Compounds, compositions, films, laminates, and display devices

Abstract

Provided is a dichroic dye compound with high heat resistance. 【Solution】A compound represented by formula (2) and having a LUMO energy level of -2.65 eV or more and -2.10 eV or less. In formula (1), Ar 23 , 21 , 24 , 22 , 22 , 22 , 23 , 23 , 24 , 21 , 22 , 23 , 24 , 21 , , Ar 22 and Ar 23 represent a 1,4-phenylene group, a 1,4-naphthylene group or a divalent aromatic condensed heterocyclic group composed of two 5-membered rings, and at least one of Ar 21 , Ar 22 and Ar 23 represents a divalent aromatic condensed heterocyclic group. m is 1 or 2. R 21 , R 22 , R 23 and R 24 represent a hydrogen atom, a linear or cyclic aliphatic group or an aryl group. At least one of the pairs of R 21 and R 22 and at least one of the pairs of R 23 and R 24 may be linked to each other to form a ring, and at least one of the methylene units constituting the ring may be substituted with an oxygen atom or a carbonyl group. At least one of R 21 , R 22 , R 23 and R 24 may be substituted with at least one of an organosilyloxy group or a polymerizable group. TIFF2026137712000028.tif23122

Description

[Technical Field]

[0001] The present invention relates to compounds, compositions, films, laminates, and display devices. [Background technology]

[0002] Polarizing films (optical films) made from compositions containing dichroic dyes are known to be used in liquid crystal display devices and the like. For example, Patent Document 1 describes the following compounds as such dichroic dyes.

[0003] [ka] [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 64-70585 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, when a polarizing film made using a dichroic dye as described in Patent Document 1 is used in a high-temperature environment of about 100°C, the absorbance at the maximum absorption wavelength of the dichroic dye sometimes decreases over time. The object of the present invention is to provide a compound with high heat resistance, a composition containing the same, a film formed from the composition, a laminate comprising the film, and a display device comprising the laminate. [Means for solving the problem]

[0006] The present invention provides the following [1] to

[11] . [1] A compound represented by the following formula (1). [ka] [In formula (1), Ar 11 , Ar 12 and Ar 13 each independently represents a 1,4-phenylene group, a 1,4-naphthylene group or a divalent aromatic condensed heterocyclic group composed of two 5-membered rings, which may have a substituent. At least one of Ar 11 , Ar 12 and Ar 13 represents a divalent aromatic condensed heterocyclic group composed of two 5-membered rings. k is 1 or 2. When k is 2, the two Ar 12 may be the same or different from each other. R 11 , R 12 , R 13 and R 14 each independently represents a hydrogen atom, a linear or cyclic aliphatic group or an aryl group which may have a substituent. At least one of the pairs of R 1 and R 2 and at least one of the pairs of R 3 and R 4 may be linked to each other to form a ring, and at least one of the methylene units constituting the formed ring may be substituted with an oxygen atom or a carbonyl group. At least one of R 11 , R 12 , R 13 and R 14 may be substituted with at least one substituent selected from the group consisting of an organosilyloxy group and a polymerizable group.] [2] In the formula (1), Ar 11 , Ar 12 and Ar 13 each independently represents a 1,4-phenylene group or a divalent sulfur-containing aromatic condensed heterocyclic group composed of two 5-membered rings, which may have a substituent. At least one of Ar 11 , Ar 12 and Ar 13 represents a divalent sulfur-containing aromatic condensed heterocyclic group composed of two 5-membered rings, the compound according to [1]. [3] In the formula (1), Ar 11 , Ar 12 and Ar 13Each independently represents a substituted 1,4-phenylene group, a thieno[3,2-d]thiazolediyl group, or a thieno[3,2-d]thiophenediyl group, and Ar 11 Ar 12 and Ar 13 The compound according to [1] or [2], wherein at least one of the groups represents a thieno[3,2-d]thiazolediyl group or a thieno[3,2-d]thiophenediyl group. [4] In formula (1) above, Ar 11 and Ar 13 Each of these independently represents a 1,4-phenylene group which may have substituents, and Ar 12 The compound according to any one of [1] to [3], wherein is a thieno[3,2-d]thiazolediyl group or thieno[3,2-d]thiophenediyl group which may have substituents, and k is 1. [5] A compound represented by the following formula (2), wherein the LUMO energy level is between -2.65 eV and -2.10 eV. [ka] [In formula (2), Ar 21 Ar 22 and Ar 23 Each independently represents a substituted 1,4-phenylene group, a 1,4-naphthylene group, a divalent sulfur-containing aromatic heterocyclic group, or a divalent sulfur-containing aromatic condensed heterocyclic group consisting of 2 to 4 aromatic rings, and Ar 21 Ar 22 and Ar 23 At least one of these represents a divalent sulfur-containing aromatic heterocyclic group, or a divalent sulfur-containing aromatic condensed heterocyclic group consisting of 2 to 4 aromatic rings. m is either 1 or 2, and if m is 2, then there are two Ar 22 These may be the same or different. R 21 , R 22 , R 23 and R 24 Each of these independently represents a hydrogen atom, a chain or cyclic aliphatic group or aryl group which may have substituents. 21and R 22 and R 23 and R 24 At least one set of these may be linked together to form a ring, and at least one of the methylene units constituting the formed ring may be substituted with an oxygen atom or a carbonyl group. 21 , R 22 , R 23 and R 24 At least one of the groups may be substituted with at least one substituent selected from the group consisting of organosilyloxy groups and polymerizable groups. However, R 21 and R 22 A combination of two groups represented by and R 23 and R 24 Except when the combination of two bases represented by is identical. [6] In formula (2) above, Ar 21 and Ar 23 Each of these independently represents a 1,4-phenylene group which may have substituents, and Ar 22 The compound according to [5], wherein m represents a thieno[3,2-d]thiazolediyl group, a thieno[3,2-d]thiophenediyl group, a thiazole-diyl group, a thiadiazolediyl group, or a thiophenediyl group, which may have substituents, and m is 1. A composition comprising a compound described in any of [1] to [6], and a liquid crystalline compound comprising at least one polymerizable liquid crystal compound and a liquid crystalline polymer compound. [8] The composition according to [7], wherein the liquid crystalline compound is a smectic liquid crystalline compound. A film formed from the composition described in [9] [7]. A laminate comprising the film described in

[10] [9].

[11] A display device comprising the laminate described in

[10] . [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a highly heat-resistant compound, a composition containing the same, a film formed from the composition, a laminate comprising the film, and a display device comprising the laminate. [Modes for carrying out the invention]

[0008] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved. Furthermore, the content of each component in a composition refers to the total amount of multiple substances present in the composition, unless otherwise specified, if multiple substances corresponding to each component exist in the composition. In addition, the upper and lower limits of the numerical ranges described herein can be arbitrarily selected and combined from the numerical values ​​exemplified as numerical ranges. Embodiments of the present invention will now be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without impairing the spirit of the invention.

[0009] compound A compound according to one embodiment of the present invention is represented by the following formula (1). The compound may be, for example, a dichroic dye compound and may be used as a material for forming a polarizing film. The compound represented by formula (1) has a divalent aromatic condensed heterocyclic group in its molecule and has amino groups at both ends, which allows it to exhibit high heat resistance in an environment of about 100°C. This is because, for example, the decomposition reaction of the compound in an environment of about 100°C is presumed to be reductive, and the presence of amino groups at both ends of the compound causes the energy level of the compound's LUMO to be within a specific range, thereby suppressing the reductive decomposition reaction.

[0010] [ka]

[0011] In formula (1), Ar 11 Ar 12 and Ar 13 Each of these independently represents a divalent aromatic condensed heterocyclic group consisting of an optionally substituted 1,4-phenylene group, an optionally substituted 1,4-naphthylene group, or two optionally substituted five-membered rings. 11 Ar12 and Ar 13 At least one of these represents a divalent aromatic condensed heterocyclic group consisting of two 5-membered rings, which may have substituents. The aromatic condensed heterocyclic group is formed by removing two hydrogen atoms from an aromatic condensed heterocyclic compound, which is formed by the condensation of two 5-membered aromatic heterocyclic compounds. Examples of 5-membered aromatic heterocyclic compounds include thiophene, thiazole, and furan. Specific examples of aromatic condensed heterocyclic groups consisting of two 5-membered rings include thieno[3,2-d]thiazolediyl group, thieno[3,2-d]thiophenediyl group, thiazolo[5,4-d]thiazolediyl group, and furano[3,2-d]thiazolediyl group, and may include at least one selected from this group. The aromatic condensed heterocyclic group, consisting of two five-membered rings, may preferably include at least one selected from the group consisting of a thieno[3,2-d]thiazolediyl group and a thieno[3,2-d]thiophenediyl group.

