption anisotropic film formed on the substrate.
The laminate of the present invention may have a λ / 4 plate provided on the light absorption anisotropic film.
Moreover, it is preferable that the laminated body of this invention has an orientation film between the said base material and the said light absorption anisotropic film.
Hereinafter, the layers other than the above-described light absorption anisotropic film among the layers constituting the laminate will be described.

〔Base material〕
As a base material, it can select according to the use of a light absorption anisotropic film, For example, glass and a polymer film are mentioned. The light transmittance of the substrate is preferably 80% or more.
When a polymer film is used as the substrate, it is preferable to use an optically isotropic polymer film. As specific examples and preferred embodiments of the polymer, the description in paragraph [0013] of JP-A-2002-22294 can be applied. Moreover, even if it is a conventionally known polymer such as polycarbonate or polysulfone that tends to exhibit birefringence, a polymer whose expression is lowered by modifying the molecule described in International Publication WO00 / 26705 should be used. You can also.

[Λ / 4 plate]
The “λ / 4 plate” that the laminate of the present invention may have is a plate having a λ / 4 function. Specifically, linearly polarized light having a specific wavelength is converted into circularly polarized light (or circularly). A plate having a function of converting polarized light into linearly polarized light.
Specific examples of the λ / 4 plate include US Patent Application Publication No. 2015/0277006.
For example, as an aspect in which the λ / 4 plate has a single layer structure, specifically, a stretched polymer film, a retardation film provided with an optically anisotropic layer having a λ / 4 function on a support, and the like can be given. Further, as an aspect in which the λ / 4 plate has a multilayer structure, specifically, a broadband λ / 4 plate formed by laminating a λ / 4 plate and a λ / 2 plate can be mentioned.
The λ / 4 plate and the light absorption anisotropic film may be provided in contact with each other, or another layer may be provided between the λ / 4 plate and the light absorption anisotropic film. . Examples of such a layer include a pressure-sensitive adhesive layer or an adhesive layer for ensuring adhesion.

(Alignment film)
The laminate of the present invention may have an alignment film between the base material and the light absorption anisotropic film.
The alignment film may be any layer as long as the liquid crystalline component contained in the colored composition of the present invention can be brought into a desired alignment state on the alignment film.
Examples of the method for forming the alignment film include a rubbing treatment of an organic compound (preferably a polymer) on the film surface, oblique deposition of an inorganic compound, formation of a layer having a microgroove, and a Langmuir Blodget method (LB film). ) Organic compounds (for example, accumulation of ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearylate, etc.). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.
Among these, in the present invention, an alignment film formed by rubbing treatment is preferable from the viewpoint of easy control of the pretilt angle of the alignment film, and a photo alignment film formed by light irradiation is also preferable from the viewpoint of uniformity of alignment.

<Rubbed alignment film>
The polymer material used for the alignment film formed by rubbing is described in a large number of documents, and a large number of commercially available products can be obtained. In the present invention, polyvinyl alcohol or polyimide and derivatives thereof are preferably used. Regarding the alignment film, reference can be made to the description on page 43, line 24 to page 49, line 8 of WO 01 / 88574A1. The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.01 to 1 μm.

<Photo-alignment film>
As a photo-alignment material used for an alignment film formed by light irradiation, there are many literatures and the like. In the present invention, for example, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007-121721, JP-A-2007. Azo compounds described in JP-A No. 140465, JP-A No. 2007-156439, JP-A No. 2007-133184, JP-A No. 2009-109831, JP-B-3888848, and JP-B-4151746, JP-A No. 2002-229039 Aromatic ester compounds described in JP-A-2002-265541, maleimide and / or alkenyl-substituted nadiimide compounds having a photo-alignment unit described in JP-A-2002-265541, JP-A-2002-317013, Patent No. 4205195, Patent No. 4205198 Photocrosslinkable Emissions derivatives, Kohyo 2003-520878, JP-T-2004-529220 discloses, or the like as a photo-crosslinkable polyimide, polyamide or ester are preferable examples described in Japanese Patent No. 4162850. More preferably, they are azo compounds, photocrosslinkable polyimides, polyamides, or esters.

