Compounds, compositions, thin films, laminates and display devices

Abstract

The compositions of the present invention comprise the compound represented by formula (1) and a liquid crystal compound. In the formula, n is 1 or 2. Ar 1, Ar 2, and Ar 3 represent 1,4-epimine, etc., at least one of which has a hydroxyl group capable of forming an intramolecular hydrogen bond. R 1 represents -OC(=O)-, -N=N-, etc. R 2 represents an alkylamine group. When Ar 1 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond, or when it has a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 1, R 3 represents an alkyldiyl, alkyldioxy, alkyldioxycarbonyl, alkyldicarbonyl, or alkyldicarbonyloxy. When Ar 1 has a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 3, R 3 represents a cyclic or chain group capable of forming a hydrogen bond with the hydroxyl group. R 4 represents a polymerizable group or a hydrogen atom.

Description

Technical Field

[0001] This invention relates to a compound, composition, thin film, laminate, and display device. Prior Technology

[0002] There is a continuous demand for thinner displays such as image display panels, and further thinning is also required for polarizing plates and polarizing elements, which are components of such displays. In response to this demand, for example, a thin subject-object type polarizing element has been proposed, which includes a polarizing film comprising a polymerizable liquid crystal compound and a pigment compound exhibiting dichroism (see, for example, Patent Documents 1 and 2). [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Publication No. 2007-510946 [Patent Document 2] Japanese Patent Application Publication No. 2013-37353 Summary of the Invention

[0004] [The problem the invention aims to solve]

[0005] However, in subject-object type polarizing elements, the absorbance may sometimes decrease if they are continuously exposed to strong ultraviolet light such as sunlight for a long time. The object of the present invention is to provide a compound with high lightfastness, a composition containing the compound, a thin film formed from the composition, a laminate having the thin film, and a light-emitting device having the laminate. [Technical means to solve the problem]

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

[12] . [1] A composition comprising: a compound represented by the following formula (1); and a liquid crystal compound comprising at least one of a polymeric liquid crystal compound and a liquid crystal polymer compound.

[0007] [Chemistry 1] In equation (1), n ​​represents an integer of 1 or 2. Ar 1, Ar 2, and Ar 3 each independently represent a 1,4-phenyl or sulfur-containing heterocyclic group that may have substituents. At least one of Ar 1, Ar 2, and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. R1 represents the selection of at least one basis from the group consisting of -OC(=O)-, -C(=O)O-, and -N=N-. R 2 represents an alkylamine group that can have polymerizable groups. When Ar 1 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond, or when there is a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 1, R 3 represents at least one group selected from the group consisting of alkadiyl groups having 4 to 20 carbon atoms, alkadioxy groups having 2 to 20 carbon atoms, alkadioxycarbonyl groups having 2 to 20 carbon atoms, alkadioxycarbonyl groups having 2 to 20 carbon atoms, and alkadioxycarbonyloxy groups having 2 to 20 carbon atoms. When Ar 1 has a hydroxyl group that can form an intramolecular hydrogen bond at the position adjacent to R 3, R 3 represents a cyclic or chain group with 2 to 20 carbon atoms that can form a hydrogen bond with the hydroxyl group. R 4 represents a polymeric group or a hydrogen atom. When n is 2, the two R1s can be the same or different, and the two Ar2s can be the same or different. [2] The composition described in [1] wherein the polymeric liquid crystal compound is a polymeric lamellar liquid crystal compound and the liquid crystal polymer is a lamellar liquid crystal polymer. [3] The composition described in [1] or [2], wherein the polymeric liquid crystal compound comprises a compound represented by the following formula (A).

[0008] [Chemistry 2] In formula (A), m represents an integer from 1 to 3. X1, X2, and X3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. When m is 2 or 3, there may be multiple X1s that are the same or different from each other. At least three X1s are selected from the group consisting of X1, X2, and X3 to represent a six-membered divalent hydrocarbon group. Y1, Y2, W1, and W2 independently represent single-bond or divalent linkage bases. When m is 2 or 3, there exist multiple Y1s that can be the same or different from each other. V1 and V2 each independently represent an alkyldiyl group having 1 to 20 carbon atoms that may have substituents. At least one of the -CH2- groups constituting the above-mentioned alkyldiyl group may also be substituted with -O-, -CO-, -S- or -NH-. U1 and U2 independently represent either a polymerizable group or a hydrogen atom, and at least one of them represents a polymerizable group. [4] The composition described in any of [1] to [3], wherein the number of hydroxyl groups of the compound represented by the above formula (1) that can form intramolecular hydrogen bonds is 1. [5] The composition described in any of [1] to [4], wherein the compound represented by formula (1) above has a hydroxyl group on Ar 1 that is capable of forming an intramolecular hydrogen bond with R 3. [6] A compound represented by the following formula (1a).

[0009] [Chemistry 3] In equation (1a), k represents an integer of 1 or 2. Ar 11, Ar 12, and Ar 13 each independently represent a 1,4-phenyl or sulfur-containing heterocyclic group that may have substituents. At least one of Ar 11 and Ar 12 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. R 11 represents the selection of at least one base from the group consisting of -OC(=O)-, -C(=O)O-, and -N=N-. R 12 indicates an alkylamine group that can have polymerizable groups. When Ar 11 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond, or when there is a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 11, R 13 represents at least one group selected from the group consisting of alkadiyl groups having 4 to 20 carbon atoms, alkadioxy groups having 2 to 20 carbon atoms, alkadioxycarbonyl groups having 2 to 20 carbon atoms, alkadioxycarbonyl groups having 2 to 20 carbon atoms, and alkadioxycarbonyloxy groups having 2 to 20 carbon atoms. When Ar 11 has a hydroxyl group that can form an intramolecular hydrogen bond in the position adjacent to R 13, R 13 represents a cyclic or chain group with 2 to 20 carbon atoms that can form a hydrogen bond with the hydroxyl group. R 14 represents a polymeric group or a hydrogen atom. When k is 2, the two R 11s can be the same or different, and the two Ar 12s can be the same or different. [7] The compound described in [6] has 1 hydroxyl group that can form an intramolecular hydrogen bond. [8] The compounds described in [6] or [7], wherein Ar 11, Ar 12 and Ar 13 are 1,4-elongylphenyl compounds that may have substituents. [9] The compound described in any of [6] to [8], wherein the Ar 11 has a hydroxyl group capable of forming an intramolecular hydrogen bond with R 13.

[10] A thin film which uses a composition as described in any one of [1] to [5] as a forming material.

[11] A laminate comprising a thin film as described in

[10] .

[12] A display device having a laminate as described in

[11] . [Effects of the Invention]

[0010] According to the present invention, a compound with high lightfastness, a composition comprising the compound, a thin film formed from the composition, a laminate having the thin film, and a light-emitting device having the laminate can be provided. Implementation

[0011] In this specification, the term "step" includes not only independent steps, but also steps that cannot be clearly distinguished from other steps, as long as the desired purpose of the step can be achieved. Furthermore, regarding the content of each component in the composition, when multiple substances corresponding to each component are present in the composition, unless otherwise specified, it refers to the total amount of those multiple substances present in the composition. Moreover, the upper and lower limits of the numerical ranges described in this specification can be arbitrarily selected and combined. Hereinafter, embodiments of the present invention will be described in detail. Furthermore, the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without prejudice to the spirit of the invention.

[0012] <Composition> The composition of this embodiment comprises a compound represented by formula (1) and a liquid crystal compound. The liquid crystal compound comprises at least one of a polymeric liquid crystal compound and a liquid crystal polymer compound. The composition can be used, for example, as a forming material for a polarizing film. That is, the composition can be a composition for forming a polarizing film. The following polarizing plate can improve the lightfastness to visible light and suppress the decrease in absorbance of the compound represented by formula (1) at the maximum absorption wavelength, and the polarizing plate has a polarizing film obtained by using the composition as a forming material.

[0013] It is believed that the lightfastness of the compound represented by the following formula (1) is improved by having at least one hydroxyl group capable of forming an intramolecular hydrogen bond among at least one of Ar 1, Ar 2 and Ar 3.

[0014] [Chemistry 4]

[0015] In formula (1), Ar1, Ar2 and Ar3 independently represent 1,4-extrinylphenyl or divalent sulfur-containing heterocyclic groups that may have substituents, preferably representing 1,4-extrinylphenyl that may have substituents. Examples of divalent sulfur-containing heterocyclic groups include benzothiazoldiyl, thienothiazoldiyl and thiazoldiyl, preferably benzothiazoldiyl.

[0016] The substituents in Ar 1, Ar 2, and Ar 3 may be at least one selected from the group consisting of halogen atoms, hydroxyl groups, methyl groups, and methoxy groups, preferably fluorine atoms, chlorine atoms, hydroxyl groups, methyl groups, or methoxy groups, and more preferably fluorine atoms or hydroxyl groups. The number of substituents in Ar 1, Ar 2, and Ar 3 may be independently, for example, 0, 1, or 2, preferably 0 or 1.

[0017] At least one of Ar 1, Ar 2 and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. The hydroxyl group capable of forming an intramolecular hydrogen bond is preferably present in at least one of Ar 1 and Ar 2, and more preferably in at least Ar 1.

[0018] The functional group capable of forming an intramolecular hydrogen bond at the hydroxyl group can exist adjacently on the same ring. That is, the hydroxyl group preferably forms an intramolecular hydrogen bond with a functional group located at its adjacent position, and more preferably forms a six-membered ring intramolecular hydrogen bond. Examples of functional groups capable of forming an intramolecular hydrogen bond at the hydroxyl group include: hydroxyl, alkoxy, azo, carbonyl, oxycarbonyl (-OC(=O)-), carbonyloxy (-C(=O)O-), 2-pyrrolididinediyl, 2-piperidinediyl, 2-pyrimidinediyl, 2-thiazolyl, 2-thiazolinediyl, 2-acezolyl, 2-acezolinediyl, etc. Functional groups capable of forming an intramolecular hydrogen bond at the hydroxyl group can be, for example, functional groups other than the azo group.

[0019] The compound represented by formula (1) preferably has a hydroxyl group capable of forming an intramolecular hydrogen bond on at least one of Ar 1 and Ar 2, and the hydroxyl group forms an intramolecular hydrogen bond with at least one of R 1 and R 3, more preferably has a hydroxyl group capable of forming an intramolecular hydrogen bond on at least Ar 1, and the hydroxyl group forms an intramolecular hydrogen bond with R 3. The number of hydroxyl groups capable of forming an intramolecular hydrogen bond in the compound represented by formula (1) can be, for example, 1. When the hydroxyl group forms an intramolecular hydrogen bond with R 1, R 1 is preferably -C(=O)O-. Furthermore, when the hydroxyl group forms an intramolecular hydrogen bond with R3, R3 is preferably a compound containing -OC (=O)-, carbonyl, 2-pyrrolididinediyl, 2-piperidinediyl, 2-pyrimidinediyl, 2-thiazolyldiyl, 2-thiazolinediyl, 2-acezolyldiyl or 2-acezolinediyl, more preferably a compound containing -OC (=O)- or carbonyl, and even more preferably an alkadioxycarbonyl or alkadioxycarbonyl with 2 to 20 carbon atoms.

