Compound, composition, film, laminate, and display device

Abstract

The present invention is a compound represented by formula (1). In formula (1), Ar11, Ar12, and Ar13 each represents a 1, 4-phenylene group, a 1, 4-naphthylene group, or a divalent aromatic fused heterocyclic group comprising two five-membered rings, and at least one of Ar11, Ar12, and Ar13 represents a divalent aromatic fused heterocyclic group. K is 1 or 2. And R11, R12, R13, and R14 each represents a hydrogen atom, a chain-like or cyclic aliphatic group, or an aryl group. At least one of R11 and R12 and R13 and R14 may be linked to each other to form a ring, and at least one methylene unit constituting the ring may be replaced with an oxygen atom or a carbonyl group. And at least one of R11, R12, R13 and R14 may be substituted with at least one of an organosilyloxy group and a polymerizable group. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a compound, a composition, a film, a laminate and a display device. Background Art

[0002] As a polarizing film (optical film) used in a liquid crystal display device, etc., a polarizing film formed of a composition containing a dichroic dye is known. As such a dichroic dye, for example, Patent Document 1 describes the following compounds.

[0003] [Chemical formula 1]

[0004]

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 64-70585 Summary of the invention

[0008] Problems to be solved by the invention

[0009] However, when a polarizing film produced 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 may decrease over time. An object of the present invention is to provide a compound having high heat resistance, a composition containing the compound, a film formed from the composition, a laminate having the film, and a display device having the laminate.

[0010] Means for solving problems

[0011] The present invention provides the following [1] to

[11] .

[0012] [1] A compound represented by the following formula (1).

[0013] [Chemical formula 2]

[0014]

[0015] [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 consisting of two 5-membered rings which may have a substituent, Ar 11 ,Ar 12 and Ar 13 At least one of them represents a divalent aromatic fused heterocyclic group formed by two 5-membered rings. k is 1 or 2. When k is 2, the two Ar 12Each may be the same or different. 11 , R 12 , R 13 and R 14 Each independently represents a hydrogen atom, a linear or cyclic aliphatic group or an aromatic group which may have a substituent. 1 With R 2 and R 3 With R 4 At least one of the groups may be linked to each other to form a ring, and at least one methylene unit constituting the formed ring may be replaced by an oxygen atom or a carbonyl group. 11 , R 12 , R 13 and R 14 At least one of them may be substituted with at least one substituent selected from the group consisting of an organosilyloxy group and a polymerizable group.]

[0016] [2] The compound according to [1], wherein in the above formula (1), Ar 11 ,Ar 12 and Ar 13 Each independently represents a 1,4-phenylene group which may have a substituent or a divalent sulfur-containing aromatic condensed heterocyclic group consisting of two 5-membered rings, Ar 11 ,Ar 12 and Ar 13 At least one of them represents a divalent sulfur-containing aromatic condensed heterocyclic group formed of two 5-membered rings.

[0017] [3] The compound according to [1] or [2], wherein in the above formula (1), Ar 11 ,Ar 12 and Ar 13 Each independently represents 1,4-phenylene, thieno[3,2-d]thiazoldiyl or thieno[3,2-d]thiophenediyl which may have a substituent, Ar 11 ,Ar 12 and Ar 13 At least one of them represents a thieno[3,2-d]thiazoldiyl group or a thieno[3,2-d]thiophenediyl group.

[0018] [4] The compound according to any one of [1] to [3], wherein in the formula (1), Ar 11 and Ar 13 Each independently represents a 1,4-phenylene group which may have a substituent, Ar 12 represents a thieno[3,2-d]thiazoldiyl group or a thieno[3,2-d]thiophenediyl group which may have a substituent, and k is 1.

[0019] [5] A compound represented by the following formula (2), wherein the LUMO level of the compound is from -2.65 eV to -2.10 eV.

[0020] [Chemical formula 3]

[0021]

[0022] [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 a substituent, Ar 21 ,Ar 22 and Ar 23 At least one of them represents a divalent sulfur-containing aromatic heterocyclic group or a divalent sulfur-containing aromatic condensed heterocyclic group composed of 2 to 4 aromatic rings.

[0023] m is 1 or 2. When m is 2, two Ar 22 Each may be the same or different.

[0024] R 21 , R 22 , R 23 and R 24 Each independently represents a hydrogen atom, a linear or cyclic aliphatic group or an aromatic group which may have a substituent. 21 With R 22 and R 23 With R 24 At least one of the groups may be linked to each other to form a ring, and at least one methylene unit constituting the formed ring may be replaced by an oxygen atom or a carbonyl group. 21 , R 22 , R 23 and R 24 At least one of the following may be substituted with at least one substituent selected from the group consisting of an organic silyloxy group and a polymerizable group. 21 and R 22 The combination of two groups represented by R 23 and R 24 The combination of the two groups represented is the same.]

[0025] [6] The compound according to [5], wherein in the above formula (2), Ar 21 and Ar 23 Each independently represents a 1,4-phenylene group which may have a substituent, Ar 22represents a thieno[3,2-d]thiazoldiyl group, a thieno[3,2-d]thiophenediyl group, a thiazoldiyl group, a thiadiazoldiyl group or a thiophenediyl group which may have a substituent, and m is 1.

[0026] [7] A composition comprising a liquid crystal compound and the compound according to any one of [1] to [6], wherein the liquid crystal compound comprises at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound.

[0027] [8] The composition according to [7], wherein the liquid crystal compound is a smectic liquid crystal compound.

[0028] [9] A film formed from the composition described in [7] as a material.

[0029]

[10] A laminate comprising the film according to [9].

[0030]

[11] A display device comprising the laminate according to

[10] .

[0031] Effects of the Invention

[0032] According to the present invention, a compound having high heat resistance, a composition containing the compound, a film formed from the composition, a laminate including the film, and a display device including the laminate can be provided. DETAILED DESCRIPTION

[0033] 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 the desired purpose of the process can be achieved. In addition, for the content of each component in the composition, when there are multiple substances belonging to each component in the composition, unless otherwise specified, it refers to the total amount of the multiple substances present in the composition. In addition, for the upper and lower limits of the numerical ranges recorded in this specification, the numerical values ​​exemplified as numerical ranges can be arbitrarily selected and combined. Below, embodiments of the present invention are described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described herein, and various changes can be made within the scope of not damaging the gist of the present invention.

[0034] Compound

[0035] The compound involved in one embodiment of the present invention is represented by the following formula (1). The compound can be, for example, a dichroic pigment compound, which can be used as a material for forming a polarizing film. The compound represented by formula (1) has a divalent aromatic fused heterocyclic group in the molecule and has amino groups at both ends, thereby being able to show high heat resistance in an environment of about 100°C. It can be considered that this is because, for example, it is inferred that the decomposition reaction of the compound in an environment of about 100°C is reductive, and since the compound has amino groups at both ends, the LUMO energy level of the compound becomes a specific range, which can suppress the reductive decomposition reaction.

[0036] [Chemical formula 4]

[0037]

[0038] In formula (1), Ar 11 ,Ar 12 and Ar 13 Each independently represents an optionally substituted 1,4-phenylene group, an optionally substituted 1,4-naphthylene group, or an optionally substituted divalent aromatic condensed heterocyclic group consisting of two 5-membered rings. 11 ,Ar 12 and Ar 13 At least one of the groups represents a divalent aromatic fused heterocyclic group formed by two 5-membered rings which may have a substituent. The aromatic fused heterocyclic group is formed by removing two hydrogen atoms from an aromatic fused heterocyclic compound formed by condensing two 5-membered aromatic heterocyclic compounds. Examples of the 5-membered aromatic heterocyclic compound include thiophene, thiazole, furan, and the like. Specifically, examples of the aromatic fused heterocyclic group formed by two 5-membered rings include thieno[3,2-d]thiazoldiyl, thieno[3,2-d]thienyl, thiazolo[5,4-d]thiazoldiyl, furano[3,2-d]thiazoldiyl, and the like, and may include at least one selected from the group consisting of these. The aromatic condensed heterocyclic group composed of two 5-membered rings may preferably include at least one selected from the group consisting of thieno[3,2-d]thiazoldiyl and thieno[3,2-d]thiophenediyl.

