JP7680199B2 - Compound, composition, film, laminate and display device - Google Patents

Description

The present invention relates to a compound, a composition, a film, a laminate, and a display device.

There is a continuing demand for thinner displays such as image display panels, and further thinner designs are also being demanded for the polarizing plates and polarizers that are one of the components of such displays. In response to such demands, for example, a thin host-guest type polarizer has been proposed that includes a polarizing film that contains a polymerizable liquid crystal compound and a dye compound that exhibits dichroism (see, for example, Patent Documents 1 and 2).

Special Publication No. 2007-510946 JP 2013-037353 A

However, in a host-guest polarizer, if the dispersibility of the dye compound in the host compound is low, the dichroic ratio (DR) may become low due to aggregation of the dye compound. Also, even if the dispersibility of the dye compound is good, if the affinity with the mesogen of the host compound is low, the dichroic ratio may become low.

The object of the present invention is to provide a compound capable of forming a polarizing film with a high dichroic ratio.

The present invention provides the following [1] to [9].
[1] A compound represented by the following formula (1):

In formula (1), P represents a single bond or one group selected from the group consisting of -O-, -OC(=O)-, and -C(=O)O-. x and y each independently represent 0, 1, or 2, and when P is a single bond, x+y≧1 is satisfied. n represents 1 or 2. R ¹ represents one group selected from the group consisting of a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, a pyrrolidyl group, an oxazolidyl group, a piperidyl group, a morpholyl group, a methoxy group, and an ethoxy group, and the hydrogen atom of these groups may be substituted with a polymerizable group. R ² and R ³ each independently represent a methyl group or an ethyl group. Q represents a single bond or one group selected from the group consisting of -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -N=N-, -NHC(=O)- and -C(=O)NH-. ^{Ar 1} and Ar ³ each independently represent a 1,4-phenylene group or a divalent sulfur-containing aromatic heterocyclic group which may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group and a methoxy group. Ar ² represents a 1,4-phenylene group which may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group and a methoxy group. When n is 2, the two Ar ² may be the same or different.

[2] The compound according to [1], wherein in formula (1), y is 0.
[3] The compound according to [1] or [2], wherein Q in the formula (1) is -N=N-.
[4] A dichroic dye comprising the compound according to any one of [1] to [3].
[5] A composition comprising the compound according to any one of [1] to [3] and a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound.
[6] The composition according to [5], wherein the liquid crystal compound is a smectic liquid crystal compound.
[7] A film comprising the compound according to any one of [1] to [3] as a forming material.
[8] A laminate comprising the film according to [7].
[9] A display device comprising the laminate according to [8].

The present invention provides a compound capable of forming a polarizing film with a high dichroic ratio.

In this specification, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. Furthermore, the content of each component in a composition means the total amount of the multiple substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified. Below, the embodiment of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiment described here, and various modifications can be made within the scope that does not impair the spirit of the present invention.

<Compound>
The compound according to the present embodiment is represented by the following formula (1). The compound represented by the following formula (1) (hereinafter also referred to as compound (1)) may be used, for example, as a dichroic dye to form a polarizing film. That is, compound (1) may be an active ingredient constituting a dichroic dye. A polarizing plate having a polarizing film containing compound (1) can achieve an excellent dichroic ratio (DR).

In formula (1), P represents a single bond or a group selected from the group consisting of -O-, -OC(=O)-, and -C(=O)O-. P is preferably a single bond, -O-, or -OC(=O)-, and more preferably -O- or -OC(=O)-.

x and y each independently represent 0, 1 or 2, and when P is a single bond, x+y ≥ 1 is satisfied. y is preferably 0.
n represents 1 or 2, and is preferably 1.

R ¹ represents one group selected from the group consisting of methylamino group, ethylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, pyrrolidyl group, oxazolidyl group, piperidyl group, morpholyl group, methoxy group and ethoxy group, and at least one of the hydrogen atoms of these groups may be substituted with a polymerizable group. R ¹ is preferably a dimethylamino group, a diethylamino group, an ethylmethylamino group, a methoxy group or an ethoxy group, and at least one of the hydrogen atoms of these groups may be substituted with a polymerizable group. Here, the polymerizable group is preferably a radical polymerizable group, for example, a radical polymerizable group such as a (meth)acrylate group ((meth)acryloyloxy group) or a styryl group (vinylphenyl group), and among them, a (meth)acrylate group is preferable. When R ¹ has a polymerizable group, the number thereof is, for example, 1 or 2, preferably 1. ^{R 2} and R ³ each independently represent a methyl group or an ethyl group. From the viewpoint of achieving both dispersibility in a host compound and affinity with the mesogen of the host compound, at least one of ^R2 and ^R3 is preferably a methyl group, and more preferably one of ^R2 and ^R3 is a methyl group and the other is an ethyl group.

Q represents a single bond or one group selected from the group consisting of -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -N=N-, -NHC(=O)- and -C(=O)NH-. Q is preferably a single bond, -OC(=O)- or -N=N-, more preferably -N=N-.

Ar ¹ and Ar ³ each independently represent a 1,4-phenylene group which may have a substituent, or a divalent sulfur-containing aromatic heterocyclic group which may have a substituent. Ar ¹ and Ar ³ each independently represent a 1,4-phenylene group which may have a substituent, a benzothiazolediyl group which may have a substituent, or a thienothiazolediyl group which may have a substituent. The benzothiazolediyl group in Ar ¹ or Ar 3 may be, for example, a benzothiazole-2,5-diyl group or a benzothiazole-2,6-diyl group. The thienothiazolediyl group in Ar ¹ or Ar ³ may be, for example, a thieno[2,3-d]thiazole-2,5-diyl group. ^{Ar 2} represents a 1,4-phenylene group which may have a substituent. When n is 2, the two Ar ³ may be the same or different.

Ar ¹ , Ar ² or Ar ³ may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group and a methoxyl group. The substituent that Ar ¹ , Ar ² and Ar ³ may have is preferably a fluorine atom, a chlorine atom, a hydroxyl group or a methoxyl group, more preferably a fluorine atom or a hydroxyl group. The number of substituents in Ar ¹ , Ar ² and Ar ³ is independently 0, 1 or 2, preferably 0 or 1.

Specific examples of compound (1) include compounds represented by the following formulas (1-1) to (1-69), but the present invention is not limited to these.

From the viewpoint of the dichroic ratio, compound (1) is preferably at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-56), and more preferably at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-35).

Compound (1) may have a maximum absorption wavelength (λmax) in the wavelength range of, for example, 350 nm or more and 650 nm or less. The maximum absorption wavelength of compound (1) may preferably be 370 nm or more and 620 nm or less. The maximum absorption wavelength is measured at room temperature (for example, 25°C) for an acetonitrile solution of compound (1).

The maximum absorption wavelength of compound (1) can be adjusted to a desired wavelength by appropriately selecting, for example, the skeleton structures of Ar ¹ and Ar ³ , the substituents in Ar ¹ , Ar ² and Ar ³ , n, R ¹ , and the like.

A film containing compound (1) as a forming material, such as a polarizing film, can achieve an excellent dichroic ratio. The dichroic ratio of a polarizing film containing compound (1) as a forming material may be, for example, 25 or more, preferably 30 or more, more preferably 35 or more, and even more preferably 40 or more, 45 or more, or 50 or more. The dichroic ratio of a polarizing film is measured by the method described below. In addition, a film containing compound (1) as a forming material includes a film containing compound (1) as an independent molecule, and a film containing a partial structure derived from compound (1) that is generated by the reaction of compound (1) with another compound (e.g., a polymerizable compound).

Compound (1) has a specific structure, and therefore can achieve both affinity and solubility with the host mesogen, and can achieve an excellent dichroic ratio when constructing a host-guest polarizer. This can be considered, for example, as follows. In compound (1), the substituents on the aromatic rings in Ar ¹ , Ar ² and Ar ³ are limited to relatively small substituents, which is considered to reduce steric hindrance and improve affinity with the host mesogen. R ¹ in formula (1) is limited to a relatively short-chain substituent, which is considered to improve affinity with the host mesogen. The soluble group bonded to Ar ¹ has specific values of x and y, which allows the branched chain portion having R ² and R ³ to have an appropriate distance from the mesogen portion, which is considered to reduce steric hindrance near the mesogen and improve affinity with the host mesogen. The branched chain portion having R ² and R ³ has a specific structure, which is considered to improve solubility in the host, suppress aggregation of compound (1), and uniformly arrange the compound throughout the film. It is believed that when Ar ² is a 1,4-phenylene group which may have a substituent, the solubility in the host is improved.