[0020] R1 indicates that at least one base is selected from the group consisting of -OC(=O)-, -C(=O)O- and -N=N-, preferably -OC(=O)-, -C(=O)O- or -N=N-.

[0021] R 2 represents an alkylamine group that can be polymerizable. The alkylamine group in R 2 can be either a monoalkylamine or a dialkylamine, preferably a dialkylamine. Examples of alkylamine groups in R 2 include: dimethylamine, diethylamine, ethylmethylamine, dipropylamine, diisopropylamine, monomethylamine, monoethylamine, monopropylamine, monoisopropylamine, pyrrolidyl, piperidinyl, α-linyl, azolidinyl, etc., and at least one can be selected from the group consisting of these. The alkylamine group in R 2 is preferably dimethylamine or diethylamine.

[0022] At least one hydrogen atom in the alkylamine group represented by R2 may be substituted with a polymerizable group. Examples of polymerizable groups include (meth)acrylate ((meth)acryloxy), vinylphenyl, vinyl, and epoxy groups. The polymerizable group is preferably a free radical polymerizable group, and more preferably a (meth)acrylate group. When R2 has a polymerizable group, the number of such groups is, for example, one or two, preferably one.

[0023] Examples of R3 include: cyclic or chain-like groups having 2 to 20 carbon atoms, alkyldioxycarbonyl groups having 2 to 20 carbon atoms, alkyldicarbonyl groups having 2 to 20 carbon atoms, alkyldiyl groups having 4 to 20 carbon atoms, alkyldioxy groups having 2 to 20 carbon atoms, alkyldicarbonyloxy groups having 2 to 20 carbon atoms, etc., preferably including at least one group selected from the group consisting of these.

[0024] When Ar 1 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond, or when there is a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 1, R 3 represents at least one group selected from the group consisting of alkadiyl groups having 4 to 20 carbon atoms, alkadioxy groups having 2 to 20 carbon atoms, alkadioxycarbonyl groups having 2 to 20 carbon atoms, alkadioxycarbonyl groups having 2 to 20 carbon atoms, and alkadioxycarbonyloxy groups having 2 to 20 carbon atoms.

[0025] Examples of alkyldiyl groups having 4 to 20 carbon atoms include those formed by removing one hydrogen atom from unsubstituted (without substituents) straight-chain or branched alkyl groups having 4 to 20 carbon atoms, such as n-butyl, isobutyl, tributyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. The number of carbon atoms in the alkyldiyl group is preferably 4 to 16, and more preferably 4 to 12.

[0026] One or more hydrogen atoms constituting an alkyl group having 4 to 20 carbon atoms may be replaced with a halogen atom (e.g., a fluorine atom), a hydroxyl group, an amino group, or a substituted amino group. Examples of substituted amino groups include N-methylamino, N-ethylamino, N,N-dimethylamino, and N,N-diethylamino, which are substituted with one or two alkyl groups having 1 to 20 carbon atoms. Examples of alkyl groups in which one or more hydrogen atoms are replaced with halogen atoms, hydroxyl groups, or amino groups include fluorobutyl and octafluorobutyl, which are haloalkyl groups having 4 to 20 carbon atoms; hydroxybutyl, hydroxypentyl, and hydroxyhexyl, which are hydroxyalkyl groups having 4 to 20 carbon atoms; and aminobutyl and 2-(N,N-dimethylamino)butyl, which are alkyl groups having 4 to 20 carbon atoms having unsubstituted or substituted amino groups.

[0027] Alkyloxy groups having 2 to 20 carbon atoms can be exemplified by removing one hydrogen atom from unsubstituted linear or branched alkoxy groups having 2 to 20 carbon atoms, such as ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tributoxy, n-pentoxy, isopentoxy, neopentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, and n-decoxy. The number of carbon atoms in the alkyloxy group is preferably 2 to 16, and more preferably 2 to 12.

[0028] One or more hydrogen atoms constituting an alkoxy group having 2 to 20 carbon atoms may be replaced with a halogen atom (e.g., a fluorine atom), a hydroxyl group, an amino group, or an amino group with a substituent. The same applies to amino groups with substituents. Examples of alkoxy groups where one or more hydrogen atoms are replaced with halogen atoms, hydroxyl groups, amino groups, etc., include: tetrafluoroethoxy, octafluorobutoxy, and other haloalkoxy groups having 2 to 20 carbon atoms; 2-hydroxyethoxy, and other hydroxyalkoxy groups having 2 to 20 carbon atoms; and aminoethoxy, 2-(N,N-dimethylamino)ethoxy, and other alkoxy groups having 2 to 20 carbon atoms with an unsubstituted amino group or a substituted amino group.

[0029] Examples of alkadioxycarbonyl groups with 2 to 20 carbon atoms include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, tributoxycarbonyl, n-pentoxycarbonyl, isopentoxycarbonyl, neopentoxycarbonyl, n-hexyloxycarbonyl, n-heptoxycarbonyl, n-octoxycarbonyl, n-nonoxycarbonyl, and n-decoxycarbonyl, which are formed by removing one hydrogen atom from unsubstituted alkoxycarbonyl groups with 2 to 20 carbon atoms. The alkadiyl moiety of the alkadioxycarbonyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 12.

[0030] One or more hydrogen atoms constituting an alkoxycarbonyl group having 2 to 20 carbon atoms may be replaced with a halogen atom (e.g., a fluorine atom), a hydroxyl group, an amino group, or an amino group with substituents. The same applies to amino groups with substituents. Examples of alkoxycarbonyl groups having one or more hydrogen atoms replaced with halogen atoms, hydroxyl groups, amino groups, etc., include fluoroethoxycarbonyl, trifluoroethoxycarbonyl, tetrafluoroethoxycarbonyl, octafluorobutoxycarbonyl, and other haloalkoxycarbonyl groups having 2 to 20 carbon atoms.

[0031] Examples of alkyldicarbonyl groups with 2 to 20 carbon atoms include alkyldicarbonyl groups formed by removing one hydrogen atom from unsubstituted alkyl groups with 2 to 20 carbon atoms, such as acetyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, tributylcarbonyl, n-pentylcarbonyl, isopentylcarbonyl, neopentylcarbonyl, n-hexylcarbonyl, n-heptylcarbonyl, n-octylcarbonyl, n-nonylcarbonyl, and n-decylcarbonyl. The alkyldicarbonyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 12.

[0032] One or more hydrogen atoms constituting an alkyl group having 2 to 20 carbon atoms may be replaced with a halogen atom (e.g., a fluorine atom), a hydroxyl group, an amino group, or an amino group with substituents. The same applies to amino groups with substituents. Examples of alkyl groups having one or more hydrogen atoms replaced with halogen atoms, hydroxyl groups, etc., include fluoroethoxycarbonyl, trifluoroethoxycarbonyl, tetrafluoroethylcarbonyl, octafluorobutylcarbonyl, and other halogen groups having 2 to 20 carbon atoms.

[0033] Examples of alkyldicarbonyloxy groups with 2 to 20 carbon atoms include acetoxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, tributylcarbonyloxy, n-pentylcarbonyloxy, isopentylcarbonyloxy, neopentylcarbonyloxy, n-hexylcarbonyloxy, n-heptylcarbonyloxy, n-octylcarbonyloxy, n-nonylcarbonyloxy, and n-decylcarbonyloxy, which are formed by removing one hydrogen atom from unsubstituted alkyloxy groups with 2 to 20 carbon atoms. The alkyldiyl moiety of the alkyldicarbonyloxy group preferably has 1 to 16 carbon atoms, more preferably 1 to 12.

[0034] One or more hydrogen atoms constituting an alkoxy group having 2 to 20 carbon atoms can be replaced with a halogen atom (e.g., a fluorine atom), a hydroxyl group, an amino group, or an amino group with substituents. The same applies to amino groups with substituents. Examples of alkoxy groups having 2 to 20 carbon atoms that have one or more hydrogen atoms replaced with halogen atoms, hydroxyl groups, etc., include tetrafluoroethyl carbonyloxy and octafluorobutyl carbonyloxy.

[0035] At least one of the -CH 2- groups constituting an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms can be substituted with at least one of -O- and -NR*-. Here, R* represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include: methyl, ethyl, butyl, hexyl, etc. Examples of substituted alkyl groups with -O- or -NR*- inserted between carbon atoms include: 2-ethoxyethyl, 2-(2-ethoxyethoxy)ethyl, 2-[2-(ethylamino)ethyl)amino]ethyl, etc.

[0036] When Ar 1 has a hydroxyl group capable of forming an intramolecular hydrogen bond at the position adjacent to R 3, R 3 represents a cyclic or chain-like group with 2 to 20 carbon atoms capable of forming an intramolecular hydrogen bond with the hydroxyl group. R 3 is preferably a chain-like group with 2 to 20 carbon atoms capable of forming an intramolecular hydrogen bond with the hydroxyl group. Examples of cyclic groups represented by R 3 capable of forming an intramolecular hydrogen bond with the hydroxyl group include: 2-pyrrolididinediyl, 2-piperidinediyl, 2-pyrimidinediyl, 2-thiazolyldiyl, 2-thiazolinediyl, 2-acezolyldiyl, 2-acezolinediyl, etc., preferably including at least one from the group consisting of these. Cyclic groups capable of forming an intramolecular hydrogen bond with the hydroxyl group may have substituents. Examples of substituents include: halogen atoms (e.g., fluorine atoms), hydroxyl groups, amino groups that may have substituents, alkoxy groups, alkyl groups, alkyl carbonyl groups, etc. When the substituent has an alkyl moiety, the number of carbon atoms can be, for example, 1 to 10.

[0037] Examples of chain groups represented by R 3 that can form intramolecular hydrogen bonds with hydroxyl groups include alkadioxycarbonyl groups having 2 to 20 carbon atoms and alkadioxycarbonyl groups having 2 to 20 carbon atoms, preferably including at least one group selected from the group consisting of these. The alkadioxycarbonyl groups having 2 to 20 carbon atoms and the alkadioxycarbonyl groups having 2 to 20 carbon atoms are as described above.

[0038] R4 represents a polymerizable group or a hydrogen atom. Examples of polymerizable groups represented by R4 include: (meth)acrylate group ((meth)acryloxy), vinylphenyl, vinyl, epoxy, etc. The polymerizable group is preferably a free radical polymerizable group, and (meth)acrylate group is particularly preferred.

