WO2017047300A1

WO2017047300A1 - Composition for anisotropic dye film and anisotropic dye film

Info

Publication number: WO2017047300A1
Application number: PCT/JP2016/073677
Authority: WO
Inventors: 政昭西村; 充哉青葉; 靖志賀; 佐野　秀雄; 浩幸相京; 輝恒大澤
Original assignee: 三菱化学株式会社
Priority date: 2015-09-18
Filing date: 2016-08-10
Publication date: 2017-03-23
Also published as: CN108139524B; JP2017058630A; JP6008031B1; CN108139524A; KR20180055811A

Abstract

The present invention addresses the problem of providing a composition for an anisotropic dye film that has excellent optical characteristics and is suitable for a process for producing displays, and an anisotropic dye film. The composition according to the present invention for an anisotropic dye film contains azo dyes and a solvent wherein the azo dyes comprise an azo dye that is represented by formula (I) in the form of a free acid and an azo dye that is represented by formula (III) in the form of a free acid. Ar¹¹-N=N-Ar¹²-N=N-Ar¹³-N=N-Ar¹⁴ (I) Ar²¹-N=N-Ar²²-N=N-Ar²³ (III)

Description

Composition for anisotropic dye film and anisotropic dye film

INDUSTRIAL APPLICABILITY The present invention is useful for anisotropic dye films formed by a wet film forming method, in particular, polarizing films included in display elements of light control elements, liquid crystal elements (LCDs), and organic electroluminescence elements (OLEDs). The present invention relates to an anisotropic dye film composition and an anisotropic dye film that exhibit high dichroism.

In the LCD, a linearly polarizing film and a circularly polarizing film are used to control optical rotation and birefringence in display. Also in the OLED, a circularly polarizing film is used for preventing reflection of external light.
Conventionally, iodine has been widely used as a dichroic material in these polarizing films. However, since iodine has a high sublimation property, when used as a polarizing element using a polarizing film, its heat resistance and light resistance are not sufficient. Further, since the extinction color is deep blue, it cannot be said that it is an ideal achromatic polarizing element over the entire visible spectrum region.

In order to obtain an ideal achromatic polarizing element, an anisotropic dye film using an organic dye as a dichroic material has been studied. As anisotropic dye films using organic dyes, conventional polymers impregnated with organic dyes, methods for obtaining films by applying organic dyes on substrates, etc. And a film formed by using a film method.
When using an anisotropic dye film in which an organic dye is impregnated in a conventional polymer, an adhesive layer is provided on the anisotropic dye film, a protective film of the adhesive layer is bonded, and the polarizing film is bonded with the protective film The process of transferring a film | membrane to a display manufacturing line, peeling off a protective film with a display manufacturing line, and bonding an anisotropic pigment | dye film | membrane to a board | substrate etc. is taken. If this is replaced with a method of forming an anisotropic dye film on a substrate such as glass or transparent film by using a wet film forming method, an anisotropic dye obtained by impregnating the above-mentioned conventional polymer with an organic dye Compared with the method using a film, the manufacturing process can be simplified, which is considered to contribute to productivity improvement.

As an anisotropic dye film formed using a wet film forming method, for example, in Patent Document 1, a film containing a dye is formed on a substrate such as glass or a transparent film using a wet film forming method. There is a method of obtaining an anisotropic dye film by orienting the dye by utilizing intermolecular interaction or the like. Patent Document 2 discloses an anisotropic dye film composition containing a trisazo dye for obtaining an anisotropic dye film having a high dichroic ratio, which was not sufficient in Patent Document 1.

A method using a plurality of dyes in an anisotropic dye film formed using a wet film forming method is shown. Patent Document 3 shows that a film showing a high dichroic ratio and a high degree of molecular orientation can be obtained while suppressing disturbance of molecular orientation by using a dye having a specific structure in combination. Further, Patent Document 4 shows that variation in the orientation direction during casting can be suppressed by combining dyes having different molecular sizes in a specific ratio.

Japanese National Table No. 8-511109 Japanese Unexamined Patent Publication No. 2010-168570 Japanese Unexamined Patent Publication No. 2010-26024 International Publication No. 2011/004759

With high performance and high performance of displays in recent years, a polarizing film is required to have high performance such as high transmittance and high dichroism. In addition, with a reduction in the cost of displays, it is also required to improve low manufacturing costs and productivity. However, although the anisotropic dye film using the dye used in Patent Document 2 exhibits high performance as a polarizing film, the composition for anisotropic dye film tends to increase in viscosity. Therefore, when it is applied to an actual display manufacturing process, the filtration for removing foreign substances performed before coating is slow, and it takes time to fill the composition into the coating apparatus, so that the slot die coating method is applied. The present inventors have found that there is a problem in process compatibility from the viewpoint of display production, such as very slow compared with the speed at which the color resist is applied by the slot die coating method in the color filter production process.
Also, Patent Documents 2 and 3 show that a high dichroic ratio and the like can be obtained, but the above-described process compatibility has not been studied.
On the other hand, Patent Document 3 only shows a combination of a disazo compound and a monoazo compound having a specific structure, and does not examine process compatibility and a composition containing a trisazo compound.
An object of the present invention is to provide an anisotropic dye film composition and an anisotropic dye film which are excellent in optical properties and used for forming an anisotropic dye film suitable for a display manufacturing process.

This invention discovered that the said subject could be solved by using the composition for anisotropic dye films containing a specific azo dye and a solvent.
That is, the gist of the present invention is as follows.

[1] An anisotropic dye film composition containing an azo dye and a solvent, wherein the azo dye has an azo dye whose free acid form is represented by the following formula (I) and a free acid form: An anisotropic dye film composition comprising an azo dye represented by the formula (III).

[In Formula (I),
Ar ¹¹ and Ar ¹² each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
Ar ¹³ is a 1,4-phenylene group optionally having an electron donating group, a 1,4-naphthylene group optionally having a substituent, or an aromatic heterocyclic ring optionally having a substituent Represents a group,
Ar ¹⁴ represents a group represented by the formula (II). ]

[In the formula (II),
R ^N11 and R ^N12 each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or an acyl group that may have a substituent. Represent,
b represents an integer of 0 to 3, and d represents 0 or 1.
The amino group represented by —NR ^N11 R ^N12 is substituted at the α-position or β-position. ]

[In Formula (III),
Ar ²¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
Ar ²² is a 1,4-phenylene group optionally having an electron donating group, a 1,4-naphthylene group optionally having a substituent, or an aromatic heterocyclic ring optionally having a substituent Represents a group,
Ar ²³ represents a group represented by formula (IV). ]

[In Formula (IV),
R ^N21 and R ^N22 each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or an acyl group that may have a substituent. Represent,
e represents an integer of 0 to 3, and f represents 0 or 1.
The amino group represented by —NR ^N21 R ^N22 is substituted at the α-position or β-position. ]
[2] The composition for anisotropic dye film according to [1], wherein Ar ^{14 in the} formula (I) is a group represented by the formula (VI).

[In Formula (VI),
g and h each independently represents 0 or 1;
Incidentally, ^d in the formula ^{(VI), R N11} and ^{R N12} is ^d of Formula ^(II), and ^{R N11} and ^{R N12} synonymous. ]
[3] The composition for anisotropic dye film according to [1] or [2], wherein Ar ^{23 in the} formula (III) is a group represented by the formula (VII).

[In the formula (VII):
i and j each independently represents 0 or 1.
Incidentally, ^f in formula ^{(VII), R N21} and ^{R N22} is ^f of formula ^(III), and ^{R N21} and ^{R N22} synonymous. ]
[4] Ar ^{12 in the} formula (I) may have a 1,4-phenylene group which may have a substituent, a 1,4-naphthylene group which may have a substituent, and a single ring or The composition for anisotropic dye film according to any one of [1] to [3], which is selected from the group consisting of an aromatic heterocyclic group which may have a bicyclic substituent object.
[5] Ar ^{11 in the} formula (I) has a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a monocyclic or bicyclic substituent. Any one of [1] to [4], which is selected from the group consisting of optionally substituted aromatic heterocyclic groups and has at least one electron-withdrawing group as a substituent. An anisotropic dye film composition.
[6] The structure excluding the substituent which may be present from at least one structure selected from Ar ¹¹ to Ar ^{14 in} the formula (I) is selected from Ar ²¹ to Ar ^{23 in} the formula (III). The composition for anisotropic dye film according to any one of [1] to [5], which is the same as the structure excluding a substituent which may be present from at least one structure.
[7] The structure excluding the substituent which may be present from at least one structure selected from Ar ¹¹ to Ar ^{13 in} the formula (I) is represented by Ar ²¹ and / or Ar ^{22 in} the formula (III). The composition for anisotropic dye film according to any one of [1] to [6], which has the same structure as the structure excluding the substituent which may have from the structure.
[8] The structure excluding the substituent which may be present from at least one structure selected from Ar ¹¹ to Ar ^{14 in} the formula (I) is selected from Ar ²¹ to Ar ^{23 in} the formula (III). Any one of [1] to [7], which is the same as the structure excluding the substituent that may be present from at least one structure, and the group of the substituents that may be present is the same. 2. The composition for anisotropic dye film according to claim 1.
[9] An anisotropic dye film comprising an azo dye whose free acid form is represented by the following formula (I) and an azo dye whose free acid form is represented by the following formula (III).

[In Formula (IV),
R ^N21 and R ^N22 each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or an acyl group that may have a substituent. Represent,
e represents an integer of 0 to 3, and f represents 0 or 1.
The amino group represented by —NR ^N21 R ^N22 is substituted at the α-position or β-position. ]

The composition for an anisotropic dye film of the present invention has excellent optical properties, low viscosity, and is suitable for a display manufacturing process. Specifically, the filterability at the time of removing foreign matters at the stage of preparing the anisotropic dye film composition is good, and the productivity of the anisotropic dye film composition is excellent. In addition, the anisotropic dye film composition of the present invention can be easily supplied to a coating apparatus, has a high coating speed by the slot die coating method, and has a highly productive anisotropic dye film manufacturing process. it can. Furthermore, an anisotropic dye film having excellent optical characteristics can be provided. A polarizing element using an anisotropic dye film having such characteristics can be used in various fields such as a light control element, a liquid crystal element, and a display element of an organic electroluminescence element that are required to have color reproducibility.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present specification, “mass%” and “wt%” and “part by mass” and “part by weight” have the same meaning. In addition, when “ppm” is simply described, it indicates “weight ppm”.

The anisotropic dye film referred to in the present invention is an electromagnetic property in any two directions selected from a total of three directions in the three-dimensional coordinate system of the thickness direction of the anisotropic dye film and any two orthogonal in-plane directions. Is a dye film having anisotropy. Examples of the electromagnetic property include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance.
Examples of the film having optical anisotropy such as absorption and refraction include a polarizing film such as a linearly polarizing film and a circularly polarizing film, a retardation film, and a conductive anisotropic film. The anisotropic dye film of the present invention is preferably used for a polarizing film, a retardation film and a conductive anisotropic film, and more preferably used for a polarizing film.

The present invention is an anisotropic dye film composition comprising an azo dye and a solvent, wherein the free acid form is represented by the formula (I) (hereinafter referred to simply as the “azo dye represented by the formula (I)”. And an azo dye whose free acid form is represented by the formula (III) (hereinafter also simply referred to as “azo dye represented by the formula (III)”).
The reason why the composition for anisotropic dye film of the present invention exhibits the effects of the present invention is presumed as follows. The azo dye represented by the formula (I) of the present invention is a trisazo dye, and when dissolved in a solvent, particularly a solvent having a high dielectric constant (for example, water), the hydrophobic portion at the center of the molecule is large. That is, the aromatic hydrocarbon ring or aromatic heterocyclic ring constituting the molecule has high planarity, and the dye molecules are easily associated to form a column. Since the columnar molecular assembly formed of the azo dye represented by the formula (I) has an ionic group such as a sulfo group on the outside and a highly polar group such as an amino group and a hydroxyl group, An electronic interaction occurs between the columns, and it is easy to take a hexagonal phase in which the columns are located at an equal distance. This hexagonal phase is a liquid crystal having a two-dimensional order, and the order is relatively high in the liquid crystal phase. That is, the molecules have fluidity but are close to the solid state.
By adding the azo dye represented by the formula (III) to the azo dye represented by the formula (I), the azo dye represented by the formula (III) is converted into an azo dye represented by the formula (I). It binds to the outside of the column consisting of ionic groups and the like. In addition, a part of the dye molecules of the column composed of the azo dye represented by the formula (I) is replaced with the azo dye represented by the formula (III), and the outside of the column becomes uneven. By being in such a state, the interaction between the columns is reduced, the state where the columns are evenly spaced is lost, and a nematic phase having a one-dimensional order is taken.
That is, it is presumed that the dye is in a liquid state closer to that of the hexagonal phase and the viscosity of the anisotropic dye film composition is lower. Thus, the addition of the azo dye represented by the formula (III) to the azo dye represented by the formula (I) is the same as the conventional additive for improving optical characteristics (dichroic ratio). It is presumed that it is different from the effect of conventional additives in that it does not change the degree of order or raise the order, but changes the interaction between columns and lowers the order.

[Anisotropic Dye Film Composition]
The composition for anisotropic dye film of the present invention includes an azo dye whose free acid form is represented by formula (I), an azo dye whose free acid form is represented by formula (III), and a solvent. Although not limited, it is preferable that the composition is in a liquid crystal phase from the viewpoint of forming an anisotropic dye film formed after the solvent evaporates with a high degree of orientation. In the present embodiment, the state of the liquid crystal phase specifically refers to 1 to 16 in “Basics and Applications of Liquid Crystal” (Shinichi Matsumoto, Ryo Tsunoda, published by Industrial Research Institute, 1991). As described on the page, it is a liquid crystal state exhibiting both liquid and crystal properties, and means a nematic phase, a cholesteric phase, a smectic phase or a discotic phase. In particular, a nematic phase is preferred because of its low order in solution and a tendency to have a low viscosity.
Moreover, binder resin, a monomer, a hardening | curing agent, an additive, etc. may be mix | blended with the composition for anisotropic dye films | membranes as needed. The anisotropic dye film composition may be in the form of a solution or gel. In the composition for anisotropic dye film, an azo dye whose free acid form is represented by formula (I) and an azo dye whose free acid form is represented by formula (III) are dissolved or dispersed in a solvent. You may be in the state.

In the present invention, in order for the anisotropic dye film to exhibit high orientation, it is preferable that the azo dye forms a molecular laminate in the composition for anisotropic dye film. It is preferable that the composition exhibits a liquid crystal phase. Here, having a liquid crystal phase means exhibiting lyotropic liquid crystallinity in a solvent. The anisotropic dye film composition may or may not exhibit a liquid crystal phase, but is preferably in a liquid crystal phase state as described above.

In addition, the azo dye used in the present invention is soluble in water or an organic solvent in order for the anisotropic dye film composition to exhibit a liquid crystal phase and to be used in the wet film formation method described later. It is preferable that it is water-soluble. Further preferred are compounds having an inorganic value smaller than the organic value as defined in “Organic Conceptual Diagram-Fundamentals and Applications” (Yoshio Koda, Sankyo Publishing, 1984). The molecular weight is preferably 200 or more, more preferably 300 or more, in a free state that does not take a salt form. Moreover, it is preferable that it is 1500 or less, and it is more preferable that it is 1200 or less. The term “water-soluble” means that the compound is dissolved in water at room temperature, usually 0.1% by mass or more, preferably 1% by mass or more.