Method for Producing Compound (1) Compound (1) can be produced by appropriately applying a conventionally known synthesis method. Specifically, the azo structure (-N=N-) in compound (1) can be constructed by converting an aromatic amine compound having a primary amino group into a diazonium salt with sodium nitrite or the like, and subjecting the diazo coupling with an aromatic compound, for example, with reference to the description of the production example in paragraphs [0220] to [0268] of International Publication WO2016/136561.

Compounds in which Q in compound (1) is a single bond can be synthesized, for example, by using a precursor having a dihydroxyboryl group or a dialkoxyboryl group and a precursor having a halogen atom, and applying the reaction conditions for Suzuki coupling with reference to Netherton, M. R.; Fu, G. C. Org. Lett. 2001, 3 (26), 4295-4298.

Compounds in which Q in compound (1) is -OC(=O)- or C(=O)O- can be synthesized, for example, by applying a dehydration condensation reaction using a precursor having a carboxyl group and a precursor having a hydroxyl group, with reference to Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y.; Ma, D. J. Org. Chem. 2009, 74 (3), 4542-4546. Specific examples of the conditions include condensation in a solvent in the presence of an esterification condensing agent.

Compounds in which Q in compound (1) is -C≡C- can be synthesized, for example, by applying Sonogashira coupling using Pd and Cu catalysts to a precursor having an ethynyl group (-C≡CH) and a precursor having a halogen atom.

Compounds in which Q in compound (1) is -C=C- can be synthesized, for example, by applying a Heck reaction using a Pd catalyst and a phosphorus ligand, using a precursor having an ethenyl group (-C=CH) and a precursor having a halogen atom.

Compounds in which Q in compound (1) is -NHC(=O)- or C(=O)NH- can be synthesized, for example, by applying a dehydration condensation reaction using a precursor having a carboxy group and a precursor having an amino group. Specific examples of the conditions include condensation in a solvent in the presence of an amidation condensing agent.

The compound (1) in which P is -O- can be synthesized, for example, by using a precursor having a halogen atom and a precursor having a hydroxyl group and applying general S _N 2 substitution reaction conditions. For the S _N 2 substitution reaction conditions, see, for example, J. Am. Chem. Soc., 2008, 130, 13079, etc.

A compound in which P in compound (1) is -OC(=O)- or C(=O)O- can be converted to a compound having the desired R ² and R ³ , for example, by a general transesterification reaction. For the transesterification reaction, a method can be applied in which TiO(acac) 2 (name: bis( _{2,4-pentanedionato)titanium(IV) oxide) is used as a Lewis acid catalyst and heated together with an alcohol compound in a solvent, with reference to, for example, Chen, C.-T.; Kuo, J.-H.; Ku, C.-H.; Weng, S.-S.; Liu, C.-Y.J. Org. Chem. 2005, 70} (4), 1328-1339.

The reaction time in the method for producing compound (1) can also be determined by appropriately sampling the reaction mixture during the reaction and confirming the degree of disappearance of the raw material compounds and the degree of production of compound (1) by known analytical means such as liquid chromatography or gas chromatography.

After the reaction, compound (1) can be extracted from the reaction mixture by known methods such as recrystallization, reprecipitation, extraction, and various types of chromatography, or by an appropriate combination of these procedures.

<Dichroic dye>
The dichroic dye of the present embodiment contains at least one type of compound (1) as an active ingredient. The dichroic dye contains compound (1), and thus can form a polarizing film with a high dichroic ratio. The dichroic dye may contain only one type of compound (1), or may contain two or more types of compounds with different structures in combination. When the dichroic dye contains two or more types of compound (1), they may have different maximum absorption wavelengths. The dichroic dye may contain other dye compounds other than compound (1) in addition to compound (1). The other dye compounds will be described later.

<Composition>
The composition of the present embodiment includes compound (1) and a liquid crystal compound including at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound. The composition is used, for example, as a material for forming a polarizing film. That is, the composition may be a composition for forming a polarizing film. A polarizing plate having a polarizing film obtained by using the composition as a material for forming the polarizing film can achieve an excellent dichroic ratio.

The content of compound (1) in the composition is, for example, preferably 50 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the solid content of the composition. Within the above range, compound (1) can be sufficiently dispersed. This makes it possible to efficiently obtain a film made of compound (1) as a forming material and in which the occurrence of defects is sufficiently suppressed. In this specification, the solid content refers to the total amount of components excluding volatile components such as solvents from the composition. The composition may contain only one type of compound (1), or may contain a combination of two or more types with different structures. When the composition contains two or more types of compound (1), they may have different maximum absorption wavelengths.

The composition may further contain at least one other dye compound other than compound (1), for example, a dichroic dye. Examples of the other dye compounds include azo dyes such as monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, and at least one selected from the group consisting of these is preferable. The composition may contain one other dye compound alone, or may contain two or more in combination. For example, when used as a coating-type polarizing plate material, it is preferable that the other dye compound contained in the composition has a maximum absorption wavelength in a wavelength range different from that of compound (1). For example, when used as a coating-type polarizing plate material, the composition preferably contains three or more dichroic dyes in combination, including compound (1), and more preferably contains three or more azo dyes in combination. By containing three or more dye compounds in combination with different maximum absorption wavelengths in the composition, for example, absorption can be obtained in the entire visible light range by a film formed from the composition.

When the composition contains other coloring compounds, the content is preferably 50 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the solid content of the composition. If it is within the above range, the other coloring compounds can be sufficiently dispersed.

The composition contains a liquid crystal compound including at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound in addition to compound (1). The composition may contain both a polymerizable liquid crystal compound and a liquid crystal polymer compound, and the composition may contain two or more types of each of the polymerizable liquid crystal compound and the liquid crystal polymer compound. By containing at least one type of the polymerizable liquid crystal compound and the liquid crystal polymer compound, a composition in which compound (1) is dispersed in the liquid crystal compound can be formed.

The liquid crystalline polymer compound may be one that constitutes a thermotropic liquid crystal polymer or one that constitutes a lyotropic liquid crystal polymer. The liquid crystalline polymer compound is preferably one that constitutes a thermotropic liquid crystal polymer, in that precise film thickness control is possible.

Liquid crystals are classified into smectic liquid crystals, nematic liquid crystals, and cholesteric liquid crystals according to the molecular arrangement structure in the liquid crystal state. Of these, smectic liquid crystals are preferably used for polarizing film applications. Therefore, the polymerizable liquid crystal compound is preferably a polymerizable smectic liquid crystal compound, and the liquid crystalline polymer compound is preferably a smectic liquid crystalline polymer compound.

By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity and a polymer compound exhibiting smectic liquid crystallinity, a polarizing film with a high degree of orientation order can be formed. The liquid crystal state exhibited by the polymerizable liquid crystal compound and the liquid crystal polymer compound is preferably a smectic phase (smectic liquid crystal state), and from the viewpoint of realizing a higher degree of orientation order, a higher order smectic phase (higher order smectic liquid crystal state) is more preferable. Here, the higher order smectic phase means a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, and a smectic L phase, and among these, the smectic B phase, the smectic F phase, and the smectic I phase are more preferable. A polarizing film with a high degree of orientation order can obtain Bragg peaks derived from a higher order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement. The Bragg peak refers to a peak derived from the planar periodic structure of molecular orientation. The periodic interval (order period) of the polarizing film obtained from the composition is preferably 0.3 nm or more and 0.6 nm or less. The polymerizable liquid crystal compound or liquid crystalline polymer compound may be a polymerizable smectic liquid crystal compound or a smectic liquid crystalline polymer compound that shows a Bragg peak derived from a higher order structure in X-ray diffraction measurement.

Compound (1) can exhibit high dichroism even when dispersed among dense molecular chains formed from at least one compound selected from a smectic liquid crystal polymerizable liquid crystal compound and a smectic liquid crystal polymer compound. Therefore, a composition containing a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound, particularly a liquid crystal compound containing at least one of a smectic liquid crystal polymerizable liquid crystal compound and a smectic liquid crystal polymer compound, and compound (1) can provide a polarizing film with a high dichroic ratio.

Polymerizable Liquid Crystal Compound A polymerizable liquid crystal compound is a compound that has at least one polymerizable group in the molecule and can exhibit a liquid crystal phase by being aligned. A polymerizable liquid crystal compound is preferably a compound that can exhibit a liquid crystal phase by being aligned alone. A polymerizable group means a functional group that can be involved in a polymerization reaction, and is preferably a radically polymerizable group.