The photo-alignment film formed from the above material is irradiated with linearly polarized light or non-polarized light to produce a photo-alignment film.
In this specification, “linearly polarized light irradiation” and “non-polarized light irradiation” are operations for causing a photoreaction in the photo-alignment material. The wavelength of light used varies depending on the photo-alignment material used, and is not particularly limited as long as it is a wavelength necessary for the photoreaction. The peak wavelength of light used for light irradiation is preferably 200 nm to 700 nm, and more preferably ultraviolet light having a peak wavelength of light of 400 nm or less.

  The light source used for light irradiation is a commonly used light source such as a tungsten lamp, a halogen lamp, a xenon lamp, a xenon flash lamp, a lamp such as a mercury lamp, a mercury xenon lamp and a carbon arc lamp, various lasers [eg, semiconductor laser, helium Neon laser, argon ion laser, helium cadmium laser and YAG (yttrium, aluminum, garnet) laser], light emitting diode, and cathode ray tube.

  As means for obtaining linearly polarized light, a method using a polarizing plate (for example, an iodine polarizing plate, a two-color dye polarizing plate, and a wire grid polarizing plate), a prism system element (for example, a Glan-Thompson prism) or a Brewster angle is used. A method using a reflective polarizer or a method using light emitted from a polarized laser light source can be employed. Moreover, you may selectively irradiate only the light of the required wavelength using a filter or a wavelength conversion element.

In the case of linearly polarized light, a method of irradiating light from the top surface or the back surface to the alignment film surface perpendicularly or obliquely to the alignment film surface is employed. Although the incident angle of light varies depending on the photo-alignment material, 0 to 90 ° (vertical) is preferable, and 40 to 90 ° is preferable.
In the case of non-polarized light, the alignment film is irradiated with non-polarized light obliquely. The incident angle is preferably 10 to 80 °, more preferably 20 to 60 °, and still more preferably 30 to 50 °.
The irradiation time is preferably 1 minute to 60 minutes, and more preferably 1 minute to 10 minutes.

  When patterning is required, a method of performing light irradiation using a photomask as many times as necessary for pattern production or a method of writing a pattern by laser beam scanning can be employed.

[Use]
The laminate of the present invention can be used as a polarizing element (polarizing plate), specifically, for example, as a linear polarizing plate or a circular polarizing plate.
When the laminate of the present invention does not have an optically anisotropic layer such as the λ / 4 plate, the laminate can be used as a linear polarizing plate. On the other hand, when the laminate of the present invention has the λ / 4 plate, the laminate can be used as a circularly polarizing plate.

[Image display device]
The image display device of the present invention includes the above-described light absorption anisotropic film or the above-described laminate.
The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, a plasma display panel, and the like.
Among these, a liquid crystal cell or an organic EL display panel is preferable, and a liquid crystal cell is more preferable. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, and an organic EL display device using an organic EL display panel as a display element, and is a liquid crystal display device. More preferred.

[Liquid Crystal Display]
As a liquid crystal display device which is an example of the image display device of the present invention, an embodiment having the above-described light absorption anisotropic film and a liquid crystal cell is preferably exemplified. More preferably, it is a liquid crystal display device having the above-described laminate (however, not including a λ / 4 plate) and a liquid crystal cell.
In the present invention, among the light absorption anisotropic films (laminates) provided on both sides of the liquid crystal cell, the light absorption anisotropic film (laminate) of the present invention is used as the front side polarizing element. Preferably, the light absorption anisotropic film (laminated body) of the present invention is more preferably used as the front side and rear side polarizing elements.
Below, the liquid crystal cell which comprises a liquid crystal display device is explained in full detail.