<Solvent>
The solvent contained in the composition for anisotropic dye film of the present invention comprises an azo dye whose free acid form is represented by formula (I), and an azo dye whose free acid form is represented by formula (III), There is no particular limitation as long as it is dissolved or dispersed. In particular, the azo dye whose free acid form is represented by the formula (I) and the azo dye whose free acid form is represented by the formula (III) are easy to form an association state such as a lyotropic liquid crystal in a solvent. Thus, the solvent is preferably water, a water-miscible organic solvent, or a mixture thereof.
Specific examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and glycerin; glycols such as ethylene glycol and diethylene glycol; cellosolves such as methyl cellosolve and ethyl cellosolve; A mixed organic solvent is mentioned.
Among these, the azo dye whose free acid form is represented by the formula (I) and the highly hydrophobic portions such as the aromatic rings of the azo dye whose free acid form is represented by the formula (III) Water, methanol or ethanol is preferable, and water is particularly preferable.

<Concentration of azo dye>
In the present invention, an anisotropic dye film composition comprising an azo dye whose free acid form is represented by formula (I) and an azo dye whose free acid form is represented by formula (III) The concentration in it depends on the solubility of the dye and the concentration of the associated state such as the lyotropic liquid crystal state, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably Is 1% by mass or more, particularly preferably 5% by mass or more. On the other hand, it is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less. Within this range, it is easy to control the thickness of the anisotropic dye film composition after coating and drying, and the coating speed in the slot die coating method tends to be high.
The composition for anisotropic dye film of the present invention may or may not exhibit a lyotropic liquid crystal phase, but only the amount of solvent in the composition for anisotropic dye film is changed when the lyotropic liquid crystal phase is not expressed. By doing so, it is preferable that a lyotropic liquid crystal phase is developed. The expression of the lyotropic liquid crystal phase is preferable because the dye exhibits a high degree of orientation in the anisotropic dye film and a high dichroic anisotropic dye film tends to be obtained.
It is more preferable that the composition for anisotropic dye film expresses a lyotropic liquid crystal phase because higher orientation in the anisotropic dye film tends to be obtained.

In the composition for anisotropic dye film of the present invention, an additive such as a surfactant can be added as necessary in order to improve the wettability to the substrate and the coating property. As the surfactant, any of anionic, cationic and nonionic types can be used. The addition concentration is preferably 0.05% by mass or more and 0.5% by mass or less.

<Viscosity>
The viscosity of the composition for anisotropic dye film of the present invention is such that the composition containing an azo dye whose free acid form is represented by the formula (I) is different from the azo compound whose free acid form is represented by the formula (III). There is no particular limitation as long as the viscosity is lowered by adding a dye and it is easy to adapt to the process of manufacturing a display such as filterability and coatability. The improvement of filterability and applicability can be determined by measuring the viscosity under the same conditions and decreasing the value.
The viscosity of the composition for anisotropic dye film can be measured by a capillary viscometer, a rotational viscometer, a falling body viscometer, a vibration viscometer, a parallel plate viscometer, or the like according to the measurement principle. Since the composition for anisotropic dye film of the present invention may exhibit thixotropic properties, it is preferably measured with a viscometer capable of varying the shear rate, such as a rotational viscometer. When measured with a rotational viscometer, it is preferably measured at 1 to 1000 s ⁻¹ .
As an example, measurement conditions and preferred ranges when measured with a rheometer are shown. After pre-shearing at 25 ° C. and a shear rate of 1000 s ⁻¹ for 5 seconds, the shear rate was changed from 1000 s ⁻¹ to 10 s ^{−1 in} 180 seconds, and a shear rate of 400 s ⁻¹ when shear rate sweep measurement was performed. The viscosity is preferably 200 cP or less, more preferably 100 cP or less, still more preferably 70 cP or less, particularly preferably 60 cP or less, and most preferably 50 cP or less. The lower limit is not particularly low and is preferably lower, but is, for example, 1 cP or more, preferably 10 cP or more.

<< Azo dye in which the form of the free acid is represented by the formula (I) >>
The anisotropic dye film composition of the present invention contains an azo dye whose free acid form is represented by the formula (I).

[In Formula (I), Ar ¹¹ and Ar ¹² each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar ¹³ is a 1,4-phenylene group optionally having an electron donating group, a 1,4-naphthylene group optionally having a substituent, or an aromatic heterocyclic ring optionally having a substituent Represents a group, and Ar ¹⁴ represents a group represented by the formula (II). ]

[In Formula (II), R ^N11 and R ^N12 each independently have a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or a substituent. And b represents an integer of 0 to 3, and d represents 0 or 1. The amino group represented by —NR ^N11 R ^N12 is substituted at the α-position or β-position. ]

<Ar ¹¹ >
Ar ¹¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

((Aromatic hydrocarbon group))
Examples of the aromatic hydrocarbon group include groups derived from a single ring and a plurality of rings. The number of rings contained in the groups derived from a plurality of rings is not particularly limited, but is usually 2 or more and 4 or less, preferably 3 or less.
For example, 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, fluorene ring, etc. having one free valence Can be mentioned.

The aromatic hydrocarbon group may have a substituent. Examples of the substituent that may have include a hydrophilic group that is usually introduced to enhance the solubility of the azo compound, and an electron-withdrawing group or electron-donating group that is introduced to adjust the color tone as a dye. preferable.
In addition, as a substituent that the aromatic hydrocarbon group may have, it is preferable to introduce a functional group that promotes the association between the dyes from the viewpoint of the dyes forming a columnar aggregate.
The interaction that promotes the association includes an electrostatic interaction, and a hydrogen bonding functional group or a functional group having a strong dipole is particularly preferable. Examples of the hydrogen bonding functional group include an alkoxy group, a hydroxyl group, an amino group, an acylamino group, a carbamoyl group, a sulfamoyl group, a carboxy group, a sulfo group, a cyano group, and a phosphate group.

A hydrophilic group is a functional group that exhibits an interaction due to hydrogen bonding with a protic substance such as water and has a property of being easily dissolved or mixed in water, and represents a functional group that is thermodynamically stabilized. . The hydrogen bonding functional group refers to a group having a lone electron pair (electron pair donor) such as a hetero atom (nitrogen, oxygen, sulfur) or a fluorine atom having a higher electronegativity than a hydrogen atom. Specific examples include alkoxy groups, hydroxyl groups, amino groups, acylamino groups, carbamoyl groups, sulfamoyl groups, carboxy groups, sulfo groups, cyano groups, and phosphate groups.

An electron withdrawing group refers to a substituent that is easier to attract electrons from the bond atom side than a hydrogen atom. When the electron withdrawing group is substituted with a phenyl group or a naphthyl group, the electron density on the benzene ring is reduced. Let In other words, there is an effect of causing shortage of electrons. An electron withdrawing group is a halogen atom; a group in which an atom having multiple electronegativity such as an oxygen atom, a nitrogen atom, or a sulfur atom is bonded to an aromatic ring; A group in which a carbon atom is bonded to an aromatic ring; a group in which a positively charged atom is bonded to an aromatic ring; and the like.
As an example of an indicator that a substituent is electron withdrawing, for example, Kenzo Konishi and Nobuhiko Kuroki, “Chemistry of Synthetic Dyes” (Tsubaki Shoten, published on February 25, 1963) pp. 23-25 It is mentioned that the substituent constant in the Hammett formula described in the above is positive. In the present invention, a substituent in which the substituent constant is positive in both the meta position and the para position is preferable. Specific examples include a carbamoyl group, a sulfamoyl group, a nitro group, a carboxy group, a sulfo group, a cyano group, a halogen atom, and a trifluoromethyl group.
The electron withdrawing group includes nonionic and ionic electron withdrawing groups. Here, the “nonionic” electron withdrawing group refers to an electron withdrawing group that is not an ionic group.

The ionic group is a hydrophilic group as described in Hiroshi Suzuki “Interface and Surfactant” (Sangyo Tosho Co., Ltd., published on January 23, 1990), pages 33-35. A group in which a part of the group is dissociated in water and separated into an anion (anion) portion and a cation (cation) portion.
Specifically, sulfo group, carboxy group, phosphate group, trimethylammonio group, J.M. N. Listed on pages 105-106 by Israel Ativiri, translated by Yasuo Kondo, Hiroyuki Oshima “Intermolecular Forces and Surface Forces” (Maglow Hill Publishing Co., Ltd., issued December 25, 1991) .
Examples of the ionic electron withdrawing group include a sulfo group and a carboxy group.

The nonionic electron withdrawing group reduces the electron density of the aromatic ring of the aromatic hydrocarbon group and does not separate the charge with water. Therefore, when the azo dye represented by the formula (I) is used in an anisotropic dye film composition containing, for example, water as a solvent, the interaction with the solvent is reduced, and Ar ¹¹ and electron-rich naphthyl are reduced. Ar ^{14 as a} group attracts strongly between molecules, and a property that molecules tend to form an associated state occurs. Note that the electron excess means a state in which the electron density on the benzene ring is enhanced.

Nonionic electron-withdrawing group includes a halogen atom; a group in which an atom having a high electronegativity such as an oxygen atom, a nitrogen atom, or a sulfur atom is bonded to an aromatic ring; a halogen atom A group in which a carbon atom substituted with is bonded to an aromatic ring; a group in which a positively charged atom is bonded to an aromatic ring; and the like.
Specific examples include a carbamoyl group, a sulfamoyl group, a nitro group, a cyano group, a halogen atom, and a trifluoromethyl group.

In the present invention, the electron donating group refers to a substituent that easily extrudes electrons from the bonding atom side compared to a hydrogen atom, and when the electron donating group is substituted with a phenyl group, the electron density on the benzene ring is increased. In other words, there is an effect of excessive electrons. Examples of an indicator that the substituent is electron donating include, for example, Kenzo Konishi and Nobuhiko Kuroki “Synthetic Dye Chemistry” (Tsubaki Shoten, published February 25, 1963), pages 23-25. It is mentioned that the substituent constant in the Hammett formula described is negative. In the present invention, a substituent in which the substituent constant is negative in both the meta position and the para position is preferable. Specific examples include an alkyl group, an alkoxy group, a hydroxyl group, an amino group, and an acylamino group.

Each group mentioned by the substituent which the said aromatic hydrocarbon group may have is demonstrated concretely.
(Alkyl group)
The alkyl group usually has 1 to 6 carbon atoms, preferably 4 or less. The alkyl group may have a substituent, and examples of the substituent include an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group.
Specific examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, an n-propyl group, a hydroxyethyl group, and a 1,2-dihydroxypropyl group.

(Alkoxy group)
The alkoxy group usually has 1 to 6 carbon atoms, preferably 3 or less. The alkoxy group may have a substituent, and examples of the substituent include an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, a sulfo group, and a carboxy group.
Specific examples of the alkoxy group include lower alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a hydroxyethoxy group, and a 1,2-dihydroxypropoxy group.

(Acylamino group)
The acylamino group is represented by —NH—C (═O) R ¹¹ . R ¹¹ represents an alkyl group, an alkenyl group, or a phenyl group.
Specific examples of the acylamino group include an acetylamino group, an acrylamino group, a methacrylamino group, and a benzoylamino group.

The alkyl group of R ¹¹ usually has 1 or more and 4 or less carbon atoms, preferably 2 or less. The alkenyl group for R ¹¹ usually has 2 or more and 4 or less carbon atoms, preferably 3 or less. The phenyl group of R ¹¹ usually has 6 to 10 carbon atoms, preferably 8 or less.
The alkyl group, alkenyl group and phenyl group of R ¹¹ may each independently have a substituent. Examples of the substituent that may have include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom.

(Amino group)
The amino group is usually represented by —NH ₂ , —NHR ²² or —NR ²³ R ²⁴ . R ²² to R ²⁴ each independently represents an alkyl group or a phenyl group.
Specific examples of the amino group include a methylamino group, an ethylamino group, a propylamino group, a dimethylamino group, and a phenylamino group.
The alkyl group of R ²² to R ²⁴ usually has 1 to 4 carbon atoms, preferably 2 or less. Further, the phenyl group of R ²² to R ²⁴ usually has 6 to 10 carbon atoms, preferably 8 or less.
The alkyl group and phenyl group of R ²² to R ²⁴ may have a substituent. Examples of the substituent that may have include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom.

(Carbamoyl group)
The carbamoyl group represents an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 6 carbon atoms, a phenylcarbamoyl group having 6 to 10 carbon atoms, or a naphthylcarbamoyl group having 10 to 14 carbon atoms. Specific examples of the carbamoyl group include a carbamoyl group, a phenylcarbamoyl group, a naphthylcarbamoyl group, and the like.
The alkylcarbamoyl group, phenylcarbamoyl group and naphthylcarbamoyl group may have a substituent. Examples of the substituent that may have include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom.

(Sulfamoyl group)
The sulfamoyl group includes an unsubstituted sulfamoyl group, an alkylsulfamoyl group having 1 to 6 carbon atoms, a phenylsulfamoyl group having 6 to 10 carbon atoms, and a naphthylsulfur group having 10 to 14 carbon atoms. Represents a moyl group. Specific examples of the sulffile group include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, an ethylsulfamoyl group, a diethylsulfamoyl group, a phenylsulfamoyl group, and a naphthylsulfamoyl group. It is done.
The alkylsulfamoyl group, phenylsulfamoyl group and naphthylsulfamoyl group may have a substituent. Examples of the substituent that may have include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a sulfo group, a carboxy group, and a halogen atom.

((Aromatic heterocyclic group))
The aromatic heterocyclic group for Ar ¹¹ is not particularly limited, but the group derived from a monocyclic or bicyclic heterocyclic ring increases the overlap between the azo dyes represented by formula (I). This is preferable in that a column can be formed. Examples of atoms other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom. In particular, since the azo dyes represented by the formula (I) tend to form a column, a nitrogen atom is preferable. When the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different. Preferable examples include pyridine ring, quinoline ring, isoquinoline ring, thiazole ring, benzothiazole ring and the like.

The aromatic heterocyclic group may have a substituent. Examples of the substituent that may have include a hydrophilic group, an electron donating group, an electron withdrawing group, and a hydrogen bonding functional group. Specific examples include an alkyl group, an alkoxy group, an acylamino group, an amino group, a carbamoyl group, a sulfamoyl group, a nitro group, a carboxy group, a sulfo group, a hydroxyl group, a cyano group, and a halogen atom. These substituent groups and substituents are respectively synonymous with those mentioned as the substituents that the aromatic hydrocarbon group of Ar ¹¹ may have, and preferred ranges and substituents that may be included. Are also synonymous.
Among these, having a sulfo group as a substituent is preferable from the viewpoint of imparting water solubility to the dye. Moreover, when it is unsubstituted, it is preferable at the point which does not prevent the interaction between atoms other than carbon contained in a heterocyclic ring, especially a nitrogen atom. The aromatic heterocyclic group may be unsubstituted or have 1 to 5 substituents as described above, and preferably is unsubstituted or has 1 to 2 substituents.

((Preferred example of Ar ¹¹ ))
Ar ¹¹ is preferably an aromatic hydrocarbon group which may have a substituent among the above, and a phenyl group which may have a substituent or a naphthyl group which may have a substituent. It is particularly preferred that
The azo dye represented by the formula (I) is formed by linking an aromatic ring and an azo group, has a wide π plane, and in a solution such as a lyotropic liquid crystal by associating molecules in a stacked π plane. A high state of association can be formed. When Ar ¹¹ is an aromatic hydrocarbon group, the flatness is high and the bias of the charge is small, so that a long column can be formed which is less likely to be displaced when molecules are stacked, and has a high degree of orientation anisotropy. It is easy to obtain a dye film. In particular, when Ar ¹¹ is a phenyl group or a naphthyl group, the size is the same as that of the other ring, in particular, the Ar ¹⁴ naphthalene ring arranged at the opposite end of one molecule of the azo dye. , Molecules are easier to stack, more preferable.

