Compound, composition, film, laminate and display device

Abstract

To provide a composition capable of forming a film having a dichroic ratio.SOLUTION: There is provided a composition which comprises a compound represented by the following formula (1) and a liquid crystalline compound, wherein, n is 1 or 2, Ar1, Ar2 and Ar3 represent a 1,4-phenylene group or the like, at least one of which has a hydroxy group capable of forming an intramolecular hydrogen bond. R1 represents an alkylamino group. When Ar1 has no hydroxy group capable of forming an intramolecular hydrogen bond or has a hydroxy group at an ortho position of an azo group, R2 represents an alkanediyl group, an alkanediyloxy group, an alkanediyloxycarbonyl group, an alkanediylcarbonyl group or an alkanediylcarbonyloxy group. When Ar1 has a hydroxy group capable forming an intramolecular hydrogen bond at an ortho position of R2, R2 represents a cyclic or chain group capable forming a hydrogen bond with the hydroxy group. R3 represents a polymerizable group or a hydrogen atom.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] There is a continuous demand for thinner displays such as image display panels, and further thinner polarizing plates, polarizers, and other components thereof are also being demanded. In response to such demands, for example, a thin host-guest polarizer has been proposed that includes a polarizing film containing a polymerizable liquid crystal compound and a dye compound exhibiting dichroism (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2007-510946 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-37353 Summary of the Invention [Problem to be solved by the invention]

[0004] In host-guest polarizers, further improvement in the dichroic ratio is required. An object of the present invention is to provide a compound having a high dichroic ratio, a composition containing the compound, a film formed from the composition, a laminate including the film, and a light-emitting device including the laminate. [Means for solving the problem]

[0005] 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 containing at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound: [ka] In formula (1), n ​​represents an integer of 1 or 2. Ar 1 , Ar 2 and Ar 3 each independently represents a 1,4-phenylene group or a sulfur-containing heterocyclic group, which may have a substituent. 1 , Ar 2 and Ar 3 At least one of the groups has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. R 1 represents an alkylamino group which may have a polymerizable group. Ar 1 When R does not have a hydroxyl group capable of forming an intramolecular hydrogen bond or has a hydroxyl group at the ortho position of the azo group, 2 represents at least one group selected from the group consisting of an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediylcarbonyl group having 2 to 20 carbon atoms, and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms. Ar 1 R is a hydroxyl group that can form an intramolecular hydrogen bond. 2 If it is in the ortho position of R 2 represents a cyclic or chain group having 2 to 20 carbon atoms that can form a hydrogen bond with the hydroxyl group. R 3 represents a polymerizable group or a hydrogen atom. When n is 2, two Ar 2 may be the same or different from each other.] [2] The composition according to [1], wherein the polymerizable liquid crystal compound is a polymerizable smectic liquid crystal compound, and the liquid crystalline polymer compound is a smectic liquid crystalline polymer compound. [3] The composition according to [1] or [2], wherein the polymerizable liquid crystal compound includes a compound represented by the following formula (A): [ka] [In formula (A), m represents an integer of 1 to 3.] X1 , X 2 and X 3 each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. When m is 2 or 3, a plurality of X 1 may be the same or different. X 1 , X 2 and X 3 At least three selected from the group consisting of: represent a divalent 6-membered hydrocarbon ring group. Y 1 , Y 2 , W 1 and W 2 each independently represents a single bond or a divalent linking group. When m is 2 or 3, a plurality of Y 1 may be the same or different from each other. V 1 and V 2 each independently represents an alkanediyl group having 1 to 20 carbon atoms which may have a substituent. At least one of -CH2- constituting the alkanediyl group may be replaced with -O-, -CO-, -S- or -NH-. U 1 and U 2 each independently represents a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group. [4] The composition according to any one of [1] to [3], wherein the compound represented by formula (1) has one hydroxyl group capable of forming an intramolecular hydrogen bond. [5] The compound represented by the above formula (1) is R 3 The hydroxyl group capable of intramolecular hydrogen bonding with Ar 1 or a hydroxyl group capable of intramolecularly hydrogen bonding with -N=N- in Ar 2 The composition according to any one of [1] to [4], [6] A compound represented by the following formula (1a): [ka] In formula (1a), k represents an integer of 1 or 2. Ar 11 , Ar 12 and Ar13 each independently represents a 1,4-phenylene group or a sulfur-containing heterocyclic group which may have a substituent. 11 and Ar 12 At least one of the groups has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. R 11 represents an alkylamino group which may have a polymerizable group. Ar 11 When R does not have a hydroxyl group capable of forming an intramolecular hydrogen bond or has a hydroxyl group at the ortho position of the azo group, 12 represents at least one group selected from the group consisting of an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms. Ar 11 R is a hydroxyl group that can form an intramolecular hydrogen bond. 12 If it is in the ortho position of R 12 represents a cyclic or chain group having 2 to 20 carbon atoms that can form a hydrogen bond with the hydroxyl group. R 13 represents a polymerizable group or a hydrogen atom. If k is 2, two Ar 12 may be the same or different from each other.] [7] The compound according to [6], wherein the number of hydroxyl groups capable of forming an intramolecular hydrogen bond is 1. [8] Ar 11 , Ar 12 and Ar 13 The compound according to [6] or [7], wherein is an optionally substituted 1,4-phenylene group. [9] R 13 The hydroxyl group that can form an intramolecular hydrogen bond with Ar 11 or a hydroxyl group capable of intramolecularly hydrogen bonding with -N=N- in Ar 12 The compound according to any one of [6] to [8],

[10] A film formed from the composition according to any one of [1] to [5].

[11] A laminate comprising the film according to

[10] .

[12] A display device comprising the laminate according to

[11] . [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a compound having a high dichroic ratio, a composition containing the compound, a film formed from the composition, a laminate including the film, and a light-emitting device including the laminate. DETAILED DESCRIPTION OF THE INVENTION

[0007] In this specification, the term "process" refers not only to an independent process, but also to processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. Furthermore, the content of each component in a composition refers to the total amount of the multiple substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component are present in the composition. Furthermore, 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. The scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention.

[0008] <Composition> The composition according to this embodiment contains a compound represented by formula (1) and a liquid crystalline compound. The liquid crystalline compound contains at least one of a polymerizable liquid crystalline compound and a liquid crystalline polymer compound. The composition is used, for example, as a material for forming a polarizing film. That is, the composition may be a composition for forming a polarizing film. A polarizing plate including a polarizing film obtained using the composition as a forming material can exhibit a high dichroic ratio (DR).

[0009] The compound represented by formula (1) is Ar 1 , Ar 2 and Ar 3When at least one of the compounds has at least one hydroxyl group capable of forming an intramolecular hydrogen bond, for example, the number of pseudo-rings increases due to the intramolecular hydrogen bond, which is thought to improve the interaction with the host compound, and this is thought to result in an increase in the dichroic ratio (DR) of a polarizing film containing the compound represented by formula (1).

[0010] [ka]

[0011] In formula (1), Ar 1 , Ar 2 and Ar 3 each independently represents an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group, preferably an optionally substituted 1,4-phenylene group. Examples of the divalent sulfur-containing heterocyclic group include a benzothiazolediyl group, a thienothiazolediyl group, and a thiazolediyl group, and preferably a benzothiazolediyl group.

[0012] Ar 1 , Ar 2 and Ar 3 The substituent in Ar may be at least one selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group, and a methoxy group, and is preferably a fluorine atom, a chlorine atom, a hydroxyl group, a methyl group, or a methoxy group, and more preferably a fluorine atom or a hydroxyl group. 1 , Ar 2 and Ar 3 The number of substituents in each independently is, for example, 0, 1 or 2, and preferably 0 or 1.

[0013] Ar 1 , Ar 2 and Ar 3 At least one of Ar has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. 1 and Ar 2 It is preferable that at least Ar1 It is more preferred that the .alpha.-hydroxybenzoate be present in the .alpha.-hydroxybenzoate.

[0014] Functional groups with which a hydroxyl group can form an intramolecular hydrogen bond may be adjacent to each other on the same ring. That is, it is preferable for a hydroxyl group to form an intramolecular hydrogen bond with a functional group located at its ortho position, and it is also preferable for a hydroxyl group to form an intramolecular hydrogen bond in a six-membered ring. Examples of functional groups with which a hydroxyl group can form an intramolecular hydrogen bond include a hydroxyl group, a methoxy group, an azo group, a carbonyl group, an oxycarbonyl group (-OC(=O)-), a carbonyloxy group (-C(=O)O-), a 2-pyrrolidinediyl group, a 2-piperidinediyl group, a 2-pyrimidinediyl group, a 2-thiazolediyl group, a 2-thiazolinediyl group, a 2-oxazolediyl group, and a 2-oxazolinediyl group. The functional group with which a hydroxyl group can form an intramolecular hydrogen bond may be, for example, a functional group other than an azo group.

[0015] The compound represented by formula (1) has a hydroxyl group capable of forming an intramolecular hydrogen bond with Ar 1 and Ar 2 and the hydroxyl group is Ar 1 and Ar 2 Azo group and R 2 It is preferable that the hydroxyl group capable of forming an intramolecular hydrogen bond with at least one of Ar 1 and the hydroxyl group is R 2 It is more preferable that the compound represented by formula (1) forms an intramolecular hydrogen bond with R. The number of hydroxyl groups capable of forming an intramolecular hydrogen bond in the compound represented by formula (1) may be, for example, 1. 2 When an intramolecular hydrogen bond is formed with R 2 preferably contains -OC(=O)-, a carbonyl group, a 2-pyrrolidinediyl group, a 2-piperidinediyl group, a 2-pyrimidinediyl group, a 2-thiazolediyl group, a 2-thiazolinediyl group, a 2-oxazolediyl group, or a 2-oxazolinediyl group, more preferably contains at least -OC(=O)- or a carbonyl group, and further preferably is an alkanediyloxycarbonyl group having 2 to 20 carbon atoms or an alkanediylcarbonyl group having 2 to 20 carbon atoms.