[0039] In formula (1), Ar 11 ,Ar 12 and Ar 13 Each of the following may independently represent a 1,4-phenylene group which may have a substituent or a divalent sulfur-containing aromatic condensed heterocyclic group which may have a substituent and is composed of two 5-membered rings, Ar 11 ,Ar 12 and Ar 13 At least one of them may represent a divalent sulfur-containing aromatic condensed heterocyclic group consisting of two 5-membered rings which may have a substituent.

[0040] In formula (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 a substituent. 12 represents a divalent aromatic fused heterocyclic group or a sulfur-containing aromatic fused heterocyclic group consisting of two 5-membered rings which may have a substituent, Ar 11 and Ar 13 Each independently represents 1,4-phenylene or 1,4-naphthylene which may have a substituent. 12 represents a thieno[3,2-d]thiazoldiyl group or a thieno[3,2-d]thiophenediyl group which may have a substituent, Ar 11 and Ar 13 Each independently represents a 1,4-phenylene group which may have a substituent.

[0041] Ar 11 ,Ar 12 and Ar 13 The substituent in may include at least one selected from the group consisting of a halogen atom, a hydroxyl 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 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. 11 ,Ar 12 and Ar 13 The number of substituents in each independently may be, for example, 0, 1 or 2, preferably 0 or 1.

[0042] k is 1 or 2, preferably 1. In the case where k is 2, two Ar 12 Each may be the same or different.

[0043] R 11 , R 12 , R 13 and R 14 Each independently represents a hydrogen atom, a linear or cyclic aliphatic group which may have a substituent, or an aryl group which may have a substituent. 11 , R 12 , R 13 or R 14 The carbon number of the aliphatic group represented by can be, for example, 1 to 20, preferably 1 to 12, or 1 to 6. The aliphatic group can be an alkyl group, an alkenyl group, or an alkynyl group, preferably an alkyl group. Specific examples of the aliphatic group include methyl, ethyl, vinyl, ethynyl, propyl, isopropyl, cyclopropyl, allyl, butyl, hexyl, ethylbutyl, ethylhexyl, hexyldodecyl, and the like. R 11 , R12 , R 13 or R 14 The aryl group represented by may have 6 to 10 carbon atoms, and preferably 6 carbon atoms.

[0044] R 11 With R 12 and R 13 With R 14 At least one of the groups may be connected to each other to form a cyclic amino group together with the nitrogen atom, and the cyclic amino group formed may be an alicyclic amino group. In addition, at least one methylene unit constituting the cyclic amino group formed may be replaced by an oxygen atom or a carbonyl group. The number of members of the cyclic amino group formed may be, for example, 5 or 6. 11 , nitrogen atom and R 12 , or R 13 , nitrogen atom and R 14 Specific examples of the cyclic amino group to be formed include pyrrolidinyl, piperidinyl, morpholinyl, oxazolidinyl, piperazinyl, N-methylpiperazinyl, and 2-oxo-3-oxazolidinyl.

[0045] By R 11 , R 12 and the amino group formed by the nitrogen atom and the 13 , R 14 At least one of the amino groups formed by the amino group and the nitrogen atom may be an alkylamino group. The alkylamino group may be a monoalkylamino group or a dialkylamino group, and preferably may be a dialkylamino group. The dialkylamino group may preferably be at least one selected from the group consisting of dimethylamino, diethylamino, ethylmethylamino, butylmethyl, butylethyl, pyrrolidinyl, piperidinyl, morpholinyl, oxazolidinyl, piperazinyl, N-methylpiperazinyl and 2-oxo-3-oxazolidinyl, or may be at least one selected from the group consisting of dimethylamino, diethylamino, ethylmethylamino, butylmethyl, butylethyl, pyrrolidinyl, piperidinyl, morpholinyl and oxazolidinyl.

[0046] As R 11 , R 12 , R 13 and R 14 The substituent in the group includes a polymerizable group; an organic silyloxy group such as a trialkylsilyloxy group, a dialkylarylsilyloxy group, an alkyldiarylsilyloxy group, and a silyloxy group having a polymerizable group; an alkoxy group; an alkylcarbonyloxy group, and the like.

[0047] Specific examples of the polymerizable group include a (meth)acrylate group ((meth)acryloyloxy group), a (meth)acryloyl group, a vinylphenyl group, a vinyl group, an epoxy group, etc. The polymerizable group may be, for example, a radical polymerizable group, and preferably a (meth)acrylate group.

[0048] The number of carbon atoms of the alkyl group in the organosilyloxy group may be, for example, 1 to 12, preferably 1 to 6. Examples of the alkyl group in the organosilyloxy group include methyl, ethyl, tert-butyl, dimethylpropyl, 2,3-dimethylbutane-2-yl, etc. The number of carbon atoms of the aryl group in the organosilyloxy group may be, for example, 6 to 18, preferably 6 to 10, or 6. Examples of the aryl group in the organosilyloxy group include phenyl, naphthyl, etc.

[0049] The number of carbon atoms in the alkyl moiety in the alkoxy group or the alkylcarbonyloxy group may be, for example, 1 to 20, preferably 1 to 12, or 1 to 6. In addition, the alkyl moiety may be linear, branched, or cyclic, or a combination thereof. Examples of the alkyl moiety in the alkoxy group or the alkylcarbonyloxy group include methyl, ethyl, butyl, ethylpentyl, and the like.

[0050] 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 When a polymerizable group is present as a substituent, the total number of the polymerizable groups may be, for example, 1 or 2, and preferably 1.

[0051] R 11 and R 12 The combination of two groups represented by R 13 and R 14 The combination of the two groups represented by may be the same or different, and preferably may be different. 11 , R 12 and the amino group formed by the nitrogen atom and the 13 , R 14 The amino groups formed by the nitrogen atom may be the same or different, and are preferably different. By making the two amino groups located at both ends of the compound represented by formula (1) asymmetric, both excellent dichroic ratio (DR) and excellent solubility can be achieved.

[0052] The compound involved in one embodiment of the present invention is represented by the following formula (2), and the LUMO energy level is greater than -2.65eV and less than -2.10eV. The compound can be, for example, a dichroic pigment compound, which can be used as a forming material for a polarizing film. The compound represented by formula (2) has a divalent aromatic fused heterocyclic group in the molecule, and the LUMO energy level is within a specific range, thereby being able to exhibit high heat resistance in an environment of about 100°C. It can be considered that this is because, for example, it is inferred that the decomposition reaction of the compound in an environment of about 100°C is reductive, and since the LUMO energy level of the compound is within a specific range, the reductive decomposition reaction can be suppressed.

[0053] [Chemical formula 5]

[0054]

[0055] In formula (2), Ar 21 ,Ar 22 and Ar 23 Each 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 an 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 them represents a divalent sulfur-containing aromatic heterocyclic group or a divalent sulfur-containing aromatic condensed heterocyclic group composed of 2 to 4 aromatic rings.

[0056] The divalent sulfur-containing aromatic heterocyclic group may be a 5-membered sulfur-containing aromatic heterocyclic group. Specific examples of the divalent sulfur-containing aromatic heterocyclic group include thiazolyldiyl, thiadiazolediyl, thiophenediyl, and the like, and the divalent sulfur-containing aromatic heterocyclic group may contain at least one selected from the group consisting of these.