The aromatic hydrocarbon group of Ar ¹¹ may be unsubstituted or may have a substituent. When it has a substituent, it preferably has at least one hydrogen-bonding functional group or electron-withdrawing group, and more preferably has an electron-withdrawing group. The electron withdrawing group tends to attenuate the electron density of the aromatic ring of the aromatic hydrocarbon group. Thereby, in the azo dye represented by the formula (I), the electron-deficient Ar ¹¹ and the electron-rich naphthyl group Ar ¹⁴ are attracted strongly between the molecules, and the molecules tend to form an associated state. Note that the electron excess means a state in which the electron density on the benzene ring is enhanced.
The electron withdrawing group may be either nonionic or ionic. In the case of an ionic electron-withdrawing group, the azo dye has a property of attracting strongly between molecules due to an acid / base bond or a hydrogen bond between the molecules of the azo dye, so that the molecules can easily form an associated state.
On the other hand, in the case of a nonionic electron-withdrawing group, there is a tendency not to separate charges with water. Accordingly, when the azo dye represented by the formula (I) is used in an anisotropic dye film composition containing, for example, water as a solvent, the dye and the solvent represented by the formula (I) are compared with those in the ionic case. Interaction is small, that is, hydrophobic interaction is strong, attracting more strongly between molecules, and molecules tend to form a laminated state.
The electron-attracting group may be either nonionic or ionic, but nonionic is preferable because lamination tends to occur strongly in terms of stronger interaction between aromatic rings.
Among these, a carbamoyl group, a sulfamoyl group, a nitro group, and a cyano group are particularly preferable in that the planarity of the molecule is maintained and the stacking of the molecules is not disturbed.
The carbamoyl group and sulfamoyl group have the same meanings as the carbamoyl group and sulfamoyl group mentioned above for the substituent that the aromatic hydrocarbon group of Ar ¹¹ may have, and the preferred substituent and preferred range Are also synonymous.

<Ar ¹² >
Ar ¹² represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
((Aromatic hydrocarbon group))
Examples of the aromatic hydrocarbon group for Ar ¹² include groups derived from a single ring and a plurality of rings. The number of rings contained in the groups derived from a plurality of rings is not particularly limited, but is usually 2 or more and 4 or less, preferably 3 or less. Examples of the aromatic hydrocarbon group include two benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, and acenaphthenes. A ring, a fluoranthene ring, a fluorene ring, and the like.
As the aromatic hydrocarbon group for Ar ^12, a phenylene group which may have a substituent or a naphthylene group which may have a substituent is preferable, and the phenylene group may have a substituent. A good 1,4-phenylene group, and the 1,4-naphthylene group which may have a substituent as the naphthylene group has a high molecular linearity, a π plane spreads in the molecular minor axis direction, and an intermolecular The π-π interaction tends to be exhibited, which is preferable from the viewpoint of improving the association property of the azo dye.

The aromatic hydrocarbon group may have a substituent. Examples of the substituent that may have include a hydrophilic group that is usually introduced to enhance the solubility of the azo compound, an electron donating group or an electron withdrawing group that is introduced to adjust the color tone as a dye. preferable.
Specifically, they are respectively synonymous with those mentioned for the substituent that the aromatic hydrocarbon group of Ar ¹¹ may have.

The aromatic hydrocarbon group for Ar ¹² may be unsubstituted or may have 1 to 5 substituents, and preferably has 1 to 2 substituents. Among the substituents that may be present, an alkyl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, a hydroxyl group, a cyano group, a sulfo group, a carboxy group, a halogen atom, or a less polar group or a hydrogen bonding functional group It is preferable from the viewpoint of improving the associative property by interaction in forming a lyotropic liquid crystal, and it is particularly preferable to have a sulfo group. By having a sulfo group, water-solubility is imparted to the azo dye, and a salt of the sulfo group is formed between the molecules of the azo dye, which has the effect of promoting the stacking (association) of the azo dye molecules. The number of molecules involved in the columnar aggregates formed in this way increases. In other words, an anisotropic dye film having a high degree of molecular orientation tends to be obtained.
The alkyl group, alkoxy group, carbamoyl group and sulfamoyl group that the aromatic hydrocarbon group of Ar ¹² may have preferably have 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Further, the alkyl group, alkoxy group, carbamoyl group and sulfamoyl group have the same meanings as those given as the substituents that the aromatic hydrocarbon group of Ar ¹² may have, and may be substituted. The group is also synonymous.

((Aromatic heterocyclic group))
The aromatic heterocyclic group for Ar ¹² is not particularly limited, but the group derived from a monocyclic or bicyclic heterocyclic ring increases the overlap between the azo dyes represented by formula (I). This is preferable in that a column can be formed. Examples of atoms other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom, but the azo dyes represented by the formula (I) tend to easily form a column. A nitrogen atom is particularly preferred. When the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different.

The aromatic heterocyclic group for Ar ¹² may have a substituent. Examples of the substituent that may have include a hydrophilic group, an electron donating group, an electron withdrawing group, and a hydrogen bonding functional group. Specific examples include an alkyl group, an alkoxy group, an acylamino group, an amino group, a carbamoyl group, a sulfamoyl group, a nitro group, a carboxy group, a sulfo group, a hydroxyl group, a cyano group, and a halogen atom.
The alkyl group, alkoxy group, acylamino group, amino group, carbamoyl group, and sulfamoyl group each may have a substituent. The substituents that may be present are the same as those described above for the substituents that the aromatic hydrocarbon group of Ar ¹¹ may have, the substituents that may be possessed, and preferred ranges. Are also synonymous.
The aromatic heterocyclic group for Ar ¹² may have 1 to 5 of the above-mentioned substituents, and is preferably unsubstituted or has 1 to 2 of these substituents. Among them, the substituent for the aromatic heterocyclic group of Ar ¹² is preferably a hydroxyl group, a sulfo group or a carboxy group from the viewpoint of water solubilization.

The aromatic heterocyclic group for Ar ¹² is more preferably a divalent aromatic heterocyclic group represented by the following formula (Ia) or (Ib). That is, it is a divalent linking group bonded at the 2,5- or 3,6-position of the nitrogen-containing aromatic six-membered ring represented by (Ia), or represented by (Ib) is preferably a divalent linking group bonded at the substitution position of y ¹ and y ⁴ of that aromatic heterocycle. By being such an aromatic heterocyclic group, the azo dyes represented by the formula (I) tend to form a column easily.

[In Formula (Ia), Q ¹ to Q ⁴ each independently represent a carbon atom or a nitrogen atom, and one or two of Q ¹ to Q ⁴ represent a nitrogen atom. Q ¹ to Q ⁴ may have a substituent. ]

[In the formula (Ib), X represents a divalent linking group forming a 5- to 7-membered ring, and the ring contains a nitrogen atom, an oxygen atom or a sulfur atom. Y ¹ to y ⁴ represent substitution positions. y ² and / or y ³ may have a substituent. ]

In the formula (Ib), a nitrogen atom, an oxygen atom or a sulfur atom is contained on the ring formed by the linking group X.
The substituent that the divalent aromatic heterocyclic group represented by the formula (Ia) or (Ib) may have is a substituent of the aromatic heterocyclic group of Ar ¹² and Ar ¹³ And the preferred ranges are also synonymous with each other.
Examples of the linking group represented by X in the formula (Ib) include —N═CH—CH═C—, —CO—NH—CO—, ═NS—N═, —CH═N—. CH = CH- and the like can be mentioned. However, C and N in CH and NH may be substituted with a substituent such as an organic group instead of H, for example, those listed as substituents of the aromatic heterocyclic group of Ar ¹² and Ar ^13. .
The carbon atom shown at the position of y ² or y ³ may be substituted with a substituent such as an organic group, for example, those listed as substituents for the aromatic heterocyclic group of Ar ¹² and Ar ¹³ . ]

The aromatic heterocyclic group represented by the formula (Ia) is a group derived from pyridine, pyridazine, pyrimidine or pyrazine and having a linking position with the azo group at the 2,5 or 3,6 position. Is mentioned.
The aromatic heterocyclic group represented by the formula (Ib) is derived from quinoline, isoquinoline, benzothiadiazole, phthalimide and the like, and the linking position with the azo group is represented by the formula (Ib). Examples include groups in the ¹ and y ⁴ positions. Specific examples include a pyridinediyl group, a quinolinediyl group, an isoquinolinediyl group, a benzothiadiazolediyl group, and a phthalimidodiyl group. Among these, a quinoline diyl group and an isoquinoline diyl group are preferable.
Among these, from the viewpoint of the planarity of the entire compound, the aromatic heterocyclic group of Ar ¹² and Ar ¹³ is preferably the one represented by the formula (Ib), and in particular, the 5,8-quinolinediyl group. Alternatively, a 5,8-isoquinolinediyl group is preferable.

<Ar ¹³ >
Ar ¹³ represents a 1,4-phenylene group optionally having an electron donating group, a 1,4-naphthalene group optionally having a substituent, or an aromatic heterocyclic ring optionally having a substituent. Represents a group. By being these groups, the association property of the azo dye is improved.
Examples of the electron donating group that the 1,4-phenylene group may have include an alkyl group, an alkoxy group, a hydroxyl group, an amino group, and an acetylamino group. Specific examples, preferred ranges, and substituents that may be included in these groups are the same as those described above for the substituent that the aromatic hydrocarbon group of Ar ¹¹ may have. Among the electron donating groups that the 1,4-phenylene group may have, the size of the substituent is small, the planarity of the entire azo dye is high, and it is easy to associate with each other, so that a methyl group, a methoxy group, An acetylamino group or an amino group is preferred.

The 1,4-naphthylene group may have a substituent. Examples of the substituent that may have include a hydrophilic group, an electron donating group, an electron withdrawing group, and a hydrogen bonding functional group. Specific examples include a hydroxyl group, a methyl group, a methoxy group, an acetylamino group, an amino group, a sulfo group, and a carboxy group. Among these, the methoxy group, the sulfo group, or the acetylamino group impairs the planarity of the whole molecule. However, it is preferable in that it exhibits a high associative property.
The aromatic heterocyclic group, wherein the same meaning as the aromatic heterocyclic group of Ar ^12, specific examples, preferred ranges, it is also synonymous such substituent which may have.

<Ar ¹⁴ >
Ar ¹⁴ is represented by the formula (II).

<R ^N11 and R ^N12 >
R ^N11 and R ^N12 each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or an acyl group that may have a substituent. To express.

(Alkyl group)
The alkyl groups of R ^N11 and R ^N12 are each independently synonymous with the alkyl groups mentioned as the substituents that the Ar ¹¹ aromatic hydrocarbon group of formula (I) may have, The preferred substituents and preferred ranges are also synonymous.

(Phenyl group)
The phenyl groups of R ^N11 and R ^N12 each independently preferably have 6 to 12 carbon atoms, more preferably 10 or less, and particularly preferably 8 or less. The phenyl group may have a substituent. Examples of the substituent that may have include a methyl group, a methoxy group, a hydroxyl group, a carboxy group, and a sulfo group.

(Acyl group)
The acyl group of R ^N11 and R ^N12 is represented by —C (═O) R ³¹ , and R ³¹ represents an alkyl group or a phenyl group. The alkyl group usually has 1 to 4 carbon atoms, preferably 2 or less carbon atoms. The phenyl group usually has 6 or more substituents, usually 10 or less, preferably 8 or less. The alkyl group and the phenyl group may have a substituent. Examples of the substituent that may have include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a sulfo group, and a carboxy group. Specific examples of the acyl group include an acetyl group and a benzoyl group.

In particular, ^RN11 or ^RN12 is a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an acetyl group, or a benzoyl group from the viewpoint that steric hindrance is difficult when molecules are stacked and lyotropic liquid crystallinity is easily exhibited. Preferably there is.
The combination of R ^N11 and R ^N12 is not particularly limited, but one of R ^N11 and R ^N12 is preferably a hydrogen atom from the viewpoint of easily exhibiting lyotropic liquid crystallinity.
In particular, it is preferable that ^RN11 and ^RN12 are hydrogen atoms from the viewpoint that the composition for an anisotropic dye film easily exhibits lyotropic liquid crystal properties at a relatively low concentration and is excellent in process suitability.

<B and d>
b represents an integer of 0 to 3. Among these, 1 or 2 is because the azo dye represented by the formula (I) tends to exhibit water solubility and tends to form an aggregate due to an intermolecular salt-mediated interaction. preferable.
d represents 0 or 1; Among these, 1 is the azo dye represented by formula (I) becomes a dye having absorption up to a long wavelength in the visible region (380 nm to 780 nm), and the obtained anisotropic dye film becomes nearly black. It is preferable because of its tendency.
In the formula (II), the amino group represented by —NR ^N11 R ^N12 is substituted at the α-position or the β-position. Substitution at this position tends to contribute to the intermolecular interaction.
Although not particularly limited, when —SO ₃ H and —NR ^N11 R ^N12 are likely to contribute to the intermolecular interaction, the position where the hydroxyl group is substituted is the 1st position, and the position where the azo group is substituted is the 2nd position. It is preferable that at least one of —SO ₃ H or —NR ^N11 R ^N12 is substituted at any of the 5, 6, 7, and 8 positions, and at least one is substituted at any of the 6, 7 positions. Is more preferable.

Among these, Ar ¹⁴ is particularly preferably represented by the formula (VI) because it tends to contribute to the intermolecular interaction and the obtained anisotropic dye film tends to be black.

[In Formula (VI), g and h represent 0 or 1 each independently. Incidentally, ^d in the formula ^{(VI), R N11} and ^{R N12} are each synonymous ^d of Formula ^(II), and ^{R N11} and ^{R N12.} ]

(G and h)
g and h each independently represents 0 or 1; Preferably the sum of g and h is 1 or 2.

<Preferable combinations of Ar ¹¹ , Ar ¹² , Ar ¹³ and Ar ¹⁴ >
The combination of Ar ¹¹ , Ar ¹² , Ar ¹³ and Ar ¹⁴ is not particularly limited, but Ar ¹¹ is a phenyl group or a naphthyl group having at least one electron-withdrawing group as a substituent, and Ar ¹² and / or Ar ¹³ Have a 1,4-phenylene group which may have a substituent, a 1,4-naphthylene group which may have a substituent, and a monocyclic or bicyclic substituent. It is preferably selected from the group consisting of aromatic heterocyclic groups, and Ar ¹⁴ is preferably represented by the formula (VI). In particular, from the viewpoint of column formation (π stacking), Ar ¹² and / or Ar ¹³ may have a 1,4-naphthylene group which may have a substituent or a bicyclic substituent. An aromatic heterocyclic group is preferable, and Ar ¹³ is a 1,4-naphthylene group which may have a substituent or an aromatic heterocyclic group which may have a bicyclic substituent. preferable.
The electron withdrawing group which the phenyl group or naphthyl group of Ar ¹¹ has may be either nonionic or ionic. In the case of an ionic electron-withdrawing group, the azo dye has a property of attracting strongly between molecules due to an acid / base bond or a hydrogen bond between the molecules of the azo dye, so that the molecules can easily form an associated state.
On the other hand, in the case of a nonionic electron-withdrawing group, there is a tendency not to separate charges with water. Accordingly, when the azo dye represented by the formula (I) is used in an anisotropic dye film composition containing, for example, water as a solvent, the dye and the solvent represented by the formula (I) are compared with those in the ionic case. Interaction is small, that is, hydrophobic interaction is strong, attracting more strongly between molecules, and molecules tend to form a laminated state.
The electron withdrawing group may be either nonionic or ionic, but it is preferable that the electron withdrawing group is nonionic in that lamination is strongly caused in terms of stronger interaction between aromatic rings.