[0039] n represents 1 or 2. When n is 2, two R1s can be the same or different, and two Ar2s can be the same or different.

[0040] The compound represented by formula (1) has at least one hydroxyl group capable of forming an intramolecular hydrogen bond on at least one of Ar 1, Ar 2, and Ar 3. The number of hydroxyl groups capable of forming an intramolecular hydrogen bond in the compound represented by formula (1) may be, for example, 1. Examples of intramolecular hydrogen bonds in the compound represented by formula (1) are shown below, but the present invention is not limited to such equivalents. In the following examples, for convenience, Ar 1, Ar 2, and Ar 3 are represented as 1,4-epenylphenyl, but are not limited thereto. Also, R 31 represents an alkyldiyl group having 2 to 20 carbon atoms.

[0041] (1) When Ar 1 has a hydroxyl group capable of forming an intramolecular hydrogen bond. The hydroxyl group on Ar1 can, for example, form a six-membered cyclic intramolecular hydrogen bond with R3 or R1. Examples of the intramolecular hydrogen bond formation between the hydroxyl group on Ar1 and R3 include (a) and (b) below. Examples of the intramolecular hydrogen bond formation between the hydroxyl group on Ar1 and R1 include (c) and (d) below.

[0042] [Chemistry 5]

[0043] (2) When there is a hydroxyl group on Ar 2 that can form an intramolecular hydrogen bond. The hydroxyl group on Ar2 can, for example, form a six-membered cyclic intramolecular hydrogen bond with R1 or the azo group linking Ar2 and Ar3. Examples of the intramolecular hydrogen bond formation between the hydroxyl group on Ar2 and R1 include (e) and (f) below. Furthermore, examples of the intramolecular hydrogen bond formation between the hydroxyl group on Ar2 and the azo group linking Ar2 and Ar3 include (g) below.

[0044] [Chemistry 6]

[0045] (3) When there is a hydroxyl group on Ar 3 that can form an intramolecular hydrogen bond. The hydroxyl group on Ar3 can, for example, form a six-membered cyclic intramolecular hydrogen bond with the azo group linking Ar2 and Ar3. Specifically, examples include (h) below.

[0046] [Chemistry 7]

[0047] From the perspective of lightfastness, the state of intramolecular hydrogen bonds is preferably any one of (a) to (h), more preferably any one of (a), (b), (c) and (e), and even more preferably any one of (a) and (b).

[0048] The presence or absence of intramolecular hydrogen bonds can be determined by measuring 1H-NMR (Nuclear Magnetic Resonance). For example, as described in https: / / www.chem-station.com / yukitopics / nmr-analysis.htm and "Identification Methods of Organic Compounds by Spectroscopy (6th Edition)" (Tokyo Chemical Dojin, 1999, pp. 162-165), the proton system of hydroxyl groups with hydrogen bonds is observed on the low magnetic field side compared to the case without hydrogen bonds. The chemical shift of hydroxyl groups with intramolecular hydrogen bonds, for example in deuterium chloroform (CDCl3), can be 9.0 ppm or higher and 18.0 ppm or lower, preferably 10.0 ppm or higher.

[0049] Furthermore, the chemical shift of hydroxyl groups is generally significantly affected by the polarity of the measuring solvent. Specifically, in highly polar solvents (e.g., DMSO-d6), the shift is greater on the low magnetic field side. However, when hydrogen bonds are formed in the hydroxyl group, the influence of the measuring solvent becomes smaller. The difference between the chemical shift of hydroxyl groups with intramolecular hydrogen bonds in highly polar solvents (e.g., DMSO-d6) and in low polar solvents (e.g., CDCl3) can be, for example, less than 1.0 ppm and less than 0.5 ppm.

[0050] The maximum absorption wavelength (λmax) of the compound represented by formula (1) can be, for example, 350 nm or more and 700 nm or less, preferably 380 nm or more and 650 nm or less. The maximum absorption wavelength is determined by measuring a chloroform solution of the compound represented by formula (1) at room temperature (e.g., 25 °C). The maximum absorption wavelength of the compound represented by formula (1) can be adjusted to the desired wavelength by appropriately selecting the skeletal structure of Ar1, Ar2 and Ar3, the substituents in Ar1, Ar2 and Ar3, n, R2, etc.

[0051] As specific examples of compounds represented by formula (1), compounds represented by formulas (1-1) to (1-75) can be cited below, but the present invention is not limited to these.

[0052] [Chemistry 8]

[0053] [Chemistry 9]

[0054] [Chemistry 10]

[0055] [Chemistry 11]

[0056] [Chemistry 12]

[0057] [Chemistry 13]

[0058] [Chemistry 14]

[0059] [Chemistry 15]

[0060] [Chemistry 16]

[0061] [Chemistry 17]

[0062] From the viewpoint of lightfastness, the compound represented by formula (1) is preferably at least one of the compounds represented by any one of formulas (1-1) to (1-46), more preferably at least one of the compounds represented by any one of formulas (1-1) to (1-35), further preferably at least one of the compounds represented by any one of formulas (1-1) to (1-27), and even more preferably at least one of the compounds represented by any one of formulas (1-1) to (1-18).

[0063] Method for manufacturing the compound represented by formula (1) The compound represented by formula (1) can be manufactured by applying previously known synthetic methods. Specifically, the azo structure (-N=N-) in the compound represented by formula (1) can be constructed, for example, by converting an aromatic amine compound having a primary amino group into a diazonium salt using sodium nitrite or the like, with reference to the manufacturing examples described in paragraphs

[0220] to

[0268] of International Publication WO2016 / 136561, and then diazo coupling it with the aromatic compound. Furthermore, the azo structure containing a thiazole structure can be constructed, for example, with reference to the description in J. Mol. Struct., 2011, 987, 158.

[0064] Compounds where R3 is an alkadioxy group can be prepared into compounds having the desired alkadioxy group by applying an SN 2 substitution reaction in a precursor having a hydroxyl group. The SN 2 substitution reaction can be carried out under previously known reaction conditions, for example, see J. Am. Chem. Soc., 2008, 130, 13079.

[0065] When the compound represented by formula (1) contains -OC(=O)- or C(=O)O-, it can be synthesized, for example, by using a precursor having a carboxyl group and a precursor having a hydroxyl group, and applying a dehydration condensation reaction with reference to Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y.; Ma, DJ Org. Chem. 2009, 74 (3), 4542-4546. Specifically, for example, the conditions under which condensation is carried out in a solvent in the presence of an esterifying condensing agent can be cited.

[0066] Literature documenting the demethylation of compounds with hydroxyl groups on Ar1, Ar2, or Ar3 by salicylic acid-type methoxy groups (e.g., Chem. Commun. 2010, 46). (9019-9021.) For reference, demethylation can be performed to convert to hydroxyl groups. Examples of conditions for using demethylating agents in solvents can be cited. Examples of solvents include aprotic polar solvents, which can be single solvents or mixed solvents. Examples of aprotic polar solvents include: amide-based solvents or lactone-based solvents, nitrogen-containing aromatic solvents, argon-based solvents, etc. Examples of amide-based solvents include: N,N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactone, N,N-dimethylformamide, N,N-diethylformamide, N,N-diethylacetamide, N-methylpropionic acid, dimethylimidazolidine, etc. Examples of lactone-based solvents include γ-butyl lactone, β-butyl lactone, etc. Lactones, etc. Examples of nitrogen-containing aromatic solvents include pyridine and quinoline. Examples of sulfide solvents include dimethyl sulfide and methylphenyl sulfide. Preferably, amide solvents such as N-methyl-2-pyrrolidone and nitrogen-containing aromatic solvents such as pyridine are used. More preferably, a mixture of N-methyl-2-pyrrolidone and pyridine is used. Lithium salts are preferred as demethylating agents, and lithium chloride is more preferred. The reaction temperature can be, for example, in the range of 0°C to 200°C, preferably in the range of 20°C to 150°C, and more preferably in the range of 50°C to 120°C. After the reaction is complete, the mixture is cooled to room temperature, and hydrochloric acid, water, or other unsuitable solvents are added dropwise to precipitate the product, thereby obtaining the demethylated product.

[0067] The reaction time in the manufacturing method of the compound represented by formula (1) can also be determined by taking appropriate samples of the reaction mixture during the reaction and using known analytical methods such as liquid chromatography and gas chromatography to confirm the degree of disappearance of the raw material compound and the degree of formation of the compound represented by formula (1).

[0068] The compound represented by formula (1) can be extracted from the reaction mixture after the reaction by known methods such as recrystallization, reprecipitation, extraction and various chromatography methods, or by appropriate combination of these operations.

[0069] The composition may further include other pigment compounds besides those represented by formula (1), such as at least one of dichroic pigments. Examples of other pigment compounds include monoazo pigments, diazo pigments, triazo pigments, tetraazo pigments, succinylazo pigments, and other azo pigments, preferably at least one selected from the group consisting of these. The composition may contain one of the other pigment compounds alone, or may contain two or more in combination. For example, when used as a coating polarizing plate material, the other pigment compounds contained in the composition preferably have a maximum absorption wavelength in a wavelength range different from that of the compound represented by formula (1). For example, when used as a coating polarizing plate material, the composition preferably contains the compound represented by formula (1) and may contain three or more dichroic pigments, more preferably three or more azo pigments. By combining three or more pigment compounds with different maximum absorption wavelengths in the composition, absorption can be obtained in the entire visible light region, for example, using a thin film formed from the composition.

[0070] When the composition contains other pigment compounds, their content relative to 100 parts by weight of the solid content of the composition is preferably 50 parts by weight or less, more preferably 0.1 parts by weight or more and 10 parts by weight or less, and even more preferably 0.1 parts by weight or more and 5 parts by weight or less. If it is within the above range, the other pigment compounds can be sufficiently dispersed.

[0071] Liquid crystal compounds In addition to the compound represented by formula (1), the composition also contains a liquid crystal compound, which includes at least one of a polymeric liquid crystal compound and a liquid crystal polymer. The composition may contain only one of a polymeric liquid crystal compound and a liquid crystal polymer, or it may contain both. Furthermore, the polymeric liquid crystal compound and the liquid crystal polymer contained in the composition may be two or more different. By including at least one of a polymeric liquid crystal compound and a liquid crystal polymer in the composition, a composition can be formed in which the compound represented by formula (1) is dispersed in a liquid crystal compound.

[0072] Liquid crystal polymers can be either thermotropic liquid crystal polymers or liquidotropic liquid crystal polymers. For better control of dense film thickness, liquid crystal polymers that form thermotropic liquid crystal polymers are preferred.