<Liquid crystal cell>
The liquid crystal cell used in the liquid crystal display device is preferably in a VA (Virtual Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic). It is not limited to.
In a TN mode liquid crystal cell, rod-like liquid crystalline molecules (rod-like liquid crystalline compounds) are substantially horizontally aligned when no voltage is applied, and are further twisted and aligned at 60 to 120 °. The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied. The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). (2) Liquid crystal cell (SID97, Digest of tech. Papers) (Preliminary Collection) in which VA mode is multi-domained (for MVA mode (Multi-domain Vertical Alignment)) for viewing angle expansion 28 (1997) 845), (3) a mode in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied, and twisted multi-domain alignment is applied when a voltage is applied (n-ASM (Axial symmetrical aligned microcell) mode). Liquid crystal cell (Preliminary Collection 58 -59 (1998)) and (4) SURVIVEAL mode liquid crystal cell (announced at LCD (liquid crystal display) International 98). Moreover, any of PVA (Patterned Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Stained Alignment) may be used. Details of these modes are described in JP-A-2006-215326 and JP-T-2008-538819.
In the IPS mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. The IPS mode displays black when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal. JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522 are methods for reducing leakage light at the time of black display in an oblique direction and improving a viewing angle using an optical compensation sheet. No. 11-133408, No. 11-305217, No. 10-307291, and the like.

[Organic EL display device]
As an organic EL display device which is an example of the image display device of the present invention, for example, an aspect having a light absorption anisotropic film, a λ / 4 plate, and an organic EL display panel in this order from the viewing side. Preferably mentioned.
More preferably, from the viewing side, the above-described laminate having the λ / 4 plate and the organic EL display panel are arranged in this order. In this case, the laminated body is arrange | positioned from the visual recognition side in order of the base material, the alignment film provided as needed, the light absorption anisotropic film, and (lambda) / 4 board.
The organic EL display panel is a display panel configured using an organic EL element in which an organic light emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[Example 1]
According to the following steps, an intermediate (1-A) represented by the following formula (1-A) was obtained, and then compound (1) was synthesized.

<Synthesis of Intermediate (1-A)>
4.68 g (20 mmol) of 5-bromo-2-methylthieno [2,3-d] thiazole synthesized according to the method described in J. Heterocyclic Chem., 1983, 20, 113 and JP 2002-23295 A, and 4 -3.54 g (20 mmol) of diethylaminobenzaldehyde was dissolved in 10 ml of tetrahydrofuran (THF) and stirred in an oil bath at 55 ° C for 15 minutes.
To this THF solution, 1.2 g of NaH (mass ratio 60% equivalent) was carefully added and stirred in an oil bath at 55 ° C. for 4 hours.
Next, the temperature was lowered to room temperature (23 ° C.), and methanol was added until no foaming occurred.
Thereafter, the mixture was suction filtered, washed with methanol and water, and dried overnight at 40 ° C. to obtain an intermediate (1-A). The yield was 1.35 g (17.2% yield).

<Synthesis of Compound (1)>
The obtained intermediate (1-A) 0.79 g (2.0 mmol), 4-hexylphenylboronic acid 0.41 g (2.0 mmol), palladium acetate 0.12 g (0.56 mmol), and xanthophos 0. The operation of adding 32 g (0.56 mmol) into 3 ml of toluene and 0.3 ml of water, degassing and filling with nitrogen was repeated three times.
The system was stirred for 7 hours in an oil bath at 100 ° C. while the system was kept in a nitrogen atmosphere.
Subsequently, after cooling to room temperature (23 degreeC), liquid separation operation was performed with ethyl acetate and water, and the organic layer was dried with magnesium sulfate. After concentration, the product was purified by a column to obtain compound (1). The yield was 100 mg (10.5% yield).
NMR (nuclear magnetic resonance) data (CDCl ₃ ) δ: 0.90 (t, 3H), 1.22 (t, 6H), 1.30-1.40 (m, 6H), 1.65 (m, 2H), 2.62 (t, 2H), 3.40 (q, 4H), 6.68 (d, 2H), 7.10 (d, 1H), 7.22 (d, 2H), 7. 35-7.40 (m, 2H), 7.42 (d, 3H), 7.54 (d, 2H)

[Example 2]
According to the following steps, an intermediate (2-B) represented by the following formula (2-B) and an intermediate (2-A) represented by the following formula (2-A) were obtained, and then the compound (2 ) Was synthesized.