The reason why these combinations are preferable is assumed as follows. In the azo dye represented by the formula (I) having a preferable combination of Ar ¹¹ , Ar ¹² , Ar ¹³ and Ar ¹⁴ as described above, the phenyl group or naphthyl group at the terminal of the azo dye molecule (Ar ¹¹ ) is substituted. By having an electron withdrawing group as a group, it is in an electron-deficient state (electron density on the aromatic ring is attenuated). On the other hand, the naphthyl group (Ar ¹⁴ ) substituted with a hydroxyl group located at the terminal opposite to this is in an electron-excess state (electron density on the benzene ring is enhanced). Therefore when the azo dye represented by formula (I) are associated with laminated, strong inquiries electron-rich the aromatic ring of an electron-deficient aromatic ring and ^{Ar 14} in the ^{Ar 11} are between the molecules, ^{Ar 14} on the ^{Ar 11} It is considered that the columns are easily arranged so as to be stacked to form a column.
Further, the Ar ¹² and Ar ¹³ rings arranged in the center of the molecule are each composed of a 1,4-phenylene group, a 1,4-naphthylene group, and a monocyclic or bicyclic aromatic heterocyclic group. By being selected, it has the property that it is easy for π-π interaction to occur between molecules, and the molecules tend to form an associated state. In particular, Ar ¹² and / or Ar ¹³ is preferably a 1,4-naphthylene group or a bicyclic aromatic heterocyclic group, since it has high π planarity and increased association. Furthermore, since Ar ¹³ is a 1,4-naphthylene group or a bicyclic aromatic heterocyclic group, it is adjacent to the Na ¹⁴ ring of Ar ¹⁴ , so that a large π plane is formed in the molecule and the associative property is increased. It is more preferable because it increases.
Therefore, the azo dye represented by the formula (I) can form a high association state in a solution such as a lyotropic liquid crystal in a composition containing the azo dye. The azo compound of the present invention is also used in an anisotropic dye film obtained by applying a process specific to the wet film-forming method to the composition containing the azo dye, that is, a lamination process such as coating on the substrate surface. Is considered to be able to provide an anisotropic dye film which is arranged in high order and exhibits high dichroism.
Further, the azo dye represented by the formula (I) has absorption in the entire visible light wavelength region by taking the combination of Ar ¹¹ , Ar ¹² , Ar ¹³ and Ar ¹⁴ as described above, and the formula (I The anisotropic dye film using the azo dye represented by) tends to be achromatic. Therefore, the azo dye of the present invention can form an achromatic anisotropic dye film having high anisotropy.
The 1,4-phenylene group, 1,4-naphthylene group, and monocyclic or bicyclic aromatic heterocyclic group may each have a substituent or may have a substituent. The substituents are as described above.

<Specific Examples of Azo Dye Represented by Formula (I)>
Specific examples of the azo dye whose free acid form is represented by the formula (I) include, but are not limited to, the dyes described below.

<< Azo Dye with Free Acid Form Represented by Formula (III) >>

[In the formula (III), Ar ²¹ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, and Ar ²² represents an electron donating group. Represents an optionally substituted 1,4-phenylene group, an optionally substituted 1,4-naphthylene group or an optionally substituted aromatic heterocyclic group, and Ar ²³ represents Represents a group represented by formula (IV). ]

[In Formula (IV), R ^N21 and R ^N22 each independently have a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or a substituent. And e represents an integer of 0 to 3, and f represents 0 or 1. The amino group represented by —NR ^N21 R ^N22 is substituted at the α-position or β-position. ]

<Ar ²¹ >
Ar ²¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar < ²¹ > is synonymous with Ar < ¹¹ > of a formula (I), and the preferable range and the substituent which you may have are also synonymous.

<Ar ²² >
Ar ²² is a 1,4-phenylene group optionally having an electron donating group, a 1,4-naphthalene group optionally having a substituent, or an aromatic heterocyclic ring optionally having a substituent. Represents a group. Ar ²² may have a 1,4-phenylene group optionally having an electron donating group, a 1,4-naphthalene group optionally having a substituent, and an aromatic heterocyclic group optionally having a substituent Has a 1,4-phenylene group which may have an electron-donating group mentioned as Ar ¹² in the formula (I), a 1,4-naphthalene group which may have a substituent, and a substituent. It is synonymous with the aromatic heterocyclic group that may be present, and the preferred range and the substituent that may be present are also synonymous.

<Ar ²³ >
Ar ²³ is represented by the formula (IV).
< ^RN21 and ^RN22 >
R ^N21 and R ^N22 each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or an acyl group that may have a substituent. To express. R ^N21 and R ^N22 have the same ^meanings as R ^N11 and R ^N12 in formula (I), respectively, and the substituents and preferred ranges that may be included are also the same. A preferred combination of R ^N21 and R ^N22 is also synonymous with R ^N11 and R ^{N12 in} formula (I).

<E and f>
e represents an integer of 0 to 3. e is synonymous with b of Formula (II), and its preferable range is also synonymous.
f represents 0 or 1; f has the same meaning as d in formula (II), and the preferred range is also the same.
In formula (IV), the amino group represented by —NR ^N21 R ^N22 is substituted at the α-position or β-position. Substitution at this position tends to contribute to the intermolecular interaction.
Although not particularly limited, when —SO ₃ H and —NR ^N21 R ^N22 are likely to contribute to the intermolecular interaction, the position where the hydroxyl group is substituted is the 1st position, and the position where the azo group is substituted is the 2nd position. It is preferable that at least one of —SO ₃ H or —NR ^N21 R ^N22 is substituted at any of the 5, 6, 7, and 8 positions, and at least one is substituted at any of the 6, 7 positions. Is more preferable.

Among these, Ar ²³ is particularly preferably represented by the formula (VII) because it tends to contribute to the intermolecular interaction and the obtained anisotropic dye film tends to be black.

[In Formula (VII), i and j each independently represents 0 or 1. Incidentally, ^f in formula ^{(VII), R N21} and ^{R N22} are each synonymous ^f of Formula ^(IV), and ^{R N21} and ^{R N22.} ]

(I and j)
i and j each independently represents 0 or 1. Preferably, the sum of i and j is 1 or 2.

<Preferable combination of Ar ²¹ , Ar ²² and Ar ²³ >
A preferred combination of Ar ²¹ , Ar ²² and Ar ²³ is not particularly limited. The combination of Ar ²¹ , Ar ²² and Ar ²³ is a phenyl group which Ar ²¹ may have a substituent or a naphthyl group which may have a substituent, and Ar ²² has an electron donating group. An optionally substituted 1,4-phenylene group, an optionally substituted 1,4-naphthylene group, and a monocyclic or bicyclic substituent optionally substituted aromatic heterocyclic group It is preferable that Ar ²³ is represented by the formula (VII).
In particular, from the viewpoint of column formation (π stacking), Ar ²² is a 1,4-naphthylene group which may have a substituent or an aromatic heterocyclic group which may have a bicyclic substituent. preferable. Furthermore, Ar ²¹ is preferably a phenyl group or a naphthyl group having at least one electron withdrawing group as a substituent.
The electron withdrawing group of the phenyl group or naphthyl group of Ar ²¹ may be either nonionic or ionic. In the case of an ionic electron-withdrawing group, the azo dye has a property of attracting strongly between molecules due to an acid / base bond or a hydrogen bond between the molecules of the azo dye, so that the molecules can easily form an associated state.
On the other hand, in the case of a nonionic electron-withdrawing group, there is a tendency not to separate charges with water. Accordingly, when the azo dye represented by the formula (III) is used in an anisotropic dye film composition containing, for example, water as a solvent, the dye and the solvent of the formula (III) are compared with those in the ionic case. Interaction is small, that is, hydrophobic interaction is strong, attracting more strongly between molecules, and molecules tend to form a laminated state.
The electron withdrawing group may be either nonionic or ionic, but it is preferable that the electron withdrawing group is nonionic in that lamination is strongly caused in terms of stronger interaction between aromatic rings.
The ring of Ar ²¹ of the azo dye represented by the formula (III) having a combination of Ar ²¹ , Ar ²² and Ar ²³ as described above has a hydroxyl group and an amino group arranged at Ar ¹⁴ of the formula (I). It is expected that molecules with each other are strongly attracted with the substituted electron-rich naphthyl group to form an associated state. Further, Ar ²² is a 1,4-phenylene group or a 1,4-naphthylene group, which may have an electron donating group, whereby Ar ¹² and / or Alternatively, the Ar ¹³ ring has a property that it is easy to take a π-π interaction between molecules and to easily form an association state between molecules. Moreover, since Ar ²³ is represented by the formula (VII), interaction with Ar ¹¹ of the formula (I) is also expected, and the above-described viscosity reduction effect can be obtained.
The phenyl group, naphthyl group, 1,4-phenylene group, 1,4-naphthylene group, and monocyclic or bicyclic aromatic heterocyclic ring each may have a substituent. The optional substituents are as described above.

<Specific Example of Azo Dye with Free Acid Form Represented by Formula (III)>
Specific examples of the azo dye in which the form of the free acid is represented by the formula (III) include, but are not limited to, the dyes described below.

<< A combination of an azo dye whose free acid form is represented by formula (I) and an azo dye whose free acid form is represented by formula (III) >>
In the present invention, the combination of the azo dyes whose free acid forms are represented by the formulas (I) and (III) is not particularly limited.
At least one structure selected from Ar ²¹ to Ar ^{23 in} the formula (III) is obtained by removing a substituent that may be present from at least one structure selected from Ar ¹¹ to Ar ^{14 in} the formula (I). The structure is preferably the same as the structure excluding the substituent which may be included in the structure. For example, when Ar ¹¹ is a naphthalene ring having a cyano group, the structure excluding the substituent that may be present from the structure of Ar ^{11 in} formula (I) is a naphthalene ring. Further, when Ar ²² is a naphthalene ring having a sulfo group, the structure excluding the substituent which may be present from the structure of Ar ^{22 in} formula (III) is a naphthalene ring. In this case, the structure excluding the substituent which may be present from at least one structure selected from Ar ¹¹ to Ar ¹⁴ in the formula (I) is selected from Ar ²¹ to Ar ^{23 in} the formula (III). It is the same as the structure excluding the substituent that may be present from at least one structure.
Further, the structure excluding the substituent which may be present from at least two structures selected from Ar ¹¹ to Ar ^{14 is present} from at least two structures selected from Ar ²¹ to Ar ^{23 in} the formula (III). It is preferable that the structure is the same as that except for the substituents that may be present, and the structure excluding the substituents that may be present from at least three structures selected from Ar ¹¹ to Ar ¹⁴ is represented by the formula ( It is preferable that each of the structures of Ar ²¹ to Ar ^{23 in} III) is the same as the structure excluding the substituent which may be included. Note that the structures selected from Ar ¹¹ to Ar ¹⁴ except for the substituents that may be present may be the same or different. Similarly, the structures selected from Ar ²¹ to Ar ²³ except for the substituents that may be present may be the same or different.
Further, the structure excluding the substituent which may be present from at least one structure selected from Ar ¹¹ to Ar ¹³ of formula (I) is derived from the structure of Ar ²¹ and / or Ar ²² of formula (III). The structure is preferably the same as the structure excluding the substituent that may have. Furthermore, the structure excluding the substituent which may be present from at least two structures selected from Ar ¹¹ to Ar ¹³ of formula (I) is derived from the structure of Ar ²¹ and / or Ar ²² of formula (III). It is preferably the same as the structure excluding the substituent which may be present, and the structure excluding the substituent which may be present from the structure of Ar ¹¹ to Ar ^{13 in} the formula (I) is represented by the formula (III It is preferable that it is the same as the structure except the substituent which you may have from the structure of Ar ²¹ and / or Ar ²² .

In the combination of the above structures, the group of substituents that may be present is preferably the same, and the substituents that may be possessed are more preferably the same. Moreover, it is preferable that the substitution position of the group of the substituent which may have and / or the substituent which may have is the same.
Further, the bonding position with the azo bond is preferably the same.
The group of substituents refers to the properties of the substituents such as the hydrophilic groups, electron donating groups, electron withdrawing groups, ionic, nonionic, hydrogen bonding functional groups, and functional groups having strong dipoles. Represents a group classified by.
As described above, the structure excluding the substituent that may be present, the group of substituents that may be present, the substituent that may be present, the group of substituents that may be present, and / or Since the substitution positions of the substituents that may be present are the same, intermolecular interactions such as π-π stacking and hydrogen bonding between substituents of the compound of formula (I) and the compound of formula (III) It tends to occur, and there is a tendency that an effect of changing the interaction between columns tends to be obtained without greatly changing the structure of the column-like aggregate formed by the formula (I) or the structure of the column aggregate.

On the other hand, at least one combination selected from the group consisting of a combination of Ar ¹¹ and Ar ^21, a combination of Ar ¹² and Ar ^{22, and} a combination of Ar ¹³ and Ar ²² excludes the substituents that may be present. The structures are preferably the same. As a result, intermolecular interactions such as π-π stacking and hydrogen bonding between substituents of the compound of formula (I) and the compound of formula (III) are likely to occur, and the columnar aggregate formed by formula (I) In addition, there is an effect of changing the interaction between columns without greatly changing the structure of the column aggregate. Further, in the above combination, the group of substituents that may be present is preferably the same, and the substituents that may be possessed are more preferably the same.
The combination of the azo dyes represented by the formulas (I) and (III) in the form of the free acid is as described above, so that the intermolecular interaction of the azo dyes represented by the formula (I) and the formula (III) It becomes easy to do. That is, the interaction between the columns of the azo dye represented by the formula (I) can be changed, the ordering can be lowered, and the viscosity of the anisotropic dye film composition tends to be lowered.

Specific combinations are not particularly limited, but the specific examples and preferred groups given for Ar ¹¹ to Ar ¹⁴ and the specific examples and preferred groups given for Ar ²¹ to Ar ²³ can be appropriately combined.
Among these, it is particularly preferable to combine the following groups of Ar ¹¹ to Ar ¹⁴ and Ar ²¹ to Ar ²³ , respectively. With these combinations, intermolecular interactions such as π-π stacking and hydrogen bonding between substituents of the compound of formula (I) and the compound of formula (III) are likely to occur, and formula (I) is formed. There is a tendency to obtain an effect of changing the interaction between columns without greatly changing the structure of the column-like aggregates or the column aggregates.
Ar ¹¹ has at least one electron-withdrawing group as a substituent, a phenyl group or a naphthyl group,
Ar ¹² and / or Ar ¹³ may have a substituent, a 1,4-phenylene group, a substituent, a 1,4-naphthylene group and a monocyclic or bicyclic substituent Selected from the group consisting of aromatic heterocyclic groups optionally having
Ar ¹⁴ is represented by the formula (VI), Ar ²¹ may have a phenyl group which may have a substituent or a naphthyl group which may have a substituent,
Ar ²² has a 1,4-phenylene group which may have an electron donating group, a 1,4-naphthylene group which may have a substituent, and a monocyclic or bicyclic substituent. Selected from the group consisting of good aromatic heterocyclic groups,
Ar ²³ is represented by the formula (VII).

<Mass fraction of azo dye whose free acid form is represented by formula (I) and azo dye whose free acid form is represented by formula (III)>
The mass ratio of the azo dye in which the form of the free acid in the composition for anisotropic dye film of the present invention is represented by formula (I) and the azo dye in which the form of the free acid is represented by formula (III) is: There is no particular limitation. The mass of the azo dye represented by the formula (III) with respect to the azo dye represented by the formula (I) is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, It is particularly preferably 0.01% by mass or more, and most preferably 0.1% by mass or more. Further, it is preferably 25% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, still more preferably 3.25% by mass or less, and 3% by mass. % Or less, more preferably 2.75% by mass or less, particularly preferably 2.5% by mass or less, and most preferably 2.0% by mass or less. While the mass ratio of the azo dye whose free acid form is represented by formula (I) and the azo dye whose free acid form is represented by formula (III) is in an appropriate range, the process suitability is improved. However, the associative property of the dye of formula (I) itself is not inhibited, and an anisotropic dye film in which the dye is well oriented tends to be obtained.

