Azo compound, composition, film, laminate and display device

Abstract

To provide an azo compound excellent in storage stability in a composition state, and capable of forming a high quality film.SOLUTION: An azo compound is represented by formula (1A). L1 and L2 are bivalent binding groups, or single bonds. y is 1 or 2. p and q is 0 or 1, and at least one of them is 1. X is an oxygen atom, or NR5, and R5 is a hydrogen atom, or an aliphatic hydrocarbon group. R12, R13, and R14 are aliphatic hydrocarbon groups and the like, and may have polymerizable groups. Q is a single bond, or a group selected from the group consisting of -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -N=N-, -NHC(=O)-, and -C(=O)NH-. Ar1, Ar2, and Ar3 are 1,4-phenylene groups, or bivalent sulfur-containing aromatic heterocyclic groups. When y is 2, two Ar3 may be same or different.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Polarizing films containing dichroic dyes are known as polarizing films (optical films) used in liquid crystal display devices, etc. Patent Document 1 proposes an azo compound having a fused heterocyclic group as a dichroic dye. Patent Document 2 also proposes a dichroic dye compound having a fused heterocyclic group with improved solubility. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 64-70585 [Patent Document 2] International Publication No. 2017 / 090668 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the polarizing film-forming composition containing the azo compound described in Patent Document 1 has insufficient storage stability, and defects may occur in the film formed, preventing the production of a high-quality polarizing film. Furthermore, further improvement in solubility is also required for the dichroic dye compound described in Patent Document 2. An object of the present invention is to provide an azo compound that can form a high-quality film even when stored for a predetermined period of time in the form of a composition containing a solvent. [Means for solving the problem]

[0005] The present invention provides the following [1] to [9]. [1] An azo compound represented by the following formula (1A): [ka] [In formula (1A), L 1 and L 2 each independently represents a divalent linking group formed from at least one selected from the group consisting of a methylene group, an oxygen atom, and a carbonyl group, or a single bond. y represents an integer of 1 or 2; p and q each independently represent 0 or 1, and at least one of p and q is 1. R 12 , R 13 and R 14 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a trialkylsiloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, or a phenyl group, which may have a substituent; R 12 , R 13 or R 14 The hydrogen atoms of may be substituted with polymerizable groups. X is an oxygen atom or NR 5 Represents. R 5 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R 13 may be bonded to each other to form a ring. Q represents a single bond or one group selected from the group consisting of -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -N=N-, -NHC(=O)- and -C(=O)NH-. Ar 1 , Ar 2 and Ar 3 each independently represents an optionally substituted 1,4-phenylene group or an optionally substituted divalent sulfur-containing aromatic heterocyclic group. If y is 2, two Ar 3 may be the same or different.] [2] The azo compound according to [1], represented by the following formula (1): [ka] In formula (1), L represents a divalent linking group formed from at least one selected from the group consisting of a methylene group, an oxygen atom, and a carbonyl group, or a single bond. y represents an integer of 1 or 2; R 1 represents one group selected from the group consisting of a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, a pyrrolidyl group, an oxazolidinyl group, a piperidyl group, a morpholino group, a methoxy group, and an ethoxy group, and a hydrogen atom of these groups may be substituted with a polymerizable group. R 2 , R 3 and R 4 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms; R 2 , R 3 or R 4 The hydrogen atoms of may be substituted with polymerizable groups. Q represents a single bond or one group selected from the group consisting of -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -N=N-, -NHC(=O)- and -C(=O)NH-. Ar 1 , Ar 2 and Ar 3 each independently represents an optionally substituted 1,4-phenylene group or an optionally substituted divalent sulfur-containing aromatic heterocyclic group. If y is 2, two Ar 3 may be the same or different.] [3] The azo compound according to [1] or [2], wherein Q in the formula (1A) or (1) is -N=N-. [4] In the formula (1A) or (1), Ar 1 and Ar 2 At least one of the above is a divalent sulfur-containing aromatic heterocyclic group. [5] A composition comprising the azo compound according to any one of [1] to [4] and a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound. [6] The composition according to [5], wherein the liquid crystal compound is a smectic liquid crystal compound. [7] A film formed from the composition according to [5] or [6]. [8] A laminate comprising the film according to [7]. [9] A display device comprising the film according to [7] or the laminate according to [8]. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide an azo compound that can form a high-quality film even when stored for a predetermined period of time in the form of a composition containing a solvent. 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 from the numerical values ​​exemplified as numerical ranges. 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 within the scope that does not impair the spirit of the present invention.