[0012] In equation (1), Ar 11 Ar 12 and Ar 13 Each of these may independently represent a substituted 1,4-phenylene group or a divalent sulfur-containing aromatic condensed heterocyclic group consisting of two substituted five-membered rings, and Ar 11 Ar 12 and Ar 13 At least one of these may represent a divalent sulfur-containing aromatic condensed heterocyclic group consisting of two five-membered rings, which may have substituents.

[0013] In equation (1), for example, Ar 12 It may represent a divalent aromatic condensed heterocyclic group or a sulfur-containing aromatic condensed heterocyclic group consisting of two 5-membered rings which may have substituents. Preferably Ar 12 Ar represents a divalent aromatic condensed heterocyclic group or a sulfur-containing aromatic condensed heterocyclic group consisting of two 5-membered rings which may have substituents, 11 and Ar 13 Each of these may independently represent a 1,4-phenylene group or a 1,4-naphthylene group, which may each have substituents. More preferably Ar12 represents a thieno[3,2-d]thiazolediyl group or a thieno[3,2-d]thiophenediyl group which may have a substituent, and Ar 11 and Ar 13 may each independently represent a 1,4-phenylene group which may have a substituent.

[0014] Ar 11 、Ar 12 and Ar 13 The substituents in may each independently contain at least one selected from the group consisting of a halogen atom, a hydroxy group, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms, preferably at least one selected from the group consisting of a halogen atom, a hydroxy group, a methyl group, and a methoxy group, more preferably at least one selected from the group consisting of a fluorine atom, a chlorine atom, a hydroxy group, a methyl group, and a methoxy group. Ar 11 、Ar 12 and Ar 13 The number of substituents in may each independently be, for example, 0, 1 or 2, preferably 0 or 1.

[0015] k is 1 or 2, preferably 1. When k is 2, the two Ar 12 may be the same or different.

[0016] R 11 、R 12 、R 13 and R 14 each independently represent a hydrogen atom, a linear or cyclic aliphatic group which may have a substituent, or an aryl group which may have a substituent. R 11 、R 12 、R 13 or R 14The number of carbon atoms in the aliphatic group represented by [aliphatic group] may be, for example, from 1 to 20, preferably from 1 to 12, or may be from 1 to 6. The aliphatic group may be an alkyl group, an alkenyl group or an alkynyl group, preferably an alkyl group. Specific examples of the aliphatic group include a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group, an isopropyl group, a cyclopropyl group, an allyl group, a butyl group, a hexyl group, an ethylbutyl group, an ethylhexyl group, a hexyldodecyl group and the like. R 11 、R 12 、R 13 or R 14 The number of carbon atoms in the aryl group represented by [aryl group] may be from 6 to 10, preferably 6.

[0017] R 11 and R 12 and R 13 and R 14 Of these, at least one pair may be linked to each other to form a cyclic amino group together with a nitrogen atom, and the cyclic amino group formed may be an alicyclic amino group. Further, at least one of the methylene units constituting the cyclic amino group formed may be substituted with an oxygen atom or a carbonyl group. The number of members of the cyclic amino group formed may be, for example, 5 or 6. R 11 and the nitrogen atom and R 12 、or R 13 and the nitrogen atom and R 14 Specific examples of the cyclic amino group formed from [cyclic amino group forming components] include a pyrrolidyl group, a piperidyl group, a morpholinyl group, an oxazolidinyl group, a piperazyl group, an N-methylpiperazinyl group, a 2-oxo-3-oxazolidinyl group and the like.

[0018] R 11 、R<At least one of the amino groups formed from the nitrogen atom may be an alkylamino group. The alkylamino group may be a monoalkylamino group or a dialkylamino group, and preferably a dialkylamino group. The dialkylamino group may preferably be at least one selected from the group consisting of dimethylamino group, diethylamino group, ethylmethylamino group, butylmethyl group, butylethyl group, pyrrolidyl group, piperidyl group, morpholinyl group, oxazolidinyl group, piperadyl group, N-methylpiperazinyl group and 2-oxo-3-oxazolidinyl group, or at least one selected from the group consisting of dimethylamino group, diethylamino group, ethylmethylamino group, butylmethyl group, butylethyl group, pyrrolidyl group, piperidyl group, morpholinyl group and oxazolidinyl group.

[0019] R 11 , R 12 , R 13 and R 14 Substituents in this compound include polymerizable groups; organosilyloxy groups such as trialkylsilyloxy groups, dialkylarylsilyloxy groups, alkyldiarylsilyloxy groups, and silyloxy groups having polymerizable groups; alkoxy groups; alkylcarbonyloxy groups, etc.

[0020] Specific examples of polymerizable groups include (meth)acrylate groups ((meth)acryloyloxy groups), (meth)acryloyl groups, vinylphenyl groups, vinyl groups, epoxy groups, and the like. The polymerizable group may be, for example, a radical polymerizable group, and preferably a (meth)acrylate group.

[0021] The number of carbon atoms in the alkyl group of the organosilyloxy group may be, for example, 1 to 12, preferably 1 to 6. Examples of alkyl groups in the organosilyloxy group include methyl, ethyl, t-butyl, dimethylpropyl, and 2,3-dimethylbutan-2-yl groups. The number of carbon atoms in the aryl group of the organosilyloxy group may be, for example, 6 to 18, preferably 6 to 10, or 6. Examples of aryl groups in the organosilyloxy group include phenyl and naphthyl groups.

[0022] The alkyl portion of the alkoxy group or alkylcarbonyloxy group may have, for example, 1 to 20 carbon atoms, preferably 1 to 12 or 1 to 6 carbon atoms. The alkyl portion may also be linear, branched, or cyclic, or a combination thereof. Examples of the alkyl portion of the alkoxy group or alkylcarbonyloxy group include methyl, ethyl, butyl, and ethylpentyl groups.

[0023] R 11 , R 12 , R 13 and R 14 The total number of substituents in R may be, for example, 0 to 4, preferably 0 to 2. 11 , R 12 , R 13 or R 14 If the molecule has polymerizable groups as substituents, the total number of polymerizable groups may be, for example, 1 or 2, and preferably 1.

[0024] R 11 and R 12 A combination of two groups represented by and R 13 and R 14 The combination of two groups represented by R may be the same or different, and preferably different. That is, R 11 , R 12 and an amino group formed from a nitrogen atom, and R 13 , R 14The amino groups formed from the nitrogen atoms may be the same or different, and preferably different. The asymmetrical arrangement of the two amino groups at both ends of the compound represented by formula (1) allows for both an excellent dicolor ratio (DR) and excellent solubility.

[0025] A compound according to one embodiment of the present invention is represented by the following formula (2), and its LUMO energy level is between -2.65 eV and -2.10 eV. The compound may be, for example, a dichroic dye compound and may be used as a material for forming polarizing films. The compound represented by formula (2) has a divalent aromatic condensed heterocyclic group in its molecule, and its LUMO energy level is within a specific range, which allows it to exhibit high heat resistance in environments of around 100°C. This can be attributed, for example, to the fact that the decomposition reaction of the compound in an environment of around 100°C is presumed to be reductive, and the LUMO energy level of the compound is within a specific range, thereby suppressing the reductive decomposition reaction.

[0026] [ka]

[0027] In formula (2), Ar 21 Ar 22 and Ar 23 Each of these independently represents an optionally substituted 1,4-phenylene group, an optionally substituted 1,4-naphthylene group, an optionally substituted divalent sulfur-containing aromatic heterocyclic group, or a optionally substituted divalent sulfur-containing aromatic condensed heterocyclic group consisting of 2 to 4 aromatic rings. 21 Ar 22 and Ar 23 At least one of these represents a divalent sulfur-containing aromatic heterocyclic group, or a divalent sulfur-containing aromatic condensed heterocyclic group consisting of 2 to 4 aromatic rings.