<< Other dyes >>
As long as the composition for anisotropic dye film of the present invention is within the range not impairing the effects of the present invention, the azo dye whose free acid form is represented by formula (I) and the free acid form is represented by formula (III) It may have a dye other than the azo dye represented by For example, a dye exemplified as a dye for blending in Japanese Patent Application Laid-Open No. 2007-126628, an anthraquinone compound described in Japanese Patent Application Laid-Open No. 2007-199333, and the form of the free acid shown below is represented by Formula (V). Azo dyes to be used.

<< Azo Dye with Free Acid Form Represented by Formula (V) >>

[In Formula (V), Ar ³¹ , Ar ³² and Ar ³³ are each independently an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. R ³⁴ represents a hydrogen atom, a hydroxyl group, an amino group or an acylamino group. ]

<Ar ³¹ >
Ar ³¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar ³¹ is synonymous with the aromatic hydrocarbon group which may have a substituent or the aromatic heterocyclic group which may have a substituent, which is mentioned as Ar ¹¹ in formula (I), and is preferable. Ranges and substituents that may be present are also synonymous.

<Ar ³² and Ar ³³ >
Ar ³² and Ar ³³ each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar ³² and Ar ³³ have the same meaning as the aromatic hydrocarbon group which may have a substituent or the aromatic heterocyclic group which may have a substituent, which is exemplified for Ar ¹² in the formula (I). The preferred range and the substituents that may be present are also synonymous.

<Preferable combination of Ar ³¹ , Ar ³² and Ar ³³ >
A preferred combination of Ar ³¹ , Ar ³² and Ar ³³ is not particularly limited. Ar ³¹ is an optionally substituted phenyl group or an optionally substituted naphthyl group, and Ar ³² and Ar ³³ are optionally substituted 1,4-phenylene A 1,4-naphthylene group which may have a group or a substituent is preferable.
Ar ³¹ is preferably a phenyl group or a naphthyl group having at least one electron withdrawing group as a substituent. Further, it is preferable to satisfy at least one of the following 1) to 3).
1) The structure excluding the substituent which may be present from the structure of Ar ³¹ is the same as the structure excluding the substituent which may be present from the structure of Ar ^{11 in} formula (I).
2) The structure excluding the substituent which may be present from the structure of Ar ³² is the same as the structure excluding the substituent which may be present from the structure of Ar ^{12 in} formula (I).
3) The structure excluding the substituent which may be present from the structure of Ar ³³ is the same as the structure excluding the substituent which may be possessed from the structure of Ar ^{13 in} formula (I).
In the combination of structures shown in the above 1) to 3), the group of substituents that may be present is preferably the same, and the substituents that may be possessed are more preferably the same. Moreover, it is preferable that the substitution position of the group of the substituent which may have and / or the substituent which may have is the same.
Further, the bonding position with the azo bond is preferably the same.
The electron withdrawing group which the phenyl group or naphthyl group of Ar ³¹ has may be either nonionic or ionic. In the case of an ionic electron-withdrawing group, the azo dye has a property of attracting strongly between molecules due to an acid / base bond or a hydrogen bond between the molecules of the azo dye, so that the molecules can easily form an associated state.
On the other hand, in the case of a nonionic electron-withdrawing group, there is a tendency not to separate charges with water. Accordingly, when the azo dye represented by the formula (V) is used in an anisotropic dye film composition containing, for example, water as a solvent, the dye and the solvent represented by the formula (V) are compared with those in the ionic case. Interaction is small, that is, hydrophobic interaction is strong, attracting more strongly between molecules, and molecules tend to form a laminated state.
The electron withdrawing group may be either nonionic or ionic, but it is preferable that the electron withdrawing group is nonionic in that lamination is strongly caused in terms of stronger interaction between aromatic rings.
The ring of Ar ³¹ of the azo dye represented by the formula (V) having a preferable combination of Ar ³¹ , Ar ³² and Ar ³³ as described above has a hydroxyl group and an amino group arranged at Ar ¹⁴ of the formula (I). It is expected that molecules with each other are strongly attracted with the substituted electron-rich naphthyl group to form an associated state. Further, Ar ³² and Ar ³³ are each a 1,4-phenylene group which may have a substituent or a 1,4-naphthylene group which may have a substituent, whereby a molecule of the formula (I) The ring of Ar ¹² and / or Ar ¹³ arranged in the center also tends to have a property that it is easy to take a π-π interaction between molecules and to form an associated state between molecules. Furthermore, when satisfying at least one of the above 1) to 3), the intermolecular interaction of the azo dyes represented by formulas (I) and (V) is large, and the azo dye represented by formula (V) is: There is a tendency that the azo dye represented by the formula (I) is not taken into the molecular aggregate formed, or the order of the aggregate is not greatly disturbed even if the aggregate is bonded with a hydrogen bond. Therefore, it is presumed that an effect of lowering the order formed only by the azo dye represented by the formula (I) and lowering the viscosity can be obtained.
The phenyl group, naphthyl group, 1,4-phenylene group and 1,4-naphthylene group may each have a substituent, and the substituents which may be present are as described above.

< ^R34 >
R ³⁴ represents a hydrogen atom, a hydroxyl group, an amino group, or acylamino. The amino group and acylamino group may each have a substituent.
The amino group and acylamino group of R ³⁴ are respectively synonymous with the amino group and acylamino group mentioned as the substituents that the aromatic hydrocarbon group of Ar ¹¹ of formula (I) may have, and have The substituents and preferred ranges that may be used are also synonymous.

<Specific Example of Azo Dye with Free Acid Form Represented by Formula (V)>
Specific examples of the azo dye whose free acid form is represented by the formula (V) include, but are not limited to, the dyes described below.

When the composition for anisotropic dye film of the present invention contains an azo dye whose free acid form is represented by the formula (V), the mass ratio is particularly limited as long as the effect of the present invention is not impaired. Not. The ratio of the mass of the azo dye represented by formula (I) and the sum of the masses of the azo dyes represented by formula (III) and formula (V) is preferably 0.0001% by mass or more, It is more preferably 0.001% by mass or more, particularly preferably 0.01% by mass or more, and most preferably 0.1% by mass or more. Further, it is preferably 50% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less, and most preferably 6.0% by mass or less. The ratio of the sum of the mass of the azo dye whose free acid form is represented by formula (I) and the mass of the azo dye whose free acid form is represented by formula (III) and formula (V) is within an appropriate range. As a result, there is a tendency that an anisotropic dye film in which the dye is well oriented can be obtained without improving the associability of the dye itself of (I) while improving process suitability.

<< Synthesis of azo dye whose free acid form is represented by formula (I), formula (III) and formula (V) >>
The azo dye whose free acid form is represented by formula (I), the azo dye whose free acid form is represented by formula (III), and the azo dye whose free acid form is represented by formula (V) are: It can be produced according to a method known per se. For example, it can be produced by the method described in Japanese Patent Application Laid-Open No. 2008-81700 and Japanese Patent Application Laid-Open No. 2007-126628.
For example, an azo compound represented by the following formula (I-1) can be produced according to the following steps (A) to (C).
(A) 4-aminobenzonitrile and 8-amino-2-naphthalenesulfonic acid (1,7-Cleves acid) are used in a conventional manner [for example, Yutaka Hosoda, “New dye chemistry” (December 21, 1973, Monoazo compound is produced through a diazotization and coupling step according to (published by Gihodo), page 396, page 409].
(B) Similarly, the obtained monoazo compound is diazotized by a conventional method and subjected to a coupling reaction with 8-amino-2-naphthalenesulfonic acid (1,7-Cleves acid) to produce a disazo compound.
(C) Similarly, the obtained disazo compound is diazotized by a conventional method, and subjected to a coupling reaction with 7-amino-1-naphthol-3,6-disulfonic acid (RR acid) to obtain the target compound represented by the following formula (I- The azo compound represented by 1) is obtained as a sodium salt.
If necessary, in each step, dissolve or suspend in a good solvent and add a salt such as sodium chloride for salting out. Dissolve or suspend in a good solvent and add a poor solvent for crystallization. It may be purified by washing, separation by column chromatography, or the like.

The azo dyes in which the free acid form of the present invention is represented by the formula (I), the formula (III) and the formula (V) may be used in the free acid form, and a part of the acid group is a salt form. You may have taken. Further, a salt-type dye and a free acid-type dye may be mixed. Moreover, when it is obtained in a salt form at the time of production, it may be used as it is or may be converted into a desired salt form. As the salt type exchange method, a known method can be arbitrarily used, and examples thereof include the following methods 4) to 7).
4) A strong acid such as hydrochloric acid is added to the aqueous solution of the dye obtained in the salt form, the dye is acidified in the free acid form, and then the dye is added with an alkaline solution having a desired counter ion (for example, an aqueous lithium hydroxide solution). A method of neutralizing acidic groups and salt exchange.
5) A method in which a large excess of a neutral salt (eg, lithium chloride) having a desired counter ion is added to an aqueous solution of a dye obtained in a salt form, and salt exchange is performed in the form of a salting-out cake.
6) An aqueous solution of a dye obtained in a salt form is treated with a strongly acidic cation exchange resin, and the dye is acidified in a free acid form, and then an alkali solution having a desired counter ion (for example, an aqueous lithium hydroxide solution) ) To neutralize the acidic group of the dye and perform salt exchange.
7) A method of performing salt exchange by allowing an aqueous solution of a dye obtained in a salt form to act on a strongly acidic cation exchange resin that has been previously treated with an alkaline solution having a desired counter ion (for example, an aqueous lithium hydroxide solution).

Whether the azo dye represented by the formula (I), the formula (III) and the formula (V) of the present invention has a free acid form or a salt form in the acidic group depends on the pKa of the dye and the dye aqueous solution. Depending on the pH of
Examples of the salt type include salts of alkali metals such as Na, Li and K, ammonium salts which may be substituted with alkyl groups or hydroxyalkyl groups, and organic amine salts.
Examples of the organic amine include a lower alkyl amine having 1 to 6 carbon atoms, a hydroxy-substituted lower alkyl amine having 1 to 6 carbon atoms, a carboxy-substituted lower alkyl amine having 1 to 6 carbon atoms, and the like. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed.

<< Method for Producing Composition for Anisotropic Dye Film >>
The manufacturing method of the composition for anisotropic dye films of this invention is not specifically limited. For example, an azo dye whose free acid form is represented by the formula (I), an azo dye whose free acid form is represented by the formula (III), other additives, a solvent, etc., are mixed at 0-100 ° C. Stir and shake to dissolve the dye. In the case of poor solubility, a homogenizer, a bead mill disperser or the like may be used.
As a manufacturing method of the composition for anisotropic dye films of this invention, you may have a filtration process in order to remove the foreign material etc. in a composition. Since the composition for anisotropic dye films of the present invention tends to have a low viscosity, the time for the filtration step tends to be shortened. As a method for removing foreign substances and the like in the composition other than filtration, there is a method using centrifugation described in Japanese Patent Application Laid-Open No. 2012-53388. In this case, too, if the viscosity is low, the time required for the centrifugation is reduced. It tends to be shortened.

<< Method for Forming Anisotropic Dye Film >>
The anisotropic dye film of the present invention is preferably produced by a wet film forming method.
The wet film forming method referred to in the present invention is a method in which a composition for an anisotropic dye film is applied on a substrate by any method, and a dye or the like is oriented and laminated on the substrate through a process of drying a solvent. In the wet film forming method, when the anisotropic dye film composition is applied on the substrate, the dye itself self-associates in the anisotropic dye film composition or in the process of drying the solvent, so that the minute amount is obtained. Orientation by area occurs. By applying an external field to this state, an anisotropic dye film having desired performance can be obtained by orienting in a certain direction in a macro region. This is different from the method based on the principle that a so-called polyvinyl alcohol (PVA) film or the like is dyed with a solution containing a dye and stretched, and the dye is oriented only by a stretching process. Here, the external field includes the influence of the alignment treatment layer previously applied on the substrate, shear force, magnetic field, and the like, and these may be used alone or in combination.

The process of applying the anisotropic dye film composition on the substrate to form a film, the process of aligning by applying an external field, and the process of drying the solvent may be performed sequentially or simultaneously.
Examples of the method for applying the anisotropic dye film composition on the substrate in the wet film forming method include a coating method, a dip coating method, an LB film forming method, a known printing method, and the like. There is also a method of transferring the anisotropic dye film thus obtained to another substrate. Among these, the present invention preferably uses a coating method.
The orientation direction of the anisotropic dye film is usually coincident with the application direction, but may be different from the application direction. In the present embodiment, the orientation direction of the anisotropic dye film is, for example, a polarizing transmission axis or absorption axis in the case of a polarizing film, and a fast axis or a slow axis in the case of a retardation film. That is.

The anisotropic dye film in this embodiment functions as a polarizing film or retardation film that obtains linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption, as well as a film forming process and a substrate. And by selecting a composition containing an organic compound (pigment or transparent material), it can be functionalized as various anisotropic dye films such as refractive anisotropy and conduction anisotropy.

The method for applying the anisotropic dye film composition to obtain the anisotropic dye film is not particularly limited. For example, Yuji Harasaki "Coating Engineering" (Asakura Shoten Co., Ltd., issued March 20, 1971) ) The method described on pages 253 to 277, supervised by Kunihiro Ichimura, “Creation and Application of Molecular Coordination Materials” (CMC Publishing Co., Ltd., published on March 3, 1998), the method described on pages 118 to 149, steps Slot die coating method, spin coating method, spray coating method, bar coating method, roll coating method, blade coating method, curtain coating method, fountain method, dipping method, etc. on a substrate having a structure (which may be subjected to orientation treatment in advance) The method of apply | coating is mentioned. Among these, the slot die coating method is preferable because an anisotropic dye film with high uniformity can be obtained.
A die coater used in the slot die coating method generally includes an applicator for discharging a coating liquid, a so-called slit die. The slit die is disclosed in, for example, Japanese Patent Application Laid-Open No. 2-164480, Japanese Patent Application Laid-Open No. 6-154687, Japanese Patent Application Laid-Open No. 9-131559, “Basics and Applications of Dispersion / Coating / Drying” (2014). Technosystem Co., Ltd., ISBN 9844924728707 C 305)), "Wet coating technology for displays and optical components" (2007, Information Technology, ISBN 9784690777752), "Precision coating and drying technology in electronics field" (2007, Technical Information Church , ISBN 97884861041389). These known slit dies can be applied even with a flexible member such as a film or a tape or a hard member such as a glass substrate.
Since the composition for anisotropic dye film of the present invention can reduce the viscosity of the composition, it is easy to supply liquid to a coating apparatus, and is practical even when coating by the slot die coating method. The coating can be performed at a withstanding coating speed, and a highly productive anisotropic dye film manufacturing process can be constructed.

Examples of the substrate used for forming the anisotropic dye film of the present invention include glass, triacetate, acrylic, polyester, polyimide, triacetylcellulose, or urethane film. In addition, in order to control the alignment direction of the dye, the substrate surface is aligned by a known method described in “Liquid Crystal Handbook” Maruzen Co., Ltd., issued October 30, 2000, pages 226 to 239, etc. A treatment layer (alignment film) may be provided. In the case where an orientation treatment layer is provided, it is considered that the dye is oriented by the influence of the orientation treatment of the orientation treatment layer and the shearing force applied to the anisotropic dye film composition during coating.

The method for supplying the composition for anisotropic dye film and the supply interval when applying the composition for anisotropic dye film are not particularly limited. When the anisotropic dye film is thin, it may continuously occur because the supply operation of the coating liquid becomes complicated and the coating film thickness may vary when the coating liquid starts and stops. It is desirable to apply while supplying the composition for anisotropic dye film.

The speed at which the composition for anisotropic dye film is applied is usually 1 mm / second or more, preferably 5 mm / second or more. Moreover, it is 1000 mm / sec or less normally, Preferably it is 200 mm / sec or less. When the coating speed is in an appropriate range, anisotropy of the anisotropic dye film is obtained, and the coating tends to be performed uniformly.
In addition, as application | coating temperature of the composition for anisotropic dye films, it is 0 degreeC or more and 80 degrees C or less normally, Preferably it is 40 degrees C or less. Moreover, the humidity at the time of application | coating of the composition for anisotropic dye films becomes like this. Preferably it is 10% RH or more, More preferably, it is 30% RH or more, Preferably it is 80% RH or less.