[0016] R 1 represents an alkylamino group which may have a polymerizable group. 1 The alkylamino group in R may be a monoalkylamino group or a dialkylamino group, and is preferably a dialkylamino group. 1 Examples of the alkylamino group in R include a dimethylamino group, a diethylamino group, an ethylmethylamino group, a dipropylamino group, a diisopropylamino group, a monomethylamino group, a monoethylamino group, a monopropylamino group, a monoisopropylamino group, a pyrrolidyl group, a piperidyl group, a morpholinyl group, and an oxazolidinyl group, and R may be at least one selected from the group consisting of these. 1 The alkylamino group in the formula (I) is preferably a dimethylamino group or a diethylamino group.

[0017] R 1 At least one hydrogen atom of the alkylamino group represented by the formula (I) may be substituted with a polymerizable group. Examples of the polymerizable group include a (meth)acrylate group (a (meth)acryloyloxy group), a vinylphenyl group, a vinyl group, and an epoxy group. The polymerizable group is preferably a radically polymerizable group, and among these, a (meth)acrylate group is preferred. R 1 When has a polymerizable group, the number thereof is, for example, 1 or 2, and preferably 1.

[0018] R 2 Examples of the alkyl group include a cyclic or chain-like group having 2 to 20 carbon atoms that can form an intramolecular hydrogen bond with a hydroxyl group, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediylcarbonyl group having 2 to 20 carbon atoms, an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms, and it is preferable that the alkyl group contains at least one selected from the group consisting of these groups.

[0019] Ar 1does not have a hydroxyl group capable of forming an intramolecular hydrogen bond, or 1 and Ar 2 is at the ortho position of the azo group to which it is linked, R 2 represents at least one group selected from the group consisting of an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediylcarbonyl group having 2 to 20 carbon atoms, and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms.

[0020] Examples of the alkanediyl group having 4 to 20 carbon atoms include an alkanediyl group formed by removing one hydrogen atom from an unsubstituted (not having a substituent) linear or branched alkyl group having 4 to 20 carbon atoms, such as an n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, or n-decyl group. The number of carbon atoms in the alkanediyl group is preferably 4 to 16, and more preferably 4 to 12.

[0021] One or more hydrogen atoms constituting the alkyl group having 4 to 20 carbon atoms may be substituted with a halogen atom (e.g., a fluorine atom), a hydroxy group, an amino group, or a substituted amino group. Examples of the substituted amino group include an amino group substituted with one or two alkyl groups having 1 to 20 carbon atoms, such as an N-methylamino group, an N-ethylamino group, an N,N-dimethylamino group, or an N,N-diethylamino group. Examples of the alkyl group having one or more hydrogen atoms substituted with a halogen atom, a hydroxy group, an amino group, or the like include haloalkyl groups having 4 to 20 carbon atoms, such as a fluorobutyl group or an octafluorobutyl group; hydroxyalkyl groups having 4 to 20 carbon atoms, such as a hydroxybutyl group, a hydroxypentyl group, or a hydroxyhexyl group; and alkyl groups having 4 to 20 carbon atoms and an unsubstituted or substituted amino group, such as an aminobutyl group or a 2-(N,N-dimethylamino)butyl group.

[0022] Examples of alkanediyloxy groups having 2 to 20 carbon atoms include alkanediyloxy groups formed by removing one hydrogen atom from an unsubstituted linear or branched alkoxy group having 2 to 20 carbon atoms, such as an ethoxy group, n-propoxy group, isopropyloxy group, n-butoxy group, isobutyloxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, or n-decyloxy group. The number of carbon atoms in the alkanediyloxy group is preferably 2 to 16, and more preferably 2 to 12.

[0023] One or more hydrogen atoms constituting the alkoxy group having 2 to 20 carbon atoms may be substituted with a halogen atom (e.g., a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent. The substituted amino group is the same as described above. Examples of the alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom, hydroxy, amino group, or the like include haloalkoxy groups having 2 to 20 carbon atoms, such as tetrafluoroethoxy and octafluorobutoxy; hydroxyalkoxy groups having 2 to 20 carbon atoms, such as 2-hydroxyethoxy; and alkoxy groups having 2 to 20 carbon atoms and an unsubstituted or substituted amino group, such as aminoethoxy and 2-(N,N-dimethylamino)ethoxy.

[0024] Examples of the alkanediyloxycarbonyl group having 2 to 20 carbon atoms include alkanediyloxycarbonyl groups formed by removing one hydrogen atom from an unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, or n-decyloxycarbonyl group. The number of carbon atoms in the alkanediyloxycarbonyl group in the alkanediyl moiety is preferably 1 to 16, and more preferably 1 to 12.

[0025] One or more hydrogen atoms constituting the alkoxycarbonyl group having 2 to 20 carbon atoms may be substituted with a halogen atom (e.g., a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent. The amino group having a substituent is the same as described above. Examples of the alkoxycarbonyl group in which one or more hydrogen atoms have been replaced with a halogen atom, a hydroxy group, an amino group, or the like include haloalkoxycarbonyl groups having 2 to 20 carbon atoms, such as a fluoroethoxycarbonyl group, a trifluoroethoxycarbonyl group, a tetrafluoroethoxycarbonyl group, and an octafluorobutoxycarbonyl group.

[0026] Examples of the alkanediylcarbonyl group having 2 to 20 carbon atoms include alkanediylcarbonyl groups formed by removing one hydrogen atom from an unsubstituted alkanoyl group having 2 to 20 carbon atoms, such as an acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, tert-butylcarbonyl group, n-pentylcarbonyl group, isopentylcarbonyl group, neopentylcarbonyl group, n-hexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, n-nonylcarbonyl group, or n-decylcarbonyl group. The number of carbon atoms in the alkanediylcarbonyl group in the alkanediyl moiety is preferably 1 to 16, and more preferably 1 to 12.

[0027] One or more hydrogen atoms constituting the alkanoyl group having 2 to 20 carbon atoms may be substituted with a halogen atom (e.g., a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent. The amino group having a substituent is the same as described above. Examples of the alkanoyl group having one or more hydrogen atoms substituted with a halogen atom, a hydroxy group, or the like include haloacyl groups having 2 to 20 carbon atoms, such as a fluoroethoxycarbonyl group, a trifluoroethoxycarbonyl group, a tetrafluoroethylcarbonyl group, and an octafluorobutylcarbonyl group.

[0028] Examples of the alkanediylcarbonyloxy group having 2 to 20 carbon atoms include alkanediylcarbonyloxy groups formed by removing one hydrogen atom from an unsubstituted alkanoyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, tert-butylcarbonyloxy group, n-pentylcarbonyloxy group, isopentylcarbonyloxy group, neopentylcarbonyloxy group, n-hexylcarbonyloxy group, n-heptylcarbonyloxy group, n-octylcarbonyloxy group, n-nonylcarbonyloxy group, or n-decylcarbonyloxy group. The number of carbon atoms in the alkanediylcarbonyloxy group in the alkanediyl moiety is preferably 1 to 16, and more preferably 1 to 12.

[0029] One or more hydrogen atoms constituting the alkanoyloxy group having 2 to 20 carbon atoms may be substituted with a halogen atom (e.g., a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent. The amino group having a substituent is the same as described above. Examples of the alkanoyloxy group in which one or more hydrogen atoms are substituted with a halogen atom, a hydroxy group, or the like include haloacyloxy groups having 2 to 20 carbon atoms, such as a tetrafluoroethylcarbonyloxy group or an octafluorobutylcarbonyloxy group.

[0030] At least one of -CH2- constituting the alkyl group moiety constituting the alkyl group having 4 to 20 carbon atoms, the alkoxy group having 2 to 20 carbon atoms, the alkoxycarbonyl group having 2 to 20 carbon atoms, the alkanoyl group having 2 to 20 carbon atoms or the alkanoyloxy group having 2 to 20 carbon atoms is -O- or -NR * -, where R * represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a butyl group, and a hexyl group. *Examples of the substituted alkyl group having - inserted therein include a 2-ethoxyethyl group, a 2-(2-ethoxyethoxy)ethyl group, and a 2-[2-(ethylamino)ethyl)amino]ethyl group.

[0031] Ar 1 However, the hydroxyl group capable of forming an intramolecular hydrogen bond is R 2 If it is in the ortho position of R 2 represents a cyclic or chain-like group having 2 to 20 carbon atoms that can form an intramolecular hydrogen bond with the hydroxyl group. 2 R may preferably be a chain-like group having 2 to 20 carbon atoms that can form an intramolecular hydrogen bond with a hydroxyl group. 2 Examples of the cyclic group represented by the formula (I) and capable of forming an intramolecular hydrogen bond with a hydroxyl group include a 2-pyrrolidinediyl group, a 2-piperidinediyl group, a 2-pyrimidinediyl group, a 2-thiazolediyl group, a 2-thiazolinediyl group, a 2-oxazolediyl group, and a 2-oxazolinediyl group, and it is preferable to include at least one selected from the group consisting of these. The cyclic group capable of forming an intramolecular hydrogen bond with a hydroxyl group may have a substituent. Examples of the substituent include a halogen atom (e.g., a fluorine atom), a hydroxy group, an amino group which may have a substituent, an alkoxy group, an alkyl group, and an alkylcarbonyl group. When the substituent has an alkyl moiety, the number of carbon atoms therein may be, for example, 1 to 10.