[0028] The divalent sulfur-containing aromatic heterocyclic group may be a five-membered sulfur-containing aromatic heterocyclic group. Specific examples of divalent sulfur-containing aromatic heterocyclic groups include, for example, thiazolediyl groups, thiadiazolediyl groups, and thiophenediyl groups, and may include at least one selected from the group consisting of these.

[0029] Furthermore, a divalent sulfur-containing aromatic condensed heterocyclic group formed by the condensation of two to four aromatic rings is constructed by removing two hydrogen atoms from an aromatic condensed heterocyclic compound formed by the condensation of two to four aromatic ring compounds. The aromatic ring compound that forms the divalent sulfur-containing aromatic condensed heterocyclic group may be a five-membered or six-membered aromatic ring compound, or a five-membered aromatic ring compound. Specific examples of aromatic ring compounds include thiophene, thiazole, thiadiazole, furan, pyrrole, imidazole, benzene, pyridine, etc., and preferably contains at least one selected from the group consisting of thiophene, thiazole, and furan. The number of condensed aromatic rings that form the divalent sulfur-containing aromatic condensed heterocyclic group may be two or three, or two. Examples of divalent sulfur-containing aromatic condensed heterocyclic groups formed by the condensation of two to four aromatic rings include thieno[3,2-d]thiazolediyl group, thieno[3,2-d]thiophenediyl group, thiazolo[5,4-d]thiazolediyl group, furano[3,2-d]thiazolediyl group, etc., and may include at least one selected from the group consisting of these.

[0030] In equation (2), for example, Ar 22 This may represent a divalent sulfur-containing aromatic heterocyclic group which may have substituents, or a divalent sulfur-containing aromatic condensed heterocyclic group which is formed by the condensation of two to four aromatic ring compounds which may have substituents. Preferably Ar 22 Ar represents a divalent sulfur-containing aromatic heterocyclic group which may have substituents, or a divalent sulfur-containing aromatic condensed heterocyclic group which is formed by the condensation of two to four aromatic ring compounds which may have substituents, 21 and Ar 23 Each of these may independently represent a 1,4-phenylene group or a 1,4-naphthylene group, which may each have substituents. More preferably Ar22 Ar represents a thiazolediyl group, thiadiazolediyl group, thiophenediyl group, thieno[3,2-d]thiazolediyl group, thieno[3,2-d]thiophenediyl group, thiazolo[5,4-d]thiazolediyl group, or furano[3,2-d]thiazolediyl group, which may have substituents. 21 and Ar 23 Each of these may independently represent a 1,4-phenylene group which may have substituents. More preferably Ar 22 Ar represents a thiazolediyl group, thiadiazolediyl group, thiophenediyl group, thieno[3,2-d]thiazolediyl group, or thieno[3,2-d]thiophenediyl group, which may have substituents. 21 and Ar 23 Each of these may independently represent a 1,4-phenylene group which may have substituents.

[0031] Ar 21 Ar 22 and Ar 23 The substituents in may include at least one selected from the group consisting of a halogen atom, a hydroxyl group, a C1 to C3 alkyl group, and a C1 to C3 alkoxy group, preferably at least one selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group, and a methoxy group, and more preferably at least one selected from the group consisting of a fluorine atom, a chlorine atom, a hydroxyl group, a methyl group, and a methoxy group. 21 Ar 22 and Ar 23 The number of substituents in each component may be independently, for example, 0, 1, or 2, and preferably 0 or 1.

[0032] m is 1 or 2, preferably 1. If m is 2, then two Ar 22 These may be the same or different.

[0033] R 21 , R 22 , R 23 and R 24Each of these independently represents a hydrogen atom, or a linear or cyclic alkyl or aryl group which may have substituents. 21 , R 22 , R 23 or R 24 The number of carbon atoms in the aliphatic group represented by may be, for example, 1 to 20, preferably 1 to 12. The aliphatic group may be an alkyl group, an alkenyl group, or an alkynyl group, preferably an alkyl group. Specific examples of aliphatic groups include methyl group, ethyl group, vinyl group, ethynyl group, propyl group, isopropyl group, cyclopropyl group, allyl group, butyl group, hexyl group, ethylbutyl group, ethylhexyl group, hexyldodecyl group, etc. 21 , R 22 , R 23 or R 24 The number of carbon atoms in the aryl group represented by can be 6 to 10, preferably 6.

[0034] R 21 and R 22 and R 23 and R 24 At least one pair of these may be linked together with a nitrogen atom to form a cyclic amino group, and the formed cyclic amino group may be an alicyclic amino group. Furthermore, at least one of the methylene units constituting the formed cyclic amino group may be substituted with an oxygen atom or a carbonyl group. The number of members in the formed cyclic amino group may be, for example, 5 or 6. 21 and nitrogen atom and R 22 , or R 23 and nitrogen atom and R 24 Specific examples of cyclic amino groups formed from these include pyrrolidyl group, piperidyl group, morpholinyl group, oxazolidinyl group, piperadyl group, N-methylpiperazinyl group, and 2-oxo-3-oxazolidinyl group.

[0035] R 21 , R 22 and an amino group formed from a nitrogen atom, and R 23 , R 24At least one of the amino groups formed from the nitrogen atom may be an alkylamino group. The alkylamino group may be a monoalkylamino group or a dialkylamino group, and preferably a dialkylamino group. The dialkylamino group may preferably be at least one selected from the group consisting of dimethylamino group, diethylamino group, ethylmethylamino group, butylmethyl group, butylethyl group, pyrrolidyl group, piperidyl group, morpholinyl group, oxazolidinyl group, piperadyl group, N-methylpiperazinyl group and 2-oxo-3-oxazolidinyl group, or at least one selected from the group consisting of dimethylamino group, diethylamino group, ethylmethylamino group, butylmethyl group, butylethyl group, pyrrolidyl group, piperidyl group, morpholinyl group and oxazolidinyl group.

[0036] R 21 , R 22 , R 23 and R 24 Substituents in this compound include polymerizable groups; organosilyloxy groups such as trialkylsilyloxy groups, dialkylarylsilyloxy groups, alkyldiarylsilyloxy groups, and silyloxy groups having polymerizable groups; alkoxy groups; alkylcarbonyloxy groups, etc.

[0037] Specific examples of polymerizable groups include (meth)acrylate groups ((meth)acryloyloxy groups), (meth)acryloyl groups, vinylphenyl groups, vinyl groups, epoxy groups, and the like. The polymerizable group may be, for example, a radical polymerizable group, and preferably a (meth)acrylate group.

[0038] The number of carbon atoms in the alkyl group of the organosilyloxy group may be, for example, 1 to 12, preferably 1 to 6. Examples of alkyl groups in the organosilyloxy group include methyl, ethyl, t-butyl, dimethylpropyl, and 2,3-dimethylbutan-2-yl groups. The number of carbon atoms in the aryl group of the organosilyloxy group may be, for example, 6 to 18, preferably 6 to 10, or 6. Examples of aryl groups in the organosilyloxy group include phenyl and naphthyl groups.

[0039] The alkyl portion of the alkoxy group or alkylcarbonyloxy group may have, for example, 1 to 20 carbon atoms, preferably 1 to 12. The alkyl portion may also be linear, branched, or cyclic, or a combination thereof. Examples of the alkyl portion of the alkoxy group or alkylcarbonyloxy group include methyl, ethyl, butyl, and ethylpentyl groups.

[0040] R 21 , R 22 , R 23 and R 24 The total number of substituents in R may be, for example, 0 to 4, preferably 0 to 2. 21 , R 22 , R 23 or R 24 If the molecule has polymerizable groups as substituents, the total number of polymerizable groups may be, for example, 1 or 2, and preferably 1.

[0041] R 21 and R 22 A combination of two groups represented by and R 23 and R 24 The combination of two groups represented by R is distinct from each other. That is, R 21 , R 22 and an amino group formed from a nitrogen atom, and R 23 , R 24 The amino groups formed from nitrogen atoms are different from each other. Also, R21 , R 22 , R 23 and R 24 Of the four groups represented by formula (2), three may be identical and one may be different. The asymmetric arrangement of the two amino groups at both ends of the compound represented by formula (2) allows for both an excellent dicolor ratio (DR) and excellent solubility. For example, increasing the bulkiness of the substituent on the amino group improves solubility, but increasing the bulkiness of both amino groups at both ends tends to decrease the DR. Therefore, increasing the bulkiness of only one of the amino groups allows for both excellent DR and solubility.