The film thickness of the anisotropic dye film is preferably 10 nm or more, more preferably 50 nm or more as a dry film thickness. On the other hand, it is preferably 30 μm or less, more preferably 1 μm or less. When the film thickness of the anisotropic dye film is within an appropriate range, uniform orientation and uniform film thickness of the dye tend to be obtained in the film.

The anisotropic dye film may be insolubilized. The insolubilization treatment means a treatment step in which the solubility of the compound in the anisotropic dye film is reduced, thereby controlling the elution of the compound from the anisotropic dye film and increasing the stability of the film.
Specifically, for example, an ion with a lower valence is replaced with an ion with a higher valence (for example, a monovalent ion is replaced with a polyvalent ion), or an organic molecule or polymer having a plurality of ionic groups. A replacement process is listed. As such a treatment method, for example, known methods such as treatment steps described in Yutaka Hosoda, “Theoretical Manufacturing, Dyeing Chemistry” (Gihodo, 1957), pages 435 to 437 can be used.
Among these, the anisotropic dye film obtained is treated by the method described in Japanese Patent Application Laid-Open No. 2007-241267, etc. to form an anisotropic dye film that is insoluble in water. It is preferable from the viewpoint of ease and durability.

[Anisotropic dye film]
The anisotropic dye film of the present invention includes an azo dye whose free acid form is represented by the following formula (I) and an azo dye whose free acid form is represented by the following formula (III).

The groups of the above formulas (I) to (IV) have the same meanings as those mentioned in the above-mentioned composition for anisotropic dye film, and the preferred range, the substituents that may be included, and the like are also the same.

When the anisotropic dye film of the present invention is used as a polarizing element for a liquid crystal display, the orientation characteristics of the anisotropic dye film can be expressed using a dichroic ratio. A dichroic ratio of 8 or more functions as a polarizing element, but is preferably 15 or more, more preferably 20 or more, further preferably 25 or more, and particularly preferably 30 or more. Moreover, the higher the dichroic ratio is, the better, and there is no upper limit. When the dichroic ratio is a specific value or more, it is useful as an optical element described later, particularly as a polarizing element.

The dichroic ratio (D) referred to in the present invention is represented by the following formula when anisotropic dyes are uniformly oriented.
D = Az / Ay
Here, Az is the absorbance observed when the polarization direction of the light incident on the anisotropic dye film is parallel to the orientation direction of the anisotropic dye, and Ay is observed when the polarization direction is perpendicular. Absorbance. Each absorbance is not particularly limited as long as the same wavelength is used, and any wavelength may be selected depending on the purpose. However, when the degree of orientation of the anisotropic dye film is expressed, the maximum absorption of the anisotropic dye film is used. It is preferable to use a value in wavelength.

Further, the transmittance in the visible light wavelength region of the anisotropic dye film of the present invention is preferably 25% or more. 35% or more is more preferable, and 40% or more is particularly preferable. Moreover, the transmittance | permeability should just be an upper limit according to a use.
For example, when increasing the degree of polarization, it is preferably 50% or less. When the transmittance is in a specific range, it is useful as the following optical element, and particularly useful as an optical element for a liquid crystal display used for color display.

[Optical element]
In the present invention, the optical element is a polarizing element that obtains linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption, a retardation element, an element having functions such as refractive anisotropy and conduction anisotropy. Represents. These functions can be appropriately adjusted according to the anisotropic dye film forming process and the selection of a composition containing a substrate or an organic compound (a dye or a transparent material). In the present invention, it is most preferably used as a polarizing element.

[Polarizing element]
In the present invention, the polarizing element may have any other film (layer) as long as it has an anisotropic dye film. For example, it can be produced by providing an alignment film on a substrate and forming an anisotropic dye film on the surface of the alignment film.
Further, the polarizing element is not limited to an anisotropic dye film, but an overcoat layer having functions such as improving polarization performance and improving mechanical strength; adhesive layer or antireflection layer; alignment film; retardation film A layer having optical functions such as a function as a brightness enhancement film, a function as a reflection film, a function as a transflective film, a function as a diffusion film, etc. A layer having various functions may be laminated by coating, bonding, or the like, and used as a laminate.
These layers can be provided as appropriate in accordance with the manufacturing process, characteristics, and functions, and the position and order of the layers are not particularly limited. For example, the positions where the above layers are formed may be formed on the anisotropic dye film, or may be formed on the opposite surface of the substrate provided with the anisotropic dye film. On the other hand, the order of forming the above layers may be before or after forming the anisotropic dye film.

These layers having an optical function can be formed by the following method.
The layer having a function as a retardation film can be formed by bonding a retardation film obtained by the following method to another layer constituting the polarizing element.
The retardation film is subjected to stretching treatment described in, for example, JP-A-2-59703, JP-A-4-230704, or the like, or described in JP-A-7-230007. It can be formed by processing.

The layer having a function as a brightness enhancement film can be formed by bonding the brightness enhancement film obtained by the following method to another layer constituting the polarizing element.
The brightness enhancement film is formed by forming micropores by a method as described in, for example, Japanese Patent Application Laid-Open No. 2002-169025 and Japanese Patent Application Laid-Open No. 2003-29030, or the central wavelength of selective reflection is different. It can be formed by overlapping two or more cholesteric liquid crystal layers.

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

The layer having a function as a retardation film or an optical compensation film is obtained by applying and aligning a liquid crystal compound such as a discotic liquid crystal compound or a nematic liquid crystal compound on another layer constituting the polarizing element. Can be formed.

When the anisotropic dye film in the present embodiment is used as an anisotropic dye film for various display elements such as LCDs and OLEDs, it is directly anisotropic on the surface of the electrode substrate or the like constituting these display elements. A dye film can be formed, or a substrate on which an anisotropic dye film is formed can be used as a constituent member of these display elements.
The optical element of the present invention can be suitably used for applications such as a flexible display because a polarizing element can be obtained by forming an anisotropic dye film on a substrate by coating or the like.

EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following description, “part” means “part by weight”.

[Synthesis examples of azo dyes]
The dye synthesized in the present invention was synthesized according to the following synthesis example, and purified and used as necessary.
<Synthesis Example 1>
8-amino-2-naphthalene dissolved in 500 parts by weight of water by adding 7.25 parts by weight of sodium nitrite to 11.8 parts by weight of 4-aminobenzonitrile and 250 parts by weight of water under acidic conditions of hydrochloric acid After coupling with 22.3 parts by weight of sulfonic acid (1,7-claveic acid), neutralization and salting out were performed, and the precipitated solid was separated by filtration to obtain a wet cake of a monoazo compound.
The wet cake of this monoazo compound was dissolved in 640 parts by weight of N-methylpyrrolidone and 400 parts by weight of water, diazotized by adding 8.97 parts by weight of sodium nitrite under hydrochloric acid conditions, and dissolved in 200 parts by weight of water. After coupling with 21.2 parts by weight of 8-amino-2-naphthalenesulfonic acid (1,7-clebic acid) at pH = 3 to 4, salting out was performed to take out the precipitate. It is dissolved in water, neutralized with sodium hydroxide, isopropyl alcohol is added, the precipitated solid is filtered and separated, the resulting wet cake is dried, and sodium azo dye represented by the following formula (V-1) 47.6 parts by weight of salt were obtained.

25.6 parts by weight of a sodium salt of an azo dye represented by the following formula (V-1) is dissolved in 600 parts by weight of N-methylpyrrolidone and 800 parts by weight of water, and 3.04 sodium nitrite under acidic conditions of hydrochloric acid. 7-amino-1-naphthol-3,6-disulfonic acid (RR acid) (purity: 96.7%) dissolved in 600 parts by weight of water and diazotized by adding parts by weight and pH = 9 Coupling was performed at ~ 10. After the reaction, the precipitated solid was separated by filtration to obtain a trisazo dye sodium salt represented by the following formula (I-1).
An aqueous solution of a sodium salt of a trisazo dye represented by the formula (I-1) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, neutralized with an aqueous lithium hydroxide solution, concentrated and dried. As a result, a lithium salt of a trisazo dye represented by the formula (I-1) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 628 nm.
Further, an aqueous solution of a sodium salt of a trisazo dye represented by the formula (I-1) is passed through a cation exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, and then the aqueous solution of the free acid is used in a weight ratio. The 80% fraction is divided into a 20% fraction, the 80% fraction is neutralized with an aqueous lithium hydroxide solution, the remaining 20% fraction free acid aqueous solution is mixed, and then concentrated to dryness. As a result, an 80 mol% lithium neutralized salt of the trisazo dye represented by the formula (I-1) was obtained.

<Synthesis Example 2>
8-amino-2-naphthalenesulfone dissolved in 240 parts by weight of 4-aminobenzamide and diazotized by adding 3.00 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid to 200 parts by weight of water After coupling with 8.93 parts by weight of acid (1,7-clebic acid) at pH = 2 to 3, neutralization and salting out were performed, and the precipitated solid was separated by filtration to obtain a wet cake of a monoazo compound. .
The wet cake of this monoazo compound was dissolved in 220 parts by weight of N-methylpyrrolidone and 110 parts by weight of water, diazotized by adding 3.00 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid, and dissolved in 200 parts by weight of water. After coupling with 8.93 parts by weight of 8-amino-2-naphthalenesulfonic acid (1,7-claveic acid) at pH = 2 to 3, the precipitate was taken out by salting out. It is dissolved in water, neutralized with sodium hydroxide, isopropyl alcohol is added, the precipitated solid is separated by filtration, and the resulting wet cake is dried to obtain an azo dye represented by the following formula (V-2). 31.1 parts by weight of sodium salt were obtained.
31.3 parts by weight of a sodium salt of an azo dye represented by the following formula (V-2) is dissolved in 200 parts by weight of N-methylpyrrolidone and 260 parts by weight of water. 19.5 parts by weight of 7-amino-1-naphthol-3,6-disulfonic acid (RR acid) (purity: 65.5%) dissolved in 400 parts by weight of water and diazotized by adding parts by weight and pH = 9 Coupling was performed at ~ 10. After the reaction, the precipitated solid was separated by filtration to obtain a trisazo dye sodium salt represented by the following formula (I-2).
An aqueous solution of a sodium salt of a trisazo dye represented by the following formula (I-2) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, and then neutralized and concentrated with an aqueous lithium hydroxide solution. By drying, a lithium salt of a trisazo dye represented by the following formula (I-2) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 627 nm.
Further, an aqueous solution of a sodium salt of a trisazo dye represented by the formula (I-2) is passed through a cation exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, and then the aqueous solution of the free acid is used in a weight ratio. The 80% fraction and 20% fraction were separated, neutralized with an aqueous lithium hydroxide solution, mixed with the remaining 20% free acid aqueous solution, and then concentrated to dryness. As a result, an 80 mol% lithium neutralized salt of a trisazo dye represented by the following formula (I-2) was obtained.

<Synthesis Example 3>
8-amino-2-naphthalenesulfone dissolved in 446 parts by weight of diamino by adding 7.59 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid to 13.61 parts by weight of 4-aminobenzamide and 272 parts by weight of water A coupling reaction was performed with 22.3 parts by weight of acid (1,7-clebic acid) at pH = 2 to 3, followed by neutralization and salting out, and the precipitated solid was separated by filtration to obtain a wet cake of a monoazo compound. It was.
The wet cake of this monoazo compound was dissolved in 392 parts by weight of N-methylpyrrolidone and 392 parts by weight of water. Thereafter, 7.59 parts by weight of sodium nitrite was added to diazotize under acidic conditions of hydrochloric acid, and 7-amino-1-naphthol-3,6-disulfonic acid (RR acid) dissolved in 975 parts by weight of water (purity 65. 5%) The coupling reaction was carried out at 48.7 parts by weight and pH = 9-10. After the reaction, the precipitated solid was separated by filtration to obtain a sodium salt of an azo dye represented by the following formula (III-1).
An aqueous solution of a sodium salt of an azo dye represented by the following formula (III-1) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, neutralized with lithium hydroxide, and concentrated and dried. As a result, a lithium salt of an azo dye represented by the following formula (III-1) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 589 nm.

<Synthesis Example 4>
An aqueous solution of a sodium salt of an azo dye represented by the following formula (V-1) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, and then neutralized and concentrated with an aqueous lithium hydroxide solution. By drying, a lithium salt of an azo dye represented by the following formula (V-1) was obtained. The absorption maximum wavelength (λmax) in a 10 ppm aqueous solution of this dye was 543 nm.

<Synthesis Example 5>
8-amino-2-naphthalene dissolved in 500 parts by weight of water by adding 7.25 parts by weight of sodium nitrite to 11.8 parts by weight of 4-aminobenzonitrile and 250 parts by weight of water under acidic conditions of hydrochloric acid After coupling with 22.3 parts by weight of sulfonic acid (1,7-claveic acid), neutralization and salting out were performed, and the precipitated solid was separated by filtration to obtain a wet cake of a monoazo compound.
The wet cake of this monoazo compound was dissolved in 640 parts by weight of N-methylpyrrolidone and 400 parts by weight of water, diazotized by adding 8.97 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid, and dissolved in 300 parts by weight of water. Coupling was performed with 45.34 parts by weight of 7-amino-1-naphthol-3,6-disulfonic acid (RR acid) (purity: 66.9%) at pH = 8-10. After the reaction, the precipitated solid was separated by filtration to obtain a sodium salt of an azo dye represented by the following formula (III-2).
An aqueous solution of a sodium salt of an azo dye represented by the following formula (III-2) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, and then neutralized and concentrated with an aqueous lithium hydroxide solution. By drying, an azo dye lithium salt represented by the following formula (III-2) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 588 nm.

<Synthesis Example 6>
An aqueous solution of a sodium salt of an azo dye represented by the following formula (V-2) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, and then neutralized and concentrated with an aqueous lithium hydroxide solution. By drying, a lithium salt of an azo dye represented by the following formula (V-2) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 541 nm.

<Synthesis Example 7>
4-Aminobenzamide was diazotized with sodium nitrite in an aqueous solvent under acidic conditions of hydrochloric acid, coupled with p-cresidine in an aqueous solvent, and the precipitate was collected by filtration to obtain a monoazo compound.
The monoazo compound is diazotized with sodium nitrite in a mixed solvent of water and N-methylpyrrolidone under acidic conditions of hydrochloric acid, and after a coupling reaction with 8-amino-2-naphthalenesulfonic acid in an aqueous solvent, The mixture was salted out and the precipitate was collected by filtration to obtain a disazo compound.
The disazo compound was diazotized with sodium nitrite in a mixed solvent of water and N-methylpyrrolidone under acidic conditions of hydrochloric acid, and 7-amino-1-naphthol-3,6-disulfonic acid and pH 8-10 in the aqueous solvent. A coupling reaction was performed. Salting out was performed, and the precipitate was collected by filtration to obtain a sodium salt of an azo dye represented by the following formula (I-3). An aqueous solution of a sodium salt of an azo dye represented by the following formula (I-3) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, and then neutralized and concentrated with an aqueous lithium hydroxide solution. By drying, an azo dye lithium salt represented by the following formula (I-3) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 619 nm.