[0032] R 2 and capable of forming an intramolecular hydrogen bond with a hydroxyl group includes an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediylcarbonyl group having 2 to 20 carbon atoms, etc., and it is preferable to include at least one selected from the group consisting of these. The alkanediyloxycarbonyl group having 2 to 20 carbon atoms and the alkanediylcarbonyl group having 2 to 20 carbon atoms are as described above.

[0033] R 3 represents a polymerizable group or a hydrogen atom. 3Examples of the polymerizable group represented by the formula (I) include a (meth)acrylate group (a (meth)acryloyloxy group), a vinylphenyl group, a vinyl group, an epoxy group, etc. The polymerizable group is preferably a radically polymerizable group, and among these, a (meth)acrylate group is preferred.

[0034] n represents 1 or 2. When n is 2, two Ar 2 may be the same or different from each other.

[0035] The compound represented by formula (1) is Ar 1 , Ar 2 and Ar 3 At least one of the hydroxyl groups has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. 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 these embodiments. In the following examples, Ar 1 , Ar 2 and Ar 3 For convenience, R is a 1,4-phenylene group, but is not limited to this. 21 represents an alkanediyl group having 2 to 20 carbon atoms.

[0036] (1) Hydroxyl groups capable of forming intramolecular hydrogen bonds are attached to Ar 1 If you have Ar 1 The hydroxyl group on the 1 and Ar 2 Azo group or R 2 It can form a six-membered ring with an intramolecular hydrogen bond. 1 The hydroxyl group on top is R 2 The following (a) can be exemplified as an embodiment in which an intramolecular hydrogen bond is formed with Ar. 1 The hydroxyl group on top is Ar 1 and Ar 2 The following (b) can be exemplified as an embodiment in which an intramolecular hydrogen bond is formed with the azo group linking the group:

[0037] [ka]

[0038] (2) Hydroxyl groups capable of forming intramolecular hydrogen bonds are attached to Ar 2 If you have Ar 2 The hydroxyl group on the 1 and Ar 2 Azo group or Ar 2 and Ar 3 It can form a six-membered ring intramolecular hydrogen bond with the azo group that connects Ar 2 The hydroxyl group on top is Ar 1 and Ar 2 The following (c) can be exemplified as a mode in which an intramolecular hydrogen bond is formed with the azo group linking Ar 2 The hydroxyl group on top is Ar 2 and Ar 3 The following (d) can be exemplified as an embodiment in which an intramolecular hydrogen bond is formed with the azo group linking the group:

[0039] [ka]

[0040] (3) Hydroxyl groups capable of forming intramolecular hydrogen bonds are attached to Ar 3 If you have Ar 3 The hydroxyl group on the 2 and Ar 3 It is possible to form a six-membered cyclic intramolecular hydrogen bond with the azo group that connects the groups. Specific examples include the following (e).

[0041] [ka]

[0042] From the viewpoint of improving the dichroic ratio, the mode of the intramolecular hydrogen bond is preferably any one of (a) to (e), more preferably any one of (a) to (d), and even more preferably any one of (a) and (c).

[0043] The presence or absence of intramolecular hydrogen bonds is 1 This can be determined by measuring H-NMR. For example, as described in "Spectroscopic Identification of Organic Compounds (6th Edition)" (Tokyo Kagaku Dojin, 1999, pp. 162-165) at https: / / www.chem-station.com / yukitopics / nmr-analysis.htm, the protons of hydroxyl groups that form hydrogen bonds are observed on the lower magnetic field side compared to those that do not form hydrogen bonds. The chemical shift of a hydroxyl group that forms an intramolecular hydrogen bond may be 9.0 ppm or more to 18.0 ppm or less, preferably 10.0 ppm or more, in deuterated chloroform (CDCl3), for example.

[0044] In general, the chemical shift of a hydroxyl group is significantly affected by the polarity of the measurement solvent. Specifically, in a highly polar solvent (e.g., DMSO-d6), the shift is significantly shifted toward the lower magnetic field. However, when the hydroxyl group forms a hydrogen bond, the influence of the measurement solvent is reduced. The difference between the chemical shift of a hydroxyl group that forms an intramolecular hydrogen bond in a highly polar solvent (e.g., DMSO-d6) and in a less polar solvent (e.g., CDCl3) may be, for example, 1.0 ppm or less, or 0.5 ppm or less.

[0045] The maximum absorption wavelength (λmax) of the compound represented by formula (1) may be, for example, 350 nm or more and 650 nm or less, and preferably 380 nm or more and 600 nm or less. The maximum absorption wavelength is measured at room temperature (e.g., 25°C) for a chloroform solution of the compound represented by formula (1). The maximum absorption wavelength of the compound represented by formula (1) can be measured, for example, by the measurement of Ar 1 , Ar 2 and Ar 3 The framework structure of Ar 1 , Ar 2 and Ar3 Substituents in, n, R 1 By appropriately selecting the above, it is possible to adjust the wavelength to a desired value.

[0046] Specific examples of the compound represented by formula (1) include compounds represented by the following formulas (1-1) to (1-78), but the present invention is not limited to these.

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] From the viewpoint of improving the dichroic ratio, the compound represented by formula (1) is preferably at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-56), more preferably at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-46), still more preferably at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-31), and particularly preferably at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-20).

[0060] Method for producing a compound represented by formula (1) The compound represented by formula (1) can be produced by appropriately applying a conventionally known synthesis method. Specifically, the azo structure (-N=N-) in the compound represented by formula (1) can be constructed by converting an aromatic amine compound having a primary amino group into a diazonium salt using sodium nitrite or the like, and then diazo-coupling it with an aromatic compound, for example, with reference to the description of the production examples in paragraphs

[0220] to

[0268] of International Publication WO 2016 / 136561. Furthermore, an azo structure containing a thiazole structure can be constructed with reference to the description in, for example, J. Mol. Struct., 2011, 987,158.

[0061] R 3A compound in which R is an alkanediyloxy group can be produced as a compound having the desired alkanediyloxy group by, for example, applying an SN2 substitution reaction to a precursor having a hydroxy group. The SN2 substitution reaction may be carried out under conventionally known reaction conditions, or the description in, for example, J. Am. Chem. Soc., 2008, 130, 13079 may be referred to.

[0062] When the compound represented by formula (1) contains -OC(=O)- or C(=O)O-, it can be synthesized, for example, by applying a dehydration condensation reaction using a precursor having a carboxy group and a precursor having a hydroxyl group, with reference to Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y.; Ma, DJ Org. Chem. 2009, 74 (3), 4542-4546. Specific examples of conditions include condensation in a solvent in the presence of an esterification condensing agent.

[0063] Ar 1 , Ar 2 or Ar 3Compounds having a hydroxyl group at the hydroxyl group can be converted to a hydroxyl group by demethylation with reference to literature on the demethylation reaction of salicylic acid-type methoxy groups (for example, (Chem. Commun. 2010, 46, 9019-9021.). For example, conditions using a demethylating agent in a solvent can be used. The solvent can be an aprotic polar solvent, which can be a single solvent or a mixed solvent. Examples of aprotic polar solvents include amide solvents, lactone solvents, nitrogen-containing aromatic solvents, sulfoxide solvents, etc. Examples of amide solvents include N,N-dimethylacetamide, N-methyl-pyrrolidone, N-methylcaprolactam, N,N-dimethylformamide, N,N-diethylformamide, N,N-diethylacetamide, N-methylpropionamide, dimethylimidazolidinone, etc. Examples of lactone solvents include γ-butyllactone, β-butyllactone, etc. Examples of aromatic solvents include pyridine and quinoline. Examples of sulfoxide solvents include dimethyl sulfoxide and methylphenyl sulfoxide. Among these, preferred examples include amide solvents such as N-methyl-2-pyrrolidone and nitrogen-containing aromatic solvents such as pyridine. Of these, a mixed solvent of N-methyl-2-pyrrolidone and pyridine is more preferred. As the demethylating agent, it is preferred to use a lithium salt, 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 completed, the reaction mixture is cooled to room temperature, and a poor solvent such as hydrochloric acid or water is added dropwise to precipitate the demethylated product.

[0064] In the production of the compound represented by formula (1), if the hydroxyl group in the synthetic intermediate inhibits the target reaction, the target reaction can be carried out by appropriately protecting the hydroxyl group and removing the protecting group after the reaction. Common protecting groups such as acetyl and silyl groups can be used. Well-known reaction conditions for protection and deprotection can be used.

[0065] The reaction time in the method for producing the compound represented by formula (1) can also be determined by appropriately sampling the reaction mixture during the reaction and confirming the degree of disappearance of the raw material compounds, the degree of production of the compound represented by formula (1), etc., using a known analytical means such as liquid chromatography or gas chromatography.

[0066] After the reaction, the compound represented by formula (1) can be isolated from the reaction mixture by known methods such as recrystallization, reprecipitation, extraction, and various types of chromatography, or by an appropriate combination of these procedures.

[0067] The composition may further contain at least one other dye compound besides the compound represented by Formula (1), for example, a dichroic dye. Examples of the other dye compound include azo dyes such as monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, and at least one selected from the group consisting of these is preferred. The composition may contain one other dye compound alone or two or more other dye compounds in combination. For example, when used as a coating-type polarizing plate material, the other dye compound contained in the composition preferably has 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-type polarizing plate material, the composition preferably contains a combination of three or more dichroic dyes, including the compound represented by Formula (1), and more preferably a combination of three or more azo dyes. By containing a combination of three or more dye compounds with different maximum absorption wavelengths in the composition, for example, a film formed from the composition can achieve absorption across the entire visible light range.

[0068] When the composition contains other coloring matter, the content thereof is preferably 50 parts by mass or less, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the solid content of the composition. Within the above range, the other coloring matter can be sufficiently dispersed.