The intermediate (2-A) was synthesized by a conventionally known method using commercially available raw materials.
Next, 0.90 g (2 mmol) of intermediate (2-A), 0.57 g (2.2 mmol) of boronic acid ester, 0.46 g (0.4 mmol) of tetrakistriphenylphosphine palladium, and 0.83 g of potassium carbonate ( (6.0 mmol) was dissolved in 10 ml of 1,4-dioxane, degassed and filled with nitrogen three times.
The system was stirred in an oil bath at 100 ° C. for 5 hours while the system was kept in a nitrogen atmosphere.
Next, after the temperature was lowered to room temperature (23 ° C.), 30 ml of water was added, and the precipitated solid was filtered to obtain a crude product. Purification by column gave compound (2). The yield was 100 mg (yield 9.9%).
NMR data (CDCl ₃ ) δ: 0.88 (t, 3H), 1.12 (d, 3H), 1.40-1.70 (m, 2H), 2.38 (m, 1H), 3. 00 (t, 2H), 3.86 (s, 3H), 4.35 (t, 2H), 6.95 (d, 2H), 7.22 (d, 1H), 7.35 (d, 2H) ), 7.50-7.58 (m, 3H), 7.82 (d, 2H), 7.92 (s, 1H)

Example 3
1.17 g (3.0 mmol) of intermediate (2-B) obtained in Example 2 and 0.53 g (3.0 mmol) of 4-butoxybenzaldehyde were added to 10 ml of toluene, and the mixture was added in an oil bath at 130 ° C. for 8 hours. Heated to reflux for hours.
After concentrating the reaction solution, a column was carried out to obtain a compound (3) represented by the following formula (3). The yield was 80 mg (yield 4.9%).
NMR data (CDCl ₃ ) δ: 0.88 (t, 3H), 1.12 (d, 3H), 1.26 (t, 6H), 1.40-1.70 (m, 2H), 2. 44 (m, 1H), 3.00 (t, 2H), 3.48 (q, 4H), 4.35 (t, 2H), 6.70 (d, 2H), 7.34 (d, 2H) ), 7.80 (d, 2H), 7.86 (d, 2H), 7.90 (s, 1H), 8.90 (s, 1H)

[Comparative Example 1]
Intermediate (2-A) 0.45 g (1.0 mmol), 4-bromo-N, N-diethylaniline 0.20 g (1.0 mmol), tetrakistriphenylphosphine palladium 0.23 g (0.20 mmol), carbonic acid 0.41 g (3.0 mmol) of potassium was dissolved in 10 ml of 1,4-dioxane, and degassing and nitrogen filling were repeated three times, followed by reaction in an external oil bath at 80 ° C. for 8 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, 30 ml of water was added and filtered.
The obtained filtrate was subjected to column purification and then recrystallized from chloroform-methanol to obtain a compound (X) represented by the following formula (X). The yield was 120 mg (yield 12%).
NMR data (CDCl ₃ ) δ: 0.88 (t, 3H), 1.12 (d, 3H), 1.26 (t, 6H), 1.40-1.70 (m, 2H), 2. 44 (m, 1H), 3.00 (t, 2H), 4.32 (t, 2H), 6.98 (d, 2H), 7.30 (d, 2H), 7.70 (d, 2H) ), 7.92 (s, 1H), 7.95 (d, 2H)

[Comparative Example 2]
4.3 g (10.0 mmol) of the intermediate (Y-1) represented by the following formula (Y-1) synthesized by a conventionally known method was added to 6 ml of hydrochloric acid and 6 ml of acetic acid, and sodium nitrite under ice cooling. 5 ml of a 0.72 g (10.5 mmol) aqueous solution was added dropwise at 0 ° C. or lower, and after stirring for 1 hour, 0.52 mg of amidosulfuric acid was added to obtain a diazonium solution.
The diazonium solution was dropped while maintaining a 10 ml methanol solution of 1.5 g of N, N-diethylaniline at 0 ° C. or lower. The temperature was raised to room temperature (23 ° C.), and after stirring for 1 hour, 30 ml of water was added and the resulting solid was filtered off.
Purification by a column yielded a black purple solid compound (Y) represented by the following formula (Y). The yield was 0.94 g (yield 16%).
NMR data (CDCl ₃ ) δ: 0.88 (t, 3H), 1.30-1.40 (m, 22H), 1.58 (m, 2H), 1.65 (m, 2H); 68 (t, 2H), 3.50 (t, 4H), 6.78 (d, 2H), 7.30 (d, 2H), 7.82 (d, 2H), 7.90 (s, 1H) 7.98 (d, 2H)

Example 4
On the alignment film produced as follows, a light absorption anisotropic film was produced using the coloring composition of Example 4 described later.