<Synthesis Example 8>
6-Amino-1-naphthalenesulfonic acid was diazotized with sodium nitrite in an aqueous solvent under acidic conditions of hydrochloric acid to obtain a diazo liquid. In a separate container, m-toluidine and sodium hydroxymethanesulfonate were taken, reacted in an aqueous solvent at 60 to 70 ° C., and then cooled to obtain a coupling solution. After reacting by adding the diazo liquid to the coupling liquid, alkaline deprotection was performed, salting out was performed, and the precipitate was collected by filtration to obtain a monoazo compound.
The monoazo compound is diazotized with sodium nitrite in a mixed solvent of water and N-methylpyrrolidone under acidic conditions of hydrochloric acid, and after a coupling reaction with 8-amino-2-naphthalenesulfonic acid in an aqueous solvent, The mixture was salted out and the precipitate was collected by filtration to obtain a disazo compound.
The disazo compound was diazotized with sodium nitrite in a mixed solvent of water and N-methylpyrrolidone under acidic conditions of hydrochloric acid, and 7-amino-1-naphthol-3,6-disulfonic acid and pH 8-10 in the aqueous solvent. A coupling reaction was performed. The precipitate was collected by filtration to obtain a sodium salt of an azo dye represented by the following formula (I-4). An aqueous solution of a sodium salt of an azo dye represented by the following formula (I-4) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, and then neutralized and concentrated with an aqueous lithium hydroxide solution. By drying, a lithium salt of a dye represented by the following formula (I-4) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 608 nm.

<Synthesis Example 9>
6-Amino-1-naphthalenesulfonic acid is diazotized with sodium nitrite under acidic conditions in hydrochloric acid in an aqueous solvent, coupled with 8-amino-2-naphthalenesulfonic acid, salted out and precipitated. The product was collected by filtration to obtain a monoazo compound.
The monoazo compound was diazotized with sodium nitrite in an aqueous solvent under acidic conditions of hydrochloric acid, and a coupling reaction was performed with 7-amino-1-naphthol-3,6-disulfonic acid in an aqueous solvent at pH 8-10. The precipitate was collected by filtration to obtain a sodium salt of an azo dye represented by the following formula (III-3). An aqueous solution of an azo dye sodium salt represented by the following formula (III-3) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, and then neutralized and concentrated with an aqueous lithium hydroxide solution. By drying, a lithium salt of a dye represented by the following formula (III-3) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 587 nm.

<Synthesis Example 10>
8-amino-2-naphthalene dissolved in 500 parts by weight of water by adding 7.59 parts by weight of sodium nitrite to 15.0 parts by weight of 3′-aminoacetanilide and 300 parts by weight of water under acidic conditions of hydrochloric acid After coupling with 22.3 parts by weight of sulfonic acid (1,7-claveic acid), neutralization and salting out were performed, and the precipitated solid was separated by filtration to obtain a wet cake of a monoazo compound.
This monoazo compound wet cake was dissolved in 640 parts by weight of N-methylpyrrolidone and 400 parts by weight of water, diazotized by adding 8.97 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid, and dissolved in 500 parts by weight of water. After coupling with 22.3 parts by weight of 8-amino-2-naphthalenesulfonic acid (1,7-claveic acid) at pH = 3 to 4, salting out was performed, and the precipitate was separated by filtration to obtain a disazo compound. A wet cake was obtained.

The wet cake of this disazo compound was dissolved in 600 parts by weight of N-methylpyrrolidone and 800 parts by weight of water, diazotized by adding 7.59 parts by weight of sodium nitrite under hydrochloric acid conditions, and dissolved in 600 parts by weight of water. Coupling was carried out with 29.7 parts by weight of 7-amino-1-naphthol-3,6-disulfonic acid (RR acid) (purity: 96.7%) at pH = 9-10. After the reaction, salting out was performed, and the precipitated solid was separated by filtration to obtain a sodium salt of a trisazo dye represented by the following formula (I-5).
An aqueous solution of a sodium salt of a trisazo dye represented by the formula (I-5) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, neutralized with an aqueous lithium hydroxide solution, concentrated and dried. As a result, a lithium salt of a trisazo dye represented by the formula (I-5) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 627 nm.
Further, an aqueous solution of a sodium salt of a trisazo dye represented by the formula (I-5) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, and then the aqueous solution of the free acid is used in a weight ratio. The 80% fraction is divided into a 20% fraction, the 80% fraction is neutralized with an aqueous lithium hydroxide solution, the remaining 20% fraction free acid aqueous solution is mixed, and then concentrated to dryness. As a result, an 80 mol% lithium neutralized salt of the trisazo dye represented by the formula (I-5) was obtained.

<Synthesis Example 11>
8-amino-2-naphthalenesulfone dissolved in 600 parts by weight of 9.45 parts by weight of 3-aminoquinoline and 300 parts by weight of water by adding 4.99 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid After coupling with 14.6 parts by weight of acid (1,7-clave acid), the mixture was neutralized and salted out, and the precipitated solid was separated by filtration to obtain a wet cake of a monoazo compound.
This monoazo compound wet cake was suspended in 200 parts by weight of N-methylpyrrolidone and 450 parts by weight of water, diazotized by adding 6.51 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid, and dissolved in 600 parts by weight of water. After coupling with 14.6 parts by weight of 8-amino-2-naphthalenesulfonic acid (1,7-clebic acid) at pH = 3-4, neutralization and salting out were performed, and the precipitated solid was separated by filtration. A wet cake of a disazo compound was obtained.
This disazo compound wet cake was suspended in 300 parts by weight of N-methylpyrrolidone and 200 parts by weight of water, diazotized by adding 5.20 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid, and dissolved in 400 parts by weight of water. Coupling was performed with 31.5 parts by weight of 7-amino-1-naphthol-3,6-disulfonic acid (RR acid) (purity: 65.5%) at pH = 9-10. After the reaction, salting out was performed, and the precipitated solid was separated by filtration to obtain a sodium salt of a trisazo dye represented by the following formula (I-6).
An aqueous solution of a sodium salt of a trisazo dye represented by the formula (I-6) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, neutralized with an aqueous lithium hydroxide solution, concentrated and dried. As a result, a lithium salt of a trisazo dye represented by the formula (I-6) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 630 nm.

<Synthesis Example 12>
To 4-amino-N-methylphthalimide (15.9 parts by weight) and water (500 parts by weight), sodium nitrite (6.83 parts by weight) was added to diazotize under acidic conditions of hydrochloric acid, and dissolved in 700 parts by weight of water. After coupling with 20.1 parts by weight of 2-naphthalenesulfonic acid (1,7-claveic acid), the mixture was neutralized and salted out, and the precipitated solid was separated by filtration to obtain a wet cake of a monoazo compound.
The wet cake of this monoazo compound was dissolved in 1000 parts by weight of N-methylpyrrolidone and 400 parts by weight of water, diazotized by adding 7.48 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid, and dissolved in 1100 parts by weight of water. Coupling was performed with 29.0 parts by weight of 7-amino-1-naphthol-3,6-disulfonic acid (RR acid) (purity: 65.5%) at pH = 9-10. After the reaction, the precipitated solid was separated by filtration to obtain a sodium salt of a disazo dye represented by the following formula (III-4).
An aqueous solution of a sodium salt of a disazo dye represented by the formula (III-4) is passed through a cation exchange resin (SK1BH manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, neutralized with an aqueous lithium hydroxide solution, concentrated and dried. As a result, a lithium salt of a disazo dye represented by the formula (III-4) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 594 nm.

<Synthesis Example 13>
Diazotization is carried out by adding 1.12 parts by weight of sodium nitrite to 4.78 parts by weight of 6-amino-1-naphthalenesulfonic acid (purity 67.3%) and 60 parts by weight of water under acidic conditions of hydrochloric acid, and 80 parts by weight of water. After coupling with 2.34 parts by weight of 3-aminophthalimide dissolved in 1 part, the mixture was neutralized and salted out, and the precipitated solid was separated by filtration to obtain a monoazo compound wet cake.
This monoazo compound wet cake was suspended in 100 parts by weight of water, diazotized by adding 1.12 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid, and 7-amino-1-naphthol-3 dissolved in 100 parts by weight of water. , 6-Disulfonic acid (RR acid) (purity: 65.5%) was coupled with 7.02 parts by weight at pH = 9-10. After the reaction, the precipitated solid was separated by filtration to obtain a sodium salt of a disazo dye represented by the following formula (III-5).
An aqueous solution of a disazo dye sodium salt represented by the formula (III-5) is passed through a cation exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, neutralized with an aqueous lithium hydroxide solution, concentrated and dried. As a result, a lithium salt of a disazo dye represented by the formula (III-5) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 526 nm.

<Synthesis Example 14>
2.88 parts by weight of 3-aminoquinoline and 2.88 parts by weight of 5-aminoquinoline dissolved in 100 parts by weight of water by adding 1.52 parts by weight of sodium nitrite to 100 parts by weight of water under acidic conditions of hydrochloric acid After coupling with the part, neutralization and salting out were performed, and the precipitated solid was separated by filtration to obtain a wet cake of a monoazo compound.
The wet cake of this monoazo compound was suspended in 100 parts by weight of N-methylpyrrolidone and 100 parts by weight of water, diazotized by adding 1.52 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid, and dissolved in 200 parts by weight of water. Coupling was conducted with 9.75 parts by weight of 7-amino-1-naphthol-3,6-disulfonic acid (RR acid) (purity: 65.5%) at pH = 9-10. After the reaction, salting out was performed, and the precipitated solid was separated by filtration to obtain a sodium salt of a disazo dye represented by the following formula (III-6).
An aqueous solution of a disazo dye sodium salt represented by the formula (III-6) is passed through a cation exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation) to make an aqueous solution of a free acid, neutralized with an aqueous lithium hydroxide solution, concentrated and dried. As a result, a lithium salt of a disazo dye represented by the formula (III-6) was obtained. The maximum absorption wavelength (λmax) of this dye in a 10 ppm aqueous solution was 581 nm.

[Measurement method of viscosity]
The viscosity of Examples 1 to 5 and Comparative Examples 1 to 4 was measured using a rheometer VAR-50 (manufactured by REOLOGICA) on a parallel plate (diameter 40 mm, gap 0.8 mm). After pre-shearing was performed at a measurement temperature of 25 ° C. and a shear rate of 1000 s ⁻¹ for 5 seconds, the shear rate was changed from 1000 s ⁻¹ to 10 s ^{−1 in} 180 seconds, and shear rate sweep measurement was performed.
In general, since the viscosity of the liquid crystalline substance varies depending on the shear rate, the viscosity at the shear rate of 400 s ⁻¹ is taken as the viscosity of each sample as a representative value.
The viscosities of Examples 6 to 8 and Comparative Examples 5 to 6 were measured using a B-type viscometer DV-I Prime (manufactured by BROOKFIELD) and a cone plate (diameter 24 mm, cone angle 0.8 °, gap 0. 0005 inch = 0.013 mm). The measurement temperature was 25 ° C., after 10 seconds Pureshea at a shear rate of 90.0s ^-1, the shear rate is varied in 720 seconds 90.0S ^-1 to 2.25s ^-1, the shear rate sweep measurement went.
In general, the viscosity of a liquid crystal substance varies depending on the shear rate. From the viewpoint of the limit measurement viscosity of this measuring apparatus, the viscosity at a shear rate of 11.3 s ^{−1 was taken as} the viscosity of each sample as a representative value.

[Measurement method of transmittance and dichroic ratio for polarized light in the absorption axis direction of anisotropic dye film]
In Examples and Comparative Examples, the transmittance and dichroic ratio for polarized light in the absorption axis direction of the anisotropic dye film were measured using a spectrophotometer equipped with a Gram Thompson polarizer (manufactured by Otsuka Electronics Co., Ltd., product name “RETS-100”). )). First, linearly polarized measuring light is incident on the anisotropic dye film, and the transmittance of the anisotropic dye film with respect to the polarized light in the absorption axis direction and the transmittance with respect to the polarized light in the direction of the polarization axis are measured. The ratio was calculated.
Dichroic ratio (D) = Az / Ay
Ay = -log (Ty)
Az = -log (Tz)
Tz: transmittance for polarized light in the direction of the absorption axis of the anisotropic dye film Ty: transmittance for polarized light in the direction of the polarization axis of the anisotropic dye film

[Method for evaluating filterability]
The filterability of the prepared solution was evaluated as follows. 5 ml of the prepared solution was prepared and filtered with a 10 ml syringe equipped with Millex-LH 0.45 · m (manufactured by Merck Millipore Ltd.). The filterability was evaluated as follows. In the present invention, ○ and Δ are practical levels.
◯: Filtered quickly.
Δ: Slow but filtered.
X: It was necessary to apply a very strong force to the syringe, or filtration was not possible.

[Example 1]
To 88.40 parts of water, 10.64 parts of a lithium salt of an azo dye represented by the following formula (I-1), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-1) 0 40 parts, 0.12 part of a lithium salt of an azo dye represented by the following formula (III-1), 0.04 part of a lithium salt of an azo dye represented by the following formula (V-1), and 0. After adding 4 parts and stirring and dissolving, it filtered and the insoluble content was removed, and the composition 1 for anisotropic dye films was obtained.
A drop of this composition 1 for an anisotropic dye film is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether or not a liquid crystal phase is expressed. It was confirmed. The viscosity of this anisotropic dye film composition 1 was measured by the method described above. The results are shown in Table 1.
On the other hand, a glass substrate (150 mm × 150 mm, thickness 1.1 mm, film thickness of about 800 mm) on which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems) is formed as a base material is rubbed with a cloth in advance. The anisotropic dye film 1 was obtained by applying the composition 1 for anisotropic dye film to an applied applicator with a gap 10 μm applicator (manufactured by Horita Seisakusho) and then naturally drying. About the obtained anisotropic pigment | dye film | membrane 1, the dichroic ratio (D) in 640 nm was measured. The results are shown in Table 1.

[Example 2]
To 88.40 parts of water, 10.64 parts of a lithium salt of an azo dye represented by the following formula (I-1), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-1) 0 40 parts, 0.12 part of a lithium salt of an azo dye represented by the following formula (III-2), 0.04 part of a lithium salt of an azo dye represented by the following formula (V-1) and 0. After adding 4 parts, stirring and dissolving, it filtered and the insoluble content was removed and the composition 2 for anisotropic dye films was obtained.
A drop of this composition for anisotropic dye film 2 is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether a liquid crystal phase is present. It was confirmed. The viscosity of this anisotropic dye film composition 2 was measured by the method described above. The results are shown in Table 1.
On the other hand, the anisotropic dye film composition 2 was applied to the same substrate as in Example 1 with an applicator (manufactured by Horita Seisakusho) with a gap of 10 μm, and then naturally dried to obtain the anisotropic dye film 2. With respect to the obtained anisotropic dye film 2, the dichroic ratio (D) at 640 nm was measured. The results are shown in Table 1.

[Example 3]
To 88.40 parts of water, 10.64 parts of a lithium salt of an azo dye represented by the following formula (I-2), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-2) 0 40 parts, 0.12 part of a lithium salt of an azo dye represented by the following formula (III-1), 0.04 part of a lithium salt of an azo compound represented by the following formula (V-2), and 0. After adding 4 parts and stirring and dissolving, it filtered and the insoluble content was removed and the composition 3 for anisotropic dye films was obtained.
A drop of this composition for anisotropic dye film 3 on a slide glass and observing a sample covered with a cover glass with a polarizing microscope to confirm whether or not a liquid crystal phase is expressed, thereby exhibiting lyotropic liquid crystallinity. It was confirmed. The viscosity of this anisotropic dye film composition 3 was measured by the method described above. The results are shown in Table 1.
On the other hand, the anisotropic dye film composition 3 was applied to the same substrate as in Example 1 with an applicator (manufactured by Horita Seisakusho) with a gap of 10 μm, and then naturally dried to obtain the anisotropic dye film 3. It was. About the obtained anisotropic pigment | dye film | membrane, the dichroic ratio (D) in 640 nm was measured. The results are shown in Table 1.