[0069] liquid crystal compound The composition contains a liquid crystalline compound including at least one of a polymerizable liquid crystalline compound and a liquid crystalline polymer compound in addition to the compound represented by formula (1). The composition may contain only one of the polymerizable liquid crystalline compound and the liquid crystalline polymer compound, or may contain both. The composition may contain two or more types of each of the polymerizable liquid crystalline compound and the liquid crystalline polymer compound. By containing at least one of the polymerizable liquid crystalline compound and the liquid crystalline polymer compound, a composition can be formed in which the compound represented by formula (1) is dispersed in the liquid crystalline compound.

[0070] The liquid crystalline polymer compound may be a thermotropic liquid crystalline polymer or a lyotropic liquid crystalline polymer, but is preferably a thermotropic liquid crystalline polymer in that it allows precise control of the film thickness.

[0071] Liquid crystals are classified into smectic liquid crystals, nematic liquid crystals, and cholesteric liquid crystals depending on the molecular arrangement structure in the liquid crystal state. Among them, smectic liquid crystals are preferably used for polarizing film applications. Therefore, the polymerizable liquid crystal compound is preferably a polymerizable smectic liquid crystal compound, and the liquid crystalline polymer compound is preferably a smectic liquid crystalline polymer compound.

[0072] By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity and a polymer compound exhibiting smectic liquid crystallinity, a polarizing film with a high degree of orientational order can be formed. The liquid crystal state exhibited by the polymerizable liquid crystal compound and the liquid crystalline polymer compound is preferably a smectic phase (smectic liquid crystal state), and from the viewpoint of achieving a higher degree of orientational order, a higher-order smectic phase (higher-order smectic liquid crystal state) is more preferable. Here, the higher-order smectic phase refers to smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase, and smectic L phase, of which smectic B phase, smectic F phase, and smectic I phase are more preferred. Polarizing films with a high degree of orientational order exhibit Bragg peaks derived from higher-order structures such as hexatic and crystalline phases in X-ray diffraction measurements. The Bragg peak refers to a peak derived from the planar periodic structure of molecular orientation. The periodic interval (order period) of a polarizing film obtained from the composition is preferably 0.3 nm or more and 0.6 nm or less. The polymerizable liquid crystal compound or liquid crystalline polymer compound may be a polymerizable smectic liquid crystal compound or a smectic liquid crystalline polymer compound that exhibits a Bragg peak derived from a higher-order structure in X-ray diffraction measurement.

[0073] Polymerizable liquid crystal compound A polymerizable liquid crystal compound is a compound that has at least one polymerizable group in the molecule and can exhibit a liquid crystal phase by being aligned. The polymerizable liquid crystal compound is preferably a compound that can exhibit a liquid crystal phase by being aligned alone. The polymerizable group refers to a functional group that can be involved in a polymerization reaction, and is preferably a radically polymerizable group.

[0074] The polymerizable liquid crystal compound is not particularly limited as long as it has at least one polymerizable group and preferably exhibits smectic liquid crystal properties, and known polymerizable liquid crystal compounds can be used. Specific examples of the polymerizable liquid crystal compound include compounds represented by the following formula (A) (hereinafter also referred to as "polymerizable liquid crystal compound (A)").

[0075] [ka]

[0076] In formula (A), k is an integer of 1 to 3. X 1 , X 2 and X 3 Each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. When k is 2 or 3, multiple X1s may be the same or different. X 1 , X 2 and X 3 At least three selected from the group consisting of Y represent a divalent 6-membered hydrocarbon ring group. 1 , Y 2 , W 1 and W 2 each independently represents a single bond or a divalent linking group. When k is 2 or 3, Y 1 may be the same or different. 1 and V 2 each independently represents an alkanediyl group having 1 to 20 carbon atoms which may have a substituent. At least one of the -CH2- moieties constituting the alkanediyl group may be substituted with -O-, -CO-, -S- or -NH-. U 1 and U 2 each independently represents a polymerizable group or a hydrogen atom, and at least one of them represents a polymerizable group.

[0077] X 1 , X 2 and X 3 Examples of the divalent aromatic group in X include a 1,4-phenylene group and a 1,4-naphthylene group (naphthalene-1,4-diyl group). Examples of the divalent alicyclic hydrocarbon group in X include a cyclohexane-1,4-diyl group. 1 , X 2 and X 3At least one of the divalent aromatic group and the divalent alicyclic hydrocarbon group in the formula (I) may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, or an n-butyl group, a cyano group, or a halogen atom. 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 having 1 to 6 carbon atoms or a phenyl group.

[0078] X 1 , X 2 and X 3 Examples of the divalent 6-membered hydrocarbon ring group in the formula include an optionally substituted 1,4-phenylene group and an optionally substituted cyclohexane-1,4-diyl group.

[0079] X 1 , X 2 and X 3 The divalent aromatic group in the formula (I) is preferably a 1,4-phenylene group which may have a substituent, more preferably an unsubstituted 1,4-phenylene group. The divalent alicyclic hydrocarbon group is preferably a cyclohexane-1,4-diyl group which may have a substituent, more preferably a trans-cyclohexane-1,4-diyl group which may have a substituent, and even more preferably an unsubstituted trans-cyclohexane-1,4-diyl group.

[0080] Y 1 and Y 2 each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include -CH2CH2-, -CHO-, -(C=O)O-, -O(C=O)O-, -N=N-, and -CR a =CR b -, -C≡C- and -CR a ═N—, where R a and R b Each of Y independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 1 is preferably —CH2CH2—, —(C═O)O— or a single bond.2 is preferably —CH2CH2— or —CH2O—.

[0081] W 1 and W 2 Each of W independently represents a single bond or a divalent linking group. The divalent linking group is, for example, at least one selected from the group consisting of -O-, -S-, -(C=O)O-, and -O(C=O)O-. 1 and W 2 are each independently preferably a single bond or —O—.

[0082] V 1 and V 2 each independently represents an alkanediyl group having 1 to 20 carbon atoms which may have a substituent. At least one of -CH2- constituting the alkanediyl group may be replaced with -O-, -CO-, -S- or -NH-.

[0083] V 1 and V 2 Examples of the alkanediyl group represented by the formula (V) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a decane-1,10-diyl group, a tetradecane-1,1-diyl group, and an icosane-1,20-diyl group. 1 and V 2 is preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably an alkanediyl group having 6 to 12 carbon atoms.

[0084] Examples of the substituent that the optionally substituted alkanediyl group having 1 to 20 carbon atoms may have include a cyano group and a halogen atom. The alkanediyl group is preferably an unsubstituted alkanediyl group, and more preferably an unsubstituted, linear alkanediyl group.

[0085] U 1and U 2 each independently represents a polymerizable group or a hydrogen atom, and at least one of them represents a polymerizable group. 1 and U 2 is preferably a polymerizable group. 1 and U 2 Preferably, both of U are polymerizable groups, and both are radically polymerizable groups. 1 and a polymerizable group represented by U 2 The polymerizable groups represented by U may be different from each other, but are preferably the same type of group. 1 and U 2 Examples of the polymerizable group in U include the same polymerizable groups as those exemplified above as the polymerizable group possessed by the polymerizable liquid crystal compound. 1 and U 2 The polymerizable group represented by the formula (I) is preferably at least one selected from the group consisting of a vinyloxy group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group, and more preferably an acryloyloxy group.

[0086] Specific examples of the polymerizable liquid crystal compound (A) include compounds represented by the following formulae (A-1) to (A-17): When the polymerizable liquid crystal compound (A) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans type.

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] Among them, the polymerizable liquid crystal compound (A) is preferably at least one selected from the group consisting of compounds represented by any of formulas (A-2), (A-3), (A-4), (A-5), (A-6), (A-7), (A-8), (A-13), (A-14), (A-15), (A-16), and (A-17). The polymerizable liquid crystal compound (A) may be used singly or in combination of two or more.

[0091] The polymerizable liquid crystal compound (A) can be produced by the method described in known documents such as Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996) and Japanese Patent No. 4719156.

[0092] Liquid crystalline polymer compound The liquid crystalline polymer compound may be a compound obtained by polymerizing the polymerizable liquid crystal compound (hereinafter also referred to as a polymer of the polymerizable liquid crystal compound), or may be any other liquid crystalline polymer compound, and is preferably a polymer of the polymerizable liquid crystal compound.

[0093] The polymer of the polymerizable liquid crystal compound may use two or more of the polymerizable liquid crystal compounds as raw material monomers, or may contain a monomer other than the polymerizable liquid crystal compound as a raw material monomer.

[0094] The content of the polymerizable liquid crystal compound in the polymer of the polymerizable liquid crystal compound is usually 1 mol% or more and 100 mol% or less, relative to the total amount of structural units derived from the polymerizable liquid crystal compound that constitute the polymer of the polymerizable liquid crystal compound. From the viewpoint of increasing the orientation of the polymer of the polymerizable liquid crystal compound, the content is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

[0095] The other liquid crystalline polymer compounds include polymer compounds having a liquid crystalline group. For example, polymer compounds serving as a backbone include polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyalkylene ethers, polyvinyl alcohols; polymethacrylic acid esters; polyacrylic acid esters; and the like, and these polymer compounds have a liquid crystalline group. Among these, polymethacrylic acid esters and polyacrylic acid esters having a liquid crystalline group are preferred.

[0096] The other liquid crystalline polymer compounds may contain two or more types of liquid crystalline groups. The liquid crystalline groups may be contained in the main chain of the polymer compound that forms the mother skeleton, in the side chain of the polymer compound that forms the mother skeleton, or in both the main chain and the side chain of the polymer compound that forms the mother skeleton. Examples of the liquid crystalline groups include groups formed by removing one hydrogen atom from a compound having at least two six-membered hydrocarbon ring structures, or groups formed by removing two hydrogen atoms from the compound.