<Preparation of alignment film>
A glass substrate (manufactured by Central Glass Co., Ltd., blue plate glass, size 300 mm × 300 mm, thickness 1.1 mm) was washed with an alkaline detergent, and after pouring pure water, the glass substrate was dried.
Next, the following alignment film forming composition 1 was applied onto a glass substrate after drying using a # 12 bar, and the applied alignment film forming composition 1 was dried at 110 ° C. for 2 minutes, A coating film was formed on a glass substrate.
The obtained coating film was rubbed once (roller rotation speed: 1000 rotations / 2.9 mm, stage speed 1.8 m / min) to produce an alignment film on the glass substrate.

―――――――――――――――――――――――――――――――――
Composition of alignment film forming composition 1 ――――――――――――――――――――――――――――――――――
Modified vinyl alcohol (following formula (PVA-1)) 2.00 parts by mass Water 74.08 parts by mass Methanol 23.86 parts by mass Photoinitiator (Irgacure 2959, manufactured by BASF) 0.06 parts by mass ―――――――――――――――――――――――――――――――――

Here, the numerical value attached | subjected to the repeating unit in the said formula (PVA-1) represents the molar ratio of each repeating unit.

<Preparation of light absorption anisotropic film>
On the obtained alignment film, the colored composition of Example 4 (see the composition below) was spin-coated using a spin coater under the condition of a rotation speed of 1000 rotations / 10 seconds, and then at room temperature (23 ° C.). A coating film was formed on the alignment film by drying for 30 seconds.
Next, the obtained coating film was heated at 180 ° C. for 15 seconds, then cooled to room temperature (23 ° C.), and the light absorption anisotropic film of Example 1 was produced on the alignment film.
―――――――――――――――――――――――――――――――――
Composition of the coloring composition of Example 4 ―――――――――――――――――――――――――――――――――
-Liquid crystalline compound (B) (see formula (B) below) 3.22 parts by mass-Compound (1) 1.73 parts by mass-Interface modifier F1 (see formula (F1) below) 0.02 parts by mass (Solvent) 95.03 parts by mass ―――――――――――――――――――――――――――――――――

Example 5
A light-absorbing anisotropic film was produced in the same manner as in Example 4 except that the compound (2) synthesized in Example 2 was used in place of the compound (1).

Example 6
A light absorption anisotropic film was produced in the same manner as in Example 4 except that the compound (3) synthesized in Example 3 was used in place of the compound (1).

[Comparative Example 3]
A light absorption anisotropic film was produced in the same manner as in Example 4 except that the compound (X) synthesized in Comparative Example 1 was used in place of the compound (1).

[Comparative Example 4]
A light absorption anisotropic film was produced in the same manner as in Example 4 except that the compound (Y) synthesized in Comparative Example 2 was used instead of the compound (1).

[Evaluation]
<Dichroic ratio>
With the linear polarizer inserted on the light source side of the optical microscope (Nikon Corporation, product name “ECLIPSE E600 POL”), each light absorption anisotropic film produced in the example and comparative example was set on the sample stage. The absorbance of the light-absorbing anisotropic film in the wavelength range of 400 to 500 nm was measured using a multichannel spectroscope (manufactured by Ocean Optics, product name “QE65000”), and the dichroic ratio was calculated by the following equation. The results are shown in Table 1 below. In Comparative Example 3, the produced light absorption anisotropic film cannot be evaluated because crystals are precipitated and the haze is large. In Table 1 below, “−” is written.
Dichroic ratio (D0) = Az0 / Ay0
In the above formula, “Az0” represents the absorbance with respect to the polarized light in the absorption axis direction of the light absorption anisotropic film, and “Ay0” represents the absorbance with respect to the polarization in the polarization axis direction of the light absorption anisotropic film.

<Surface shape>
When the light-absorbing anisotropic film is produced, the coating film formed on the alignment film is visually observed, and “C” indicates that white particles are visible on the coating film (that can be judged that crystals are precipitated). When the white grains were not seen but had haze (white turbidity), it was evaluated as “B”, and those that appeared transparent were judged as “A”. The results are shown in Table 1 below.