The polymerizable liquid crystal compound is not particularly limited as long as it has at least one polymerizable group and preferably exhibits smectic liquid crystal properties, and any known polymerizable liquid crystal compound can be used. Specific examples of the polymerizable liquid crystal compound include a compound represented by the following formula (A) (hereinafter, also referred to as "polymerizable liquid crystal compound (A)").
U ¹ -V ¹ -W ¹ -(X ¹ -Y ¹ ) _m -X ² -Y ² -X ³ -W ² -V ² -U ² (A)

In formula (A), m is an integer of 1 to 3. ^{X 1} , X ² and X ³ each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. When m is 2 or 3, X ¹ may be the same as or different from each other. At least three selected from the group consisting of X ¹ , X ² and X ³ represent a divalent 6-membered hydrocarbon ring group. Y ¹ , Y ² , W ¹ and W ² each independently represent a single bond or a divalent linking group. When m is 2 or 3, Y ¹ may be the same as or different from each other. V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent. At least one of -CH ₂ - constituting the alkanediyl group may be substituted with -O-, -CO-, -S- or -NH-. ^U1 and ^U2 each independently represent a polymerizable group or a hydrogen atom, and at least one of them represents a polymerizable group.

Examples of the divalent aromatic group in X ¹ , X ² and X ³ include a 1,4-phenylene group and a 1,4-naphthylene group. Examples of the divalent alicyclic hydrocarbon group include a cyclohexane-1,4-diyl group. At least one of the divalent aromatic group and the divalent alicyclic hydrocarbon group in ^{X 1} , X ² and X ³ may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group and an n-butyl group, a cyano group and a halogen atom. At least one of -CH ₂ - constituting the divalent alicyclic hydrocarbon group may be substituted with -O-, -S- or -NR-. Here, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.

The divalent 6-membered hydrocarbon ring group for X ¹ , X ² and X ³ includes a 1,4-phenylene group which may have a substituent, and a cyclohexane-1,4-diyl group which may have a substituent.

The divalent aromatic group in X ¹ , X ² and X ³ is preferably a 1,4-phenylene group which may have a substituent, more preferably an unsubstituted 1,4-phenylene group, and the divalent alicyclic hydrocarbon group is preferably a cyclohexane-1,4-diyl group which may have a substituent, more preferably a trans-cyclohexane-1,4-diyl group which may have a substituent, and even more preferably an unsubstituted trans-cyclohexane-1,4-diyl group.

Y ¹ and Y ² each independently represent a single bond or a divalent linking group. The divalent linking group is, for example, at least one selected from the group consisting of -CH ₂ CH ₂ -, -CH ₂ O-, -(C=O)O-, -O(C=O)O-, -N=N-, -CR ^a ═CR ^b -, -C≡C- and -CR ^a ═N-. Here, R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ¹ is preferably -CH ₂ CH ₂ -, -(C=O)O- or a single bond. Y ² is preferably -CH ₂ CH ₂ - or -CH ₂ O-.

W ¹ and W ² each independently represent a single bond or a divalent linking group. The divalent linking group is, for example, at least one selected from the group consisting of -O-, -S-, -(C=O)O-, and -O(C=O)O-. ^{W 1} and W ² each independently represent preferably a single bond or -O-.

^V1 and ^V2 each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, in which at least one of _-CH2- constituting the alkanediyl group may be replaced by -O-, -CO-, -S- or -NH-.

Examples of the alkanediyl group represented by V ¹ and V ² include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a decane-1,10-diyl group, a tetradecane-1,1-diyl group, and an icosane-1,20-diyl group. ^{V 1} and V ² are preferably alkanediyl groups having 2 to 12 carbon atoms, more preferably alkanediyl groups having 6 to 12 carbon atoms.

The optional substituent of the alkanediyl group having 1 to 20 carbon atoms, which may have a substituent, includes a cyano group and a halogen atom. The alkanediyl group is preferably an alkanediyl group having no substituent, and more preferably an alkanediyl group having no substituent and being linear.

U ¹ and U ² each independently represent a polymerizable group or a hydrogen atom, and at least one of them represents a polymerizable group. ^{U 1} and U ² are preferably polymerizable groups. It is preferable that both ^{U 1} and U ² are polymerizable groups, and it is preferable that both are radically polymerizable groups. The polymerizable group represented by U ¹ and the polymerizable group represented by U ² may be different from each other, but it is preferable that they are the same type of group. As the polymerizable group in ^{U 1} and U ² , the same polymerizable group as exemplified above as the polymerizable group possessed by the polymerizable liquid crystal compound can be mentioned. Among them, the polymerizable group represented by U ¹ and U ² is preferably at least one selected from the group consisting of a vinyloxy group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group, and an acryloyloxy group is more preferable.

Specific examples of the polymerizable liquid crystal compound (A) include compounds represented by the following formulas (A-1) to (A-17). When the polymerizable liquid crystal compound (A) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans type.

Among them, the polymerizable liquid crystal compound (A) is preferably at least one selected from the group consisting of compounds represented by any of formulas (A-2), (A-3), (A-4), (A-5), (A-6), (A-7), (A-8), (A-13), (A-14), (A-15), (A-16), and (A-17). The polymerizable liquid crystal compound (A) may be used alone or in combination of two or more.

The polymerizable liquid crystal compound (A) can be produced by the method described in the known literature, for example, Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996) and Japanese Patent No. 4719156.

Liquid crystalline polymer compound The liquid crystalline polymer compound may be a compound obtained by polymerizing the polymerizable liquid crystal compound (hereinafter also referred to as a polymer of the polymerizable liquid crystal compound) or may be another liquid crystalline polymer compound, and is preferably a polymer of the polymerizable liquid crystal compound.

The polymer of the polymerizable liquid crystal compound may use two or more of the polymerizable liquid crystal compounds as raw material monomers. The polymer of the polymerizable liquid crystal compound may also contain other monomers as raw material monomers other than the polymerizable liquid crystal compound.

The content ratio of the polymerizable liquid crystal compound in the polymer of the polymerizable liquid crystal compound is usually 1 mol% or more and 100 mol% or less with respect to the total amount of the constituent units derived from the polymerizable liquid crystal compound constituting the polymer of the polymerizable liquid crystal compound, and from the viewpoint of increasing the orientation of the polymer of the polymerizable liquid crystal compound, it is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

The other liquid crystal polymer compounds include polymer compounds having liquid crystal groups. For example, polymer compounds that serve as the backbone include polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyalkylene ethers, polyvinyl alcohols; polymethacrylic acid esters; polyacrylic acid esters; and the like, and these polymer compounds have liquid crystal groups. Among these, polymethacrylic acid esters and polyacrylic acid esters having liquid crystal groups are preferred.

The other liquid crystalline polymer compounds may contain two or more types of liquid crystalline groups. The liquid crystalline groups may be contained in the main chain of the polymer compound that serves as the mother skeleton, in the side chain of the polymer compound that serves as the mother skeleton, or in both the main chain and the side chain of the polymer compound that serves as the mother skeleton. Examples of liquid crystalline groups include groups formed by removing one hydrogen atom from a compound having at least two 6-membered hydrocarbon ring structures, or groups formed by removing two hydrogen atoms from the compound.

The content of liquid crystalline groups in the other liquid crystalline polymer compounds is usually 1 mol% or more and 100 mol% or less relative to the total amount of the structural units constituting the polymer compound that is the parent skeleton of the other liquid crystalline polymer compounds. From the viewpoint of increasing the orientation of the other liquid crystalline polymer compounds, the content is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

When two or more types of polymerizable liquid crystal compounds are combined in the composition, it is preferable that at least one of them is a polymerizable liquid crystal compound (A), and more preferably, two or more of them are polymerizable liquid crystal compounds (A). By combining two or more types of polymerizable liquid crystal compounds, the liquid crystal phase may be temporarily maintained even at a temperature below the liquid crystal-crystal phase transition temperature. The content of the polymerizable liquid crystal compound (A) contained in the composition is preferably 40 mass% or more, more preferably 60 mass% or more, in total, based on the total mass of all polymerizable liquid crystal compounds in the composition, and all of the polymerizable liquid crystal compounds may be polymerizable liquid crystal compounds (A). When the content of the polymerizable liquid crystal compound (A) is within the above range, the polymerizable liquid crystal compounds are easily aligned with a high degree of orientation order, and the compound represented by formula (1) is aligned along this order, so that a polarizing film having excellent polarization performance can be obtained.

From the viewpoint of increasing the orientation of the polymerizable liquid crystal compound and the liquid crystalline polymer compound, the total content of the polymerizable liquid crystal compound and the liquid crystalline polymer compound in the composition is, for example, 50 parts by mass or more, preferably 70 parts by mass or more and 99.9 parts by mass or less, more preferably 70 parts by mass or more and 99.5 parts by mass or less, even more preferably 80 parts by mass or more and 99 parts by mass or less, particularly preferably 80 parts by mass or more and 94 parts by mass or less, and even more preferably 80 parts by mass or more and 90 parts by mass or less, relative to 100 parts by mass of the solid content of the composition.