[0097] The content of the liquid crystalline group in the other liquid crystalline polymer compound is usually 1 mol% or more and 100 mol% or less relative to the total amount of structural units constituting the polymer compound that forms the backbone of the other liquid crystalline polymer compound. From the viewpoint of increasing the orientation of the other liquid crystalline polymer compound, the content is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

[0098] When two or more polymerizable liquid crystal compounds are combined in a composition, it is preferable that at least one of them is the polymerizable liquid crystal compound (A), and more preferably, two or more of them are the polymerizable liquid crystal compound (A). By combining two or more polymerizable liquid crystal compounds, the liquid crystal phase may be temporarily maintained even at temperatures below the liquid crystal-crystalline phase transition temperature. The total content of the polymerizable liquid crystal compound (A) in the composition is preferably 40% by mass or more, more preferably 60% by mass or more, based on the total mass of all polymerizable liquid crystal compounds in the composition. All of the polymerizable liquid crystal compounds may be the polymerizable liquid crystal compound (A). When the content of the polymerizable liquid crystal compound (A) is within the above range, the polymerizable liquid crystal compounds are likely to align with a high degree of orientational order, and the compound represented by formula (1) is oriented along this order, thereby enabling the production of a polarizing film with excellent polarization performance.

[0099] From the viewpoint of increasing the orientation of the polymerizable liquid crystal compound and the liquid crystalline polymer compound, the total content of the polymerizable liquid crystal compound and the liquid crystalline polymer compound in the composition is, for example, 50 parts by mass or more, preferably 70 parts by mass or more and 99.9 parts by mass or less, more preferably 70 parts by mass or more and 99.5 parts by mass or less, even more preferably 80 parts by mass or more and 99 parts by mass or less, particularly preferably 80 parts by mass or more and 94 parts by mass or less, and even more preferably 80 parts by mass or more and 90 parts by mass or less, relative to 100 parts by mass of the solid content of the composition.

[0100] The total content of the compounds represented by formula (1) in the composition is usually 0.1 to 50 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound. When the total content of the compounds represented by formula (1) relative to the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound is 50 parts by mass or less, it tends to be possible to obtain a polarizing film with little disorder in the orientation of the polymerizable liquid crystal compound, the liquid crystalline polymer compound, and the compound represented by formula (1), and with a high degree of orientational order.

[0101] polymer compound The composition may further contain a polymer compound in addition to the compound represented by formula (1) and the polymerized liquid crystal compound. When the composition contains a polymer compound, the compound represented by formula (1) may be more easily dispersed in the composition. The polymer compound that the composition may contain is not particularly limited as long as it can disperse the compound represented by formula (1). Acrylic polymers such as polymethyl methacrylate (PMMA) are preferred because they facilitate uniform dispersion of the compound represented by formula (1). The polymer compound may also be a polymer compound obtained by polymerizing the polymerizable liquid crystal compound described above. The weight-average molecular weight of the polymer compound, calculated in terms of polystyrene, is, for example, 10,000 to 200,000, and preferably 20,000 to 150,000.

[0102] When the composition contains a polymer compound, the content thereof can be appropriately selected depending on the purpose, etc. The content of the polymer compound is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less, per 100 parts by mass of the solid content of the composition.

[0103] The composition preferably further contains a liquid medium such as a solvent and a polymerization initiator, and may further contain a photosensitizer, a polymerization inhibitor, a leveling agent, etc., as necessary.

[0104] solvent The solvent is preferably a solvent that can completely dissolve the compound represented by formula (1), the polymerizable liquid crystal compound, the liquid crystalline polymer compound, and the polymer compound, and is preferably a solvent that is inactive to the polymerization reaction of the polymerizable liquid crystal compound.

[0105] Examples of the solvent include alcohol solvents, ester solvents, ketone solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, nitrile solvents, ether solvents, chlorine-containing solvents, etc. These solvents may be used alone or in combination of two or more.

[0106] When the composition contains a solvent, the content of the solvent 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 content of the solid content in the composition is preferably 2% by mass or more and 50% by mass or less. When the solid content is 50% by mass or less, the viscosity of the composition is low, and the film obtained from the composition, for example, the thickness of the film, tends to be approximately uniform and the film tends to be less prone to unevenness. The content of the solid content can be determined taking into account the thickness of the film to be produced.

[0107] polymerization initiator The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound. The polymerization initiator is preferably a photopolymerization initiator, since it can initiate the polymerization reaction under lower temperature conditions. Specifically, a photopolymerization initiator capable of generating active radicals or acids under the action of light can be mentioned, and among these, a photopolymerization initiator that generates radicals under the action of light is preferred.

[0108] Examples of the polymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts. The polymerization initiator can be appropriately selected from known polymerization initiators depending on the purpose. The polymerization initiator can be used alone or in combination of two or more.

[0109] When the composition contains a polymerization initiator, its content can be appropriately determined depending on the type and amount of the polymerizable liquid crystal compound contained in the composition. The content of the polymerization initiator is, for example, 0.001 parts by mass or more, 0.01 parts by mass or more, 0.1 parts by mass or more, or 0.5 parts by mass or more, and, for example, 30% by mass or less, 10% by mass or less, or 8% by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound. The content of the polymerization initiator is preferably 0.001 parts by mass or more and 30 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the polymerization initiator is within the above range, polymerization can be performed without disturbing the alignment of the polymerizable liquid crystal compound.

[0110] Photosensitizers When the composition contains a photopolymerization initiator, the composition may preferably contain at least one photosensitizer. The inclusion of a photopolymerization initiator and a photosensitizer in the composition tends to further accelerate the polymerization reaction of the polymerizable liquid crystal compound. Examples of the photosensitizer include xanthone compounds such as xanthone and thioxanthone; anthracene compounds such as anthracene and alkoxy-substituted anthracene; phenothiazine and rubrene; and the like. The photosensitizers can be used alone or in combination of two or more.

[0111] When the composition contains a photosensitizer, the content of the photosensitizer in the composition may be appropriately determined depending on the type and amount of the photopolymerization initiator and the polymerizable liquid crystal compound. The content of the photosensitizer in the composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0112] Polymerization inhibitor The composition may contain at least one polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (e.g., butylcatechol), pyrogallol, radical scavengers such as 2,2,6,6-tetramethyl-1-piperidinyloxy radical, thiophenols, β-naphthylamines, and β-naphthols. By including a polymerization inhibitor in the composition, the degree of progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled.

[0113] When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0114] Leveling Agent The composition may contain at least one leveling agent. The leveling agent adjusts the fluidity of the composition and functions to make the coating film obtained by applying the composition smoother. Specific examples include surfactants. The leveling agent is preferably at least one selected from the group consisting of leveling agents containing a polyacrylate compound as the main component and leveling agents containing a fluorine atom-containing compound as the main component. The leveling agents may be used alone or in combination of two or more.

[0115] When the composition contains a leveling agent, the content of the leveling agent is preferably 0.05 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound. When the content of the leveling agent is within the above range, the polymerizable liquid crystal compound and the liquid crystalline polymer compound are easily horizontally aligned, unevenness is less likely to occur, and a smoother film, such as a polarizing film, tends to be obtained.

[0116] When the content of the leveling agent is within the above range, it is easy to horizontally align the polymerizable liquid crystal compound and the liquid crystalline polymer compound, and the obtained film tends to be smoother. When the content of the leveling agent exceeds the above range relative to the polymerizable liquid crystal compound and the liquid crystalline polymer compound, the obtained film tends to be uneven.

[0117] antioxidants The composition may contain an antioxidant. The antioxidant is not particularly limited as long as the composition can exhibit the effects of the present invention, and known antioxidants can be used. From the viewpoint of having a high inhibitory effect against light degradation of the compound represented by formula (1), the antioxidant is preferably a so-called primary antioxidant that has the effect of capturing radicals and preventing autoxidation. Therefore, it is more preferable that the antioxidant contained in the composition is at least one selected from the group consisting of phenolic compounds, alicyclic alcohol compounds, and amine compounds. The antioxidant may be used alone or in combination of two or more.

[0118] The content of the antioxidant in the composition is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 15 parts by mass, even more preferably 0.5 to 12 parts by mass, and even more preferably 10 to 10 parts by mass, per 100 parts by mass of the composition. When the content of the antioxidant is equal to or greater than the lower limit, photodegradation of the compound represented by formula (1) can be more effectively suppressed. When the content of the antioxidant is equal to or less than the upper limit, the alignment of the polymerizable liquid crystal compound is less likely to be disturbed, and a more effective suppression of photodegradation of the compound represented by formula (1) can be expected.

[0119] The composition may contain additives other than those described above. Examples of the additives include a release agent, a stabilizer, a colorant such as a bluing agent, a flame retardant, and a lubricant. When the composition contains other additives, the content of the additives is preferably more than 0% and not more than 20% by mass, more preferably more than 0% and not more than 10% by mass, based on the solid content of the composition.

[0120] The composition can be produced by a conventionally known method for preparing a composition, for example, by mixing and stirring the compound represented by formula (1), a liquid crystalline compound, and, if necessary, additives such as an antioxidant and a leveling agent.

[0121] <Compound> The compound according to this embodiment is represented by the following formula (1a).

[0122] [ka]

[0123] In formula (1a), k represents an integer of 1 or 2. When k is 2, two Ar 12 may be the same or different from each other.

[0124] Ar 11 , Ar 12 and Ar 13 each independently represents a 1,4-phenylene group or a sulfur-containing heterocyclic group which may have a substituent. 11 and Ar 12 At least one of Ar has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. 11 , Ar 12 and Ar 13 The details of Ar in formula (1) 1 , Ar 2 and Ar 3 The same applies to each of the above, and the preferred embodiments are also the same.

[0125] R 11 represents an alkylamino group which may have a polymerizable group. 11 The details of R in Equation (1) 1 The same applies to the preferred embodiments.