[0073] Liquid crystals can be classified according to the molecular arrangement in their liquid crystal state into slab liquid crystals, nematic liquid crystals, and cholesteric liquid crystals. Among these, slab liquid crystals are preferred for polarizing film applications. Therefore, polymerizable liquid crystal compounds are preferably polymerizable slab liquid crystal compounds, and liquid crystal polymers are preferably slab liquid crystal polymers.

[0074] By using polymeric liquid crystal compounds and polymeric compounds exhibiting lamellar liquid crystal properties, polarizing films with high alignment order can be formed. The liquid crystal state exhibited by the polymeric liquid crystal compounds and liquid crystal polymeric compounds is preferably a lamellar phase (lamellar liquid crystal state), and from the viewpoint of achieving even higher alignment order, higher-order lamellar phases (higher-order lamellar liquid crystal states) are more preferred. Here, higher-order lamellar phases refer to lamellar phases B, D, E, F, G, H, I, J, K, and L, among which lamellar phases B, F, and I are more preferred. Polarizing films with high alignment order can obtain Bruger peaks from higher-order structures such as hexagonal phases or crystalline phases in X-ray diffraction measurements. The Brügger peak refers to the peak originating from the periodic structure of the molecular alignment plane. 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 polymeric liquid crystal compound or liquid crystal polymer can be a polymeric lamellae liquid crystal compound or lamellae liquid crystal polymer that exhibits Brügger peaks originating from higher-order structures in X-ray diffraction measurements.

[0075] Polymerized liquid crystal compounds Polymerizable liquid crystal compounds are compounds that have at least one polymerizable group within their molecules and can display a liquid crystal phase by alignment. Preferably, polymerizable liquid crystal compounds are compounds that can display a liquid crystal phase by alignment alone. A polymerizable group refers to a functional group capable of participating in a polymerization reaction, preferably a free radical polymerizable group.

[0076] As for the polymerizable liquid crystal compound, there is no particular limitation as long as it has at least one polymerizable group, preferably a display layer type liquid crystal compound, and known polymerizable liquid crystal compounds can be used. Specifically, as a polymerizable liquid crystal compound, the compound represented by the following formula (A) (hereinafter also referred to as "polymerizable liquid crystal compound (A)") can be preferably exemplified.

[0077] [Chemistry 18]

[0078] In formula (A), k is an integer from 1 to 3. X1, X2, and X3 independently represent divalent aromatic groups or divalent alicyclic hydrocarbon groups. When k is 2 or 3, the plurality of X1s may be the same or different. At least three of the groups formed by X1, X2, and X3 are selected to represent divalent six-membered cyclic hydrocarbon groups. Y1, Y2, W1, and W2 independently represent single bonds or divalent linked groups. When k is 2 or 3, Y1s may be the same or different. V1 and V2 independently represent alkadiyl groups with 1 to 20 carbon atoms that may have substituents. At least one of the -CH2- groups constituting the alkadiyl group may be substituted with -O-, -CO-, -S-, or -NH-. U1 and U2 independently represent polymerizable groups or hydrogen atoms, and at least one of them represents a polymerizable group.

[0079] Examples of divalent aromatic groups in X1, X2, and X3 include 1,4-epenylphenyl and 1,4-epenharyl (naphthalene-1,4-diyl). Examples of divalent alicyclic hydrocarbon groups include cyclohexane-1,4-diyl. At least one of the divalent aromatic groups and divalent alicyclic hydrocarbon groups in X1, X2, and X3 may have substituents. Examples of substituents include alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, and n-butyl, cyano groups, and halogen atoms. At least one of the -CH2- groups constituting the divalent alicyclic hydrocarbon group may be substituted with -O-, -S-, or -NR-. Here, R represents an alkyl group with 1 to 6 carbon atoms or a phenyl group.

[0080] Examples of divalent hydrocarbon six-membered cyclic groups in X1, X2 and X3 include 1,4-phenylene, which may have substituents, and cyclohexane-1,4-diyl, which may have substituents.

[0081] The divalent aromatic group in X1, X2, and X3 is preferably a 1,4-epenylphenyl group with substituents, and more preferably an unsubstituted 1,4-epenylphenyl group. Furthermore, the divalent alicyclic hydrocarbon group is preferably a cyclohexane-1,4-diyl group with substituents, more preferably a trans-cyclohexane-1,4-diyl group with substituents, and even more preferably an unsubstituted trans-cyclohexane-1,4-diyl group.

[0082] Y1 and Y2 each independently represent a single bond or a divalent linker. The divalent linker is, for example, at least one selected from the group consisting of -CH2CH2-, -CH2O-, -(C=O)O-, -O(C=O)O-, -N=N-, -CRa=CRb-, -C≡C-, and -CRa=N-. Here, Ra and Rb each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y1 is preferably -CH2CH2-, -(C=O)O-, or a single bond. Y2 is preferably -CH2CH2- or -CH2O-.

[0083] W1 and W2 each independently represent a single bond or a divalent linkage. The divalent linkage is, for example, at least one of the groups consisting of -O-, -S-, -(C=O)O-, and -O(C=O)O-. W1 and W2 are preferably each independently a single bond or -O-.

[0084] V1 and V2 each independently represent an alkyldiyl group having 1 to 20 carbon atoms that may have substituents. At least one of the -CH2- groups constituting the above-mentioned alkyldiyl group may also be substituted with -O-, -CO-, -S- or -NH-.

[0085] Examples of alkyldiyl groups represented by V1 and V2 include: methylene, ethyl, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10-diyl, tetradecane-1,1-diyl, and eicosane-1,20-diyl. V1 and V2 are preferably alkyldiyl groups with 2 to 12 carbon atoms, and more preferably alkyldiyl groups with 6 to 12 carbon atoms.

[0086] Examples of substituents that can be arbitrarily present in an alkyl dienyllium having 1 to 20 carbon atoms include cyano groups and halogen atoms. The alkyl dienyllium is preferably an unsubstituent alkyl dienyllium, and more preferably an unsubstituent, straight-chain alkyl dienyllium.

[0087] U1 and U2 each independently represent a polymerizable group or a hydrogen atom, and at least one of them represents a polymerizable group. U1 and U2 are preferably polymerizable groups. Preferably, both U1 and U2 are polymerizable groups, and more preferably, both are free radical polymerizable groups. The polymerizable group represented by U1 and the polymerizable group represented by U2 may be different from each other, but are preferably of the same kind. As the polymerizable group in U1 and U2, examples can be the same as the polymerizable groups exemplified above as polymerizable groups possessed by polymerizable liquid crystal compounds. Among them, the polymerizable group represented by U1 and U2 is preferably selected from at least one of the group consisting of ethyleneoxy, acryloxy, methacryloxy, ethylene oxide, and oxacyclobutyl, more preferably acryloxy.

[0088] As a specific example of a polymerizable liquid crystal compound (A), compounds represented by formulas (A-1) to (A-17) can be cited. When the polymerizable liquid crystal compound (A) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably in the trans form.

[0089] [Chemistry 19]

[0090] [Chemistry 20]

[0091] [Chemistry 21]

[0092] The polymerizable liquid crystal compound (A) is preferably at least one compound selected from the group consisting of compounds represented by any one of formulas (A-2), (A-3), (A-4), (A-5), (A-6), (A-7), (A-8), (A-13), (A-14), (A-15), (A-16), and (A-17). The polymerizable liquid crystal compound (A) may be used alone or in combination of two or more compounds.

[0093] Polymerizable liquid crystal compound (A) can be manufactured, for example, by methods described in known documents such as Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996) and Japanese Patent No. 4719156.

[0094] Liquid crystal polymers The liquid crystal polymer can be a compound formed by polymerizing the above-mentioned polymeric liquid crystal compound (hereinafter also referred to as a polymer of polymeric liquid crystal compound), or other liquid crystal polymers, preferably a polymer of the above-mentioned polymeric liquid crystal compound.

[0095] The polymer of the aforementioned polymeric liquid crystal compound may also use two or more of the aforementioned polymeric liquid crystal compounds as raw material monomers. Furthermore, the polymer of the aforementioned polymeric liquid crystal compound may also include monomers other than the aforementioned polymeric liquid crystal compounds as raw material monomers.

[0096] Relative to the total amount of structural units of the polymeric liquid crystal compound from the polymer constituting the polymeric liquid crystal compound, the content ratio of the polymeric liquid crystal compound in the polymeric liquid crystal compound is generally 1 mol% or more and 100 mol% or less. From the viewpoint of improving the orientation of the polymeric liquid crystal compound, it is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

[0097] Examples of other liquid crystal polymers mentioned above include polymers having liquid crystal groups. For instance, examples of polymers forming the parent structure include: polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyalkylene ethers and polyvinyl alcohol; polymethyl methacrylate; and polyacrylates, all of which have liquid crystal groups. Among these, polymethyl methacrylate and polyacrylates having liquid crystal groups are preferred.

[0098] The aforementioned other liquid crystal polymers may also contain two or more liquid crystal groups. The liquid crystal group may be contained in the main chain of the polymer that forms the parent skeleton, in the side chain of the polymer that forms the parent skeleton, or in both the main chain and side chain of the polymer that forms the parent skeleton. Examples of liquid crystal groups include those formed by removing one hydrogen atom from a compound having at least two six-membered hydrocarbon rings, or those formed by removing two hydrogen atoms from the same compound.

[0099] Relative to the total amount of structural units of the polymeric compounds that constitute the parent skeleton of the aforementioned other liquid crystal polymeric compounds, the content ratio of liquid crystal groups in the aforementioned other liquid crystal polymeric compounds is generally 1 mol% or more and 100 mol% or less. From the viewpoint of improving the orientation of the aforementioned other liquid crystal polymeric compounds, it is preferable to be 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

[0100] When two or more polymerizable liquid crystal compounds are combined in the composition, it is preferable that at least one of them is a polymerizable liquid crystal compound (A), and more preferably that two or more of them are polymerizable liquid crystal compounds (A). By combining two or more polymerizable liquid crystal compounds, the liquid crystal phase can sometimes be temporarily maintained even at temperatures below the liquid crystal-crystallization phase transition temperature. The total content of polymerizable liquid crystal compound (A) in the composition is preferably 40% by mass or more, more preferably 60% by mass or more, relative to the total mass of all polymerizable liquid crystal compounds in the composition, or all polymerizable liquid crystal compounds may be polymerizable liquid crystal compounds (A). If the content of polymerizable liquid crystal compound (A) is within the above range, the polymerizable liquid crystal compounds are more likely to be arranged with a higher degree of alignment order, and the compound represented by formula (1) is aligned accordingly, thereby obtaining a polarizing film with excellent polarization performance.