The content of compound (1) in the composition is usually 0.1 parts by mass or more and 50 parts by mass or less, preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystal polymer compound. When the content of compound (1) relative to the total amount of the polymerizable liquid crystal compound and the liquid crystal polymer compound is 50 parts by mass or less, there is a tendency that the orientation of the polymerizable liquid crystal compound, the liquid crystal polymer compound, and compound (1) is less disturbed, and a polarizing film having a high degree of orientation order can be obtained.

Polymer Compound The composition may further contain a polymer compound in addition to the compound (1), the polymerizable liquid crystal compound, and the liquid crystal polymer compound. When the composition contains a polymer compound, the compound (1) may be easily dispersed in the composition. The polymer compound that the composition may contain is not particularly limited as long as it can disperse the compound (1). In terms of easiness in uniformly dispersing the compound (1), an acrylic polymer such as polymethyl methacrylate (PMMA) is preferred. The polymer compound may also be a polymer compound obtained by polymerizing the above-mentioned polymerizable liquid crystal compound. The weight average molecular weight of the polymer compound in terms of polystyrene is, for example, 10,000 to 200,000, preferably 20,000 to 150,000.

When the composition contains a polymeric compound, the content thereof can be appropriately selected depending on the purpose, etc. The content of the polymeric compound is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less, per 100 parts by mass of the solid content of the composition.

The composition preferably further contains a liquid medium such as a solvent and a polymerization initiator, and may further contain a photosensitizer, a polymerization inhibitor, a leveling agent, etc., as necessary.

The solvent is preferably a solvent capable of completely dissolving the compound (1), the polymerizable liquid crystal compound, the liquid crystalline polymer compound, and the polymer compound, and is preferably a solvent inactive to the polymerization reaction of the polymerizable liquid crystal compound.

Examples of solvents include alcohol solvents, ester solvents, ketone solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, nitrile solvents, ether solvents, and chlorine-containing solvents. These solvents may be used alone or in combination of two or more.

When the composition contains a solvent, the content of the solvent is preferably 50% by mass or more and 98% by mass or less with respect to the total amount of the composition. In other words, the content of the solid content in the composition is preferably 2% by mass or more and 50% by mass or less. If the solid content is 50% by mass or less, the viscosity of the composition is low, and the film obtained from the composition, for example, the thickness of the film, tends to be approximately uniform, and unevenness in the film tends to be less likely to occur. The content of the solid content can be determined taking into consideration the thickness of the film to be produced.

Polymerization initiator The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound. The polymerization initiator is preferably a photopolymerization initiator, since it can initiate the polymerization reaction under lower temperature conditions. Specifically, a photopolymerization initiator capable of generating active radicals or acids under the action of light is exemplified, and among them, a photopolymerization initiator capable of generating radicals under the action of light is preferred.

Examples of polymerization initiators include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts. The polymerization initiator can be appropriately selected from known polymerization initiators depending on the purpose. The polymerization initiators can be used alone or in combination of two or more.

When the composition contains a polymerization initiator, the content of the polymerization initiator may be appropriately determined according to the type and amount of the polymerizable liquid crystal compound contained in the composition. The content of the polymerization initiator is, for example, 0.001 parts by mass or more, 0.01 parts by mass or more, 0.1 parts by mass or more, or 0.5 parts by mass or more, and is, for example, 30% by mass or less, 10% by mass or less, or 8% by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound. The content of the polymerization initiator is preferably 0.001 parts by mass or more and 30 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the polymerization initiator is within the above range, the polymerizable liquid crystal compound can be polymerized without disturbing the orientation.

Photosensitizer When the composition contains a photopolymerization initiator, the composition may preferably contain at least one photosensitizer. The composition contains a photopolymerization initiator and a photosensitizer, which tends to promote the polymerization reaction of the polymerizable liquid crystal compound. Examples of the photosensitizer include xanthone compounds such as xanthone and thioxanthone; anthracene compounds such as anthracene and alkoxy-substituted anthracene; phenothiazine and rubrene; and the like. The photosensitizer can be used alone or in combination of two or more.

When the composition contains a photosensitizer, the content of the photosensitizer in the composition may be appropriately determined depending on the type and amount of the photopolymerization initiator and the polymerizable liquid crystal compound. The content of the photosensitizer in the composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.

Polymerization Inhibitor The composition may contain at least one type of polymerization inhibitor. Examples of the polymerization inhibitor include radical scavengers such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (e.g., butylcatechol), pyrogallol, and 2,2,6,6-tetramethyl-1-piperidinyloxy radical; thiophenols; β-naphthylamines and β-naphthols. By including a polymerization inhibitor in the composition, the degree of progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled.

When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.

Leveling Agent The composition may contain at least one leveling agent. The leveling agent has the function of adjusting the fluidity of the composition and making the coating film obtained by applying the composition flatter, and specifically includes a surfactant. As the leveling agent, at least one selected from the group consisting of leveling agents mainly composed of a polyacrylate compound and leveling agents mainly composed of a fluorine atom-containing compound is preferable. The leveling agent may be used alone or in combination of two or more kinds.

When the composition contains a leveling agent, the content of the leveling agent is preferably 0.05 parts by mass or more and 5 parts by mass or less, and more preferably 0.05 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound. When the content of the leveling agent is within the above range, the polymerizable liquid crystal compound and the liquid crystalline polymer compound are easily aligned horizontally, and unevenness is less likely to occur, and a smoother film, such as a polarizing film, tends to be obtained.

When the content of the leveling agent is within the above range, it is easy to align the polymerizable liquid crystal compound and the liquid crystalline polymer compound horizontally, and the resulting film tends to be smoother. When the content of the leveling agent relative to the polymerizable liquid crystal compound and the liquid crystalline polymer compound exceeds the above range, the resulting film tends to be more prone to unevenness.

Antioxidant The composition may contain an antioxidant. The antioxidant is not particularly limited as long as the composition can exhibit the effects of the present invention, and known antioxidants can be used. From the viewpoint of having a high inhibitory effect against photodegradation of compound (1), the antioxidant is preferably a so-called primary antioxidant that has an action of preventing autoxidation by capturing radicals. Therefore, it is more preferable that the antioxidant contained in the composition is at least one selected from the group consisting of phenolic compounds, alicyclic alcohol compounds, and amine compounds. The antioxidant may be used alone or in combination of two or more kinds.

The content of the antioxidant in the composition is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the composition. When the content of the antioxidant is equal to or more than the lower limit, the photodegradation of compound (1) can be more effectively suppressed. When the content of the antioxidant is equal to or less than the upper limit, the orientation of the polymerizable liquid crystal compound is less likely to be disturbed, and a higher effect of suppressing the photodegradation of compound (1) can be expected.

The composition may contain additives other than those described above. Examples of the additives include release agents, stabilizers, colorants such as bluing agents, flame retardants, and lubricants. When the composition contains other additives, the content of the other additives is preferably more than 0% and not more than 20% by mass, more preferably more than 0% and not more than 10% by mass, based on the solid content of the composition.

The composition can be produced by a conventional method for preparing a composition. For example, the composition can be prepared by mixing and stirring compound (1), a liquid crystal compound, and, if necessary, additives such as an antioxidant and a leveling agent.

<Membrane>
The film according to the present embodiment contains compound (1) as a forming material. The film may be obtained by using a composition containing compound (1) and a liquid crystal compound as a forming material. The film made of the composition may be formed by applying the composition to a substrate and forming a film. In addition, when the composition contains a polymerizable liquid crystal compound, the film containing a cured product obtained by polymerizing the polymerizable liquid crystal compound may be formed by applying the composition to a substrate, forming a film, and then polymerizing and curing the polymerizable liquid crystal compound.

The composition can form a film with a high degree of orientation order, such as a polarizing film. Therefore, the film according to this embodiment is a polarizing film formed from a composition containing compound (1) and a liquid crystal compound, and includes a polarizing film with a high degree of orientation order.

Here, in a polarizing film with a high degree of orientational order, a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystalline phase is obtained in an X-ray diffraction measurement. Therefore, in a polarizing film formed from the composition, it is preferable that the polymerizable liquid crystal compound or the liquid crystalline polymer compound is oriented so as to show a Bragg peak in an X-ray diffraction measurement, and it is more preferable that the molecules of the polymerizable liquid crystal compound or the liquid crystalline polymer compound are oriented in the direction in which light is absorbed, that is, "horizontal orientation". A high degree of orientational order that shows a Bragg peak can be achieved by controlling the type of polymerizable liquid crystal compound or liquid crystalline polymer compound used, the amount of compound (1), etc.

The compound (1) and the liquid crystal compound constituting the composition used to form the film are as described above.