[Example 4]
In 90.68 parts of water, 8.20 parts of a lithium salt of an azo dye represented by the following formula (I-3), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-3) 0 .64 parts, 0.16 part of a lithium salt of an azo dye represented by the following formula (III-1) and 0.32 part of lithium chloride are added, dissolved by stirring, and then filtered to remove insoluble matters. This obtained composition 4 for anisotropic dye films.
A drop of this composition for anisotropic dye film 4 is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether a liquid crystal phase is expressed. It was confirmed. The viscosity of this anisotropic dye film composition 4 was measured by the method described above. The results are shown in Table 1.
On the other hand, the anisotropic dye film composition 4 was applied to the same substrate as in Example 1 with an applicator (manufactured by Horita Seisakusho) with a gap of 2 μm, and then naturally dried to obtain the anisotropic dye film 4. It was. About the obtained anisotropic pigment | dye film | membrane, the dichroic ratio (D) in 640 nm was measured. The results are shown in Table 1.

[Example 5]
In 80.86 parts of water, 16.82 parts of a lithium salt of an azo dye represented by the following formula (I-4), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-4) 1 .32 parts, 0.34 parts of lithium salt of azo dye represented by the following formula (III-3) and 0.66 parts of lithium chloride are added, dissolved by stirring, and then filtered to remove insolubles. Thus, a composition 5 for anisotropic dye film was obtained.
A drop of this composition for anisotropic dye film 5 on a slide glass and observing a sample covered with a cover glass with a polarizing microscope to confirm whether or not a liquid crystal phase is expressed, thereby exhibiting lyotropic liquid crystal properties. It was confirmed. The viscosity of this anisotropic dye film composition 5 was measured by the method described above. The results are shown in Table 1.
On the other hand, the anisotropic dye film composition 5 was applied to the same substrate as in Example 1 with an applicator (manufactured by Horita Seisakusho) with a gap of 2 μm, and then naturally dried to obtain the anisotropic dye film 5. It was. About the obtained anisotropic pigment | dye film | membrane, the dichroic ratio (D) in 640 nm was measured. The results are shown in Table 1.

[Example 6]
In 83.78 parts of water, 14.35 parts of a lithium salt of an azo dye represented by the following formula (I-5), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-5) 1 .10 parts, 0.22 part of a lithium salt of an azo dye represented by the following formula (III-4) and 0.55 part of lithium chloride are added, dissolved by stirring, and then filtered to remove insoluble matters. This obtained composition 6 for anisotropic dye films.
A drop of this composition for anisotropic dye film 6 is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether a liquid crystal phase is expressed. It was confirmed. The viscosity of this anisotropic dye film composition 6 was measured by the method described above. The results are shown in Table 2.

[Example 7]
In 83.78 parts of water, 14.35 parts of a lithium salt of an azo dye represented by the following formula (I-5), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-5) 1 .10 parts, 0.22 part of a lithium salt of an azo dye represented by the following formula (III-5) and 0.55 part of lithium chloride are added, dissolved by stirring, and then filtered to remove insoluble matters. As a result, a composition 7 for anisotropic dye film was obtained.
A drop of this composition 7 for an anisotropic dye film is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether a liquid crystal phase is expressed. It was confirmed. The viscosity of this anisotropic dye film composition 7 was measured by the method described above. The results are shown in Table 2.

[Example 8]
To 91.245 parts of water, 8.500 parts of a lithium salt of an azo dye represented by the following formula (I-6) and 0.255 part of a lithium salt of an azo dye represented by the following formula (III-6) were added, After stirring and dissolving, the composition for anisotropic dye film 8 was obtained by filtering to remove insoluble matter.
A drop of this composition for anisotropic dye film 8 is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether or not a liquid crystal phase is expressed. It was confirmed. The viscosity of this anisotropic dye film composition 8 was measured by the method described above. The results are shown in Table 2.

[Comparative Example 1]
To 88.4 parts of water, 10.80 parts of a lithium salt of an azo dye represented by the following formula (I-1), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-1) 0 .40 parts and 0.40 part of lithium chloride were added, dissolved by stirring, and then filtered to remove insolubles, thereby obtaining an anisotropic dye film composition 31.
A drop of this composition 31 for an anisotropic dye film is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether a liquid crystal phase is expressed. It was confirmed. The viscosity of this anisotropic dye film composition 31 was measured by the method described above. The results are shown in Table 1.
On the other hand, the anisotropic dye film composition 31 was applied to the same substrate as in Example 1 with an applicator (manufactured by Horita Seisakusho) with a gap of 10 μm, and then naturally dried to obtain the anisotropic dye film 31. About the obtained anisotropic dye film 31, the dichroic ratio (D) in 640 nm was measured. The results are shown in Table 1.

[Comparative Example 2]
To 88.4 parts of water, 10.80 parts of a lithium salt of an azo dye represented by the following formula (I-2), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-2) 0 .40 parts and 0.40 part of lithium chloride were added, dissolved by stirring, and then filtered to remove insolubles, thereby obtaining anisotropic dye film composition 32.
A drop of this composition for anisotropic dye film 32 is dropped on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether a liquid crystal phase is expressed. It was confirmed. The viscosity of this anisotropic dye film composition 32 was measured by the method described above. The results are shown in Table 1.
On the other hand, the anisotropic dye film composition 32 was applied to the same substrate as in Example 1 with an applicator (manufactured by Horita Seisakusho) with a gap of 10 μm, and then naturally dried to obtain the anisotropic dye film 32. About the obtained anisotropic dye film | membrane 32, the dichroic ratio (D) in 640 nm was measured. The results are shown in Table 1.

[Comparative Example 3]
In 90.68 parts of water, 8.36 parts of a lithium salt of an azo dye represented by the following formula (I-3), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-3) 0 .64 parts and 0.32 parts of lithium chloride were added, dissolved by stirring, and then filtered to remove insolubles, thereby obtaining anisotropic dye film composition 33.
A drop of this composition for anisotropic dye film 33 is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether or not a liquid crystal phase is expressed. It was confirmed. The viscosity of the anisotropic dye film composition 33 was measured by the method described above. The results are shown in Table 1.
On the other hand, the anisotropic dye film composition 33 was applied to the same substrate as in Example 1 with an applicator (manufactured by Horita Seisakusho) with a gap of 2 μm, and then naturally dried to obtain the anisotropic dye film 33. It was. About the obtained anisotropic pigment | dye film | membrane 33, the dichroic ratio (D) in 640 nm was measured. The results are shown in Table 1.

[Comparative Example 4]
In 80.87 parts of water, 17.15 parts of a lithium salt of an azo dye represented by the following formula (I-4), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-4) 1 .32 parts and 0.66 parts of lithium chloride were added, dissolved by stirring, and then filtered to remove insolubles, whereby a composition 34 for anisotropic dye film was obtained.
A drop of this anisotropic dye film composition 34 is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether a liquid crystal phase is expressed. It was confirmed. The viscosity of the anisotropic dye film composition 34 was measured by the method described above. The results are shown in Table 1.
On the other hand, the anisotropic dye film composition 34 was applied to the same substrate as in Example 1 with an applicator (manufactured by Horita Seisakusho) with a gap of 2 μm, and then naturally dried to obtain the anisotropic dye film 34. It was. About the obtained anisotropic pigment | dye film | membrane, the dichroic ratio (D) in 640 nm was measured. The results are shown in Table 1.

[Comparative Example 5]
In 84.00 parts of water, 14.35 parts of a lithium salt of an azo dye represented by the following formula (I-5), 80 mol% lithium neutralized salt of an azo dye represented by the following formula (I-5) 1 10 parts and 0.55 parts of lithium chloride were added and dissolved by stirring, followed by filtration to remove insolubles, thereby obtaining an anisotropic dye film composition 35.
A drop of this anisotropic dye film composition 35 is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether or not a liquid crystal phase is expressed. It was confirmed. The viscosity of this anisotropic dye film composition 35 was measured by the method described above. The results are shown in Table 2.

[Comparative Example 6]
To 91.50 parts of water, 8.50 parts of a lithium salt of an azo dye represented by the following formula (I-6) was added, dissolved by stirring, and then filtered to remove insoluble matters. An isotropic dye film composition 36 was obtained.
A drop of this composition for anisotropic dye film 36 is placed on a slide glass, and a sample covered with a cover glass is observed with a polarizing microscope to confirm whether a liquid crystal phase is expressed. It was confirmed. The viscosity of the anisotropic dye film composition 36 was measured by the method described above. The results are shown in Table 2.

[Example 9]
A glass substrate (100 mm × 100 mm, thickness 1.1 mm, film thickness of about 800 mm) on which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems) was formed as a base material was previously rubbed with a cloth. The above-mentioned composition 3 for anisotropic dye film was applied using a die coater so that the film thickness at the time of application was 4.5 μm. When the upper limit of the coating speed was determined so that the entire surface of the substrate could be coated with no defects, the coating could be performed at 25 mm / s. Thereafter, the anisotropic dye film 6 was obtained by natural drying. About the obtained anisotropic pigment | dye film | membrane 6, the dichroic ratio (D) in 640 nm was measured. The results are shown in Table 3.

[Comparative Example 7]
Coating was performed in the same manner as in Example 9 except that the anisotropic dye film composition 3 was changed to the anisotropic dye film composition 32. When an upper limit coating speed that can be applied to the entire surface of the substrate without any defects was determined, the coating could be performed at 5 mm / s. Thereafter, the anisotropic dye film 37 was obtained by natural drying. With respect to the obtained anisotropic dye film 37, the dichroic ratio (D) at 640 nm was measured. The results are shown in Table 3.

The anisotropic dye film compositions 1 and 2 of the present invention (Examples 1 and 2) were excellent in filterability when removing foreign matters at the production stage of the anisotropic dye film composition. Further, the composition of the present invention allows the composition for anisotropic dye film while maintaining the dichroic ratio of the anisotropic dye film with respect to the composition 31 for anisotropic dye film (Comparative Example 1). It was shown that the viscosities of products 1 and 2 were reduced. By reducing the viscosity of the composition for anisotropic dye film, the coating speed can be improved. This is as shown in Example 9 and Comparative Example 7 in which the anisotropic dye film composition 3 and the anisotropic dye film composition 32 were applied by a die coater.
Similarly, the anisotropic dye film composition 3 (Example 3), the anisotropic dye film composition 32 (Comparative Example 2), and the anisotropic dye film composition 4 (Example 4) are anisotropic. Composition 33 (Comparative Example 3), anisotropic dye film composition 4 (Example 4) and anisotropic dye film composition 34 (Comparative Example 3), anisotropic dye film composition Also from the product 5 (Example 5) and the composition 35 for the anisotropic dye film (Comparative Example 4), the constitution of the present invention provides excellent filterability and maintains the dichroic ratio of the anisotropic dye film. However, it was shown that the viscosity of the composition for anisotropic dye films was lowered.
Further, the composition for anisotropic dye film 6 (Example 6), the composition for anisotropic dye film 7 (Example 7) and the composition for anisotropic dye film 35 (Comparative Example 5), anisotropy Also from the composition 8 for the dye film (Example 8) and the composition 36 for the anisotropic dye film (Comparative Example 6), the composition of the present invention provides excellent filterability and the composition for the anisotropic dye film. It has been shown to reduce the viscosity of the product.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2015-185709) filed on Sep. 18, 2015, the contents of which are incorporated herein by reference.

Claims

An anisotropic dye film composition comprising an azo dye and a solvent, wherein the azo dye has a free acid form represented by the following formula (I) and a free acid form represented by the following formula (III): The composition for anisotropic dye films | membranes containing the azo dye represented by this.

[In Formula (I),
Ar 11 and Ar 12 each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
Ar 13 is a 1,4-phenylene group optionally having an electron donating group, a 1,4-naphthylene group optionally having a substituent, or an aromatic heterocyclic ring optionally having a substituent Represents a group,
Ar 14 represents a group represented by the formula (II). ]

[In the formula (II),
R N11 and R N12 each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or an acyl group that may have a substituent. Represent,
b represents an integer of 0 to 3, and d represents 0 or 1.
The amino group represented by —NR N11 R N12 is substituted at the α-position or β-position. ]

[In Formula (III),
Ar 21 represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
Ar 22 is a 1,4-phenylene group optionally having an electron donating group, a 1,4-naphthylene group optionally having a substituent, or an aromatic heterocyclic ring optionally having a substituent Represents a group,
Ar 23 represents a group represented by formula (IV). ]

[In Formula (IV),
R N21 and R N22 each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or an acyl group that may have a substituent. Represent,
e represents an integer of 0 to 3, and f represents 0 or 1.
The amino group represented by —NR N21 R N22 is substituted at the α-position or β-position. ]
Ar 14 in the formula (I) is a group represented by the formula (VI), an anisotropic dye film composition according to claim 1.

[In Formula (VI),
g and h each independently represents 0 or 1;
Incidentally, d in the formula (VI), R N11 and R N12 is d of Formula (II), and R N11 and R N12 synonymous. ]
The composition for anisotropic dye films according to claim 1 or 2, wherein Ar 23 in the formula (III) is a group represented by the formula (VII).

[In the formula (VII):
i and j each independently represents 0 or 1.
Incidentally, f in formula (VII), R N21 and R N22 is f of formula (III), and R N21 and R N22 synonymous. ]
Ar 12 in the formula (I) may have a 1,4-phenylene group which may have a substituent, a 1,4-naphthylene group which may have a substituent, and a monocyclic or bicyclic group The composition for an anisotropic dye film according to any one of claims 1 to 3, wherein the composition is selected from the group consisting of an aromatic heterocyclic group which may have a substituent.
Ar 11 in the formula (I) has a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a monocyclic or bicyclic substituent. The anisotropy according to any one of claims 1 to 4, which is selected from the group consisting of good aromatic heterocyclic groups and has at least one electron withdrawing group as a substituent. A composition for a dye film.
At least one structure selected from Ar 21 to Ar 23 in the formula (III) is a structure obtained by removing a substituent that may be present from at least one structure selected from Ar 11 to Ar 14 in the formula (I). The composition for anisotropic dye film according to any one of claims 1 to 5, which has the same structure as that obtained by removing a substituent which may be present from one structure.
The structure excluding the substituent which may be present from at least one structure selected from Ar 11 to Ar 13 in the formula (I) is present from the structure of Ar 21 and / or Ar 22 in the formula (III). The composition for an anisotropic dye film according to any one of claims 1 to 6, which has the same structure except for an optionally substituted group.
At least one structure selected from Ar 21 to Ar 23 in the formula (III) is a structure obtained by removing a substituent that may be present from at least one structure selected from Ar 11 to Ar 14 in the formula (I). The structure according to any one of claims 1 to 7, wherein the structure is the same as the structure excluding the substituents that may be present from one structure, and the group of the substituents that may be present is the same. An anisotropic dye film composition.
An anisotropic dye film comprising an azo dye having a free acid form represented by the following formula (I) and an azo dye having a free acid form represented by the following formula (III):

[In Formula (I),
Ar 11 and Ar 12 each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
Ar 13 is a 1,4-phenylene group optionally having an electron donating group, a 1,4-naphthylene group optionally having a substituent, or an aromatic heterocyclic ring optionally having a substituent Represents a group,
Ar 14 represents a group represented by the formula (II). ]

[In the formula (II),
R N11 and R N12 each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or an acyl group that may have a substituent. Represent,
b represents an integer of 0 to 3, and d represents 0 or 1.
The amino group represented by —NR N11 R N12 is substituted at the α-position or β-position. ]

[In Formula (III),
Ar 21 represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
Ar 22 is a 1,4-phenylene group optionally having an electron donating group, a 1,4-naphthylene group optionally having a substituent, or an aromatic heterocyclic ring optionally having a substituent Represents a group,
Ar 23 represents a group represented by formula (IV). ]

[In Formula (IV),
R N21 and R N22 each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or an acyl group that may have a substituent. Represent,
e represents an integer of 0 to 3, and f represents 0 or 1.
The amino group represented by —NR N21 R N22 is substituted at the α-position or β-position. ]