[0057] In addition, the divalent sulfur-containing aromatic fused heterocyclic group formed by condensing 2 to 4 aromatic rings is formed by removing 2 hydrogen atoms from an aromatic fused heterocyclic compound formed by condensing 2 to 4 aromatic ring compounds. The aromatic ring compound forming the divalent sulfur-containing aromatic fused heterocyclic group can be a 5-membered or 6-membered aromatic ring compound, or a 5-membered aromatic ring compound. As the aromatic ring compound, specifically, for example, thiophene, thiazole, thiadiazole, furan, pyrrole, imidazole, benzene, pyridine, etc. can be cited, and it can preferably contain at least one selected from the group consisting of thiophene, thiazole, and furan. The number of condensed aromatic rings forming the divalent sulfur-containing aromatic fused heterocyclic group can be 2 or 3, or can be 2. Specific examples of the divalent sulfur-containing aromatic condensed heterocyclic group formed by condensing two to four aromatic rings include thieno[3,2-d]thiazoldiyl, thieno[3,2-d]thienyl, thiazolo[5,4-d]thiazoldiyl, furano[3,2-d]thiazoldiyl, and the like, and the group may contain at least one selected from the group consisting of these.

[0058] In formula (2), for example, Ar 22 It may represent a divalent sulfur-containing aromatic heterocyclic group which may have a substituent, or a divalent sulfur-containing aromatic condensed heterocyclic group which may have a substituent and is formed by condensing 2 to 4 aromatic ring compounds. 22 represents a divalent sulfur-containing aromatic heterocyclic group which may have a substituent, or a divalent sulfur-containing aromatic condensed heterocyclic group which may have a substituent and is formed by condensing 2 to 4 aromatic ring compounds, Ar 21 and Ar 23 Each independently represents 1,4-phenylene or 1,4-naphthylene which may have a substituent. 22 represents a thiazolyl group, a thiadiazolyl group, a thiophene group, a thieno[3,2-d]thiazolyl group, a thieno[3,2-d]thiophene group, a thiazolyl[5,4-d]thiazolyl group or a furo[3,2-d]thiazolyl group which may have a substituent, Ar 21 and Ar 23 Each independently represents a 1,4-phenylene group which may have a substituent. 22 represents a thiazolyl group, a thiadiazolyl group, a thiophene group, a thieno[3,2-d]thiazolyl group or a thieno[3,2-d]thiophene group which may have a substituent, Ar 21 and Ar 23 Each independently represents a 1,4-phenylene group which may have a substituent.

[0059] Ar 21 ,Ar 22 and Ar 23The substituent in may include at least one selected from the group consisting of a halogen atom, a hydroxyl 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 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 independently may be, for example, 0, 1 or 2, preferably 0 or 1.

[0060] m is 1 or 2, preferably 1. In the case where m is 2, two Ar 22 Each may be the same or different.

[0061] R 21 , R 22 , R 23 and R 24 Each independently represents a hydrogen atom, a chain or cyclic alkyl group or an aryl group which may have a substituent. 21 , R 22 , R 23 or R 24 The carbon number of the aliphatic group represented by can be, for example, 1 to 20, preferably 1 to 12. The aliphatic group can be an alkyl group, an alkenyl group or an alkynyl group, preferably an alkyl group. Specific examples of the aliphatic group include methyl, ethyl, vinyl, ethynyl, propyl, isopropyl, cyclopropyl, allyl, butyl, hexyl, ethylbutyl, ethylhexyl, hexyldodecyl and the like. R 21 , R 22 , R 23 or R 24 The aryl group represented by may have 6 to 10 carbon atoms, and preferably 6 carbon atoms.

[0062] R 21 With R 22 and R 23 With R 24 At least one of the groups may be connected to each other to form a cyclic amino group together with the nitrogen atom, and the cyclic amino group formed may be an alicyclic amino group. In addition, at least one methylene unit constituting the cyclic amino group formed may be replaced by an oxygen atom or a carbonyl group. The number of members of the cyclic amino group formed may be, for example, 5 or 6. 21 , nitrogen atom and R 22 , or R 23 , nitrogen atom and R 24 Specific examples of the cyclic amino group to be formed include pyrrolidinyl, piperidinyl, morpholinyl, oxazolidinyl, piperazinyl, N-methylpiperazinyl, and 2-oxo-3-oxazolidinyl.

[0063] By R 21 , R 22 and the amino group formed by the nitrogen atom and the 23 , R 24 At least one of the amino groups formed by the amino group and the nitrogen atom may be an alkylamino group. The alkylamino group may be a monoalkylamino group or a dialkylamino group, and preferably may be a dialkylamino group. The dialkylamino group may preferably be at least one selected from the group consisting of dimethylamino, diethylamino, ethylmethylamino, butylmethyl, butylethyl, pyrrolidinyl, piperidinyl, morpholinyl, oxazolidinyl, piperazinyl, N-methylpiperazinyl and 2-oxo-3-oxazolidinyl, or may be at least one selected from the group consisting of dimethylamino, diethylamino, ethylmethylamino, butylmethyl, butylethyl, pyrrolidinyl, piperidinyl, morpholinyl and oxazolidinyl.

[0064] As R 21 , R 22 , R 23 and R 24 The substituent in the group includes a polymerizable group; an organic silyloxy group such as a trialkylsilyloxy group, a dialkylarylsilyloxy group, an alkyldiarylsilyloxy group, and a silyloxy group having a polymerizable group; an alkoxy group; an alkylcarbonyloxy group, and the like.

[0065] Specific examples of the polymerizable group include a (meth)acrylate group ((meth)acryloyloxy group), a (meth)acryloyl group, a vinylphenyl group, a vinyl group, an epoxy group, etc. The polymerizable group may be, for example, a radical polymerizable group, and preferably a (meth)acrylate group.

[0066] The number of carbon atoms of the alkyl group in the organosilyloxy group may be, for example, 1 to 12, preferably 1 to 6. Examples of the alkyl group in the organosilyloxy group include methyl, ethyl, tert-butyl, dimethylpropyl, 2,3-dimethylbutane-2-yl, etc. The number of carbon atoms of the aryl group in the organosilyloxy group may be, for example, 6 to 18, preferably 6 to 10, or 6. Examples of the aryl group in the organosilyloxy group include phenyl, naphthyl, etc.

[0067] The number of carbon atoms in the alkyl portion of the alkoxy group or the alkylcarbonyloxy group may be, for example, 1 to 20, preferably 1 to 12. In addition, the alkyl portion may be linear, branched or cyclic, or a combination thereof. Examples of the alkyl portion in the alkoxy group or the alkylcarbonyloxy group include methyl, ethyl, butyl, ethylpentyl and the like.

[0068] R 21 , R 22 , R 23 and R 24The 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 When a polymerizable group is present as a substituent, the total number of the polymerizable groups may be, for example, 1 or 2, and preferably 1.

[0069] R 21 and R 22 The combination of two groups represented by R 23 and R 24 The combinations of the two groups represented by are different from each other. 21 , R 22 and the amino group formed by the nitrogen atom and the 23 , R 24 and the amino groups formed by the nitrogen atoms are different from each other. 21 , R 22 , R 23 and R 24 Three of the four groups represented by formula (2) are the same and one is different. By making the two amino groups at both ends of the compound represented by formula (2) asymmetric, an excellent dichroic ratio (DR) and excellent solubility can be achieved simultaneously. This is considered to be because, for example, although the solubility is improved by making the substituent of the amino group bulky, if the amino groups at both ends are bulky, there is a tendency for the DR to decrease. Therefore, by making only the amino group on one side bulky, excellent DR and solubility can be achieved simultaneously.

[0070] The LUMO energy level of the compound represented by formula (2) can preferably be above -2.60 eV or above -2.55 eV, and can preferably be below -2.20 eV or below -2.30 eV. Here, the LUMO energy level is calculated by density functional theory (DFT method). Specifically, the software Gaussian16 is used to calculate the LUMO energy level by density functional theory using B3LYP as a functional and 6-31G (d) as a prescribed function.

[0071] Specific examples of the compound represented by formula (1) include compounds represented by the following formulae (1-1) to (1-62), but the present invention is not limited thereto.