[0101] From the viewpoint of improving the orientation of the polymerizable liquid crystal compound and the liquid crystal polymer, the total content ratio of the polymerizable liquid crystal compound and the liquid crystal polymer in the composition, relative to 100 parts by mass of the solid content of the composition, is, for example, 50 parts by mass or more, preferably 70 parts by mass or more and 99.9 parts by mass or less, more preferably 70 parts by mass or more and 99.5 parts by mass or less, further preferably 80 parts by mass or more and 99 parts by mass or less, particularly preferably 80 parts by mass or more and 94 parts by mass or less, and even more preferably 80 parts by mass or more and 90 parts by mass or less.

[0102] Relative to the total mass of 100 parts by mass of the polymeric liquid crystal compound and the liquid crystal polymer compound, the total content of the compound represented by formula (1) in the composition is generally 0.1 parts by mass or more and 50 parts by mass or less, preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 5 parts by mass or less. If the total content of the compound represented by formula (1) is 50 parts by mass or less relative to the total mass of the polymeric liquid crystal compound and the liquid crystal polymer compound, there is less disorder in the alignment of the polymeric liquid crystal compound, the liquid crystal polymer compound and the compound represented by formula (1), and a polarizing film with a higher degree of alignment order can be obtained.

[0103] polymers In addition to the compound represented by formula (1) and the polymeric liquid crystal compound, the composition may also contain a polymeric compound. By including a polymeric compound in the composition, the compound represented by formula (1) is easily dispersed in the composition. There are no particular limitations on the polymeric compound that can be included in the composition, as long as it can disperse the compound represented by formula (1). From the perspective of easily dispersing the compound represented by formula (1) uniformly, acrylic polymers such as polymethyl methacrylate (PMMA) are preferred. Furthermore, the polymeric compound may also be a polymeric compound formed by polymerizing the polymeric liquid crystal compound described above. The weight average molecular weight of the polymeric compound, converted from polystyrene, is, for example, 10,000 or more and 200,000 or less, preferably 20,000 or more and 150,000 or less.

[0104] When the composition contains a polymeric compound, its content can be appropriately selected according to the purpose, etc. The content of the polymeric compound is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less, relative to 100 parts by mass of the solid content of the composition.

[0105] The composition preferably includes a liquid medium such as a solvent and a polymerization initiator, and may also include photosensitizers, polymerization inhibitors, leveling agents, etc., as needed.

[0106] solvent The solvent is preferably one that can completely dissolve the compound represented by formula (1), the polymerizable liquid crystal compound, the liquid crystal polymer compound, and the polymer compound. Furthermore, it is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound.

[0107] Examples of solvents include: alcohol solvents, ester solvents, ketone solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, nitrile solvents, ether solvents, and chlorinated solvents. Only one of these solvents may be used, or two or more may be used in combination.

[0108] When the composition contains a solvent, the solvent content is preferably 50% by mass or more and 98% by mass or less relative to the total amount of the composition. In other words, the solid content in the composition is preferably 2% by mass or more and 50% by mass or less. If the solid content is 50% by mass or less, the viscosity of the composition decreases, and the film obtained from the composition, for example, becomes substantially uniform in thickness, making it less prone to unevenness in the film. The solid content can be determined with consideration of the thickness of the film to be manufactured.

[0109] Polymerization initiator A polymerization initiator is a compound that can initiate the polymerization reaction of a polymerizable liquid crystal compound. From the perspective of initiating the polymerization reaction at lower temperatures, a photopolymerization initiator is preferred. Specifically, examples include photopolymerization initiators that can generate active free radicals or acids through the action of light, among which photopolymerization initiators that generate free radicals through the action of light are preferred.

[0110] Examples of polymerization initiators include: benzoin compounds, benzophenone compounds, alkyl phenyl ketone compounds, phosphine oxide compounds, triterpenoid compounds, ferrous salts, and strontium salts. The polymerization initiator can be appropriately selected from known polymerization initiators depending on the intended purpose. Furthermore, a polymerization initiator can be used alone or in combination of two or more.

[0111] When the composition contains a polymerization initiator, its content can be appropriately determined based on the type and amount of the polymerizable liquid crystal compound contained in the composition. Relative to 100 parts by mass of the polymerizable liquid crystal compound, the content of the polymerization initiator is, for example, 0.001 parts by mass or more, 0.01 parts by mass or more, 0.1 parts by mass or more, or 0.5 parts by mass or more, and for example, 30% by mass or less, 10% by mass or less, or 8% by mass or less. Furthermore, relative to 100 parts by mass of the polymerizable liquid crystal compound, the content of the polymerization initiator is preferably 0.001 parts by mass or more and 30 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 8 parts by mass or less. If the content of the polymerization initiator is within the above range, polymerization can be achieved without disturbing the orientation of the polymerizable liquid crystal compound.

[0112] photosensitizer When the composition contains a photopolymerization initiator, it is preferable that the composition also contains at least one photosensitizer. By containing both a photopolymerization initiator and a photosensitizer, the composition tends to further promote the polymerization reaction of the polymerizable liquid crystal compound. Examples of such photosensitizers include ketone and 9-oxothioketone. Anthracene compounds such as anthracene and alkoxy-substituted anthracene; phenanthrene and fluorescein, etc. Photosensitizers can be used alone or in combination of two or more.

[0113] When the composition contains a photosensitizer, the content of the photosensitizer in the composition can be appropriately determined based on the type and amount of the photopolymerization initiator and the polymerizable liquid crystal compound. Relative to 100 parts by mass of the polymerizable liquid crystal compound, the content of the photosensitizer in the composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less.

[0114] Polymer inhibitors The composition may also contain at least one polymerization inhibitor. Examples of polymerization inhibitors include: hydroquinone, alkoxylated hydroquinone, alkoxylated catechol (e.g., butylated catechol), pyrogallol, free radical scavengers such as 2,2,6,6-tetramethyl-1-piperidinoxy radical; thiophenols; β-naphthylamines and β-naphthols. By including a polymerization inhibitor in the composition, the extent of polymerization of the polymerizable liquid crystal compound can be controlled.

[0115] When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the composition is preferably 0.1 parts by mass and 30 parts by mass or less, more preferably 0.5 parts by mass and 10 parts by mass or less, and even more preferably 0.5 parts by mass and 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0116] Leveling agent The composition may also include at least one leveling agent. The leveling agent has the function of adjusting the flowability of the composition, resulting in a smoother coating obtained by applying the composition; specifically, surfactants can be cited as examples. Preferably, the leveling agent is selected from at least one of the group consisting of leveling agents with polyacrylate compounds as the main component and leveling agents with fluorine-containing compounds as the main component. One leveling agent may be used alone or in combination of two or more.

[0117] When the composition contains a leveling agent, the leveling agent content is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.05 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the polymeric liquid crystal compound and the liquid crystal polymer compound. If the leveling agent content is within the above range, it is easier to achieve horizontal alignment of the polymeric liquid crystal compound and the liquid crystal polymer compound, and it is less likely to produce unevenness, thus tending to obtain a smoother film, such as a polarizing film.

[0118] If the leveling agent content is within the above range, it tends to facilitate the horizontal alignment of the polymeric liquid crystal compound and the liquid crystal polymer compound, resulting in a smoother film. If the leveling agent content exceeds the above range relative to the polymeric liquid crystal compound and the liquid crystal polymer compound, it tends to produce unevenness in the resulting film.

[0119] antioxidants The composition may also contain an antioxidant. There is no particular limitation on the antioxidant, as long as the composition can achieve the effects of the present invention, and known antioxidants may be used. From the viewpoint of having a higher inhibitory effect on the photodegradation of the compound represented by formula (1), the antioxidant is preferably a so-called primary antioxidant that captures free radicals and has an anti-auto-oxidation effect. Therefore, the antioxidant contained in the composition is preferably selected from at least one of the group consisting of phenolic compounds, alicyclic alcohols, and amines. An antioxidant may be used alone or in combination of two or more.

[0120] Relative to 100 parts by mass of the composition, the content of the antioxidant in the composition is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 12 parts by mass or less, and more preferably 10 parts by mass or less. If the content of the antioxidant is at or above the lower limit, the photodegradation of the compound represented by formula (1) can be more effectively suppressed. Furthermore, if the content of the antioxidant is below the upper limit, the alignment of the polymerizable liquid crystal compound is less likely to be disturbed, and a higher suppression effect on the photodegradation of the compound represented by formula (1) can be expected.

[0121] The composition may contain other additives besides 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 relative to the solid content of the composition is preferably more than 0% and less than 20% by mass, and more preferably more than 0% and less than 10% by mass.

[0122] The composition can be manufactured by methods of composition preparation previously known. For example, it can be prepared by mixing the compound represented by formula (1), a liquid crystal compound, an antioxidant as needed, and additives such as leveling agents, and stirring.

[0123] <Compound> The compound in this embodiment is represented by the following formula (1a).

[0124] [Chemistry 22]

[0125] In equation (1a), k represents an integer of 1 or 2. When k is 2, the two R 11 can be the same or different, and the two Ar 12 can be the same or different.

[0126] Ar 11, Ar 12, and Ar 13 each independently represent a 1,4-phenylene group or a sulfur-containing heterocyclic group that may have substituents. At least one of Ar 11 and Ar 12 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. The details of Ar 11, Ar 12, and Ar 13 are the same as those of Ar 1, Ar 2, and Ar 3 in formula (1), and the preferred embodiments are also the same.

[0127] R 11 indicates that at least one base is selected from the group consisting of -OC(=O)-, -C(=O)O- and -N=N-, preferably -OC(=O)-, -C(=O)O- or -N=N-.

[0128] R12 represents an alkylamine group that can have polymerizable groups. The details of R12 are the same as those of R2 in formula (1), and the preferred state is also the same.

[0129] Examples of R 13 include: cyclic or chain groups with 2 to 20 carbon atoms capable of forming intramolecular hydrogen bonds with hydroxyl groups, alkyldioxycarbonyl groups with 2 to 20 carbon atoms, alkyldicarbonyl groups with 2 to 20 carbon atoms, alkyldiyl groups with 4 to 20 carbon atoms, alkyldioxy groups with 2 to 20 carbon atoms, etc., preferably including at least one group selected from the group consisting of these. The details of R 13 are the same as those of R 3 in formula (1), and the preferred form is also the same.

[0130] R 14 represents a polymerizable group or a hydrogen atom. The details of R 14 are the same as those of R 4 in formula (1), and the preferred state is also the same.

[0131] <Film> The thin film of this embodiment can be a thin film containing the compound represented by formula (1) as a forming material, or it can be a thin film obtained by using a composition containing the compound represented by formula (1) and a liquid crystal compound as a forming material. The thin film containing the composition can be formed by applying the composition to a substrate and performing film formation. Furthermore, when the composition contains a polymerizable liquid crystal compound, the thin film containing a hardened product obtained by polymerizing the polymerizable liquid crystal compound can be formed by applying the composition to a substrate, performing film formation, and then polymerizing the polymerizable liquid crystal compound and hardening it.