[0042] The LUMO energy level of the compound represented by formula (2) is preferably -2.60 eV or higher, or -2.55 eV or higher, and also preferably -2.20 eV or lower, or -2.30 eV or lower. Here, the LUMO energy level is calculated by density functional theory (DFT). Specifically, the LUMO energy level is calculated using density functional theory with the software Gaussian16, using B3LYP as the functional and 6-31G(d) as the normative function.

[0043] Specific examples of compounds represented by formula (1) include those represented by formulas (1-1) to (1-62) below, but the present invention is not limited to these.

[0044] [ka]

[0045] [ka]

[0046] Furthermore, specific examples of compounds represented by formula (2) include, in addition to the compounds represented by formulas (1-1) to (1-37) described above, the compounds represented by formulas (2-1) to (2-33) below, but the present invention is not limited to these.

[0047] [ka]

[0048] From the viewpoint of heat resistance, the compound represented by formula (1) preferably contains at least one selected from the group consisting of compounds represented by any of the following formulas: (1-1) to (1-5), (1-8) to (1-23), (1-26) to (1-34), (1-38) to (1-41), and (1-44) to (1-59), and formulas (1-1), (1-2), (1-4), (1-20) to (1-23), and formula It is more preferable to include at least one compound selected from the group consisting of compounds represented by any of formulas (1-32) to (1-34), (1-38), (1-39) and (1-56) to (1-59), and even more preferable to include at least one compound selected from the group consisting of compounds represented by any of formulas (1-1), (1-2), (1-21), (1-23), (1-34) and (1-38).

[0049] Furthermore, from the viewpoint of heat resistance, the compound represented by formula (2) preferably contains at least one selected from the group consisting of compounds represented by any of the following: formulas (1-1) to (1-5), formulas (1-8) to (1-23), formulas (1-26) to (1-34), formulas (2-1) to (2-16), and formulas (2-19) to (2-33), and formulas (1-1), (1-2), (1-4), formulas (1-20) to (1-23), and formula (1 It is more preferable to include at least one compound selected from the group consisting of compounds represented by formulas (1-34), (2-1) to (2-3), (2-13) to (2-16), and (2-24), and even more preferable to include at least one compound selected from the group consisting of compounds represented by formulas (1-1), (1-2), (1-21), (1-23), (1-34), and (1-38).

[0050] Method for producing compounds Compounds represented by formula (1) or formula (2) can be produced by appropriately applying conventionally known synthesis methods. Specifically, the azo structure (-N=N-) in compounds represented by formula (1) or formula (2) can be constructed by converting an aromatic amine compound having a primary amino group into a diazonium salt using sodium nitrite, nitrosyl sulfate, etc. (reaction a-1), and then diazo-coupling it with the aromatic compound (reaction a-2). Here, the conversion to a diazonium salt with sodium nitrite can be referenced, for example, from the production examples described in paragraphs 0220 to 0268 of International Publication No. 2016 / 136561. Furthermore, the conversion to a diazonium salt with nitrosyl sulfate can be referenced, for example, from the production examples described in paragraphs 0017 to 0034 of Japanese Patent Publication No. 2009-215442.

[0051] The divalent five-membered ring condensation site having a thiazole ring in the compound represented by formula (1) or formula (2) can be synthesized using an amino group precursor, a thiocyanate, and bromine, under general thiazole cyclization conditions in a solvent such as acetic acid (reaction b). For thiazole cyclization conditions, see, for example, the preparation examples described in paragraphs 0065 to 0076 of International Publication No. 2017 / 090668, Stuckwisch, Cg; J. Am. Chem. Soc. 1949, 71, 3417, Ismail, iA; Sharp, dE; Chedekel, MR; J. Org. Chem. 1980, 45, 2243, etc.

[0052] The amino group in the compound represented by formula (1) or formula (2) can be synthesized using a halogen-containing precursor and an amine compound, under the conditions of a general aromatic nucleophilic substitution reaction in the presence of a base (reaction c). For conditions of aromatic nucleophilic substitution reactions, see, for example, Hou, Y.; Eur. J. Med. Chem. 2019, 163, 690, etc.

[0053] The silyloxy group substituted with an aliphatic hydrocarbon group in the compound represented by formula (1) or formula (2) can be synthesized using a precursor having a hydroxyl group and a halogenated silane substituted with an aliphatic hydrocarbon group, by applying general silylation reaction conditions in the presence of a base (reaction d). For conditions of SN2 substitution reactions, see, for example, J. Am. Chem. Soc., 1972, 94, 6190.

[0054] The specific method for producing the compound represented by formula (1) or formula (2) will be described below. 1 Ar 2 Ar 3 , R 1 , R 2 , R 3 and R 4 The definition of is Ar in equation (1) 11 Ar 12 Ar 13 , R 11 , R 12 , R 13 and R 14 Are they equivalent to each other, or in equation (2) Ar 21 Ar 22 Ar 23 , R 21 , R 22 , R 23 and R 24 These are synonymous with each other. First, the diazonium salt represented by formula (1T) (hereinafter also referred to as compound (1T)) is synthesized from the compound represented by formula (1S) (hereinafter also referred to as compound (1S)) by reaction a-1.

[0055] [ka]

[0056] Next, the compound represented by formula (1V) (hereinafter also referred to as compound (1V)) is synthesized via either step A or step B.

[0057] In process A, Ar 2aA compound containing [a certain compound] is reacted with a diazonium salt compound (1T) to form an azo structure, and then ring formation occurs via [another compound]. 2a Ar 2 This converts to compound (1V). Specifically, compound (1T) is synthesized via reaction a-2 to form compound (1U) (hereinafter also referred to as compound (1U)), and then compound (1V) is synthesized via reaction b.

[0058] [ka]

[0059] In step B, compound (1V) is synthesized from compound (1T) via reaction a-2.

[0060] [ka]

[0061] For compound (1V), the same synthesis process as the synthesis process from compound (1S) to compound (1V) may be repeated once more. This makes it possible to produce a compound represented by formula (1W) (hereinafter referred to as compound (1W)) in which p=2. Note that in compound (1W), Ar 2 If multiple instances exist, Ar 2 They may be the same or different.

[0062] [ka]

[0063] From compound (1W) and an aromatic amine compound, a compound represented by formula (1X) (hereinafter also referred to as compound (1X)) can be produced via reactions a-1 and a-2.

[0064] [ka]

[0065] From compound (1X) and an amine compound, a compound represented by formula (1) or formula (2) can be produced via reaction c. The produced compound represented by formula (1) or formula (2) can then be subjected to reaction d, etc., to R 1 , R 2 , R 3 or R 4 Further substituents can be introduced.

[0066] [ka]

[0067] The reaction time in a method for producing the compound represented by formula (1) or formula (2) can also be determined by appropriately sampling the reaction mixture during the reaction and confirming the degree of disappearance of the starting compound, the degree of formation of the compound represented by formula (1) or formula (2), etc., using known analytical means such as liquid chromatography or gas chromatography.

[0068] From the reaction mixture after the reaction, the compound represented by formula (1) or formula (2) can be isolated by known methods such as recrystallization, reprecipitation, extraction, and various types of chromatography, or by appropriately combining these operations.

[0069] A compound according to one embodiment of the present invention may be a compound represented by the following formula (3). The compound represented by formula (3) is useful as a synthetic intermediate for the compound represented by formula (1) or formula (2).

[0070] [ka]

[0071] In formula (3), Ar 31 Ar 32 and Ar 33Each of these independently represents an optionally substituted 1,4-phenylene group, an optionally substituted 1,4-naphthylene group, a optionally substituted divalent aromatic condensed heterocyclic group consisting of two optionally substituted five-membered rings, an optionally substituted thiazolediyl group, or an optionally substituted thiadiazolediyl group. 31 Ar 32 and Ar 33 At least one of these represents a divalent aromatic condensed heterocyclic group consisting of two optionally substituted five-membered rings, an optionally substituted thiazolediyl group, or an optionally substituted thiadiazolediyl group.