[0072] [Chemical formula 6]

[0073]

[0074] [Chemical formula 7]

[0075]

[0076] In addition, as specific examples of the compound represented by formula (2), in addition to the compounds represented by formula (1-1) to formula (1-37) described above, the compounds represented by the following formula (2-1) to formula (2-33) can also be mentioned, but the present invention is not limited to this.

[0077] [Chemical formula 8]

[0078]

[0079] From the viewpoint of heat resistance, the compound represented by formula (1) preferably includes at least one selected from the group consisting of compounds represented by any one of 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 more preferably includes at least one selected from the group consisting of compounds represented by formulas (1-1), (1-2), (1-4), (1-50), (1-51), (1-52), (1-53), (1-54), (1-55), (1-56), (1-57), (1-58), (1-59), (1-60), (1-61), (1-62), (1-64), (1-65), (1-66), (1-67), (1-68), (1-69), (1-70), (1-71), (1-72), (1-73), (1-74), (1-75), (1-76), (1-77), (1-78), (1-79), (1-80), (1-81), (1-82), (1-83), (1-84), (1-85), (1-86), (1-87), (1-88), (1-89), (1-90), (1-91), (1 The present invention further preferably comprises at least one of the group consisting of compounds represented by any one of formula (1-1), formula (1-2), formula (1-21), formula (1-23), formula (1-34) and formula (1-38), formula (1-39) and formula (1-56) to formula (1-59), and further preferably comprises at least one of the group consisting of compounds represented by any one of formula (1-1), formula (1-2), formula (1-21), formula (1-23), formula (1-34) and formula (1-38).

[0080] In addition, from the viewpoint of heat resistance, the compound represented by formula (2) preferably includes at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-5), (1-8) to (1-23), (1-26) to (1-34), (2-1) to (2-16), and (2-19) to (2-33), and more preferably includes at least one selected from the group consisting of compounds represented by formulas (1-1), (1-2), (1-4), (1-20) to (1-31). ) to (1-23), (1-32) to (1-34), (2-1) to (2-3), (2-13) to (2-16) and (2-24), and further preferably includes at least one selected from the group consisting of compounds represented by any one of formula (1-1), (1-2), (1-21), (1-23), (1-34) and (1-38).

[0081] Method for producing compound

[0082] The compound represented by formula (1) or formula (2) can be manufactured by appropriately applying a previously known synthesis method. Specifically, the azo structure (-N=N-) in the compound represented by formula (1) or formula (2) can be constructed in the following manner: an aromatic amine compound having a primary amino group is converted into a diazonium salt (reaction a-1) using sodium nitrite, nitrosyl sulfuric acid, etc., and diazo coupling is performed with an aromatic compound (reaction a-2). Here, the conversion to a diazonium salt using sodium nitrite can be referred to, for example, the description of the preparation examples from paragraphs 0220 to 0268 of International Publication No. 2016 / 136561. In addition, the conversion to a diazonium salt using nitrosyl sulfuric acid can be referred to, for example, the description of the preparation examples from paragraphs 0017 to 0034 of Japanese Patent Publication No. 2009-215442.

[0083] The divalent five-membered ring condensed part having a thiazole ring in the compound represented by formula (1) or formula (2) can be synthesized by using a precursor having an amino group, thiocyanate and bromine, and applying the conditions of the usual thiazole cyclization reaction in a solvent such as acetic acid (reaction b). The conditions of the thiazole cyclization reaction can be, for example, referred to the description of the preparation examples from 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.

[0084] The amino group in the compound represented by formula (1) or formula (2) can be synthesized by using a precursor having a halogen group and an amine compound and applying the conditions of a conventional aromatic nucleophilic substitution reaction in the presence of a base (reaction c). The conditions of the aromatic nucleophilic substitution reaction can be, for example, referred to Hou, Y.; Eur. J. Med. Chem. 2019, 163, 690, etc.

[0085] The silyloxy group substituted with an aliphatic hydrocarbon group in the compound represented by formula (1) or formula (2) can be synthesized by using a precursor having a hydroxyl group and a halogenated silane substituted with an aliphatic hydrocarbon group, and applying the conditions of a conventional silylation reaction in the presence of a base (reaction d). The conditions of the SN2 substitution reaction can be, for example, referred to J.Am.Chem.Soc., 1972, 94, 6190, etc.

[0086] A specific method for producing the compound represented by formula (1) or formula (2) is described below. 1 ,Ar 2 ,Ar 3 , R 1 , R 2, R 3 and R 4 The definitions of are respectively the same as Ar in formula (1) 11 ,Ar 12 ,Ar 13 , R 11 , R 12 , R 13 and R 14 or Ar in formula (2) 21 ,Ar 22 ,Ar 23 , R 21 , R 22 , R 23 and R 24 First, a diazonium salt represented by the formula (1T) (hereinafter also referred to as the compound (1T)) is synthesized from a compound represented by the formula (1S) (hereinafter also referred to as the compound (1S)) by reaction a-1.

[0087] [Chemical formula 9]

[0088]

[0089] Next, through step A or step B, a compound represented by formula (1V) (hereinafter also referred to as compound (1V)) is synthesized.

[0090] In the A step, the Ar 2a The compound of the present invention reacts with the diazonium salt compound (1T) to form an azo structure, and then Ar is cyclized. 2a Converted to Ar 2 That is, the compound represented by the formula (1U) (hereinafter also referred to as the compound (1U)) is synthesized from the compound (1T) through reaction a-2, and further through reaction b, the compound (1V) is synthesized.

[0091] [Chemical formula 10]

[0092]

[0093] In step B, compound (1V) is synthesized from compound (1T) via reaction a-2.

[0094] [Chemical formula 11]

[0095]

[0096] The same synthesis steps as those for compound (1S) to compound (1V) can be repeated for compound (1V). Thus, a compound represented by formula (1W) (hereinafter referred to as compound (1W)) in which p=2 can be produced. It should be noted that in compound (1W), Ar2 When there are multiple 2 Can be the same or different.

[0097] [Chemical formula 12]

[0098]

[0099] The compound represented by the formula (1X) (hereinafter also referred to as the compound (1X)) can be produced from the compound (1W) and an aromatic amine compound via reactions a-1 and a-2.

[0100] [Chemical formula 13]

[0101]

[0102] The compound (1X) and an amine compound can be reacted via reaction c to produce a compound represented by formula (1) or (2). The produced compound represented by formula (1) or (2) can be further reacted via reaction d or the like to produce R 1 , R 2 , R 3 or R 4 Introduce substituents.

[0103] [Chemical formula 14]

[0104]

[0105] Regarding the reaction time in the method for producing the compound represented by formula (1) or (2), the reaction mixture in the middle of the reaction can also be appropriately sampled and the degree of disappearance of the raw material compound, the degree of generation of the compound represented by formula (1) or (2), etc. can be confirmed by known analytical means such as liquid chromatography and gas chromatography.

[0106] The compound represented by formula (1) or (2) can be isolated from the reaction mixture after the reaction by known methods such as recrystallization, reprecipitation, extraction and various chromatography, or by a suitable combination of these operations.

[0107] The 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 of the compound represented by formula (1) or formula (2).

[0108] [Chemical formula 15]

[0109]

[0110] In formula (3), Ar 31 ,Ar 32 and Ar 33Each independently represents an optionally substituted 1,4-phenylene group, an optionally substituted 1,4-naphthylene group, an optionally substituted divalent aromatic condensed heterocyclic group consisting of two 5-membered rings, an optionally substituted thiazolyl group, or an optionally substituted thiadiazole group. 31 ,Ar 32 and Ar 33 At least one of them represents a divalent aromatic condensed heterocyclic group consisting of two 5-membered rings which may have a substituent, a thiazolyl group which may have a substituent, or a thiadiazole group which may have a substituent.