[0126] R 12R preferably contains at least one selected from the group consisting of cyclic or chain-like groups having 2 to 20 carbon atoms that can form an intramolecular hydrogen bond with a hydroxyl group, alkanediyloxycarbonyl groups having 2 to 20 carbon atoms, alkanediylcarbonyl groups having 2 to 20 carbon atoms, alkanediyl groups having 4 to 20 carbon atoms, and alkanediyloxy groups having 2 to 20 carbon atoms. 12 The details of R in Equation (1) 2 The same applies to the preferred embodiments.

[0127] R 13 represents a polymerizable group or a hydrogen atom. 13 The details of R in Equation (1) 3 The same applies to the preferred embodiments.

[0128] <Membrane> The film according to this embodiment may be a film containing a compound represented by formula (1) as a forming material, or may be a film obtained by using a composition containing a compound represented by formula (1) and a liquid crystalline compound as a forming material. A film made of the composition may be formed by applying the composition to a substrate and forming a film. Furthermore, when the composition contains a polymerizable liquid crystal compound, a film containing a cured product obtained by polymerizing the polymerizable liquid crystal compound may be formed by applying the composition to a substrate, forming a film, and then polymerizing and curing the polymerizable liquid crystal compound.

[0129] The composition can form a film with a high dichroic ratio, such as a polarizing film. Therefore, the film according to this embodiment includes a polarizing film formed from a composition containing a compound represented by formula (1) and a liquid crystalline compound, and has a high dichroic ratio. The composition can also form a film with a high degree of orientational order, such as a polarizing film. Therefore, the film according to this embodiment includes a polarizing film formed from a composition containing a compound represented by formula (1) and a liquid crystalline compound, and has a high degree of orientational order.

[0130] In polarizing films with a high degree of orientational order, Bragg peaks resulting from higher-order structures such as hexatic and crystalline phases are observed in X-ray diffraction measurements. Therefore, in polarizing films formed from the composition, the polymerizable liquid crystal compound or liquid crystalline polymer compound is preferably oriented so as to exhibit a Bragg peak in X-ray diffraction measurements, and more preferably exhibits "horizontal orientation," in which the molecules of the polymerizable liquid crystal compound or liquid crystalline polymer compound are oriented in the direction in which light is absorbed. A high degree of orientational order that exhibits a Bragg peak can be achieved by controlling the type of polymerizable liquid crystal compound or liquid crystalline polymer compound used, the amount of the compound represented by formula (1), and the like.

[0131] The compound represented by formula (1) and the liquid crystal compound constituting the composition used to form the film are as described above.

[0132] The membrane can be produced, for example, by a method including the following steps. Step A: forming a coating film of a composition containing a compound represented by formula (1), a liquid crystal compound, and a solvent; Step B: Removing at least a portion of the solvent from the coating; Step C: raising the temperature to a temperature at which the liquid crystalline compound undergoes a phase transition to a liquid phase or higher, and then lowering the temperature to cause the liquid crystalline compound to undergo a phase transition to a smectic phase (smectic liquid crystal state); and Step D: If necessary, polymerizing the polymerizable liquid crystal compound while maintaining the smectic phase (smectic liquid crystal state).

[0133] The coating film of the composition can be formed, for example, by applying the composition onto a substrate, an alignment film described later, etc. Alternatively, the composition may be directly applied onto a retardation film or other layer constituting a polarizing plate.

[0134] The substrate is usually a transparent substrate. When the substrate is not placed on the display surface of a display element, for example, when the laminate from which the substrate has been removed is placed on the display surface of a display element, the substrate does not need to be transparent. A transparent substrate refers to a substrate that is transparent enough to transmit light, particularly visible light, and transparency refers to a property in which the transmittance for light in the wavelength range of 380 nm to 780 nm is 80% or more. A specific example of a transparent substrate is a translucent resin substrate.

[0135] Examples of resins constituting the light-transmitting resin substrate include polyolefins, cyclic olefin resins, polyvinyl alcohol, polyethylene terephthalate, polymethacrylic acid esters, polyacrylic acid esters, cellulose esters, polyethylene naphthalate, polycarbonates, polysulfones, polyether sulfones, polyether ketones, polyphenylene sulfide, and polyphenylene oxide. From the viewpoints of availability and transparency, polyethylene terephthalate, polymethacrylic acid esters, cellulose esters, cyclic olefin resins, and polycarbonates are preferred.

[0136] The properties required for the substrate vary depending on the film configuration, but a substrate with as little retardation as possible is usually preferred. Examples of substrates with as little retardation as possible include cellulose ester films with no retardation, such as Zerotack (Konica Minolta Opto, Inc.) and Z-Tack (Fujifilm Corporation). Unstretched cyclic olefin resin substrates are also preferred. The surface of the substrate on which no film is laminated may be subjected to hard coating treatment, antireflection treatment, antistatic treatment, etc.

[0137] The thickness of the substrate is usually 5 μm or more and 300 μm or less, preferably 20 μm or more and 200 μm or less, and more preferably 20 μm or more and 100 μm or less. If the thickness is equal to or more than the lower limit, the decrease in strength is suppressed and the processability tends to be good.

[0138] Examples of a method for applying the composition to a substrate or the like include known methods such as coating methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods, and printing methods such as flexography.

[0139] Next, at least a part of the solvent contained in the coating film obtained from the composition is removed by drying or the like to form a dried coating film. Furthermore, when a polymerizable liquid crystal compound is contained in the coating film, the dried coating film is formed by drying under conditions that do not polymerize the polymerizable liquid crystal compound. Examples of methods for drying the coating film include natural drying, forced air drying, heat drying, and reduced pressure drying.

[0140] Furthermore, in order to cause the liquid crystal compound to undergo a phase transition to a liquid phase, the temperature is raised to a temperature at which the liquid crystal compound undergoes a phase transition to a liquid phase or higher, and then the temperature is lowered to cause the liquid crystal compound to undergo a phase transition to a smectic phase (smectic liquid crystal state). Such a phase transition may be carried out after or simultaneously with the removal of the solvent in the coating film.

[0141] When the composition contains a polymerizable liquid crystal compound, a film containing a cured product of the polymerizable liquid crystal compound is formed by polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound. Photopolymerization is a preferred polymerization method. In photopolymerization, the light irradiated onto the dried coating film is appropriately selected depending on the type of photopolymerization initiator contained in the dried coating film, the type of polymerizable liquid crystal compound (particularly the type and amount of polymerizable groups possessed by the polymerizable liquid crystal compound), and the amount of the light. Specific examples include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays, and actinic electron beams. Among these, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction and allows the use of photopolymerization equipment widely used in the field. It is preferable to select the type of polymerizable liquid crystal compound and photopolymerization initiator contained in the composition so that the composition can be photopolymerized by ultraviolet light. Furthermore, the polymerization temperature can be controlled by irradiating the dried coating film with light while cooling it with an appropriate cooling means. By adopting such a cooling means, polymerization of the polymerizable liquid crystal compound can be carried out at a lower temperature, and even if a substrate having a relatively low heat resistance is used, a film can be appropriately formed. During photopolymerization, a patterned film can also be obtained by performing masking and development.

[0142] Examples of the light source for the actinic energy rays include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, an LED light source emitting light in the wavelength range of 380 nm or more and 440 nm or less, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

[0143] The UV irradiation intensity is usually 10 mW / cm 2 More than 3,000mW / cm 2The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating a photopolymerization initiator. The light irradiation time may usually be from 0.1 seconds to 10 minutes, preferably from 0.1 seconds to 5 minutes, more preferably from 0.1 seconds to 3 minutes, and even more preferably from 0.1 seconds to 1 minute. When irradiating once or multiple times with such ultraviolet irradiation intensity, the cumulative light amount is 10 mJ / cm. 2 More than 3,000mJ / cm 2 It is preferable that:

[0144] By photopolymerization, the polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of a smectic phase, preferably a high-order smectic phase, to form a film. The film obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of a smectic phase has the advantage of higher polarization performance, due in part to the action of the dichroic dye, compared to conventional host-guest polarizing films, i.e., films consisting of a liquid crystal state of a nematic phase. Furthermore, it also has the advantage of superior strength compared to films coated with only a dichroic dye or lyotropic liquid crystal.

[0145] The thickness of the film can be appropriately selected depending on the display device to which it is applied, and is preferably 0.5 μm to 10 μm, more preferably 1 μm to 5 μm, and even more preferably 1 μm to 3 μm.

[0146] When the film is used as a polarizing film, it is preferably formed on an alignment film. The alignment film has an alignment control force that aligns the polymerizable liquid crystal compound and the liquid crystalline polymer compound in the desired direction. The alignment film preferably has solvent resistance that prevents the liquid crystal compound containing at least one of the polymerizable liquid crystal compound and the liquid crystalline polymer compound from dissolving when applied, and also has heat resistance during heat treatment for removing the solvent and orienting the polymerizable liquid crystal compound. Examples of such alignment films include alignment films containing an orienting polymer, photo-alignment films, and groove alignment films having a concavo-convex pattern or multiple grooves on the surface. Photo-alignment films are preferred from the viewpoints of alignment angle precision and quality.

[0147] <Laminate> The laminate according to this embodiment may include a film containing the compound represented by formula (1) as a forming material, or may include a film formed from a composition containing the compound represented by formula (1) and a liquid crystalline compound. The laminate may include a substrate and a film containing the compound represented by formula (1) as a forming material and disposed on the substrate, or may include a substrate, an alignment film disposed on the substrate, and a film containing the compound represented by formula (1) as a forming material and disposed on the alignment film. The film containing the compound represented by formula (1) as a forming material may constitute a polarizing film. The substrate may also be a retardation film. The laminate can constitute, for example, a polarizing plate. The laminate can be produced, for example, by forming a film on a substrate in accordance with the above-described film production method.