The membrane can be produced, for example, by a method comprising the following steps.
Step A: forming a coating film of a composition containing compound (1), a liquid crystalline compound, and a solvent;
Step B: Removing at least a portion of the solvent from the coating;
Step C: raising the temperature to a temperature at which the liquid crystalline compound undergoes a phase transition to a liquid phase or higher, and then lowering the temperature to cause the liquid crystalline compound to undergo a phase transition to a smectic phase (smectic liquid crystal state); and Step D: as necessary, polymerizing the polymerizable liquid crystalline compound while maintaining the smectic phase (smectic liquid crystal state).

The coating film of the composition can be formed, for example, by applying the composition onto a substrate, an alignment film (described later), or the like. The composition may also be applied directly onto a retardation film or other layer that constitutes a polarizing plate.

The substrate is usually a transparent substrate. When the substrate is not placed on the display surface of a display element, for example, when a laminate obtained by removing the substrate from the film is placed on the display surface of a display element, the substrate does not have to be transparent. A transparent substrate means a substrate having transparency capable of transmitting light, particularly visible light, and transparency refers to a property in which the transmittance for light rays in the wavelength range of 380 nm or more and 780 nm or less is 80% or more. A specific example of a transparent substrate is a translucent resin substrate.

Resins constituting the light-transmitting resin substrate include polyolefins; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid esters; polyacrylic acid esters; cellulose esters; polyethylene naphthalate; polycarbonate; polysulfones; polyethersulfones; polyetherketones; polyphenylene sulfide, and polyphenylene oxide. From the viewpoints of availability and transparency, polyethylene terephthalate, polymethacrylic acid esters, cellulose esters, cyclic olefin resins, and polycarbonates are preferred.

The properties required of the substrate vary depending on the film configuration, but a substrate with as little retardation as possible is usually preferred. Examples of substrates with as little retardation as possible include cellulose ester films with no retardation, such as Zerotac (Konica Minolta Opto, Inc.) and Ztac (Fujifilm Corporation). Unstretched cyclic olefin resin substrates are also preferred. Surfaces of the substrate on which no film is laminated may be subjected to hard coat treatment, anti-reflection treatment, anti-static treatment, etc.

The thickness of the substrate is usually 5 μm or more and 300 μm or less, preferably 20 μm or more and 200 μm or less, and more preferably 20 μm or more and 100 μm or less. If the thickness is equal to or more than the lower limit, the decrease in strength is suppressed and the processability tends to be good.

Methods for applying the composition to a substrate or the like include known methods such as coating methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods, and printing methods such as flexography.

Then, at least a part of the solvent contained in the coating film obtained from the composition is removed by drying or the like to form a dry coating film. Furthermore, when the coating film contains a polymerizable liquid crystal compound, the dry coating film is formed by drying under conditions in which the polymerizable liquid crystal compound does not polymerize. Examples of methods for drying the coating film include natural drying, ventilation drying, heat drying, and reduced pressure drying.

Furthermore, in order to cause the liquid crystal compound to undergo a phase transition to a liquid phase, the temperature is raised to a temperature at which the liquid crystal compound undergoes a phase transition to a liquid phase or higher, and then the temperature is lowered to cause the liquid crystal compound to undergo a phase transition to a smectic phase (smectic liquid crystal state). Such a phase transition may be performed after the solvent in the coating film is removed, or may be performed simultaneously with the removal of the solvent.

When the composition contains a polymerizable liquid crystal compound, the polymerizable liquid crystal compound is polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, thereby forming a film containing a cured product of the polymerizable liquid crystal compound. Photopolymerization is preferred as the polymerization method. In photopolymerization, the light irradiated to the dried coating film is appropriately selected according to the type of photopolymerization initiator contained in the dried coating film, the type of polymerizable liquid crystal compound (particularly the type of polymerizable group possessed by the polymerizable liquid crystal compound) and the amount thereof. Specific examples include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays and γ-rays, active electron beams, etc. Among them, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction and because photopolymerization devices widely used in this field can be used. It is preferable to select the type of polymerizable liquid crystal compound and photopolymerization initiator contained in the composition so that photopolymerization is possible by ultraviolet light. In addition, the polymerization temperature can be controlled by irradiating light while cooling the dried coating film with an appropriate cooling means during polymerization. By using such a cooling method, the polymerization of the polymerizable liquid crystal compound can be carried out at a lower temperature, and even if a substrate with relatively low heat resistance is used, a suitable film can be formed. During photopolymerization, a patterned film can also be obtained by performing masking and development.

Examples of light sources for the active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, LED light sources emitting light in the wavelength range of 380 nm to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, etc.

The ultraviolet irradiation intensity may be generally 10 mW/cm ² or more and 3,000 mW/cm ² or less. The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating a photopolymerization initiator. The time for irradiating light may be generally 0.1 seconds or more and 10 minutes or less, preferably 0.1 seconds or more and 5 minutes or less, more preferably 0.1 seconds or more and 3 minutes or less, and even more preferably 0.1 seconds or more and 1 minute or less. When irradiating once or multiple times with such ultraviolet irradiation intensity, the integrated light amount is preferably 10 mJ/cm ² or more and 3,000 mJ/cm ² or less.

By carrying out photopolymerization, the polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of the smectic phase, preferably the high-order smectic phase, to form a film. The film obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase has the advantage of having higher polarization performance due to the action of the dichroic dye, compared to conventional host-guest type polarizing films, that is, films consisting of a liquid crystal state of the nematic phase. In addition, it has the advantage of being stronger than films coated with only the dichroic dye or lyotropic liquid crystal.

The thickness of the film can be appropriately selected depending on the display device to which it is applied, and is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and even more preferably 1 μm or more and 3 μm or less.

When the film is used as a polarizing film, it is preferable that it is formed on an alignment film. The alignment film has an alignment control force that aligns the polymerizable liquid crystal compound and the liquid crystal polymer compound in the desired direction. The alignment film is preferably solvent-resistant so that it is not dissolved by coating a composition containing a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound, and is also heat-resistant in a heat treatment for removing the solvent or orienting the polymerizable liquid crystal compound. Examples of such alignment films include alignment films containing an orienting polymer, photo-alignment films, and groove alignment films having a concave-convex pattern or multiple grooves on the surface, and photo-alignment films are preferable from the viewpoint of the accuracy and quality of the alignment angle.

<Laminate>
The laminate according to the present embodiment includes a film containing compound (1) as a forming material. The laminate may include a substrate and a film containing compound (1) as a forming material arranged on the substrate, or may include a substrate, an alignment film arranged on the substrate, and a film containing compound (1) as a forming material arranged on the alignment film. The film containing compound (1) as a forming material may constitute a polarizing film. The substrate may be a retardation film. The laminate may constitute, for example, a polarizing plate. The laminate may be manufactured, for example, by forming a film on a substrate according to the above-mentioned method for manufacturing a film.

From the viewpoint of the flexibility and visibility of the display device, the thickness of the laminate is preferably 10 μm or more and 300 μm or less, more preferably 20 μm or more and 200 μm or less, and even more preferably 25 μm or more and 100 μm or less.

When the laminate has a retardation film as the substrate, the thickness of the retardation film can be appropriately selected depending on the display device to which it is applied.

<Display device>
The display device of the present embodiment includes the laminate, and the laminate may be a polarizing plate. The display device can be obtained, for example, by bonding the laminate as a polarizing plate to the surface of the display device via a pressure-sensitive adhesive layer. The display device is a device having a display element, and is a device including a light-emitting element or a light-emitting device as a light-emitting source. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, an electron emission display device (e.g., a field emission display device (FED), a surface field emission display device (SED)), an electronic paper (a display device using electronic ink, an electrophoretic element, etc.), a plasma display device, a projection display device (e.g., a display device having a grating light valve (GLV) display device, a digital micromirror device (DMD)), and a piezoelectric ceramic display. The liquid crystal display device includes any of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection liquid crystal display device. These display devices may be display devices that display two-dimensional images, or stereoscopic display devices that display three-dimensional images. In particular, as the display device, an organic EL display device and a touch panel display device are preferable, and an organic EL display device is particularly preferable.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1: Synthesis of compound (1-1) To synthesize compound (1-1), first compound (1-1-a) was synthesized into compound (1-1-b), which was then alkylated to obtain compound (1-1).