[0111] The divalent aromatic condensed heterocyclic group formed of two 5-membered rings in formula (3) has the same meaning as the divalent aromatic condensed heterocyclic group formed of two 5-membered rings in formula (1), and the preferred embodiments are also the same. 31 ,Ar 32 or Ar 33 The substituents in the formula (1) are the same as Ar 11 ,Ar 12 and Ar 13 The substituents in have the same meanings and preferred embodiments are also the same.

[0112] n is 1 or 2. When n is 2, two Ar 32 Each may be the same or different.

[0113] R 31 and R 32 Each independently represents a linear or cyclic aliphatic group which may have a substituent, or an aryl group which may have a substituent. 31 or R 32 The aliphatic group or aromatic group in formula (1) 11 The aliphatic group or the aryl group in the above and the like have the same meanings and the preferred embodiments are also the same.

[0114] Dichroic Pigments

[0115] With regard to dichroic pigment, dichroic pigment comprises at least one of the compound represented by formula (1) or formula (2) as an effective ingredient. By making dichroic pigment comprise the compound represented by formula (1) or formula (2), a polarizing film with excellent heat resistance can be formed. Dichroic pigment can comprise only one of the compound represented by formula (1) or formula (2), or it can comprise two or more of different structures in combination. In the case where dichroic pigment comprises the compound represented by formula (1) or formula (2) of more than two kinds, they can have maximum absorption wavelengths different from each other. In addition, dichroic pigment can also comprise other pigment compounds in addition to the compound represented by formula (1) or formula (2).

[0116] Composition

[0117] The composition of the present embodiment includes at least one of the compounds represented by formula (1) or formula (2) and a liquid crystal compound, wherein the liquid crystal compound includes at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound. The composition can be used as a forming material for a polarizing film, for example. That is, the composition can be a composition for forming a polarizing film. The polarizing film obtained by using the composition as a forming material is a high-quality polarizing film showing excellent heat resistance. By making the composition include a compound represented by formula (1) or formula (2) as a dichroic pigment, a polarizing film showing excellent heat resistance can be formed.

[0118] Relative to 100 parts by mass of the solid content of the composition, the content of the compound represented by formula (1) or formula (2) in the composition can be, for example, less than 50 parts by mass, preferably less than 10 parts by mass or less than 5 parts by mass. If within the above range, the dispersion of the compound represented by formula (1) or formula (2) can be fully carried out. It should be noted that, in this specification, the so-called solid content refers to the total amount of the components obtained by removing volatile components such as solvents from the composition. The composition can contain only one compound represented by formula (1) or formula (2), or it can contain two or more compounds with different structures in combination. When the composition contains two or more compounds, they can have maximum absorption wavelengths different from each other.

[0119] The composition may further include other pigment compounds other than the compound represented by formula (1) or formula (2), such as at least one of the dichroic pigments. As other pigment compounds, for example, azo pigments such as monoazo pigments, disazo pigments, triazo pigments, tetrazo pigments, stilbene azo pigments can be cited, preferably at least one selected from the group consisting of them. The composition may contain one other pigment compound alone, or may contain two or more in combination. For example, in the case of being used as a coating type polarizing plate material, the other pigment compounds contained in the composition preferably have a maximum absorption wavelength in a wavelength range different from the compound represented by formula (1) or formula (2). For example, in the case of being used as a coating type polarizing plate material, the composition preferably contains more than three dichroic pigments including the compound represented by formula (1) or formula (2), and more preferably contains more than three azo pigments in combination. By making the composition contain more than three pigment compounds with different maximum absorption wavelengths, for example, it is possible to obtain absorption in the entire visible light domain using a film formed by the composition.

[0120] When composition comprises other pigment compounds, relative to 100 mass parts of the solid component of composition, its content can be for example below 50 mass parts, preferably can be below 10 mass parts or above 5 mass parts of 0.1 mass parts. If within the above-mentioned scope, the dispersion of other pigment compounds can be fully carried out.

[0121] The composition further comprises a liquid crystal compound in addition to the compound represented by formula (1) or formula (2), and the liquid crystal compound comprises at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound. The composition may comprise both a polymerizable liquid crystal compound and a liquid crystal polymer compound, and the polymerizable liquid crystal compound and the liquid crystal polymer compound contained in the composition may each be two or more. By making the composition comprise at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound, a composition in which the compound represented by formula (1) or formula (2) is dispersed in a liquid crystal compound can be constituted.

[0122] The liquid crystalline polymer compound may be a polymer compound constituting a thermotropic liquid crystalline polymer or a polymer compound constituting a lyotropic liquid crystalline polymer. From the viewpoint of enabling precise film thickness control, the liquid crystalline polymer compound is preferably a polymer compound constituting a thermotropic liquid crystalline polymer.

[0123] As a classification of liquid crystal, according to the structure of molecular arrangement in the liquid crystal state, it can be divided into smectic liquid crystal, nematic liquid crystal, and cholesteric liquid crystal. Among them, in the use of polarizing film, smectic liquid crystal is preferably used. Therefore, the polymerizable liquid crystal compound is preferably a polymerizable smectic liquid crystal compound, and the liquid crystal polymer compound is preferably a smectic liquid crystal polymer compound.

[0124] By using a polymerizable liquid crystal compound exhibiting smectic liquid crystal properties and a polymer compound exhibiting smectic liquid crystal properties, a polarizing film with a high degree of orientation order can be formed. The liquid crystal state presented 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 being able to achieve a higher degree of orientation order, a high-order smectic phase (high-order smectic liquid crystal state) is more preferably used. Here, the so-called high-order smectic phase refers to 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, among which smectic B phase, smectic F phase and smectic I phase are more preferably used. The polarizing film with a high degree of orientation order can obtain Bragg peaks derived from high-order structures such as hexagonal phases and crystalline phases in X-ray diffraction measurements. The so-called Bragg peak refers to the peak of the planar periodic structure derived from molecular orientation. The period interval (ordered period) possessed by the polarizing film obtained by the composition is preferably 0.3nm or more and 0.6nm or less. The polymerizable liquid crystal compound or liquid crystalline high molecular compound may be a polymerizable smectic liquid crystal compound or a smectic liquid crystalline high molecular compound which shows a Bragg peak derived from a high-order structure in X-ray diffraction measurement.

[0125] The compound represented by formula (1) or formula (2) can show high dichroism even when dispersed between tight molecular chains formed by at least one of the compounds of smectic liquid crystal polymerizable liquid crystal compound and smectic liquid crystal polymer compound. Therefore, a composition containing at least one liquid crystal compound including a polymerizable liquid crystal compound and a liquid crystal polymer compound (especially a liquid crystal compound including at least one of a polymerizable liquid crystal compound and a smectic liquid crystal polymer compound) and a compound represented by formula (1) or formula (2) can provide a polarizing film with excellent heat resistance and a high dichroic ratio.

[0126] The so-called polymerizable liquid crystal compound is a compound having at least one polymerizable group in the molecule and capable of presenting a liquid crystal phase by orientation. The polymerizable liquid crystal compound is preferably a compound capable of presenting a liquid crystal phase by orientation alone. The so-called polymerizable group refers to a functional group that can participate in a polymerization reaction, preferably a free radical polymerizable group. As a polymerizable liquid crystal compound, specifically, for example, the polymerizable liquid crystal compound described in paragraphs 0062 to 0079 of Japanese Patent Publication No. 2022-088325 can be used.

[0127] In addition, as the liquid crystalline polymer compound, for example, the liquid crystalline polymer compounds described in paragraphs 0080 to 0085 of JP-A-2022-088325 can be used.

[0128] From the viewpoint of improving the orientation of polymerizable liquid crystal compounds and liquid crystalline polymer compounds, the total content ratio of polymerizable liquid crystal compounds and liquid crystalline polymer compounds in the composition relative to 100 parts by mass of the solid content of the composition can be, for example, 50 parts by mass or more, 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 more, or 80 parts by mass or more and 90 parts by mass or less.