[0132] The composition can form a thin film with excellent lightfastness and high absorbance retention, such as a polarizing film. Therefore, the thin film of this embodiment includes a polarizing film formed from a composition comprising a compound represented by formula (1) and a liquid crystal compound, and has excellent absorbance retention. Furthermore, the composition can form a thin film with high alignment order, such as a polarizing film. Therefore, the thin film of this embodiment includes a polarizing film formed from a composition comprising a compound represented by formula (1) and a liquid crystal compound, and has high alignment order.

[0133] Here, regarding polarizing films with a high degree of alignment order, Brügner peaks from higher-order structures such as hexagonal phases or crystalline phases can be obtained in X-ray diffraction measurements. Therefore, in polarizing films formed from compositions, it is preferable that the polymeric liquid crystal compound or liquid crystal polymer is aligned in a manner that will display a Brügner peak in X-ray diffraction measurements, and more preferably "horizontal alignment," that is, the molecules of the polymeric liquid crystal compound or liquid crystal polymer are aligned along the direction of light absorption. A higher degree of alignment order that displays a Brügner peak can be achieved by controlling the type of polymeric liquid crystal compound or liquid crystal polymer used, the amount of the compound represented by formula (1), etc.

[0134] Regarding the compounds represented by formula (1) that constitute the composition for forming the thin film and the liquid crystal compounds, as described above.

[0135] Thin films can be manufactured, for example, by a method including the following steps. Step A: Forming a coating film comprising a compound represented by formula (1), a liquid crystal compound, and a solvent; Step B: Remove at least a portion of the solvent from the above coating; Step C: Heat the temperature above the temperature at which the liquid crystal compound phase transitions to a liquid phase, then cool it down to allow the liquid crystal compound phase to transition to a lamellae phase (lamellae-type liquid crystal state); and Step D: If necessary, polymerize the polymerizable liquid crystal compound while maintaining the above-mentioned layered phase (layered liquid crystal state).

[0136] The coating of the composition can be formed, for example, by coating the composition onto a substrate, an alignment film, etc. Alternatively, the composition can be directly coated onto the retardation film constituting the polarizing plate, and other layers.

[0137] The substrate is typically a transparent substrate. Furthermore, when the substrate is not disposed on the display surface of the display element, for example, when a laminate after removing the substrate from a thin film is disposed on the display surface of the display element, the substrate may also be opaque. A transparent substrate refers to a substrate that allows light, especially visible light, to pass through. Transparency refers to the characteristic of having a transmittance of 80% or more for light in the wavelength range of 380 nm to 780 nm. A specific example of a transparent substrate is a light-transmitting resin substrate.

[0138] Examples of resins constituting a transparent resin substrate include: polyolefins; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; cellulose ester; polyethylene naphthalate; polycarbonate; polyurethane; polyether ether; polyether ketone; polyphenylene sulfide; and polyphenylene ether. From the viewpoint of availability or transparency, polyethylene terephthalate, polymethacrylate, cellulose ester, cyclic olefin resins, or polycarbonate are preferred.

[0139] The required properties of the substrate vary depending on the composition of the film. Generally, a substrate with minimal phase difference is preferred. Examples of substrates with minimal phase difference include cellulose ester films such as ZeroTAC (Konica Minolta Opto Co., Ltd.) and Z-TAC (Fujifilm Co., Ltd.), which do not exhibit phase difference. Furthermore, a non-extended cyclic olefin resin substrate is also preferred. Hard coating, anti-reflective treatment, and antistatic treatment can be applied to the surface of the substrate without laminated films.

[0140] The thickness of the substrate is typically 5 μm or more and 300 μm or less, preferably 20 μm or more and 200 μm or less, and even more preferably 20 μm or more and 100 μm or less. If the thickness is above the lower limit of the above values, the reduction in strength is suppressed and the processability tends to improve.

[0141] Examples of methods for coating a composition onto a substrate include: spin coating, extrusion coating, gravure coating, die coating, bar coating, smear coating, and other known methods such as printing methods such as flexographic printing.

[0142] Subsequently, at least a portion of the solvent contained in the coating film obtained from the composition is removed by drying or the like, thereby forming a dried coating film. Furthermore, when the coating film contains a polymerizable liquid crystal compound, a dried coating film is formed by drying under conditions where the polymerizable liquid crystal compound does not polymerize. Examples of drying methods for the above-mentioned coating film include: natural drying, ventilation drying, heating drying, and reduced pressure drying.

[0143] Furthermore, in order to transfer the liquid crystal compound phase into a liquid phase, the temperature is raised above the temperature at which the liquid crystal compound phase transfers into a liquid phase, and then cooled to transfer the liquid crystal compound phase into a lamellar phase (lamellar liquid crystal state). This phase transfer can be performed after the solvent in the coating film is removed, or it can be performed simultaneously with the solvent removal.

[0144] When the composition contains a polymerizable liquid crystal compound, the polymerizable liquid crystal compound is polymerized while maintaining its lamellar liquid crystal state, thereby forming a thin film containing a hardened polymerizable liquid crystal compound. Photopolymerization is preferred as the polymerization method. In photopolymerization, the light used to irradiate the dried coating is appropriately selected based on the type of photopolymerization initiator contained in the dried coating, the type of polymerizable liquid crystal compound (especially the type of polymerizable groups 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 from the perspective of easy control of the polymerization reaction and the availability of photopolymerization devices widely used in this field. Furthermore, it is preferable to pre-select the polymerizable liquid crystal compound contained in the composition and the type of photopolymerization initiator by using ultraviolet light energy for photopolymerization. Furthermore, during polymerization, the polymerization temperature can be controlled by simultaneously cooling the dried coating using an appropriate cooling method and irradiating it with light. By employing this cooling method, if the polymerization of polymerizable liquid crystal compounds is carried out at a lower temperature, a thin film can be appropriately formed even if a substrate with relatively low heat resistance is used. During photopolymerization, patterned thin films can also be obtained by masking or developing processes.

[0145] Examples of light sources for the aforementioned active energy lines include: low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, LED (Light Emitting Diode) light sources that emit light in the wavelength range of 380 nm to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.

[0146] The intensity of ultraviolet (UV) irradiation is typically above 10 mW / cm² and below 3,000 mW / cm². Preferably, the UV irradiation intensity is within the wavelength range effective for activating the photopolymerization initiator. The irradiation time is typically above 0.1 seconds and below 10 minutes, preferably above 0.1 seconds and below 5 minutes, more preferably above 0.1 seconds and below 3 minutes, and even more preferably above 0.1 seconds and below 1 minute. If irradiation is performed once or multiple times at this UV irradiation intensity, the cumulative light intensity is preferably above 10 mJ / cm² and below 3,000 mJ / cm².

[0147] By photopolymerization, polymerizable liquid crystal compounds polymerize in a liquid crystal state while maintaining a lamellar phase, preferably a higher-order lamellar phase, to form a thin film. The thin film obtained by polymerizing the liquid crystal compound in a liquid crystal state while maintaining a lamellar phase also exhibits the effect of dichroic pigments, offering higher polarization performance compared to previous host-guest type polarizing films, i.e., thin films containing a nematic phase liquid crystal state. Furthermore, it also exhibits superior strength compared to films coated only with dichroic pigments or liquidotropic liquid crystals.

[0148] The thickness of the film can be appropriately selected according to the display device to which it is applied, preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and even more preferably 1 μm or more and 3 μm or less.

[0149] When using a thin film as a polarizing film, it is preferable to form it on an alignment film. The alignment film has an alignment restraint force that causes the polymeric liquid crystal compound and the liquid crystal polymer to align in the desired direction. Preferably, the alignment film possesses solvent resistance, which is not dissolved by coatings containing a composition comprising at least one of the polymeric liquid crystal compound and the liquid crystal polymer; and has heat resistance for solvent removal or heat treatment during the alignment of the polymeric liquid crystal compound. Examples of such alignment films include alignment films containing alignment polymers, photoalignment films, and groove alignment films with raised or recessed patterns or multiple grooves on the surface. From the viewpoint of alignment angle accuracy and quality, a photoalignment film is preferred.

[0150] <Laminated Body> The laminate of this embodiment may include a thin film containing a compound represented by formula (1) as a forming material, or a thin film containing a combination of a compound represented by formula (1) and a liquid crystal compound as a forming material. The laminate may include a substrate, a thin film containing a compound represented by formula (1) as a forming material disposed on the substrate, and may also include a substrate, an alignment film disposed on the substrate, and a thin film containing a compound represented by formula (1) as a forming material disposed on the alignment film. The thin film containing a compound represented by formula (1) as a forming material may constitute a polarizing film. Furthermore, the substrate may also be a retardation film. The laminate may, for example, constitute a polarizing plate. The laminate may, for example, be manufactured by forming a thin film on a substrate according to the above-described thin film manufacturing method.

[0151] From the viewpoint of the flexibility or visibility of the display device, the thickness of the laminate is preferably 10 μm or more and 300 μm or less, more preferably 20 μm or more and 200 μm or less, and even more preferably 25 μm or more and 100 μm or less.

[0152] When the laminate has a phase retardation film as a substrate, the thickness of the phase retardation film can be appropriately selected according to the display device to which it is applied.

[0153] <Display Device> The display device of this embodiment includes the aforementioned laminate, which can be a polarizing plate. The display device can be obtained, for example, by attaching the laminate, which serves as the polarizing plate, to the surface of the display device via an adhesive layer. The display device is a device having display elements, which includes a light-emitting element or light-emitting device as a light source. Examples of display devices include: liquid crystal display devices, organic electroluminescent (EL) display devices, inorganic electroluminescent (EL) display devices, electron emission display devices (e.g., field emission display devices (FED), surface field emission display devices (SED)), electronic paper (display devices using electronic ink, electrophoretic elements, etc.), plasma display devices, projection display devices (e.g., grating light valve (GLV) display devices, display devices with digital micromirror devices (DMD), and piezoelectric ceramic displays, etc.). Liquid crystal display devices include any one of transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct-viewing liquid crystal display devices, and projection liquid crystal display devices. These display devices can be display devices for displaying two-dimensional images or stereoscopic display devices for displaying three-dimensional images. In particular, organic EL display devices and touch panel display devices are preferred, especially organic EL display devices. [Example]

[0154] The present invention will now be specifically described by way of examples, but the present invention is not limited to these examples. Furthermore, unless otherwise specified, "parts" and "%" are based on mass. Also, "room temperature" and "RT" are 23°C.