Synthesis of Compound (1-1-a) 6-Methoxybenzo[d]thiazol-2-amine (9.01 g, 50.0 mmol), acetic acid (30.0 mL), water (70.0 mL), and sulfuric acid (4.0 mL, 75 mmol) were mixed and cooled to 0°C to 5°C, and a 40% sulfuric acid solution of nitrosylsulfuric acid (31.8 g, 100 mmol) was added dropwise thereto. After that, the mixture was stirred for 30 minutes while maintaining the temperature at 0°C to 5°C, and amidosulfuric acid (4.85 g, 50.0 mmol) was added to prepare a diazo liquid. On the other hand, sodium (phenylamino)methanesulfonate (11.6 g, 55.0 mmol) and water (300 mL) were mixed and cooled to 0°C to 5°C, and the entire amount of the diazo liquid previously prepared was added dropwise. After the dropwise addition, the mixture was heated to room temperature, and the precipitated solid was collected by filtration and washed with acetonitrile to obtain a black solid. The obtained solid, sodium hydroxide (5.96 g, 149 mmol), and water (300 mL) were mixed and stirred under heating at 90° C. for 2 hours. The precipitated solid was collected by filtration to obtain compound (1-1-a) (8.61 g, yield 61%).

Synthesis of Compound (1-1-b) Compound (1-1-a) (5.69 g, 20.0 mmol), 35% hydrochloric acid (5.9 mL, 67 mmol), acetic acid (48.0 mL), and water (8.0 mL) were mixed and cooled to 0°C to 5°C, and a solution of sodium nitrite (4.14 g, 60.0 mmol) in water (6.0 mL) was added dropwise thereto. After that, the mixture was stirred for 30 minutes while maintaining the temperature at 0°C to 5°C, and amidosulfuric acid (3.88 g, 40.0 mmol) was added to prepare a diazo liquid. Meanwhile, phenol (5.64 g, 60.0 mmol), sodium acetate (9.85 g, 120 mmol), and water (140 mL) were mixed and cooled to 0°C to 5°C, and the entire amount of the diazo liquid previously prepared was added dropwise thereto. After the dropwise addition was completed, the temperature was raised to room temperature, and the precipitated solid was filtered off to obtain compound (1-1-b) (7.11 g, yield 91%).

Synthesis of Compound (1-1) Compound (1-1-b) (0.300 g, 0.770 mmol), 2-methylbutyl p-toluenesulfonate (0.75 g, 3.1 mmol), potassium carbonate (0.43 g, 3.1 mmol), and N,N-dimethylacetamide (5.0 g) were mixed and heated with stirring at 90° C. for 2 hours. Water was added to the reaction solution, and the precipitated solid was filtered off and washed with methanol. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent to obtain compound (1-1) (0.28 g, yield 79%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.20-8.17 (m, 2H), 8.08 (d, 1H), 8.06-8.03 (m, 2H), 7.98-7.94 (m, 2H), 7.33 (d, 1H), 7.14 (dd, 1H), 7.05-7.01 (m, 2H), 3.9 5-3.91 (m, 1H), 3.93 (s, 3H), 3.87-3.83 (m, 1H), 1.98-1.86 (m, 1H), 1.66-1.55 (m, 1H), 1.37-1.26 (m, 1H), 1.05 (d, 2H), 0.98 (t, 3H).
UV-visible spectrum: λmax=453 nm (in acetonitrile)

Synthesis Example 2: Synthesis of Compound (1-2) Compound (1-1-b) (3.70 g, 9.50 mmol), 1-bromo-2-methylpropane (2.62 g, 19.1 mmol), potassium carbonate (3.94 g, 28.5 mmol), and N,N-dimethylacetamide (47.5 mL) were mixed and heated with stirring at 90° C. for 4 hours. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent, and further purified by reprecipitation from chloroform/methanol to obtain compound (1-2) (1.93 g, yield 46%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.21-8.17 (m, 2H), 8.08 (d, 1H), 8.06-8.03 (m, 2H), 7.99-7.95 (m, 2H), 7.34 (d, 1H) , 7.15 (dd, 1H), 7.05-7.01 (m, 2H), 3.93 (s, 3H), 3.83 (d, 2H), 2.19-2.09 (m, 1H), 1.07 (d, 6H).
UV-visible spectrum: λmax=452 nm (in acetonitrile)

Synthesis Example 3: Synthesis of Compound (1-3) Compound (1-1-b) (0.586 g, 1.50 mmol), 1-bromo-3-methylbutane (0.453 g, 3.01 mmol), potassium carbonate (0.622 g, 4.50 mmol), and N,N-dimethylacetamide (7.5 mL) were mixed and heated with stirring at 100° C. for 1 hour. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent, and further purified by reprecipitation from chloroform/methanol to obtain compound (1-3) (0.397 g, yield 57%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.21-8.17 (m, 2H), 8.08 (d, 1H), 8.06-8.03 (m, 2H), 7.99-7.95 (m, 2H), 7.34 (d, 1H), 7.15 (dd, 1H), 7.05-7.01 (m, 2H), 4.10 (t, 2H), 3.93 (s, 3H), 1.92-1.83 (m, 1H), 1.74 (q, 2H), 1.00 (d, 6H).
UV-visible spectrum: λmax=452 nm (in acetonitrile)

Synthesis Example 4: Synthesis of Compound (1-4) Compound (1-1-b) (0.585 g, 1.50 mmol), 2-propanol (0.25 mL, 3.2 mmol), triphenylphosphine (0.473 g, 1.80 mmol), a 1.9 M toluene solution of diisopropyl azodicarboxylate (0.85 mL, 1.6 mmol), and THF (9.5 mL) were mixed and stirred at room temperature for 2 hours. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent, and further purified by reprecipitation from chloroform/methanol to obtain compound (1-4) (0.268 g, yield 41%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.21-8.17 (m, 2H), 8.08 (d, 1H), 8.06-8.03 (m, 2H), 7.99-7.95 (m, 2H), 7.3 4 (d, 1H), 7.15 (dd, 1H), 7.05-7.01 (m, 2H), 4.69 (sep, 1H), 3.93 (s, 3H), 1.41 (d, 6H).
UV-visible spectrum: λmax=455 nm (in acetonitrile)

Synthesis Example 5: Synthesis of compound (1-5) To synthesize compound (1-5), first compound (1-5-a) was synthesized into compound (1-5-b), which was then alkylated to obtain compound (1-5).

Synthesis of Compound (1-5-a) 6-ethoxybenzo[d]thiazol-2-amine (9.71 g, 50.0 mmol), acetic acid (70.0 mL), water (70.0 mL), and sulfuric acid (4.0 mL, 75 mmol) were mixed and cooled to 0°C to 5°C, and a 40% sulfuric acid solution of nitrosylsulfuric acid (31.8 g, 100 mmol) was added dropwise thereto. After that, the mixture was stirred for 30 minutes while maintaining the temperature at 0°C to 5°C, and amidosulfuric acid (4.85 g, 50.0 mmol) was added to prepare a diazo liquid. Meanwhile, sodium (phenylamino)methanesulfonate (11.5 g, 55.1 mmol) and water (300 mL) were mixed and cooled to 0°C to 5°C, and the entire amount of the diazo liquid previously prepared was added dropwise. After the dropwise addition, the mixture was heated to room temperature, and the precipitated solid was collected by filtration and washed with acetonitrile to obtain a black solid. The obtained solid, sodium hydroxide (6.00 g, 150 mmol), and water (300 mL) were mixed and stirred under heating at 90° C. for 2 hours. The precipitated solid was collected by filtration to obtain compound (1-5-a) (8.48 g, yield 57%).

Synthesis of Compound (1-5-b) Compound (1-5-a) (5.97 g, 20.0 mmol), 35% hydrochloric acid (5.9 mL, 67 mmol), acetic acid (48.0 mL), and water (8.0 mL) were mixed and cooled to 0°C to 5°C, and a solution of sodium nitrite (4.14 g, 60.0 mmol) in water (6.0 mL) was added dropwise thereto. After that, the mixture was stirred for 30 minutes while maintaining the temperature at 0°C to 5°C, and amidosulfuric acid (3.89 g, 40.1 mmol) was added to prepare a diazo liquid. Meanwhile, phenol (5.65 g, 60.0 mmol), sodium acetate (9.84 g, 120 mmol), and water (140 mL) were mixed and cooled to 0°C to 5°C, and the entire amount of the diazo liquid previously prepared was added dropwise thereto. After the dropwise addition was completed, the temperature was raised to room temperature, and the precipitated solid was filtered off to obtain compound (1-5-b) (7.01 g, yield 87%).