[0129] Relative to the total amount of 100 parts by mass of the polymerizable liquid crystal compound and the liquid crystalline polymer compound, the content of the compound represented by formula (1) or formula (2) in the composition can be, for example, 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, 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. If the content of the compound represented by formula (1) or formula (2) relative to the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound is 50 parts by mass or less, there is a tendency that the orientation disorder of the polymerizable liquid crystal compound, the liquid crystalline polymer compound and the compound represented by formula (1) or formula (2) is less, and a polarizing film with a high degree of orientation order can be obtained.

[0130] The composition may further contain a polymer compound in addition to the compound represented by formula (1) or formula (2) and the liquid crystal compound. As the polymer compound, for example, the polymer compound described in paragraphs 0089 to 0090 of JP-A-2022-088325 can be used.

[0131] The composition may also include a liquid medium such as a solvent and a polymerization initiator, and further include a photosensitizer, an inhibitor, a leveling agent, etc. as needed. As a solvent, for example, a solvent described in paragraphs 0092 to 0094 of Japanese Patent Publication No. 2022-088325 can be used. As a polymerization initiator, for example, a polymerization initiator described in paragraphs 0095 to 0097 of the publication can be used with respect to the content of the composition described. As a photosensitizer, for example, a photosensitizer described in paragraphs 0098 to 0099 of Japanese Patent Publication No. 2022-088325 can be used with respect to the content of the composition described. As an inhibitor, for example, an inhibitor described in paragraphs 0100 to 0101 of the publication can be used with respect to the content of the composition described. As a leveling agent, for example, a leveling agent described in paragraphs 0102 to 0104 of the publication can be used with respect to the content of the total amount of the liquid crystal compound described. As the antioxidant, for example, the antioxidant described in paragraphs 0105 and 0106 of the publication can be used in the content relative to the described composition.

[0132] The composition may contain other additives other than those mentioned above. Examples of other additives include mold 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 greater than 0% and less than 20% by mass, more preferably greater than 0% and less than 10% by mass, relative to the solid content of the composition.

[0133] The composition can be produced by a conventionally known method for producing a composition, for example, by mixing and stirring the compound represented by formula (1) or (2), a liquid crystal compound, and additives such as an antioxidant and a leveling agent as required.

[0134] membrane

[0135] The film involved in this embodiment may be a film comprising a compound represented by formula (1) or (2) as a forming material, or a film obtained by using a composition comprising a compound represented by formula (1) or (2) and a liquid crystal compound as a forming material. The film formed by the composition can be formed by imparting the composition to a substrate and forming a film. In addition, in the case where the composition comprises a polymerizable liquid crystal compound, a film comprising a cured product obtained by polymerizing the polymerizable liquid crystal compound can be formed by imparting the composition to a substrate, forming a film, and then polymerizing the polymerizable liquid crystal compound to cure it.

[0136] The composition can form a film with high orientation order and excellent heat resistance, such as a polarizing film. Therefore, the film involved in this embodiment includes a polarizing film formed by a composition comprising a compound represented by formula (1) or (2) and a liquid crystal compound, and the polarizing film has high orientation order and excellent heat resistance.

[0137] For polarizing films with high orientation order, Bragg peaks derived from high-order structures such as hexagonal phases and crystalline phases can be obtained in X-ray diffraction measurements. Therefore, for polarizing films formed from the composition, it is preferred that the liquid crystal compound is oriented in a manner that shows a Bragg peak in the X-ray diffraction measurement, and more preferably a "horizontal orientation" in which the molecules of the liquid crystal compound are oriented in the direction of light absorption. Such a high orientation order that shows a Bragg peak can be achieved by controlling the type of liquid crystal compound used, the amount of the compound represented by formula (1) or (2), and the like.

[0138] The compound represented by formula (1) or (2) and the liquid crystal compound constituting the film-forming composition are as described above.

[0139] The film can be produced, for example, by a method including the following steps.

[0140] Step A: forming a coating film of a composition comprising a compound represented by formula (1) or (2), a liquid crystal compound and a solvent;

[0141] Step B: removing at least a portion of the solvent from the coating film;

[0142] Step C: raising the temperature to a temperature above the temperature at which the liquid crystal compound undergoes phase transition to a liquid phase, and then lowering the temperature to allow the liquid crystal compound to undergo phase transition to a smectic phase (smectic liquid crystal state); and

[0143] Step D: If necessary, polymerize the polymerizable liquid crystal compound while maintaining the smectic phase (smectic liquid crystal state).

[0144] The coating film of the composition can be formed by, for example, applying the composition on a substrate, an alignment film described later, etc. Alternatively, the composition may be directly applied on a retardation film or other layers constituting a polarizing plate.

[0145] As the substrate, for example, the substrates described in paragraphs 0115 to 0118 of Japanese Patent Application Laid-Open No. 2022-088325 can be used. As a method for applying the composition to a substrate, etc., 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 flexographic methods can be cited.

[0146] Next, at least a portion of the solvent contained in the coating film obtained by the composition is removed by drying, etc., thereby forming a dried coating film. In addition, when a polymerizable liquid crystal compound is included in the coating film, a dried coating film is formed by drying under conditions where the polymerizable liquid crystal compound does not polymerize. As the drying method of the aforementioned coating film, natural drying, ventilation drying, heating drying, reduced pressure drying, etc. can be cited.

[0147] In addition, in order to make the liquid crystal compound phase transition to the liquid phase, the temperature is raised to a temperature above the temperature at which the liquid crystal compound phase transitions to the liquid phase, and then the temperature is lowered to make the liquid crystal compound phase transition to the smectic phase (smectic liquid crystal state). The phase transition can be performed after removing the solvent in the coating film, or it can be performed simultaneously with the removal of the solvent.

[0148] In the case where the composition includes 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 of a cured product containing the polymerizable liquid crystal compound. As a polymerization method, photopolymerization is preferably used. In photopolymerization, the light irradiated to the dry coating can be appropriately selected according to the type of photopolymerization initiator contained in the dry coating, the type of polymerizable liquid crystal compound (especially the type of polymerizable group possessed by the polymerizable liquid crystal compound) and its amount. As a specific example, one or more 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. can be cited. Among them, from the aspect of easy control of the progress of the polymerization reaction, the device that can be used as a photopolymerization device and widely used in this field is considered, preferably ultraviolet light, preferably in a way that can be photopolymerized using ultraviolet light. The type of polymerizable liquid crystal compound and photopolymerization initiator contained in the composition is selected in advance. In addition, during polymerization, light irradiation can also be performed while the dry coating is cooled using a suitable cooling means, thereby controlling the polymerization temperature. If the polymerization of the polymerizable liquid crystal compound is carried out at a lower temperature by adopting such a cooling means, a film can be suitably formed even if a substrate with low heat resistance is used. During photopolymerization, a patterned film can also be obtained by shielding, developing, etc. Here, regarding the light source of the active energy ray and the ultraviolet irradiation intensity, for example, reference can be made to the records of paragraphs 0123 to 0124 of Japanese Patent Publication No. 2022-088325.

[0149] By photopolymerization, the polymerizable liquid crystal compound is polymerized while maintaining a liquid crystal state of a smectic phase, preferably a high-order smectic phase, to form a film. The film obtained by polymerizing the polymerizable liquid crystal compound while maintaining a liquid crystal state of a smectic phase is also accompanied by the effect of a dichroic pigment, thereby having an advantage of high polarization performance compared to a conventional guest-host polarizing film, that is, a film formed by a liquid crystal state of a nematic phase. In addition, compared to a film coated only with a dichroic pigment or a lyotropic liquid crystal, it also has an advantage of excellent strength.

[0150] The thickness of the film can be appropriately selected depending on the display device to which it is applied, and may be, for example, 0.5 μm to 10 μm, preferably 1 μm to 5 μm, or 1 μm to 3 μm.