[0155] Example 1: Synthesis of Compound 1-1 To synthesize compound 1-1, compounds 1-1-a and 1-1-b were first synthesized. Then, dehydration condensation esterification was performed to obtain compound 1-1.

[0156] Synthesis of compound 1-1-a 4-Amino-2-fluorobenzoic acid (7.76 g, 50.0 mmol), 35% hydrochloric acid (13.2 mL, 150 mmol), and water (100 mL) were mixed and cooled to 0-5°C. A solution of sodium nitrite (3.55 g, 51.5 mmol) in water (6.5 mL) was added dropwise. The mixture was then stirred for 30 minutes while maintaining the temperature at 0-5°C to prepare a diazo solution. Meanwhile, N,N-dimethylaniline (9.10 g, 75.1 mmol), sodium acetate (16.4 g, 200 mmol), methanol (67.0 mL), and water (33.0 mL) were cooled to 0-5°C, and the entire diazo solution prepared earlier was added dropwise. After the addition was complete, the mixture was heated to room temperature, and the precipitated solid was filtered to obtain compound 1-1-a (14.0 g, 97% yield).

[0157] [Chemistry 23]

[0158] Synthesis of compound 1-1-b 2,4-Dihydroxybenzoic acid (3.08 g, 20.0 mmol), 1-butanol (30.0 mL, 327 mmol), and DMAP (abbreviation of N,N-dimethylaminopyridine, 0.245 g, 2.01 mmol) were mixed, and EDC·HCl (abbreviation of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 4.61 g, 24.0 mmol) was added. The mixture was stirred at room temperature for 18 hours. The reaction solution was diluted with ethyl acetate (100 mL), washed three times with water (100 mL), and the organic layer was dried with magnesium sulfate. The solid was then concentrated. The solid was purified by silicone column chromatography (developing solvent: chloroform) to obtain compound 1-1-b (3.20 g, 76% yield).

[0159] [Chemistry 24]

[0160] Synthesis of Compound 1-1 1-1-a (0.287 g, 0.998 mmol), 1-1-b (0.258 g, 1.23 mmol), DMAP (13.3 mg, 0.109 mmol), and tetrahydrofuran (10.0 mL) were mixed, and EDC·HCl (0.236 g, 1.23 mmol) was added. The reaction solution was stirred at room temperature for 4 hours. Water was added to the reaction solution, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid was purified by silicone column chromatography with chloroform as the developing solvent, and further purified by chloroform / methanol reprecipitation to obtain compound 1-1 (0.304 g, 63% yield).

[0161] [Chemistry 25]

[0162] 1H-NMR (400 MHz, CDCl 3): δ (ppm) = 11.02 (s, 1H), 8.19 (t, 1H), 7.93-7.91 (m, 3H), 7.74 (dd, 1H), 7.64 (dd, 1H), 6.91 (d, 1H), 6.82 (dd, 1H), 6.77 (d, 2H), 4.38 (t, 2H), 3.14 (s, 6H), 1.78 (quin, 2H), 1.55-1.45 (m, 2H), 1.00 (t, 3H).

[0163] In compound 1-1, the chemical shift of the hydroxyl group in CDCl3 is 11.02 ppm, which corresponds to a low magnetic field, indicating the formation of intramolecular hydrogen bonds.

[0164] Example 2: Synthesis of Compounds 1-2 To synthesize compound 1-2, compound 1-2-a was first synthesized, followed by compounds 1-2-b, 1-2-c, and 1-2-d. Dehydration condensation esterification was then performed to obtain compound 1-2.

[0165] Synthesis of compound 1-2-a Sodium bisulfite (78.0 g, 750 mmol) and water (150 mL) were mixed and heated to 70 °C. A 37% formaldehyde aqueous solution (44.3 mL, 600 mmol) was added dropwise. After the entire solution was added, the mixture was cooled to 40 °C, and aniline (45.7 mL, 500 mmol) was added dropwise over 1 hour with stirring for 9 hours. The mixture was cooled to 0 °C, and the precipitated solid was filtered to obtain compound 1-2-a (96.0 g, 100% yield).

[0166] [Chemistry 26]

[0167] Synthesis of compound 1-2-b 4-Amino-2-methoxybenzoic acid (8.36 g, 50.0 mmol), 35% hydrochloric acid (13.2 mL, 150.0 mmol), and water (100 mL) were cooled to 0-5°C, and a solution of sodium nitrite (3.62 g, 52.5 mmol) in water (7.0 mL) was added dropwise. The mixture was then stirred for 4 hours while maintaining the temperature at 0-5°C to prepare a diazo solution. Meanwhile, compound 1-2-a (15.7 g, 75.0 mmol), and water (200 mL) were mixed, cooled to 0-5°C, and the entire amount of the previously prepared diazo solution was added dropwise. After the addition was complete, the mixture was stirred at 0-5°C for 3 hours, then heated to room temperature and stirred for 16 hours. Subsequently, sodium hydroxide (24.0 g, 600 mmol) was added, the temperature was raised to 90°C, and the mixture was stirred for 2 hours. Cool to room temperature, add hydrochloric acid (52 mL, 589 mmol), filter and separate the precipitated solid, then wash with water to obtain compound 1-2-b as a solid. Without purification, it is used for the following diazo coupling.

[0168] [Chemistry 27]

[0169] Synthesis of compound 1-2-c Compound 1-2-b was mixed with 35% hydrochloric acid (8.8 mL, 100.0 mmol), acetic acid (50.0 mL), and water (50.0 mL), cooled to 0-5°C, and a solution of sodium nitrite (3.62 g, 52.5 mmol) in water (7.0 mL) was added dropwise. The mixture was then stirred for 1 hour while maintaining the temperature at 0-5°C to prepare a diazo solution. Separately, N,N-dimethylaniline (9.08 g, 75.0 mmol), sodium acetate (16.4 g, 200 mmol), methanol (67.0 mL), and water (34.0 mL) were mixed, cooled to 0-5°C, and the entire amount of the previously prepared diazo solution was added dropwise. After the addition was completed, the mixture was stirred at 0 to 5°C for 2 hours, then heated to room temperature. The precipitated solid was filtered and separated, and then washed with acetonitrile / water to obtain compound 1-2-c (13.9 g, 69% yield based on 4-amino-2-methoxybenzoic acid).

[0170] [Chemistry 28]

[0171] Synthesis of compound 1-2-d Compound 1-2-c (13.7 g, 34 mmol), lithium chloride (4.32 g, 100 mmol), N-methyl-2-pyrrolidone (68 mL), and pyridine (22.7 mL) were mixed, heated to 100 °C, and stirred for 16 hours. Afterward, the mixture was cooled to room temperature, and hydrochloric acid (28 mL, 317 mmol) was added dropwise. The precipitated solid was separated by filtration and then washed with water to obtain compound 1-2-d (15.0 g, 104% yield).

[0172] [Chemistry 29]

[0173] Synthesis of Compounds 1-2 Compound 1-2-d (6.39 g, 15.0 mmol), 1-butanol (13.8 mL, 150 mmol), DMAP (2.02 g, 16.5 mmol), and tetrahydrofuran (50.0 mL) were mixed, and EDC·HCl (4.31 g, 22.5 mmol) was added. The reaction solution was heated to 50 °C and stirred for 4 hours. Water (150 mL) was added to the reaction solution, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid was purified by silicone column chromatography with chloroform as the developing solvent, and further purified by chloroform / methanol reprecipitation to obtain compound 1-2 (1.93 g, 29% yield).

[0174] [Chemistry 30]

[0175] 1H-NMR (400 MHz, CDCl 3): δ (ppm) = 10.98 (s, 1H), 8.07 (d, 2H), 8.01-7.98 (m, 3H), 7.93 (dd, 2H), 7.52 (d, 1H), 7.45 (dd, 1H), 6.78 (d, 2H), 4.40 (t, 2H), 3.12 (s, 6H), 1.81 (quin, 2H), 1.56-1.47 (m, 2H), 1.01 (t, 3H).

[0176] 1H-NMR (400 MHz, DMSO-d 6): δ (ppm) = 10.78(br,1H), 8.08 (d, 2H), 7.99-7.97 (m, 3H), 7.86 (d, 2H), 7.48 (dd, 1H), 7.45 (d, 1H), 6.88 (d, 2H), 4.36 (t, 2H), 3.10 (s, 6H), 1.74 (quin, 2H), 1.50-1.41 (m, 2H), 0.96 (t, 3H)

[0177] Compounds 1-2 are believed to have formed intramolecular hydrogen bonds, as described below. Regarding compounds 1-2, the chemical shift of the hydroxyl group in CDCl3 is 10.98 ppm, located on the low magnetic field side, reflecting the formation of intramolecular hydrogen bonds. Furthermore, the difference between the chemical shift of the proton of the hydroxyl group in the low-polarity deuterated solvent CDCl3 and the chemical shift of the proton of the hydroxyl group in the high-polarity deuterated solvent DMSO-d6 (10.78 ppm) is only 0.2 ppm, which is relatively small, also reflecting the formation of intramolecular hydrogen bonds.

[0178] Comparative Example 1: Synthesis of Compound C-1 To synthesize compound C-1, compound 1-2-a was first synthesized. Then, dehydration condensation esterification was performed to obtain compound C-1.

[0179] Synthesis of compound C-1 Compound 1-2-a (0.291 g, 1.01 mmol), 4-n-butylresorcinol (0.199 g, 1.20 mmol), DMAP (76.0 mg, 0.622 mmol), and tetrahydrofuran (10.0 mL) were mixed, and EDC·HCl (0.233 g, 1.22 mmol) was added. The reaction solution was stirred at room temperature for 18 hours. Water was added to the reaction solution, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid was purified by silicone column chromatography with chloroform as the developing solvent, and further purified by water / methanol reprecipitation to obtain compound C-1 (0.064 g, 12% yield).

[0180] [Chemistry 31]

[0181] 1H-NMR (400 MHz, CDCl 3): δ (ppm) = 8.18 (t, 1H), 7.92 (d, 2H), 7.73 (dd, 1H), 7.63 (dd, 1H), 7.15 (d, 1H), 6.79-6.72 (m, 4H), 4.77 (s, 1H), 3.14 (s, 6H), 2.61 (t, 2H), 1.65-1.57 (m, 2H), 1.45-1.36 (m, 2H), 0.96 (t, 3H).

[0182] 1H-NMR (400 MHz, DMSO-d 6): δ (ppm) = 9.64(br,1H), 8.19 (t, 1H), 7.87 (d, 2H), 7.76 (dd, 1H), 7.67 (dd, 1H), 7.11 (d, 1H), 6.88 (d, 2H), 6.69 (d, 1H), 6.64 (dd, 1H), 3.12 (s, 6H), 1.53 (quin, 2H), 1.38-1.28 (m, 2H), 0.91 (t, 3H).