Synthesis of Compound (1-5) Compound (1-5-b) (0.400 g, 0.991 mmol), 2-methylbutyl p-toluenesulfonate (0.96 g, 4.0 mmol), potassium carbonate (0.55 g, 4.0 mmol), and N,N-dimethylacetamide (5.0 g) were mixed and heated with stirring at 90° C. for 2 hours. Water was added to the reaction solution, and the precipitated solid was filtered off and washed with methanol. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent to obtain compound (1-5) (0.24 g, yield 51%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.20-8.17 (m, 2H), 8.07 (d, 1H), 8.06-8.03 (m, 2H), 7.98- 7.94 (m, 2H), 7.32 (d, 1H), 7.13 (dd, 1H), 7.05-7.01 (m, 2H), 4.15 (q, 2 H), 3.95-3.91 (m, 1H), 3.87-3.83 (m, 1H), 1.98-1.86 (m, 1H), 1.66-1. 55 (m, 1H), 1.49 (t, 3H), 1.36-1.25 (m, 1H), 1.05 (d, 2H), 0.98 (t, 3H).
UV-visible spectrum: λmax=455 nm (in acetonitrile)

Synthesis Example 6: Synthesis of compound (1-6) In order to synthesize compound (1-6), first compound (1-6-a) was synthesized into compound (1-6-b), followed by transesterification to obtain compound (1-6).

Synthesis of Compound (1-6-a) Sodium nitrite (4.15 g, 60.1 mmol) was added little by little to sulfuric acid (50.0 mL), and the mixture was heated and stirred at 50° C. for 15 minutes to prepare a sodium nitrosyl sulfate solution. Ethyl 2-aminobenzothiazole-6-carboxylate (4.45 g, 20.0 mmol), acetic acid (70.0 mL), water (70.0 mL), and sulfuric acid (12.0 mL) were mixed and cooled to 0° C. to 5° C., and the entire amount of the sodium nitrosyl sulfate solution previously prepared was added dropwise thereto. After that, the mixture was stirred for 3 hours while maintaining the temperature at 0° C. to 5° C., and amidosulfuric acid (3.89 g, 40.0 mmol) was added to prepare a diazo solution. Meanwhile, aniline (2.06 g, 22.1 mmol), water (28.0 mL), and sulfuric acid (12.0 mL) were mixed and cooled to 0° C. to 5° C., and the entire amount of the diazo solution previously prepared was added dropwise thereto. After the dropwise addition, the mixture was stirred for 3 hours while maintaining the temperature at 0°C to 5°C, and aniline (2.06 g, 22.1 mmol) was added. After stirring for another hour while maintaining the temperature at 0°C to 5°C and raising the temperature to room temperature, the mixture was poured into a 28% aqueous sodium acetate solution (830 g), and the precipitated solid was collected by filtration and washed with methanol to obtain a black solid. The obtained solid was purified by silica gel column chromatography (methanol/chloroform=1/99) to obtain compound (1-6-a) (1.76 g, yield 27%).

Synthesis of Compound (1-6-b) Compound (1-6-a) (0.850 g, 2.60 mmol), 35% hydrochloric acid (0.40 mL, 1.5 mmol), acetic acid (18.0 mL), and water (3.0 mL) were mixed and cooled to 0°C to 5°C, and a solution of sodium nitrite (0.535 g, 7.75 mmol) in water (3.0 mL) was added dropwise thereto. The mixture was then stirred for 30 minutes while maintaining the temperature at 0°C to 5°C, and amidosulfuric acid (0.504 g, 5.19 mmol) was added to prepare a diazo solution. Meanwhile, N,N-diethylaniline (1.16 g, 7.79 mmol), sodium acetate (1.28 g, 15.6 mmol), methanol (40.0 mL), and water (20.0 mL) were mixed and cooled to 0°C to 5°C, and the entire amount of the diazo solution previously prepared was added dropwise thereto. After the dropwise addition was completed, the temperature was raised to room temperature, and the precipitated solid was filtered off to obtain compound (1-6-b) (0.711 g, yield 56%).

Synthesis of Compound (1-6) Compound (1-6-b) (0.146 g, 0.300 mmol), TiO(acac) ₂ (abbreviation of bis(2,4-pentanedionato)titanium(IV) oxide, 40 mg, 0.15 mmol), 3-methyl-1-butanol (1.0 mL, 9.2 mmol), and p-xylene (15.0 mL) were mixed and heated under reflux for 3 hours. The reaction solution was poured into methanol (100 mL) and separated with ethyl acetate/water, and the organic layer was washed with water and then with saturated saline, dried over magnesium sulfate, and concentrated with an evaporator. The obtained solid was purified by silica gel column chromatography (methanol/chloroform=0.5/99.5) to obtain compound (1-6) (75.1 mg, yield 47%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.62 (d, 1H), 8.23-8.18 (m, 4H), 8.03-7.99 (m, 2H), 7.94-7.90 (m, 2H), 6.77-6.73 (m, 2H), 4.43 (t, 2H), 3.50 (q, 4H), 1.89-1.79 (m, 1H), 1.72 (q, 2H), 1.26 (t, 6H), 1.01 (d, 6H).
UV-visible spectrum: λmax=568 nm (in acetonitrile)

Synthesis Example 7: Synthesis of compound (1-7) To synthesize compound (1-7), first compound (1-7-a) was synthesized, followed by alkylation to obtain compound (1-7).

Synthesis of Compound (1-7-a) 4-amino-4'-dimethylaminoazobenzene (1.20 g, 4.99 mmol), 35% hydrochloric acid (1.50 mL, 17.0 mmol), and water (15.0 mL) were mixed and cooled to 0°C to 5°C, and a solution of sodium nitrite (0.380 g, 5.51 mmol) in 2.5 mL of water was added dropwise to prepare a diazo liquid. Meanwhile, phenol (0.707 g, 7.52 mmol), sodium acetate (2.46 g, 30.0 mmol), and water (15.0 mL) were mixed and cooled to 0°C to 5°C, and the entire amount of the diazo liquid previously prepared was added dropwise. After the dropwise addition, the temperature was raised to room temperature, and the precipitated solid was filtered off to obtain compound (1-7-a) (1.62 g, yield 94%).

Synthesis of Compound (1-7) Compound (1-7-a) (0.345 g, 1.00 mmol), 1-bromo-3-methylbutane (0.322 g, 2.04 mmol), potassium carbonate (0.423 g, 3.00 mmol), and N,N-dimethylacetamide (5.0 mL) were mixed and heated with stirring at 100° C. for 30 minutes. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent, and further purified by reprecipitation from chloroform/ethyl acetate to obtain compound (1-7) (0.238 g, yield 57%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.01-7.90 (m, 8H), 7.03-7.00 (m, 2H), 6.80-6.76 (m, 2H), 4 .09 (t, 2H), 3.11 (s, 6H), 1.92-1.82 (m, 1H), 1.73 (q, 2H), 0.99 (d, 6H).
UV-visible spectrum: λmax=483 nm (in acetonitrile)

Comparative Synthesis Example 1: Synthesis of Compound (2-1) Compound (1-5-b) (0.606 g, 1.50 mmol), 1-iodobutane (0.555 g, 3.02 mmol), potassium carbonate (0.624 g, 4.51 mmol), and N,N-dimethylacetamide (7.5 mL) were mixed and heated with stirring at 100° C. for 1.5 hours. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent, and further purified by reprecipitation from chloroform/methanol to obtain compound (2-1) (0.309 g, yield 45%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.20-8.17 (m, 2H), 8.07 (d, 1H), 8.06-8.02 (m, 2H), 7.98-7.94 (m, 2H), 7.31 (d, 1H), 7.13 (dd , 1H), 7.05-7.01 (m, 2H), 4.15 (q, 2H), 4.07 (t, 2H), 1.86-1.79 (m, 2H), 1.58-1.47 (m, 5H), 1.01 (t, 3H).
UV-visible spectrum: λmax=456 nm (in acetonitrile)

Comparative Synthesis Example 2: Synthesis of Compound (2-2) Compound (1-1-b) (0.391 g, 1.00 mmol), 1-bromo-3,7-dimethyloctane (0.444 g, 2.01 mmol), potassium carbonate (0.415 g, 3.00 mmol), and N,N-dimethylacetamide (5.0 mL) were mixed and heated with stirring at 100° C. for 1 hour. Water was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent, and further purified by reprecipitation from chloroform/methanol to obtain compound (2-2) (0.128 g, yield 24%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.21-8.17 (m, 2H), 8.08 (d, 1H), 8.06-8.03 (m, 2H), 7.99-7.95 (m, 2H), 7.34 (d, 1H), 7.15 (dd, 1H), 7.05-7.01 (m , 2H), 4.15-4.06 (m, 2H), 3.93 (s, 3H), 1.92-1.84 (m, 1H), 1.75-1.46 (m, 3H), 1.40-1.15 (m, 6H), 0.97 (d, 3H), 0.88 (d, 6H).
UV-visible spectrum: λmax=452 nm (in acetonitrile)

Comparative Synthesis Example 3: Synthesis of Compound (2-3) Compound (1-1-b) (0.584 g, 1.50 mmol), 1-iodohexane (0.637 g, 3.00 mmol), potassium carbonate (0.622 g, 4.50 mmol), and N,N-dimethylacetamide (7.5 mL) were mixed and heated with stirring at 100° C. for 1 hour. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography (chloroform/hexane=9/1) and further purified by reprecipitation from chloroform/methanol to obtain compound (2-3) (0.403 g, yield 57%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.20-8.17 (m, 2H), 8.08 (d, 1H), 8.06-8.03 (m, 2H), 7.98-7.94 (m, 2H), 7.33 (d, 1H), 7.14 (dd, 1H), 7 .04-7.01 (m, 2H), 4.06 (t, 2H), 3.93 (s, 3H), 1.83 (tt, 2H), 1.53-1.46 (m, 2H), 1.39-1.34 (m, 4H), 0.92 (d, 3H).
UV-visible spectrum: λmax=452 nm (in acetonitrile)

Comparative Synthesis Example 4: Synthesis of Compound (2-4) In order to synthesize compound (2-4), first compound (2-4-b) was synthesized via compound (2-4-a). Subsequently, compound (2-4-b) was subjected to Negishi coupling with n-butyl zinc bromide to obtain compound (2-4).