[0151] When the film is used as a polarizing film, it is preferably formed on an alignment film. An alignment film is a film with an alignment control force that allows a polymerizable liquid crystal compound and a liquid crystal polymer compound to be oriented in a desired direction. As an alignment film, it is preferably a film having solvent resistance that does not dissolve due to the coating of a composition containing at least one liquid crystal compound of a polymerizable liquid crystal compound and a liquid crystal polymer compound, and having heat resistance in a heating treatment for the removal of a solvent and the orientation of a polymerizable liquid crystal compound. As the alignment film, an alignment film containing an oriented polymer, a photo-aligned film, and a groove-aligned film having a concave-convex pattern and a plurality of grooves on the surface can be cited. From the perspective of the accuracy and quality of the orientation angle, a photo-aligned film is preferably used.

[0152] Laminated body

[0153] The laminated body involved in this embodiment may have a film containing a compound represented by formula (1) or formula (2) as a forming material, or may have a film containing a composition of a compound represented by formula (1) or formula (2) and a liquid crystal compound as a forming material. The laminated body may have a substrate, and a film containing a compound represented by formula (1) or formula (2) as a forming material disposed on the substrate, or may have a substrate, an oriented film disposed on the substrate, and a film containing a compound represented by formula (1) or formula (2) as a forming material disposed on the oriented film. The film containing a compound represented by formula (1) or formula (2) as a forming material may constitute a polarizing film. In addition, the substrate may also be a phase difference film. The laminated body may, for example, constitute a polarizing plate. The laminated body may, for example, be manufactured by forming a film on a substrate according to the above-mentioned film manufacturing method.

[0154] From the viewpoint of the bendability and visual recognition of the display device, the thickness of the laminate can be, for example, 10 μm to 300 μm, preferably 20 μm to 200 μm, or 25 μm to 100 μm. It should be noted that when the laminate has a phase difference film as a substrate, the thickness of the phase difference film can be appropriately selected according to the display device to which it is applied.

[0155] Display device

[0156] The display device of the present embodiment has the aforementioned laminate, and the laminate can be a polarizing plate. The display device can be obtained, for example, by attaching the laminate as a polarizing plate to the surface of the display device via an adhesive layer. The so-called display device is a device having a display element, and is a device comprising a light-emitting element or a light-emitting device as a light source. As a display device, for example, a liquid crystal display device, an organic electroluminescent (EL) display device, an inorganic electroluminescent (EL) display device, an electron emission display device (for example, 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 type display device (for example, a grating light valve (GLV) display device, a display device having a digital micromirror device (DMD)), and a piezoelectric ceramic display, etc. The liquid crystal display device includes any device in 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 type 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 preferred, and an organic EL display device is particularly preferred.

[0157] Example

[0158] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to these Examples.

[0159] In the following examples, the LUMO energy level was calculated by the density functional theory (DFT method). Specifically, the LUMO energy level was calculated by the density functional theory using B3LYP as a functional and 6-31G(d) as a prescribed function using Gaussian16 software.

[0160] Example 1

[0161] The following compound 1-1-d was synthesized by a diazo coupling method, and compound 1-1 was synthesized by an aromatic nucleophilic substitution reaction using a secondary amine compound.

[0162] Synthesis of compound 1-1-a

[0163] Compound 1-1-a was synthesized from 2-nitrothiophene according to the method described in the literature (Journal of Medicinal Chemistry, 2005, Vol48, 5794).

[0164] [Chemical formula 16]

[0165]

[0166] Synthesis of compound 1-1-b

[0167] 4-Fluoroaniline (0.8 g, 7.1 mmol) was added to 1.2 mL of hydrochloric acid and 5 mL of water, and the solution was cooled so that the internal temperature was below 3°C, and 1.1 mL of an aqueous solution of sodium nitrite (0.53 g, 7.4 mmol) was added dropwise so that the internal temperature did not exceed 3°C. Stir for 30 minutes at an internal temperature 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) so that the internal temperature did not exceed 3°C. The reaction solution was raised to room temperature and stirred for 1 hour. Then, an aqueous sodium bicarbonate solution was added until the pH of the reaction solution reached 7 to 8, and the precipitated solid was separated by filtration and dried to obtain 1.6 g of an orange solid target. It was used in the next step without purification.

[0168] [Chemical formula 17]

[0169]

[0170] Synthesis of compound 1-1-c

[0171] 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 about 1 hour. After stirring at room temperature for 1 hour, 100 mL of water was added, and the precipitated solid was separated by filtration and dried to obtain 2.3 g of the purple solid target product. It was used in the next step without purification.

[0172] [Chemical formula 18]

[0173]

[0174] Synthesis of compound 1-1-d

[0175] 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, and the mixture was cooled to a temperature below 3°C. Nitrosylsulfuric acid (2.8 g, 8.9 mmol in 40 wt% sulfuric acid) was added dropwise little by little until the internal temperature did not exceed 3°C. The mixture was stirred for 30 minutes at a temperature below 3°C to prepare a diazonium solution. Next, 55 mL of an aqueous solution of sodium acetate (36 g, 437 mmol) was added to 75 mL of a methanol solution of N,N-diethylaniline (0.80 g, 5.3 mmol), and the mixture was cooled to a temperature below 3°C. The diazonium solution prepared above was added dropwise little by little until the internal temperature did not exceed 3°C. The reaction mixture was allowed to rise to room temperature and stirred for 1 hour. Then, 300 mL of water was added, and the precipitated solid was separated by filtration and dried to obtain 1.1 g of a purple-black solid target. The mixture was used in the next step without purification.

[0176] 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)

[0177] [Chemical formula 19]

[0178]

[0179] Synthesis of compound 1-1

[0180] 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, the temperature was raised to 70 ° C, and stirred for 2 hours. Water was added to the reaction container, the precipitated solid was separated by filtration, and washed with methanol. The obtained solid was purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound 1-1 (0.02 g, yield 10%).

[0181] LUMO=2.50eV.

[0182] 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)

[0183] [Chemical formula 20]

[0184]

[0185] Example 2

[0186] The following compound 1-1-d was synthesized by diazo coupling, and compound 1-2-a was synthesized by aromatic nucleophilic substitution reaction using a secondary amine compound, and then reacted with chlorosilane to obtain compound 1-2.

[0187] Synthesis of Compound 1-2

[0188] 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), and N-methylethanolamine (0.226 g, 2.98 mmol) was added, and the temperature was raised to 70°C and stirred for 2 hours. Water was added to the reaction container, and the precipitated solid was separated by filtration and washed with methanol to obtain compound 1-2-a. Compound 1-2-a was used in the next step without purification.

[0189] 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 dimethyl tert-hexyl chlorosilane (0.026 g, 0.138 mmol) was added, returned to room temperature, and stirred for 2 hours. Water was added to the reaction vessel, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid was purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound (1-2) (0.022 g, yield was 11%).

[0190] LUMO=2.51eV.

[0191] 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)

[0192] [Chemical formula 21]

[0193]

[0194] Synthesis example

[0195] The following compound C-1, compound C-2-a and compound C-3-a were synthesized by a known diazo coupling method.

[0196] [Chemical formula 22]

[0197]

[0198] Comparative Example 1

[0199] Synthesis of compound C-2

[0200] 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 dimethyl tert-hexyl chlorosilane (0.112 g, 0.626 mmol) was added, returned to room temperature, and stirred for 5 hours. Water was added to the reaction vessel, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid was purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound C-2 (0.130 g, yield of 75%).

[0201] LUMO=-2.78eV

[0202] 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)

[0203] [Chemical formula 23]

[0204]

[0205] Comparative Example 2

[0206] Synthesis of compound C-3

[0207] 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, tert-butyldiphenylsilyl chloride (0.11 g, 0.40 mmol) was added, returned to room temperature, and stirred for 2 hours. Water was added to the reaction vessel, the precipitated solid was separated by filtration, and washed with methanol. The obtained solid was purified by silica gel column chromatography using chloroform as the developing solvent to obtain compound C-3 (0.086 g, yield of 61%).