[0072] The divalent aromatic fused heterocyclic group consisting of two five-membered rings in formula (3) is equivalent to the divalent aromatic fused heterocyclic group consisting of two five-membered rings in formula (1), and the preferred embodiment is also the same. 31 Ar 32 or Ar 33 The substituent in formula (1) is Ar 11 Ar 12 and Ar 13 This is synonymous with the substituent in [the given expression], and the preferred embodiment is similar.

[0073] n is either 1 or 2, and if n is 2, then there are two Ar 32 These may be the same or different.

[0074] R 31 and R 32 Each of these independently represents an optionally substituted linear or cyclic aliphatic group, or an optionally substituted aryl group. 31 or R 32 In formula (1), the aliphatic group or aryl group is R 11 This is synonymous with an aliphatic group or aryl group in the above, and the preferred embodiment is the same.

[0075] Dichroic pigments A dichroic dye contains at least one compound represented by formula (1) or formula (2) as an active ingredient. By containing a compound represented by formula (1) or formula (2), a dichroic dye can form a polarizing film with excellent heat resistance. A dichroic dye may contain only one compound represented by formula (1) or formula (2), or it may contain a combination of two or more compounds with different structures. If a dichroic dye contains two or more compounds represented by formula (1) or formula (2), they may have different maximum absorption wavelengths. In addition, a dichroic dye may contain other dye compounds in addition to the compounds represented by formula (1) or formula (2).

[0076] composition The composition of this embodiment comprises at least one compound represented by formula (1) or formula (2), and a liquid crystalline compound comprising at least one polymerizable liquid crystal compound and a liquid crystalline 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. The polarizing film obtained using the composition as a forming material is a high-quality polarizing film exhibiting excellent heat resistance. By including a compound represented by formula (1) or formula (2) as a dichroic dye in the composition, a polarizing film exhibiting excellent heat resistance can be formed.

[0077] The content of the compound represented by formula (1) or formula (2) in the composition may be, for example, 50 parts by mass or less per 100 parts by mass of the solid content of the composition, preferably 0.1 parts by mass or more and 10 parts by mass or 0.1 parts by mass or more and 5 parts by mass. Within the above range If present, the dispersion of the compound represented by formula (1) or formula (2) will be sufficiently possible. In this specification, solids refer to the total amount of components remaining after removing volatile components such as solvents from the composition. The composition may contain only one compound represented by formula (1) or formula (2), or it may contain a combination of two or more compounds with different structures. If the composition contains two or more compounds, they may have different maximum absorption wavelengths.

[0078] The composition may further contain at least one other dye compound other than the compound represented by formula (1) or formula (2), such as a dichroic dye. Examples of other dye compounds include azo dyes such as monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbeneazo dyes, and at least one selected from the group consisting of these is preferred. The composition may contain one other dye compound alone or two or more in combination. For example, when used as a coated polarizing plate material, it is preferable that the other dye compounds included in the composition have a maximum absorption wavelength in a different wavelength range than the compound represented by formula (1) or formula (2). For example, when used as a coated polarizing plate material, it is preferable that the composition includes a combination of three or more dichroic dyes, including the compound represented by formula (1) or formula (2), and more preferably a combination of three or more azo dyes. By including a combination of three or more dye compounds with different maximum absorption wavelengths in the composition, absorption across the entire visible light spectrum can be obtained, for example, by a film formed from the composition.

[0079] If the composition contains other dye compounds, their content may be, for example, 50 parts by mass or less per 100 parts by mass of the solid content of the composition, preferably 0.1 parts by mass or more and 10 parts by mass or 0.1 parts by mass or more and 5 parts by mass. Within the above range, sufficient dispersion of the other dye compounds is possible.

[0080] The composition contains a crystalline compound comprising a compound represented by formula (1) or formula (2), in addition to at least one polymerizable liquid crystal compound and a crystalline polymer compound. The composition may contain both a polymerizable liquid crystal compound and a crystalline polymer compound, and there may be two or more polymerizable liquid crystal compounds and crystalline polymer compounds included in the composition. By containing at least one polymerizable liquid crystal compound and a crystalline polymer compound, the composition can be made in which the compound represented by formula (1) or formula (2) is dispersed in the crystalline compound.

[0081] The liquid crystalline polymer compound may constitute a thermotropic liquid crystal polymer or a lyotropic liquid crystal polymer. It is preferable that the liquid crystalline polymer compound constitutes a thermotropic liquid crystal polymer because it allows for precise control of film thickness.

[0082] Liquid crystals are classified into smectic liquid crystals, nematic liquid crystals, and cholesteric liquid crystals based on the molecular arrangement structure in the liquid crystal state. Among these, smectic liquid crystals are preferred for polarizing film applications. Therefore, polymerizable liquid crystal compounds are preferably polymerizable smectic liquid crystal compounds, and liquid crystalline polymer compounds are preferably smectic liquid crystal polymer compounds.

[0083] By using polymerizable liquid crystal compounds exhibiting smectic liquid crystal properties and polymer compounds exhibiting smectic liquid crystal properties, a polarizing film with a high degree of orientational order can be formed. The liquid crystal state exhibited by the polymerizable liquid crystal compound and the liquid crystal polymer compound is preferably the smectic phase (smectic liquid crystal state), and more preferably the higher-order smectic phase (higher-order smectic liquid crystal state) from the viewpoint of achieving a higher degree of orientational order. Here, the higher-order smectic phase refers to the smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase, and smectic L phase, and among these, the smectic B phase, smectic F phase, and smectic I phase are more preferred. A polarizing film with a high degree of orientational order yields Bragg peaks derived from higher-order structures such as the hexatic phase and crystal phase in X-ray diffraction measurements. A 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 exhibits a Bragg peak derived from a higher-order structure in X-ray diffraction measurements.

[0084] Compounds represented by formula (1) or formula (2) can exhibit high dichroism even when dispersed between dense molecular chains formed from at least one polymerizable smectic liquid crystalline compound and a smectic liquid crystalline polymer compound. Therefore, a composition containing a liquid crystalline compound comprising at least one polymerizable liquid crystalline compound and a liquid crystalline polymer compound, particularly a liquid crystalline compound comprising at least one polymerizable smectic liquid crystalline compound and a smectic liquid crystalline polymer compound, and a compound represented by formula (1) or formula (2), can provide a polarizing film with excellent heat resistance and a high dichroism ratio.

[0085] A polymerizable liquid crystal compound is a compound that has at least one polymerizable group in its molecule and can exhibit a liquid crystal phase by orientation. Preferably, a polymerizable liquid crystal compound is a compound that can exhibit a liquid crystal phase by orientation alone. A polymerizable group refers to a functional group that can participate in polymerization reactions, and is preferably a radical polymerizable group. Specifically, as a polymerizable liquid crystal compound, for example, the polymerizable liquid crystal compounds described in paragraphs 0062 to 0079 of Japanese Patent Application Publication No. 2022-088325 can be used.

[0086] Furthermore, as the liquid crystalline polymer compound, for example, the liquid crystalline polymer compound described in paragraphs 0080 to 0085 of Japanese Patent Publication No. 2022-088325 can be used.

[0087] The total content ratio of polymerizable liquid crystal compounds and liquid crystalline polymer compounds in the composition may be, for example, 50 parts by mass or more per 100 parts by mass of solid content of the composition, preferably 70 parts by mass or more and 99.9 parts by mass or less, 70 parts by mass or more and 99.5 parts by mass or less, 80 parts by mass or more and 99 parts by mass or less, 80 parts by mass or more and 94 parts by mass or less, or 80 parts by mass or more and 90 parts by mass or less, from the viewpoint of increasing the orientation of polymerizable liquid crystal compounds and liquid crystalline polymer compounds.

[0088] The content of the compound represented by formula (1) or formula (2) in the composition may be, for example, 0.1 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the total amount of polymerizable liquid crystal compound and liquid crystalline polymer compound, preferably 0.1 parts by mass or more and 20 parts by mass or less, 0.1 parts by mass or more and 10 parts by mass or less, or 0.1 parts by mass or more and 5 parts by mass or less. When the content of the compound represented by formula (1) or formula (2) relative to the total amount of polymerizable liquid crystal compound and liquid crystalline polymer compound is 50 parts by mass or less, there is a tendency to obtain a polarizing film with less disorder in the orientation of the polymerizable liquid crystal compound, liquid crystalline polymer compound and the compound represented by formula (1) or formula (2), and a high degree of orientational order.