<Maximum absorption wavelength>
(1) Solution About each compound synthesize | combined in Examples 1-3 and Comparative Examples 1-2, the absorption maximum wavelength in a cyclopentanone solvent was measured with spectrophotometer UV-2550 (made by Shimadzu Corp.). The results are shown in Table 1 below.
(2) Film In the above-described measurement of the dichroic ratio, the absorption maximum wavelength of each of the light absorption anisotropic films prepared in Examples and Comparative Examples was measured with an optical microscope (product name “ECLIPSE E600 POL” manufactured by Nikon Corporation). Measured with The results are shown in Table 1 below. In Comparative Example 3, since the dichroic ratio could not be measured, “−” is shown in Table 1 below.

From the results shown in Table 1, the predetermined linking group bonded to the thienothiazole ring has any linking group selected from the group consisting of —CH═CH—, —CH═N— and —N═CH—. It was found that when a compound that was not used was used, the dichroic ratio of the light absorption anisotropic film in the wavelength range of 390 to 550 nm was low (Comparative Examples 3 and 4).
As the predetermined linking group bonded to the thienothiazole ring, at least one linking group is any linking group selected from the group consisting of —CH═CH—, —CH═N— and —N═CH—. Thus, it was found that the dichroic ratio of the light absorption anisotropic film in the wavelength region of 390 to 550 nm was increased (Examples 4 to 6).

Claims (15)

A dichroic dye compound having a structure represented by the following formula (I).
Here, in the formula (I),
X ¹ and X ² each independently represent a substituent, m and n each independently represent an integer of 0 to 2, and when m is 2, a plurality of X ¹ may be the same It may be different, and when n is 2, the plurality of X ² may be the same or different.
Ar ¹ and Ar ³ each independently represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and Ar ² represents an aromatic group in which two hetero 5-membered rings optionally having a substituent are condensed. Represents a family heterocycle.
L ¹ and L ² are each independently a single bond, —N═N—, —CH═CH—, —CH═N—, —N═CH—, —C≡C—, and a carbon atom. Represents an linking group selected from the group consisting of an alkylene group optionally substituted with an oxygen atom or a sulfur atom, and at least one of L ¹ and L ² is —CH═CH—, —CH═ It represents any linking group selected from the group consisting of N- and -N = CH-. The L ² in the formula (I) represents any one of the linking groups selected from the group consisting of —CH═CH—, —CH═N— and —N═CH—. Chromatic dye compound. The dichroic dye compound according to claim 1 or 2, wherein Ar ¹ and Ar ³ in the formula (I) are both benzene rings. L < ¹ > in said Formula (I) represents any one coupling group selected from the group which consists of a single bond, -N = N-, and -CH = CH-. The dichroic dye compound described in 1. X ¹ and X ² in the formula (I) each independently represent any substituent selected from the group consisting of an alkyl group, an alkoxy group, an ester group, an amide group, and an amino group. The dichroic dye compound of any one of -4. The dichroic dye compound according to any one of claims 1 to 5, wherein Ar ² in the formula (I) is an aromatic heterocyclic ring represented by the following formula (II).
Here, in the formula (II), * 1 represents a bonding position with L ¹ , * 2 represents a bonding position with L ^2, and X ³ represents a hydrogen atom or a substituent. The dichroic dye compound according to claim 6, wherein L ¹ in the formula (I) is a single bond. The dichroic dye compound according to claim 6 or 7, wherein L ² in the formula (I) is -CH = CH-. The dichroic dye compound according to any one of claims 6 to 8, wherein X ¹ in the formula (I) is an alkyl group, and X ² in the formula (I) is an amino group. .   A coloring composition comprising the dichroic dye compound according to claim 1 and a liquid crystalline compound.   Furthermore, the coloring composition of Claim 10 containing a horizontal alignment agent.   The light absorption anisotropic film formed using the coloring composition of Claim 10 or 11.   The laminated body which has a base material and the light absorption anisotropic film of Claim 12 provided on the said base material.   Furthermore, the laminated body of Claim 13 which has a (lambda) / 4 board provided on the said light absorption anisotropic film.   An image display device comprising the light-absorbing anisotropic film according to claim 12 or the laminate according to claim 13 or 14.