[0208] LUMO=-2.66eV

[0209] 1 H-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)

[0210] [Chemical formula 24]

[0211]

[0212] Example 3: Preparation of composition E1

[0213] The following components were mixed and stirred at 80° C. for 1 hour to obtain composition E1.

[0214]

[0215] Polymerizable liquid crystal compound A-6 and polymerizable liquid crystal compound A-7

[0216] [Chemical formula 25]

[0217]

[0218] It should be noted that 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). In addition, the polymerizable liquid crystal compound A-7 was prepared according to the same method.

[0219] Example 4: Preparation of composition E2

[0220] 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.

[0221] Comparative Examples 1 to 3: Preparation of Compositions C1, C2 and C3

[0222] The same operation as in Example 1 was carried out except that Compound C-1, Compound C-2 or Compound C-3 represented by the above formula whose synthesis method was described above was used instead of Compound 1-1 to obtain Compositions C1, C2 and C3 of Comparative Examples 1 to 3, respectively.

[0223] Manufacturing of polarizing plates

[0224] 1. Formation of oriented film

[0225] A glass substrate was used as a transparent substrate. A 2 mass % aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by FUJIFILM Wako Pure Chemical Corporation) (composition for forming an alignment layer) was applied to the glass substrate by spin coating, and after drying, a film with a thickness of 100 nm was formed. Next, the surface of the obtained film was subjected to a rubbing treatment to form an alignment film, thereby obtaining a substrate having an alignment film formed on the glass substrate.

[0226] 2. Formation of polarizing film

[0227] The composition obtained above is applied to the oriented film of the substrate obtained above by spin coating, and after heating and drying on a heating plate at 120°C for 3 minutes, it is rapidly cooled to below 70°C (the temperature at which a smectic liquid crystal phase is exhibited when cooled), to obtain a laminate having a dry coating formed on the oriented film.

[0228] Next, a UV irradiation device (SPOT CURE SP-7; manufactured by USHIO Inc.) was used at an exposure dose of 2400 mJ / cm 2 The dried film is irradiated with ultraviolet rays under conditions of 100 nm (365 nm as a reference), 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 is formed from the dried film to obtain a polarizing plate.

[0229] evaluate

[0230] A protective film (40 μm TAC (manufactured by KONICA MINOLTA Co., Ltd., "KC4UY")) was placed on the surface of the polarizing film obtained above, and the film was heated in an oven tank for only a specified time under the following conditions to conduct a heat resistance test and evaluate the heat resistance of the polarizing film. Using a device in which a bracket with a polarizing plate is provided on a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation), the absorbance (A1) in the absorption axis direction of the polarizing film before the heat resistance test and the absorbance (A2) in the absorption axis direction of the polarizing film after the heat resistance test at the maximum absorption wavelength of the polarizing film before the heat resistance test were measured by a double beam method. The absorbance (A2) in the absorption axis direction of the polarizing film after the heat resistance test was divided by the absorbance (A1) in the absorption axis direction of the polarizing film before the heat resistance test to obtain a percentage as the absorbance maintenance rate (%). The results are shown in Table 1. In addition, when the absorbance maintenance rate exceeded 85%, it was judged that it was good as a polarizing film.

[0231] The heating conditions in the heat resistance test are as follows.

[0232] Equipment used: DN411I manufactured by Yamato Scientific Co., Ltd.

[0233] Test time: 240 hours

[0234] Temperature: 105℃.

[0235] [Table 1]

[0236] Compound LUMO Absorbance maintenance rate Example 3 1-1 -2.50 89％ Example 4 1-2 -2.51 89％ Comparative Example 1 C-1 -2.72 80％ Comparative Example 2 C-2 -2.78 78％ Comparative Example 3 C-3 -2.66 84％

[0237] As can be seen from Table 1, the polarizing plate including a film formed of a composition containing Compound 1-1 or Compound 1-2 has high heat resistance.

Claims

1. A compound represented by the following formula (1), [Chemical formula 1] 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 consisting of two 5-membered rings which may have a substituent, Ar 11 ,Ar 12 and Ar 13 At least one of represents a divalent aromatic fused heterocyclic group formed by two 5-membered rings; k is 1 or 2. When k is 2, two Ar 12 Each can be the same or different; R 11 , R 12 , R 13 and R 14 Each independently represents a hydrogen atom, a chain or cyclic aliphatic group or an aromatic group which may have a substituent; R 11 With R 12 and R 13 With R 14 At least one of the groups may be connected to each other to form a ring, and at least one methylene unit constituting the formed ring may be replaced by an oxygen atom or a carbonyl group; R 11 , R 12 , R 13 and R 14 At least one of the groups may be substituted with at least one substituent selected from the group consisting of an organosilyloxy group and a polymerizable group.

2. The compound according to claim 1, wherein In the formula (1), Ar 11 ,Ar 12 and Ar 13 Each independently represents a 1,4-phenylene group which may have a substituent or a divalent sulfur-containing aromatic condensed heterocyclic group consisting of two 5-membered rings, Ar 11 ,Ar 12 and Ar 13 At least one of them represents a divalent sulfur-containing aromatic condensed heterocyclic group formed of two 5-membered rings.

3. The compound according to claim 1, wherein In the formula (1), Ar 11 ,Ar 12 and Ar 13 Each independently represents 1,4-phenylene, thieno[3,2-d]thiazoldiyl or thieno[3,2-d]thiophenediyl which may have a substituent, Ar 11 ,Ar 12 and Ar 13 At least one of them represents a thieno[3,2-d]thiazoldiyl group or a thieno[3,2-d]thiophenediyl group.

4. The compound according to claim 1, wherein In the formula (1), Ar 11 and Ar 13 Each independently represents a 1,4-phenylene group which may have a substituent, Ar 12 represents a thieno[3,2-d]thiazoldiyl group or a thieno[3,2-d]thiophenediyl group which may have a substituent, and k is 1.

5. A compound represented by the following formula (2), wherein the LUMO energy level of the compound is from -2.65 eV to -2.10 eV, [Chemical formula 2] 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 a substituent, Ar 21 ,Ar 22 and Ar 23 At least one of them represents a divalent sulfur-containing aromatic heterocyclic group, or a divalent sulfur-containing aromatic condensed heterocyclic group formed by 2 to 4 aromatic rings; m is 1 or 2. When m is 2, two Ar 22 Each can be the same or different; R 21 , R 22 , R 23 and R 24 Each independently represents a hydrogen atom, a chain or cyclic aliphatic group or an aromatic group which may have a substituent; R 21 With R 22 and R 23 With R 24 At least one of the groups may be connected to each other to form a ring, and at least one methylene unit constituting the formed ring may be replaced by an oxygen atom or a carbonyl group; R 21 , R 22 , R 23 and R 24 At least one of them may be substituted with at least one substituent selected from the group consisting of an organic silyloxy group and a polymerizable group; wherein, Not including R 21 and R 22 The combination of two groups represented by R 23 and R 24 The combination of two groups represented is the same.

6. The compound according to claim 5, wherein In the formula (2), Ar 21 and Ar 23 Each independently represents a 1,4-phenylene group which may have a substituent, Ar 22 represents a thieno[3,2-d]thiazoldiyl group, a thieno[3,2-d]thiophenediyl group, a thiazoldiyl group, a thiadiazoldiyl group or a thiophenediyl group which may have a substituent, and m is 1. 7 . A composition comprising a liquid crystal compound and the compound according to claim 1 , wherein the liquid crystal compound comprises at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound.

8. The composition of claim 7, wherein The liquid crystal compound is a smectic liquid crystal compound.

9. A film formed of the composition according to claim 7. 10 . A laminate comprising the film according to claim 9 .

11. A display device comprising the laminate according to claim 10.

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