[0089] The composition may further contain a polymer compound in addition to the compound represented by formula (1) or formula (2) and the liquid crystalline compound. As the polymer compound, for example, the polymer compounds described in paragraphs 0089 to 0090 of Japanese Patent Application Publication No. 2022-088325 can be used.

[0090] The composition further comprises a liquid medium such as a solvent and a polymerization initiator, and may optionally further comprise a photosensitizer, polymerization inhibitor, leveling agent, etc. As the solvent, for example, the solvent described in paragraphs 0092 to 0094 of Japanese Patent Publication No. 2022-088325 can be used. As the polymerization initiator, for example, the polymerization initiator described in paragraphs 0095 to 0097 of the same publication can be used in the amount relative to the described composition. As the photosensitizer, for example, the photosensitizer described in paragraphs 0098 to 0099 of the same publication can be used in the amount relative to the described composition. As the polymerization inhibitor, for example, the polymerization inhibitor described in paragraphs 0100 to 0101 of the same publication can be used in the amount relative to the described composition. As the leveling agent, for example, the leveling agent described in paragraphs 0102 to 0104 of the same publication can be used in the amount relative to the total amount of the described liquid crystalline compound. As antioxidants, for example, the antioxidants described in paragraphs 0105 to 0106 of the same publication can be used in the amounts described for the composition.

[0091] The composition may contain other additives not listed above. Examples of other additives include mold release agents, stabilizers, colorants such as bluing agents, flame retardants, and lubricants. If the composition contains other additives, the content of the other additives is preferably more than 0% and 20% by mass or less, and more preferably more than 0% and 10% by mass or less, relative to the solid content of the composition.

[0092] The composition can be prepared by conventionally known methods for preparing compositions. For example, it can be prepared by mixing and stirring a compound represented by formula (1) or (2), a liquid crystalline compound, and, if necessary, additives such as antioxidants and leveling agents.

[0093] film The film according to this embodiment may be a film containing a compound represented by formula (1) or (2) as a forming material, or it may be a film obtained using a composition containing a compound represented by formula (1) or (2) and a liquid crystalline compound as a forming material. A film made of a composition may be formed by applying the composition to a substrate and forming a film. Furthermore, if the composition contains a polymerizable liquid crystal compound, a 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, then polymerizing the polymerizable liquid crystal compound and curing it.

[0094] The composition can form a film with a high degree of orientation order and excellent heat resistance, such as a polarizing film. Therefore, the film according to this embodiment includes a polarizing film formed from a composition comprising a compound represented by formula (1) or (2) and a liquid crystalline compound, which has a high degree of orientation order and excellent heat resistance.

[0095] In polarizing films with a high degree of orientational order, Bragg peaks originating from higher-order structures such as the hexatic phase and the crystalline phase can be obtained in X-ray diffraction measurements. Therefore, it is preferable that the polarizing film formed from the composition is oriented such that the liquid crystalline compound exhibits a Bragg peak in X-ray diffraction measurements, and it is more preferable that the molecules of the liquid crystalline compound are oriented in a "horizontal orientation" that is such that they are oriented in the direction that absorbs light. A high degree of orientational order that exhibits a Bragg peak can be achieved by controlling the type of liquid crystalline compound used, the amount of the compound represented by formula (1) or (2), etc.

[0096] The compounds represented by formula (1) or (2) and the liquid crystalline compounds that constitute the composition used to form the film are as previously described.

[0097] The membrane can be manufactured, for example, by a method including the following steps: Step A: Forming a coating film of a composition containing a compound represented by formula (1) or (2), a liquid crystalline compound, and a solvent. Step B: Remove at least a portion of the solvent from the coating film. Step C: After raising the temperature to a temperature above which the liquid crystalline compound undergoes a phase transition to the liquid phase, the temperature is lowered to cause the liquid crystalline compound to undergo a phase transition to the smectic phase (smectic liquid crystal state), and Step D: If necessary, polymerize the polymerizable liquid crystal compound while maintaining the smectic phase (smectic liquid crystal state).

[0098] The composition can be formed by, for example, applying it to a substrate, an alignment film (described later), or the like. Alternatively, the composition may be directly applied to a phase difference film or other layers that constitute a polarizing plate.

[0099] As a substrate, for example, the substrate described in paragraphs 0115 to 0118 of Japanese Patent Publication No. 2022-088325 can be used. As methods for applying the composition to the substrate, known methods include coating methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator coating, and printing methods such as flexographic coating.

[0100] Next, a dried coating film is formed by removing at least a portion of the solvent contained in the coating film obtained from the composition by drying or other means. Furthermore, if the coating film contains a polymerizable liquid crystal compound, a dried coating film is formed by drying under conditions in which the polymerizable liquid crystal compound does not polymerize. Examples of drying methods for the coating film include natural drying, forced-air drying, heat drying, and reduced-pressure drying.

[0101] Furthermore, in order to induce a phase transition of the liquid crystalline compound to the liquid phase, the temperature is raised to above the temperature at which the liquid crystalline compound transitions to the liquid phase, and then the temperature is lowered to induce a phase transition of the liquid crystalline compound to the smectic phase (smectic liquid crystal state). This phase transition may be performed after the removal of the solvent from the coating film, or it may be performed simultaneously with the removal of the solvent.

[0102] When the composition contains a polymerizable liquid crystal compound, a film containing a cured product of the polymerizable liquid crystal compound is formed by polymerizing the polymerizable liquid crystal compound while maintaining its smectic liquid crystal state. Photopolymerization is preferred as the polymerization method. In photopolymerization, the light irradiated onto the dry coating film is appropriately selected according to the type of photopolymerization initiator contained in the dry coating film, the type of polymerizable liquid crystal compound (especially the type of polymerizable group possessed by the polymerizable liquid crystal compound), and its amount. Specific examples include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, and gamma rays, and active electron beams. Among these, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction and because photopolymerization equipment 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 with ultraviolet light. Furthermore, the polymerization temperature can also be controlled by irradiating the dry coating film with light while cooling it with an appropriate cooling means during polymerization. By employing such cooling methods, polymerization of polymerizable liquid crystal compounds can be carried out at lower temperatures, allowing for the formation of appropriate films even when using substrates with relatively low heat resistance. Patterned films can also be obtained by performing masking or development during photopolymerization. For information regarding the light source of active energy rays and ultraviolet irradiation intensity, refer to paragraphs 0123 to 0124 of Japanese Patent Application Publication No. 2022-088325, for example.

[0103] By photopolymerization, the polymerizable liquid crystal compound polymerizes while maintaining the liquid crystal state of the smectic phase, preferably a higher-order smectic phase, thereby forming 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 higher polarization performance compared to conventional host-guest type polarizing films, i.e., films consisting of a liquid crystal state of the nematic phase, due to the action of dichroic dyes. Furthermore, it also has the advantage of superior strength compared to films coated only with dichroic dyes or lyotropic liquid crystals.

[0104] The film thickness can be appropriately selected depending on the applicable display device, etc., and may be, for example, 0.5 μm to 10 μm, preferably 1 μm to 5 μm, or 1 μm to 3 μm.

[0105] When the film is used as a polarizing film, it is preferable that it be formed on an alignment film. The alignment film has an alignment-regulating force that causes polymerizable liquid crystal compounds and liquid crystalline polymer compounds to liquid crystal orientation in a desired direction. Preferably, the alignment film has solvent resistance so as not to dissolve when a composition containing a liquid crystalline compound, which includes at least one polymerizable liquid crystal compound and a liquid crystalline polymer compound, is applied, and also has heat resistance for solvent removal and heat treatment for orientation of the polymerizable liquid crystal compound. Examples of such alignment films include alignment films containing an oriented polymer, photo-alignment films, and groove-alignment films having an uneven pattern or multiple grooves on their surface, and photo-alignment films are preferred from the viewpoint of accuracy of the orientation angle and quality.