[0148] From the viewpoint of flexibility and visibility of the display device, the thickness of the laminate is preferably 10 μm or more and 300 μm or less, more preferably 20 μm or more and 200 μm or less, and even more preferably 25 μm or more and 100 μm or less.

[0149] When the laminate includes a retardation film as the substrate, the thickness of the retardation film can be appropriately selected depending on the display device to which it is applied.

[0150] <Display device> The display device of this embodiment includes the laminate, which may be a polarizing plate. The display device can be obtained, for example, by bonding the laminate as a polarizing plate to the surface of the display device via a pressure-sensitive adhesive layer. A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light source. Examples of display devices include liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, electron emission display devices (e.g., field emission display devices (FEDs) and surface field emission display devices (SEDs)), 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 having digital micromirror devices (DMDs)), and piezoelectric ceramic displays. Liquid crystal display devices include transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, and projection liquid crystal display devices. These display devices may display two-dimensional images or stereoscopic display devices displaying three-dimensional images. In particular, organic EL display devices and touch panel display devices are preferred as display devices, and organic EL display devices are particularly preferred. [Example]

[0151] The present invention will be described in more detail below with reference to examples, but is not limited to these examples. Unless otherwise specified, "parts" and "%" are by weight. "Room temperature" and "RT" refer to 23°C.

[0152] Example 1: Synthesis of Compound 1-1 To synthesize compound 1-1, compounds 1-1-a, 1-1-b, and 1-1-c were first synthesized, followed by deacetylation to obtain compound 1-1.

[0153] Synthesis of compound 1-1-a Ethyl 4-aminobenzoate (1.65 g, 10.0 mmol), 35% hydrochloric acid (2.65 mL, 30.0 mmol), and water (25.0 mL) were mixed and cooled to 0 to 5°C. A solution of sodium nitrite (0.724 g, 1.05 mmol) in water (1.3 mL) was added dropwise. The mixture was then stirred for 1 hour while maintaining the temperature at 0 to 5°C. A solution of amidosulfuric acid (49.0 mg, 0.505 mmol) in water (0.3 mL) was added to prepare a diazotane solution. Meanwhile, 3-aminophenol (2.183 g, 20.0 mmol), sodium acetate (4.14 g, 50.5 mmol), and water (75.0 mL) were mixed and cooled to 0 to 5°C. The entire diazotane solution prepared above was added dropwise. After the dropwise addition, the mixture was heated to room temperature and stirred for 1 hour. The precipitated solid was filtered off to obtain compound 1-1-a (2.28 g, yield 80%).

[0154] [ka]

[0155] Synthesis of compound 1-1-b Compound 1-1-a (0.856 g, 3.00 mmol), DMAP (N,N-dimethylaminopyridine, 38.0 mg, 0.301 mmol), triethylamine (0.365 g, 3.61 mmol), and chloroform (60.0 mL) were mixed and cooled to 0 to 5°C, and acetic anhydride (0.368 g, 3.60 mmol) was added dropwise. The reaction solution was then warmed to room temperature and stirred for 21 hours. Water was added to the reaction solution, and the organic layer was dried over magnesium sulfate and concentrated. The resulting solid was purified by silica gel column chromatography using chloroform / methanol as a developing solvent to obtain compound 1-1-b (0.232 g, 24% yield).

[0156] [ka]

[0157] Synthesis of compound 1-1-c Compound 1-1-b (0.213 g, 0.651 mmol), 35% hydrochloric acid (0.20 mL, 2.10 mmol), acetic acid (3.5 mL), and water (0.9 mL) were mixed and cooled to 0 to 5 °C. A solution of sodium nitrite (67.0 mg, 0.971 mmol) in water (0.1 mL) was added dropwise. The mixture was then stirred for 30 minutes while maintaining the temperature at 0 to 5 °C. A solution of amidosulfuric acid (32.0 mg, 0.330 mmol) in water (0.2 mL) was added to prepare a diazotane solution. Meanwhile, N,N-dimethylaniline (0.236 g, 1.95 mmol), sodium acetate (0.320 g, 3.90 mmol), methanol (4.3 mL), and water (4.3 mL) were mixed and cooled to 0 to 5 °C. The entire diazotane solution prepared above was added dropwise. After the dropwise addition, the temperature was raised to room temperature, and the precipitated solid was filtered off to obtain compound 1-1-c (0.282 g, yield 94%).

[0158] [ka]

[0159] Synthesis of Compound 1-1 Compound 1-1-c (0.260 g, 0.566 mmol), potassium carbonate (0.162 g, 1.17 mmol), methanol (5.0 mL), and tetrahydrofuran (5.0 mL) were mixed and stirred at room temperature for 4 hours. The reaction solution was neutralized with aqueous ammonium chloride solution, and the organic layer was concentrated, diluted with ethyl acetate, and separated with water and brine. The organic layer was dried over magnesium sulfate and concentrated to obtain a solid. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent and further purified by reprecipitation from chloroform / methanol to obtain compound 1-1 (0.164 g, yield 69%).

[0160] [ka]

[0161] 1H-NMR (400MHz, CDCl3): δ(ppm)=13.07(s,1H),8.20(d,2H),8.05(d,1H),7.95-7.92(m ,4H),7.59(dd,1H),7.49(d,1H),6.77(d,2H),4.43(q,2H),3.13(s,6H),1.44(t,3H).

[0162] In compound 1-1, the chemical shift of the hydroxyl group in CDCl3 is 13.07 ppm, reflecting the formation of an intramolecular hydrogen bond.

[0163] Example 2: Synthesis of Compound 1-2 To synthesize compound 1-2, first compound 1-2-a was synthesized, followed by compound 1-2-b, compound 1-2-c, and compound 1-2-d, which were then synthesized. Compound 1-2 was then obtained by dehydration condensation esterification.

[0164] Synthesis of compound 1-2-a Sodium bisulfite (78.0 g, 750 mmol) and water (150 mL) were mixed and heated to 70 °C, followed by dropwise addition of 37% aqueous formaldehyde solution (44.3 mL, 600 mmol). After the entire amount was added, the mixture was cooled to 40 °C, and aniline (45.7 mL, 500 mmol) was added dropwise over 1 hour, followed by stirring for 9 hours. The mixture was then cooled to 0 °C, and the precipitated solid was filtered off to obtain compound 1-2-a (96.0 g, 100% yield).

[0165] [ka]

[0166] 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 mixed and cooled to 0°C to 5°C. 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°C to 5°C to prepare a diazo solution. Meanwhile, compound 1-2-a (15.7 g, 75.0 mmol) and water (200 mL) were mixed and cooled to 0°C to 5°C. The entire amount of the diazo solution prepared above was added dropwise. After the addition, the mixture was stirred at 0°C to 5°C for 3 hours, then warmed to room temperature and stirred for 16 hours. Sodium hydroxide (24.0 g, 600 mmol) was then added, and the mixture was heated to 90°C and stirred for 2 hours. After cooling to room temperature, hydrochloric acid (52 mL, 589 mmol) was added dropwise, and the precipitated solid was filtered and washed with water to obtain solid Compound 1-2-b, which was used in the subsequent diazo coupling without purification.

[0167] [ka]

[0168] 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) and cooled to 0 to 5°C. 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 to 5°C to prepare a diazotane solution. Meanwhile, 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 and cooled to 0 to 5°C. The entire amount of the diazotane solution prepared above was added dropwise. After the dropwise addition, the mixture was stirred at 0 to 5°C for 2 hours, and then the temperature was raised to room temperature. The precipitated solid was filtered off and washed with acetonitrile / water to obtain compound 1-2-c (13.9 g, 69% yield based on 4-amino-2-methoxybenzoic acid).

[0169] 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. After cooling to room temperature, hydrochloric acid (28 mL, 317 mmol) was added dropwise, and the precipitated solid was filtered and washed with water to obtain compound 1-2-d (15.0 g, 104% yield).

[0170] [ka]

[0171] Synthesis of Compound 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 h. Water (150 mL) was added to the reaction solution, and the precipitated solid was filtered and washed with methanol. The resulting solid was purified by silica gel column chromatography using chloroform as a developing solvent and further purified by reprecipitation from chloroform / methanol to obtain compound 1-2 (1.93 g, 29% yield).

[0172] [ka]

[0173] 1 H-NMR (400MHz, CDCl3): 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).

[0174] 1H-NMR(400MHz,DMSO-d6):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)

[0175] In compound 1-2, the chemical shift of the hydroxyl group in CDCl3 is 10.98 ppm, reflecting the formation of an intramolecular hydrogen bond. In addition, the difference in the chemical shift of the hydroxyl group proton (10.78 ppm) between the low-polarity deuterated solvent CDCl3 and the high-polarity deuterated solvent DMSO-d6 is only 0.2 ppm, also reflecting the formation of an intramolecular hydrogen bond.

[0176] Example 3: Synthesis of Compounds 1-64 Diazo coupling reaction gave compound 1-64.

[0177] Synthesis of Compounds 1-64 4-Aminoazobenzene-4'-butylbenzoate (0.595 g, 2.00 mmol), acetic acid (6.00 mL), water (6.00 mL), and 35% hydrochloric acid (0.530 mL, 6.00 mmol) were mixed and cooled to 0°C to 5°C. A solution of sodium nitrite (0.146 g, 2.11 mmol) in water (0.4 mL) was added dropwise and stirred for 30 minutes while maintaining the temperature at 0°C to 5°C to prepare a diazo solution. Meanwhile, 3-(dimethylamino)phenol (0.411 g, 2.99 mmol), sodium acetate (0.662 g, 8.07 mmol), water (5.0 mL), and methanol (7.5 mL) were mixed and cooled to 0°C to 5°C. The entire diazo solution prepared earlier was added dropwise and stirred for 1 hour while maintaining the temperature at 0°C to 5°C. The mixture was then warmed to room temperature, and the precipitated solid was collected by filtration. The obtained solid was purified by silica gel column chromatography using chloroform / methanol (99:3) as a developing solvent, and further purified by reprecipitation from chloroform / methanol to obtain compound 1-64 (0.153 g, yield 17%).