[0183] Unlike the compounds in the examples, the chemical shift of the hydroxyl group in CDCl3 in C-1 is 4.77 ppm, which is on the high magnetic field side, indicating that no intramolecular hydrogen bonds have formed. Furthermore, the difference between the chemical shift of the proton of the hydroxyl group in CDCl3 (a low-polarity deuterated solvent) and the chemical shift of the proton of the hydroxyl group in the high-polarity deuterated solvent DMSO-d6 (9.64 ppm) is 4.87 ppm, which is relatively large, indicating that it is significantly affected by the difference in polarity of the measuring solvent. This situation also reflects the lack of intramolecular hydrogen bonds.

[0184] Comparative Example 2 Compound (C-2) was synthesized according to the manufacturing method of Manufacturing Example 6 (1-34) disclosed in Japanese Patent Application Publication No. 2017-082217.

[0185] [Chemistry 32]

[0186] Example 11: Preparation of composition E1 containing compound 1-1 The following ingredients are mixed and stirred at 80°C for 1 hour to obtain composition E1. • Polymerizable liquid crystal compound (A-6) 75 parts by weight • Polymerizable liquid crystal compound (A-7) 25 parts by weight Compound 1-1 4.0 parts by weight • Polymerization initiator: 6 parts by weight of 2-dimethylamino-2-benzyl-1-(4-oxolinylphenyl)butane-1-one (Irgacure 369; manufactured by BASF Japan). • Leveling agent: Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.2 parts by weight Solvent: 250 parts by weight of o-xylene

[0187] Polymerizable liquid crystal compound (A-6)

[0188] [Chemistry 33]

[0189] Polymerizable liquid crystal compound (A-7)

[0190] [Chemistry 34]

[0191] Furthermore, the polymeric liquid crystal compound (A-6) was synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). Also, according to this method, the polymeric liquid crystal compound (A-7) was prepared.

[0192] Example 12: Preparation of Composition E2 Composition E2 of Example 12 was obtained in the same manner as in Example 1, except that compound 1-2 was used instead of compound 1-1.

[0193] Comparative Examples 11 and 12: Preparation of Compositions C1 and C2 Except that compounds 1-1 were replaced by compounds C-1 or C-2, which were represented by the formulas described above for the synthesis method, the compositions C1 and C2 of Comparative Examples 11 and 12 were obtained in the same manner as in Example 1.

[0194] <Manufacturing of Polarizing Plates> 1. Formation of alignment thin films 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 Wako Pure Chemical Industries, Ltd.) (a composition for forming an alignment layer) was coated onto the glass substrate by spin coating. After drying, a thin film with a thickness of 100 nm was formed. Subsequently, an alignment film was formed by rubbing the surface of the obtained film, thus obtaining a substrate with an alignment film formed on the glass substrate.

[0195] 2. Formation of polarizing thin films The above-obtained composition is coated onto the alignment film of the substrate obtained above by spin coating, heated and dried on a heating plate at 120°C for 3 minutes, and then rapidly cooled to below 70°C (the temperature at which the laminar liquid crystal phase is displayed during cooling) to obtain a laminate with a dried film formed on the alignment film.

[0196] Subsequently, a UV (Ultra Violet) irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) was used to irradiate the dried film with ultraviolet light at an exposure dose of 1000 mJ / cm 2 (365 nm standard). This caused the polymerizable liquid crystal compound contained in the dried film to polymerize while maintaining the liquid crystal state of the composition, thereby forming a polarizing film from the dried film to obtain a polarizing plate.

[0197] <Evaluation> The dichroic ratio of the obtained polarizing plate was measured as follows. A spectrophotometer (Shimadzu UV-3150, manufactured by Shimadzu Corporation) with a holder containing the polarizing plate was used. The absorbance along the transmission axis (A1) and the absorbance along the absorption axis (A2) of the polarizing film at the wavelength of maximum absorption (λmax) were measured using the double-beam method. A screen with a 50% cutoff for light intensity was placed on the reference side of the holder. The ratio (A2 / A1) was calculated from the measured absorbance along the transmission axis (A1) and the absorbance along the absorption axis (A2), and this ratio was set as the dichroic ratio (DR). The dichroic ratios before the lightfastness test are shown in Tables 1 and 2.

[0198] Furthermore, a protective film (40 μm TAC (KC4UY manufactured by Konica Minolta Co., Ltd.)) was applied to the surface of the formed polarizing film, and light was irradiated onto it under the following conditions to evaluate its lightfastness. Using a spectrophotometer (Shimadzu Corporation UV-3150) with a holder equipped with a polarizing plate, the absorbance (A3) along the absorption axis of the polarizing film after the lightfastness test was measured at the wavelength of maximum absorption before the test using the double-beam method. The absorbance (A3) along the absorption axis of the polarizing film after the lightfastness test was divided by the absorbance (A2) along the absorption axis of the polarizing film before the lightfastness test, and the percentage was calculated as the absorbance retention rate (%). The results are shown in Tables 1 and 2. Furthermore, when the absorbance retention rate exceeds 80%, the polarizing film is considered to be of better quality.

[0199] The light exposure conditions for the lightfastness test are as follows. Equipment used: Ci4000 manufactured by ATLAS Light source: Xenon arc lamp Exposure conditions: 120 W / m² (300 nm-400 nm) Test duration: 40 hours Exposure level: 17280 KJ / m² Temperature: 65℃.

[0200] [Table 1] compound Dichroic ratio before light fastness test Absorbance retention rate Chemical shift of hydroxyl groups (CDCl 3, ppm) Example 11 1-1 32 92% 11.02 Comparative Example 11 C-1 17 73% 4.77

[0201] [Table 2] compound Dichroic ratio before light fastness test Absorbance retention rate Chemical shift of hydroxyl groups (CDCl 3, ppm) Example 12 1-2 52 83% 10.98 Comparative Example 12 C-2 41 78% -

[0202] As shown in Table 1, the polarizing plate has higher light resistance under harsh operating conditions. In addition, it can improve the dichroism ratio. The polarizing plate has a thin film formed by a composition of a compound represented by formula (1).

Claims

1. A composition comprising: a compound represented by the following formula (1); and a liquid crystal compound comprising at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound, [Chemical 1] [In formula (1), n ​​represents an integer of 1 or 2; Ar1, Ar2 and Ar3 each independently represent a 1,4-phenyl or sulfur-containing heterocyclic group that may have substituents; at least one of Ar1, Ar2 and Ar3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond; R1 represents at least one group selected from the group consisting of -OC(=O)-, -C(=O)O- and -N=N-; R2 represents an alkylamine group that may have a polymerizable group; When Ar1 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond, or when it has a hydroxyl group capable of forming an intramolecular hydrogen bond at the position adjacent to R1, R3 represents at least one group selected from the group consisting of alkadiyl groups with 4 to 20 carbon atoms, alkadioxy groups with 2 to 20 carbon atoms, alkadioxycarbonyl groups with 2 to 20 carbon atoms, alkadioxycarbonyl groups with 2 to 20 carbon atoms, and alkadioxycarbonyloxy groups with 2 to 20 carbon atoms; when Ar1 has a hydroxyl group capable of forming an intramolecular hydrogen bond at the position adjacent to R3, R3 represents a cyclic or chain-like group with 2 to 20 carbon atoms capable of forming a hydrogen bond with the hydroxyl group; R4 represents a polymerizable group or a hydrogen atom; when n is 2, the two R1s may be the same or different from each other, and the two Ar2s may be the same or different from each other.

2. The composition of claim 1, wherein the polymeric liquid crystal compound is a polymeric lamellar liquid crystal compound and the liquid crystal polymer is a lamellar liquid crystal polymer.

3. The composition of claim 1, wherein the polymerizable liquid crystal compound comprises a compound represented by formula (A) below, [Chemical 2] [In formula (A), m represents an integer from 1 to 3; X1, X2 and X3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group; when m is 2 or 3, there are multiple X1s that may be the same or different; at least 3 selected from the group consisting of X1, X2 and X3 represent a divalent six-membered cyclic hydrocarbon group; Y1, Y2, W1 and W2 each independently represent a single bond or a divalent linker group; when m is 2 or 3, there are multiple Y1s that may be the same or different; V1 and V2 each independently represent an alkadiyl group with 1 to 20 carbon atoms that may have substituents; at least one of the -CH2- groups constituting the alkadiyl group may also be substituted with -O-, -CO-, -S- or -NH-; U1 and U2 independently represent either a polymerizable group or a hydrogen atom, and at least one of them represents a polymerizable group.

4. The composition of claim 1, wherein the number of hydroxyl groups of the compound represented by formula (1) above capable of forming intramolecular hydrogen bonds is 1.

5. The composition of any one of claims 1 to 4, wherein the compound represented by formula (1) above has a hydroxyl group on Ar1 that is capable of forming an intramolecular hydrogen bond with R3.

6. A compound represented by the following formula (1a), [Chemical 3] [In formula (1a), k represents an integer of 1 or 2; Ar11, Ar12 and Ar13 each independently represent a 1,4-phenyl or sulfur-containing heterocyclic group that may have substituents; at least one of Ar11 and Ar12 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond; R11 represents at least one group selected from the group consisting of -OC(=O)-, -C(=O)O- and -N=N-; R12 represents an alkylamine group that may have polymerizability; When Ar11 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond, or when there is a hydroxyl group capable of forming an intramolecular hydrogen bond at the position adjacent to R11, R13 represents at least one group selected from the group consisting of alkadiyl groups with 4 to 20 carbon atoms, alkadioxy groups with 2 to 20 carbon atoms, alkadioxycarbonyl groups with 2 to 20 carbon atoms, alkadioxycarbonyl groups with 2 to 20 carbon atoms, and alkadioxycarbonyloxy groups with 2 to 20 carbon atoms; when Ar11 has a hydroxyl group capable of forming an intramolecular hydrogen bond at the position adjacent to R13, R13 represents a cyclic or chain-like group with 2 to 20 carbon atoms capable of forming a hydrogen bond with the hydroxyl group; R14 represents a polymerizable group or a hydrogen atom; when k is 2, the two R11s may be the same or different from each other, and the two Ar12s may be the same or different from each other.

7. The compound of claim 6 has 1 hydroxyl group capable of forming an intramolecular hydrogen bond.

8. The compound of claim 6, wherein Ar11, Ar12 and Ar13 are 1,4-epylphenyl compounds that may have substituents.

9. A compound of any one of claims 6 to 8, wherein it has a hydroxyl group on Ar11 capable of forming an intramolecular hydrogen bond with R13.

10. A thin film comprising a composition of any one of claims 1 to 5 as a forming material.

11. A laminate comprising a thin film as claimed in claim 10.

12. A display device having a laminate as claimed in claim 11.