[0106] Laminate The laminate according to this embodiment may comprise a film containing a compound represented by formula (1) or formula (2) as a forming material, or a film comprising a composition comprising a compound represented by formula (1) or formula (2) and a liquid crystalline compound as a forming material. The laminate may comprise a substrate and a film containing a compound represented by formula (1) or formula (2) as a forming material disposed on the substrate, or a substrate, an alignment film disposed on the substrate, and a film comprising a compound represented by formula (1) or formula (2) as a forming material disposed on the alignment film. The film containing a compound represented by formula (1) or formula (2) as a forming material may constitute a polarizing film. The substrate may also be a phase difference film. The laminate can constitute, for example, a polarizing plate. The laminate can be manufactured, for example, by forming a film on a substrate in accordance with the film manufacturing method described above.

[0107] The thickness of the laminate may be, for example, 10 μm to 300 μm, preferably 20 μm to 200 μm, or 25 μm to 100 μm, from the viewpoint of the flexibility and visibility of the display device. If the laminate includes a phase difference film as a base material, the thickness of the phase difference film can be appropriately selected depending on the applicable display device.

[0108] display device The display device of this embodiment comprises the laminate, which 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 an adhesive layer. A display device is a device having a display element and including a light-emitting element or a light-emitting device as a light source. Examples of display devices include liquid crystal displays, organic electroluminescent (EL) displays, inorganic electroluminescent (EL) displays, electron emission displays (e.g., electric field emission displays (FEDs), surface field emission displays (SEDs)), electronic paper (display devices using electronic ink, electrophoretic elements, etc.), plasma displays, projection displays (e.g., grating light bulb (GLV) displays, displays having digital micromirror devices (DMDs)), and piezoelectric ceramic displays. Liquid crystal displays include transmissive liquid crystal displays, semi-transmissive liquid crystal displays, reflective liquid crystal displays, direct-view liquid crystal displays, and projection liquid crystal displays. These display devices may be displays that display two-dimensional images or stereoscopic displays that display three-dimensional images. In particular, organic EL displays and touch panel displays are preferred as display devices, with organic EL displays being especially preferred. [Examples]

[0109] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0110] In the following examples, the LUMO energy levels were calculated using density functional theory (DFT). Specifically, the LUMO energy levels were calculated using density functional theory with the Gaussian16 software, using B3LYP as the functional and 6-31G(d) as the normative function.

[0111] Example 1 Compound 1-1-d was synthesized by diazo coupling, and compound 1-1 was synthesized by aromatic nucleophilic substitution with a secondary amine compound.

[0112] Synthesis of compound 1-1-a Compound 1-1-a was synthesized from 2-nitrothiophene according to the method described in the literature (Journal of Medicinal Chemistry, 2005, Vol48, 5794).

[0113] [ka]

[0114] Synthesis of compound 1-1-b 4-Fluoroaniline (0.8 g, 7.1 mmol) was added to 1.2 mL of hydrochloric acid and 5 mL of water. The mixture was cooled to below 3°C, and 1.1 mL of an aqueous solution of sodium nitrite (0.53 g, 7.4 mmol) was added dropwise, ensuring the internal temperature did not exceed 3°C. The mixture was stirred for 30 minutes at below 3°C to prepare a diazonium solution. Next, the diazonium solution prepared above was added dropwise to 24 mL of a methanol solution of compound 1-1-a (2.4 g, 17.6 mmol), ensuring the internal temperature did not exceed 3°C. The reaction mixture was raised to room temperature and stirred for 1 hour. Then, an aqueous solution of sodium bicarbonate was added until the pH of the reaction solution changed from 7 to 8. The precipitated solid was filtered and dried to obtain 1.6 g of the target product, an orange solid. This was used in the next step without purification.

[0115] [ka]

[0116] Synthesis of compound 1-1-c Compound 1-1-b (1.6 g, 7.0 mmol) was dissolved in 23 mL of acetic acid, and potassium thiocyanate (1.1 g, 10.6 mmol) was added at room temperature. 8.3 mL of acetic acid solution of bromine (0.6 g, 3.7 mmol) was added dropwise to the above solution over approximately 1 hour. After stirring at room temperature for 1 hour, 100 mL of water was added, and the precipitated solid was filtered and dried to obtain 2.3 g of the target product, a purple solid. This was used in the next step without purification.

[0117] [ka]

[0118] Synthesis of compound 1-1-d Compound 1-1-c (1.0 g, 3.5 mmol) was added to 10 mL of sulfuric acid, 10 mL of water, and 10 mL of acetic acid. The mixture was cooled to below 3°C, and nitrosyl sulfuric acid (2.8 g, 8.9 mmol in 40 wt% sulfuric acid) was added dropwise, ensuring the internal temperature did not exceed 3°C. The mixture was stirred at below 3°C for 30 minutes to prepare a diazonium solution. Next, 55 mL of aqueous sodium acetate (36 g, 437 mmol) was added to 75 mL of methanol solution of N,N-diethylaniline (0.80 g, 5.3 mmol), and the mixture was cooled to below 3°C. The diazonium solution prepared above was added dropwise, ensuring the internal temperature did not exceed 3°C. The reaction mixture was raised to room temperature and stirred for 1 hour. Then, 300 mL of water was added, and the precipitated solid was filtered and dried to obtain 1.1 g of the target product, a blackish-purple solid. This was used in the next step without purification.

[0119] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.98-7.83(m, 5H), 7.18(d, 2H), 6.74(d, 2H), 3.49(q, 4H), 1.25(t, 6H)

[0120] [ka]

[0121] Synthesis of compound 1-1 Compound 1-1-d (0.200 g, 0.395 mmol) and potassium carbonate (0.276 g, 1.98 mmol) were dissolved in N,N-dimethylformamide (8.0 mL), N-methylbutylamine (0.371 g, 3.95 mmol) was added, and the mixture was heated to 70°C and stirred for 2 hours. Water was added to the reaction vessel, the precipitated solid was filtered off, and washed with methanol. The obtained solid was purified by silica gel column chromatography with chloroform as the developing solvent to obtain compound 1-1 (0.02 g, yield 10%).

[0122] LUMO = -2.50 eV. 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.91(d, 2H), 7.78(d, 2H), 7.67(s, 1H), 6.71(dd, 4H), 3.49( q, 4H), 3.42(t, 2H), 3.06(s, 3H), 1.62(quin, 2H), 1.37(sext, 2H), 1.26(t, 6H), 0.96(t, 3H)

[0123] [ka]

[0124] Example 2 Compound 1-1-d was synthesized by diazo coupling, and compound 1-2-a was synthesized by aromatic nucleophilic substitution with a secondary amine compound. Compound 1-2 was then obtained by reacting it with a silyl chloride.

[0125] Synthesis of Compounds 1-2 Compound 1-1-d (0.200 g, 0.298 mmol) and potassium carbonate (0.208 g, 1.49 mmol) were dissolved in N,N-dimethylformamide (6.0 mL), N-methylethanolamine (0.226 g, 2.98 mmol) was added, and the mixture was heated to 70°C and stirred for 2 hours. Water was added to the reaction vessel, the precipitated solid was filtered off, washed with methanol, and compound 1-2-a was obtained. Compound 1-2-a was used in the next step without purification.

[0126] Compound 1-2-a (0.170 g, 0.069 mmol) and imidazole (0.015 g, 0.21 mmol) were dissolved in N,N-dimethylformamide (0.7 mL), cooled to 0°C, and then dimethylsilyl texyl chloride (0.026 g, 0.138 mmol) was added. The mixture was returned to room temperature and stirred for 2 hours. Water was added to the reaction vessel, the precipitated solid was filtered off, and washed with methanol. The obtained solid was purified by silica gel column chromatography with chloroform as the developing solvent to obtain compound (1-2) (0.022 g, yield 11%).

[0127] LUMO = -2.51 eV. 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.91(d, 2H), 7.78(d, 2H), 7.68(s, 1H), 6.73(dd, 4H), 3.79(t, 2H), 3.58 (t, 2H), 3.49(q, 4H), 3.11(s, 3H), 1.63-1.58(m, 1H), 1.26(t, 6H), 0.85(m, 6H), 0.81(m, 6H), 0.04(s, 6H)

[0128] [ka]

[0129] Example of synthesis Compounds C-1, C-2-a, and C-3-a were synthesized by known diazo coupling methods.