[0178] [ka]

[0179] 1 H-NMR (400MHz, CDCl3): δ(ppm)=15.14(br,1H),8.20(d,2H),8.05(d,2H),7.96(d,2H),7.83(d,2H),7.52(d ,2H),6.48(dd,1H),6.05(d,1H),4.37(t,2H),3.15(s,6H),1.79(quin,2H),1.56-1.47(m,2H),1.01(t,3H).

[0180] In compound 1-64, the chemical shift of the hydroxyl group in CDCl3 is 15.14 ppm, suggesting that an intramolecular hydrogen bond is formed.

[0181] Comparative Example 1: Synthesis of Compound C-1 To synthesize compound C-1, the aforementioned compound 1-2-a was first synthesized, followed by dehydration condensation esterification to obtain compound C-1.

[0182] 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, EDC·HCl (0.233 g, 1.22 mmol) was added, and the reaction solution was stirred at room temperature for 18 hours. Water was added to the reaction solution, and the precipitated solid was filtered and washed with methanol. The resulting solid was purified by silica gel column chromatography using chloroform as a developing solvent and further purified by reprecipitation from water / methanol to obtain compound C-1 (0.064 g, 12% yield).

[0183] [ka]

[0184] 1 H-NMR (400MHz, CDCl3): 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).

[0185] 1 H-NMR (400MHz, DMSO-d6): 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).

[0186] Unlike the compounds in the examples, the chemical shift of the hydroxyl group in C-1 in CDCl3 is 4.77 ppm, reflecting the absence of intramolecular hydrogen bonds. Furthermore, the difference in the chemical shift of the hydroxyl group proton (9.64 ppm) between the low-polarity deuterated solvent CDCl3 and the high-polarity deuterated solvent DMSO-d6 is large at 4.87 ppm, indicating that the compound is significantly affected by the polarity difference of the deuterated solvent. This also reflects the absence of intramolecular hydrogen bonds.

[0187] Example 11: Preparation of composition E11 containing compound 1-1 The following components were mixed and stirred at 80° C. for 1 hour to obtain composition E1. ·Polymerizable liquid crystal compound (A-6) 75 parts by mass ·Polymerizable liquid crystal compound (A-7) 25 parts by mass ·Compound (1-1) 4.0 parts by mass Polymerization initiator: 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan) 6 parts by mass Leveling agent: 1.2 parts by mass of polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) Solvent: o-xylene 250 parts by weight

[0188] Polymerizable liquid crystal compound (A-6) [ka]

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

[0190] The polymerizable liquid crystal compound (A-6) was synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). The polymerizable liquid crystal compound (A-7) was also produced in accordance with this method.

[0191] Examples 12 and 13: Preparation of Compositions E12 and E13 Compositions E12 and E13 of Examples 12 and 13 were obtained in the same manner as in Example 11, except that compounds 1-2 and 1-64 were used instead of compound 1-1, respectively.

[0192] Comparative Example 1: Preparation of Composition C11 A composition C11 of Comparative Example 11 was obtained in the same manner as in Example 11, except that compound C-1, the synthesis method of which was described above, was used instead of compound 1-1.

[0193] Polarizing plate manufacturing 1. Formation of alignment layer A glass substrate was used as a transparent substrate. A 2% by mass aqueous solution (composition for forming an alignment layer) of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate by spin coating, and after drying, a film with a thickness of 100 nm was formed. Subsequently, an alignment film was formed by rubbing the surface of the obtained film, and a substrate with an alignment film formed on the glass substrate was obtained.

[0194] 2. Formation of polarizing film The composition obtained above was applied by spin coating onto the alignment film of the substrate obtained above, and then heated and dried on a hot plate at 120°C for 3 minutes.Then, it was quickly cooled to below 70°C (the temperature at which the film exhibits a smectic liquid crystal phase when cooled), thereby obtaining a laminate with a dry film formed on the alignment film.

[0195] Next, ultraviolet light was applied using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.) at an exposure dose of 1000 mJ / cm 2 The dried film was irradiated with light of 365 nm (reference wavelength), whereby the polymerizable liquid crystal compound contained in the dried film was polymerized while maintaining the liquid crystal state of the composition, and a polarizing film was formed from the dried film to obtain a polarizing plate.

[0196] <Evaluation> The dichroic ratio of the resulting polarizing plate was measured as follows. The absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction at the maximum absorption wavelength (λmax) of the polarizing film of the polarizing plate were measured by the double-beam method using a spectrophotometer (Shimadzu UV-3150) equipped with a folder containing the polarizing plate. A mesh was installed on the reference side of the folder to cut the amount of light by 50%. The ratio (A2 / A1) was calculated from the measured absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction, and this was used as the dichroic ratio (DR). The results are shown in Table 1.

[0197] [Table 1]

[0198] It is clear from Table 1 that a polarizing plate having a film made of a composition containing a compound represented by formula (1) can achieve a high dichroic ratio.

Claims

1. A composition comprising a compound represented by the following formula (1) and a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound: 【Chemical 1】 [In formula (1), n ​​represents an integer of 1 or 2. Ar １ , Ar ２ and Ar ３ each independently represents a 1,4-phenylene group or a sulfur-containing heterocyclic group, which may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group, and a methoxy group. １ , Ar ２ and Ar ３ At least one of the groups has at least one hydroxyl group capable of forming an intramolecular hydrogen bond, and the hydroxyl group is directly bonded to the 1,4-phenylene group or the sulfur-containing heterocyclic group. R １ represents an alkylamino group which may have a polymerizable group. Ar １ When R does not have a hydroxyl group capable of forming an intramolecular hydrogen bond or has a hydroxyl group on the carbon atom adjacent to the carbon atom to which the azo group is bonded, ２ represents at least one group selected from the group consisting of an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediylcarbonyl group having 2 to 20 carbon atoms, and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms. Ar １ R is a hydroxyl group that can form an intramolecular hydrogen bond. ２ is on the carbon atom adjacent to the carbon atom to which it is bonded, R ２ represents a cyclic or chain group having 2 to 20 carbon atoms that can form a hydrogen bond with the hydroxyl group. R ３ represents a polymerizable group or a hydrogen atom. When n is 2, two Ar ２ may be the same or different from each other.]

2. 2. The composition according to claim 1, wherein the polymerizable liquid crystal compound is a polymerizable smectic liquid crystal compound, and the liquid crystalline polymer compound is a smectic liquid crystalline polymer compound.

3. The composition according to claim 1 or 2, wherein the polymerizable liquid crystal compound comprises a compound represented by the following formula (A): 【Chemistry 2】 In formula (A), m represents an integer of 1 to 3. X １ , X ２ and X ３ each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. When m is 2 or 3, a plurality of X １ may be the same or different. １ , X ２ and X ３ At least three selected from the group consisting of: represent a divalent 6-membered hydrocarbon ring group. Y １ , Y ２ , W １ and W ２ each independently represents a single bond or a divalent linking group. When m is 2 or 3, a plurality of Y １ may be the same or different from each other. V １ and V ２ each independently represents an alkanediyl group having 1 to 20 carbon atoms which may have a substituent. ２ At least one of - may be replaced by -O-, -CO-, -S- or -NH-. U １ and U ２ each independently represents a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group.

4. 4. The composition according to claim 1, wherein the compound represented by formula (1) has one hydroxyl group capable of forming an intramolecular hydrogen bond.

5. The compound represented by the above formula (1) is R ３ A hydroxyl group capable of intramolecular hydrogen bonding with Ar １ or a hydroxyl group capable of intramolecularly hydrogen bonding with -N=N- ２ 5. The composition of claim 1, wherein

6. A compound represented by the following formula (1a): 【Chemistry 3】 In formula (1a), k represents an integer of 1 or 2. Ar １１ , Ar １２ and Ar １３ each independently represents a 1,4-phenylene group or a sulfur-containing heterocyclic group which may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a methyl group, and a methoxy group. １１ and Ar １２ At least one of the groups has at least one hydroxyl group capable of forming an intramolecular hydrogen bond, and the hydroxyl group is directly bonded to the 1,4-phenylene group or the sulfur-containing heterocyclic group. R １１ represents an alkylamino group which may have a polymerizable group. Ar １１ When R does not have a hydroxyl group capable of forming an intramolecular hydrogen bond or has a hydroxyl group on the carbon atom adjacent to the carbon atom to which the azo group is bonded, １２ represents at least one group selected from the group consisting of an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediylcarbonyl group having 2 to 20 carbon atoms, and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms. Ar １１ R is a hydroxyl group that can form an intramolecular hydrogen bond. １２ is on the carbon atom adjacent to the carbon atom to which it is bonded, R １２ represents a cyclic or chain group having 2 to 20 carbon atoms that can form a hydrogen bond with the hydroxyl group. R １３ represents a polymerizable group or a hydrogen atom. When k is 2, two Ar １２ may be the same or different from each other.]

7. 7. The compound according to claim 6, wherein the number of hydroxyl groups capable of forming an intramolecular hydrogen bond is 1.

8. Ar １１ , Ar １２ and Ar １３ The compound according to claim 6 or 7, wherein is an optionally substituted 1,4-phenylene group.

9. R １３ A hydroxyl group capable of forming an intramolecular hydrogen bond with Ar １１ or Ar 12 has a hydroxyl group capable of forming an intramolecular hydrogen bond with —N═N—.

10. A film formed from the composition according to any one of claims 1 to 5.

11. A laminate comprising the film of claim 10.

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

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