Synthesis of Compound (2-4-a) 4-Bromo-3-fluoroaniline (9.50 g, 50.0 mmol), 35% hydrochloric acid (14.8 mL, 167 mmol), and water (95 mL) were mixed and cooled to 0°C to 5°C, and a solution of sodium nitrite (3.45 g, 50.0 mmol) in water (5 mL) was added dropwise to prepare a diazo liquid. Meanwhile, sodium (phenylamino)methanesulfonate (11.5 g, 55.0 mmol), sodium acetate (16.4 g, 55.0 mmol), and water (100 mL) were mixed and cooled to 0°C to 5°C, and the entire amount of the diazo liquid previously prepared was added dropwise. After the dropwise addition, the temperature was raised to room temperature, sodium hydroxide (12.0 g, 300 mmol) was added, and the mixture was heated and stirred at 90°C for 2.5 hours. The precipitated solid was collected by filtration to obtain compound (2-4-a) (13.9 g, yield 94%).

Compound (2-4-a) (1.47 g, 10.0 mmol), 35% hydrochloric acid (1.5 mL, 17 mmol), and water (9 mL) were mixed and cooled to 0 to 5°C, and a solution of sodium nitrite (345 mg, 5.00 mmol) in water (1 mL) was added dropwise. The mixture was then stirred for 45 minutes while maintaining the temperature at 10 to 15°C to prepare a diazo liquid. Meanwhile, N,N-diethylaniline (895 mg, 6.00 mmol), sodium acetate (1.64 g, 20.0 mmol), methanol (20 mL), and water (10 mL) were mixed and cooled to 10 to 15°C, and the entire amount of the diazo liquid previously prepared was added dropwise. After the addition was completed, the mixture was heated to room temperature, and the precipitated solid was collected by filtration, dissolved in chloroform, and washed with water and then with saturated saline. The mixture was dried over magnesium sulfate and concentrated in an evaporator. The resulting solid was purified by silica gel column chromatography (chloroform/hexane = 50/50) to obtain compound (2-4-b) (1.26 g, yield 55%).

A mixed solution of compound (2-4-b) (213 mg, 0.500 mmol), PdCl2dppf (8.1 mg, 0.010 mmol), and THF (5.0 mL) was heated and stirred at 55°C, and 0.50 M n-butylzinc bromide (1.2 mL, 0.60 mmol) was added dropwise. The mixture was then heated under reflux for 3.5 hours. Water (20 mL) was added to the reaction solution, and the precipitated solid was collected by filtration. The resulting solid was purified by silica gel column chromatography (chloroform/hexane = 50/50). The solid was further purified by reprecipitation from chloroform/hexane to obtain compound (2-4) (137 mg, yield 64%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.03-8.00 (m, 2H), 7.98-7.95 (m, 2H), 7.92-7.88 (m, 2H), 7.71 (dd, 1H), 7.60 (dd, 1H), 7.34 (dd , 1H), 6.76-6.72 (m, 2H), 3.46 (q, 4H), 2.72 (t, 2H), 1.65 (tt, 2H), 1.41 (tq, 2H), 1.25 (t, 6H), 0.96 (t, 3H).
UV-visible spectrum: λmax=495 nm (in acetonitrile)

Example 1: Preparation of composition E1 containing compound (1-1) The following components were mixed and stirred at 80°C for 1 hour to obtain composition E1.
Polymerizable liquid crystal compound (A-6) 75 parts by mass Polymerizable liquid crystal compound (A-7) 25 parts by mass Compound (1-1) 4.0 parts by mass Polymerization initiator: 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan Ltd.)
Leveling agent: polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.2 parts by weight Solvent: o-xylene 250 parts by weight

Polymerizable liquid crystal compound (A-6)

Polymerizable liquid crystal compound (A-7)

The polymerizable liquid crystal compound (A-6) was synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). The polymerizable liquid crystal compound (A-7) was also produced according to this method.

<Examples 2 to 7> Preparation of compositions E2 to E7 Compositions E2 to E7 of Examples 2 to 7, respectively, were obtained in the same manner as in Example 1, except that compounds (1-2) to (1-7), respectively, were used instead of compound (1-1).

Comparative Examples 1 to 4: Preparation of Compositions C1 to C4 Compositions C1 to C4 of Comparative Examples 1 to 4, respectively, were obtained in the same manner as in Example 1, except that compounds (2-1) to (2-4), respectively, were used instead of compound (1-1).

<Production of Polarizing Plate>
1. Formation of alignment film
A glass substrate was used as a transparent substrate. A 2% by mass aqueous solution (composition for forming an alignment layer) of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate by spin coating, and after drying, a film having a thickness of 100 nm was formed. Subsequently, an alignment film was formed by subjecting the surface of the obtained film to a rubbing treatment, and a substrate having an alignment film formed on the glass substrate was obtained.

2. Formation of polarizing film
The composition obtained above was applied by spin coating onto the alignment film of the substrate obtained above, and the resultant was dried by heating on a hot plate at 120°C for 3 minutes, and then quickly cooled to below 70°C (the temperature at which the film exhibits a smectic liquid crystal phase when cooled), to obtain a laminate in which a dry film was formed on the alignment film.

Next, the dried film was irradiated with ultraviolet light at an exposure dose of 2,400 mJ/cm ² (based on 365 nm) using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.), thereby polymerizing the polymerizable liquid crystal compound contained in the dried film while maintaining the liquid crystal state of the composition, and a polarizing film was formed from the dried film to obtain a polarizing plate.

<Evaluation>
The dichroic ratio of the obtained polarizing plate was measured as follows. The absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction at the maximum absorption wavelength (λmax) of the polarizing film of the polarizing plate were measured by the double beam method using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) in which a folder equipped with a polarizing plate was set. A mesh that cuts the amount of light by 50% was placed on the reference side of the folder. The ratio (A2/A1) was calculated from the measured values of the absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction, and was taken as the dichroic ratio (DR). The results are shown in Table 1.

From Table 1, it can be seen that a polarizing plate having a film containing compound (1) as a forming material can achieve an excellent dichroic ratio (DR).

Claims (9)

A compound represented by the following formula (1) (excluding cases where the compound is an optically active substance) :

In formula (1), P represents one group selected from the group consisting of -O- , -OC(=O)- and -C(=O)O-.
x and y each independently represent 0, 1 or 2, and when P is a single bond, x+y≧1 is satisfied.
n represents 1.
^R1 represents one group selected from the group consisting of a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, a pyrrolidyl group, an oxazolidyl group, a piperidyl group, a morpholyl group, a methoxy group, and an ethoxy group, and a hydrogen atom of these groups may be substituted with a polymerizable group.
^R2 and ^R3 each independently represent a methyl group or an ethyl group.
Q represents a single bond or a group selected from the group consisting of -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -N=N-, -NHC(=O)- and -C(=O)NH-.
Ar ¹ and Ar ³ each independently represent a 1,4-phenylene group or a divalent sulfur-containing aromatic heterocyclic group which may have at least one substituent selected from the group consisting of a halogen atom, a hydroxy group, and a methoxy group.
^Ar2 represents a 1,4-phenylene group which may have at least one substituent selected from the group consisting of a halogen atom, a hydroxy group, and a methoxy group.] The compound according to claim 1, wherein in formula (1), y is 0. The compound according to claim 1 or 2, wherein Q in formula (1) is -N=N-. A dichroic dye comprising the compound according to any one of claims 1 to 3. A composition comprising the compound according to any one of claims 1 to 3 and a liquid crystal compound comprising at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound. The composition according to claim 5, wherein the liquid crystal compound is a smectic liquid crystal compound. A film containing the compound according to any one of claims 1 to 3 as a forming material. A laminate comprising the film according to claim 7. A display device comprising the laminate according to claim 8.