[0130] [ka]

[0131] Comparative Example 1 Synthesis of compound C-2 Compound C-2-a (0.139 g, 0.299 mmol) and imidazole (0.061 g, 0.90 mmol) were dissolved in N,N-dimethylformamide (5.0 mL), cooled to 0°C, and then chlorodimethyltexylsilane (0.112 g, 0.626 mmol) was added. The mixture was returned to room temperature and stirred for 5 hours. Water was added to the reaction vessel, the precipitated solid was filtered off, and washed with methanol. The obtained solid was purified by silica gel column chromatography with chloroform as the developing solvent to obtain compound C-2 (0.130 g, yield 75%).

[0132] LUMO = -2.78 eV 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.95(d, 2H), 7.91(s, 1H), 7.80(d, 2H), 7.33(d, 2H), 6.75(d, 2H), 3.84( t, 2H), 3.52(q, 4H), 2.88(t, 2H), 1.63-1.58(m, 1H), 1.28(t, 6H), 0.86(m, 6H), 0.82(m, 6H), 0.03(s, 6H)

[0133] [ka]

[0134] Comparative Example 2 Synthesis of compound C-3 Compound C-3-a (0.096 g, 0.20 mmol) and imidazole (0.041 g, 0.60 mmol) were dissolved in N,N-dimethylformamide (2.0 mL), cooled to 0°C, and then tert-butyldiphenylchlorosilane (0.11 g, 0.40 mmol) was added. The mixture was returned to room temperature and stirred for 2 hours. Water was added to the reaction vessel, the precipitated solid was filtered off, and washed with methanol. The obtained solid was purified by silica gel column chromatography with chloroform as the developing solvent to obtain compound C-3 (0.086 g, yield 61%).

[0135] LUMO = -2.66 eV 1H-NMR (400MHz, CDCl3): δ(ppm)=7.93(d, 2H), 7.84(s, 1H), 7.82(d, 2H), 7.71(d, 4H), 7.40(m, 6) H), 6.94(d, 2H), 6.73(d, 2H), 4.14(t, 2H), 4.02(t, 2H), 3.50(q, 4H), 1.27(t, 6H), 1.23(s, 9H)

[0136] [ka]

[0137] Example 3: Preparation of Composition E1 Composition E1 was obtained by mixing the following components and stirring at 80°C for 1 hour. ·Polymerizable liquid crystal compound A-6 75 parts by mass ·Polymerizable liquid crystal compound A-7 25 parts by mass ·Compound 1-1 4 parts by mass • Polymerization initiator: 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan) 6 parts by mass • Leveling agent: Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.2 parts by mass • Solvent: o-xylene 250 parts by mass

[0138] Polymerizable liquid crystal compound A-6 and polymerizable liquid crystal compound A-7 [ka]

[0139] Polymerizable liquid crystal compound A-6 was synthesized using the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). Polymerizable liquid crystal compound A-7 was also prepared using the same method.

[0140] Example 4: Preparation of Composition E2 Composition E2 of Example 2 was obtained in the same manner as in Example 1, except that compound 1-2 was used instead of compound 1-1.

[0141] Comparative Examples 1 to 3: Preparation of compositions C1, C2, and C3 Compositions C1, C2, and C3 of Comparative Examples 1 to 3 were obtained in the same manner as in Example 1, except that compound C-1, compound C-2, or compound C-3, represented by the above formula as described above, were used instead of compound 1-1, respectively, by the synthesis method.

[0142] Manufacturing of polarizing plates 1. Formation of the orientation film A glass substrate was used as the transparent substrate. A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (composition for forming an orientation layer) was applied to the glass substrate by spin coating, and after drying, a film with a thickness of 100 nm was formed. Subsequently, an orientation layer was formed by rubbing the surface of the obtained film, and a substrate with an orientation layer formed on the glass substrate was obtained.

[0143] 2. Formation of polarizing film The composition obtained above was applied to the alignment film of the substrate obtained above by spin coating, heated and dried on a hot plate at 120°C for 3 minutes, and then rapidly cooled to 70°C or below (the temperature at which the smectic liquid crystal phase is observed during cooling) to obtain a laminate in which a dried film was formed on the alignment film.

[0144] Next, using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.), ultraviolet light was applied at an exposure dose of 2400 mJ / cm². 2 By irradiating the dried film with light at 365 nm (based on a 365 nm wavelength), the polymerizable liquid crystal compounds contained in the dried film were polymerized while maintaining the liquid crystal state of the composition, forming a polarizing film from the dried film and obtaining a polarizing plate.

[0145] evaluation A protective film (40 μm TAC (Konica Minolta, Inc. "KC4UY")) was placed on the surface of the polarizing film obtained above, and a heat resistance test was conducted by heating it in an oven chamber for a specified time under the following conditions to evaluate the heat resistance of the polarizing film. The absorbance in the direction of the absorption axis of the polarizing film before the heat resistance test (A1) and the absorbance in the direction of the absorption axis of the polarizing film after the heat resistance test (A2) at the maximum absorption wavelength of the polarizing film before the heat resistance test were measured using the double-beam method with a spectrophotometer (Shimadzu Corporation UV-3150) equipped with a holder containing a polarizing plate. The absorbance in the direction of the absorption axis of the polarizing film after the heat resistance test (A2) was divided by the absorbance in the direction of the absorption axis of the polarizing film before the heat resistance test (A1) to obtain the absorbance retention rate (%). The results are shown in Table 1. Note that if the absorbance retention rate exceeds 85%, it is judged to be a good polarizing film.

[0146] The heating conditions for the heat resistance test are as follows: Equipment used: DN411I manufactured by Yamato Scientific Co., Ltd. Exam duration: 240 hours Temperature: 105℃.

[0147] [Table 1]

[0148] Table 1 shows that polarizing plates equipped with a film formed from a composition containing compound 1-1 or compound 1-2 exhibit high heat resistance.

Claims

1. A compound represented by the following formula (2), wherein the LUMO energy level is between -2.65 eV and -2.10 eV. 【Chemistry 1】 [In formula (2), Ar ２１ Ar ２２ and Ar ２３ Each independently represents a 1,4-phenylene group, a 1,4-naphthylene group, a divalent sulfur-containing aromatic heterocyclic group, or a divalent sulfur-containing aromatic condensed heterocyclic group consisting of 2 to 4 aromatic rings, which may have substituents, and Ar ２１ Ar ２２ and Ar ２３ At least one of these represents a divalent sulfur-containing aromatic heterocyclic group, or a divalent sulfur-containing aromatic condensed heterocyclic group consisting of two to four aromatic rings. m is either 1 or 2, and if m is 2, then there are two Ar ２２ These may be the same or different. R ２１ 、R ２２ 、R ２３ and R ２４ each independently represents a hydrogen atom, a linear or cyclic aliphatic group or an aryl group which may have a substituent. R ２１ and R ２２ and R ２３ and R ２４ at least one pair of which may be linked to each other to form a ring, and at least one of the methylene units constituting the formed ring may be substituted with an oxygen atom or a carbonyl group. R ２１ 、R ２２ 、R ２３ and R ２４ at least one of which may be substituted with at least one substituent selected from the group consisting of an organosilyloxy group and a polymerizable group. However, except when the combination of the two groups represented by R ２１ and R ２２ is the same as the combination of the two groups represented by R ２３ and R ２４ . ]

2. In the above formula (2), Ar ２１ and Ar ２３ Each of these independently represents a 1,4-phenylene group which may have substituents, and Ar ２２ The compound according to claim 1, wherein m represents a thieno[3,2-d]thiazolediyl group, a thieno[3,2-d]thiophenediyl group, a thiazole-diyl group, a thiadiazolediyl group, or a thiophenediyl group, which may have substituents, and m is 1.

3. A composition comprising the compound according to claim 1 or claim 2, and a liquid crystalline compound comprising at least one polymerizable liquid crystal compound and a liquid crystalline polymer compound.

4. The composition according to claim 3, wherein the liquid crystalline compound is a smectic liquid crystalline compound.

5. A film formed using the composition described in claim 3 as the forming material.

6. A laminate comprising the film described in claim 5.

7. A display device comprising the laminate according to claim 6.

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