[0008] Azo compound The azo compound according to this embodiment is represented by the following formula (1A): The azo compound represented by the following formula (1A) (hereinafter also referred to as azo compound (1A)) may be used, for example, as a dichroic dye to form a polarizing film. That is, the azo compound (1A) may be an active ingredient constituting the dichroic dye. The azo compound (1A) has excellent stability as a composition, and can form a high-quality film, even when stored for a predetermined period of time in the form of a composition containing a solvent. The stability as a composition means that aggregation, precipitation, etc. of the azo compound (1A) in the composition is suppressed. Furthermore, a high-quality film may be, for example, a film in which precipitation of the azo compound (1A) is suppressed, or a polarizing film in which the occurrence of alignment defects is suppressed. Furthermore, storage for a predetermined period of time means, for example, storage at room temperature (25°C) for one day or more, preferably five days or more.

[0009] [ka]

[0010] In formula (1A), L 1 and L 2 each independently represents a divalent linking group formed from at least one selected from the group consisting of a methylene group, an oxygen atom, and a carbonyl group, or a single bond. y represents an integer of 1 or 2. p and q each independently represent 0 or 1, with at least one of p and q being 1. R 12 , R 13 and R 14 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a trialkylsiloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, or a phenyl group, which may have a substituent; R 12 , R 13 or R 14 The hydrogen atom of may be substituted with a polymerizable group. X is an oxygen atom or NR 5 Represents R 5 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R 13and may be bonded to each other to form a ring. Q represents a single bond or a group selected from the group consisting of -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -N=N-, -NHC(=O)-, and -C(=O)NH-. Ar 1 , Ar 2 and Ar 3 each independently represents a 1,4-phenylene group which may have a substituent or a divalent sulfur-containing aromatic heterocyclic group which may have a substituent. When y is 2, two Ar 3 may be the same or different.

[0011] L 1 or L 2 Specific examples of the divalent linking group represented by the formula (1A) include an alkylene group having 1 to 4 carbon atoms, an alkyleneoxy group having 1 to 4 carbon atoms or an oxyalkylene group having 1 to 4 carbon atoms, an alkyleneoxycarbonyl group having 1 to 4 carbon atoms or a carbonyloxyalkylene group having 1 to 4 carbon atoms, an alkylenecarbonyloxy group having 1 to 4 carbon atoms or an oxycarbonylalkylene group having 1 to 4 carbon atoms, an alkylenecarbonyl group having 1 to 4 carbon atoms or a carbonylalkylene group having 1 to 4 carbon atoms, etc. From the viewpoint of stability as a composition containing the azo compound (1A), in formula (1A), an oxygen atom and Ar 1 Alternatively, the number of atoms directly connecting X (the number of atoms in the main chain) may be 1 or more and 4 or less, preferably 1 or more and 3 or more and 2 or more and 3 or less. That is, the number of atoms in L excluding hydrogen atoms and carbonyl oxygen 1 and L 2 The number of atoms constituting the group may be 1 or more and 4 or less, preferably 1 or more and 3 or less, or 2 or more and 3 or less.

[0012] From the viewpoint of the stability of the azo compound (1A), it is preferable that L1 and L2 are selected so that the formula (1A) does not contain an oxygen-oxygen bond or an oxygen-nitrogen bond. That is, when p=1, L 1 may be expressed by the following formula (2), and when q=1, L 2 may be expressed by the following formula (2a):

[0013] [ka]

[0014] In formula (2), x represents an integer of 0 to 4. P represents a single bond or a group selected from the group consisting of -O-, -OC(=O)-, and -C(=O)O-. However, when P is a single bond, -O-, or -OC(=O)-, x represents an integer of 1 to 4. P is preferably a single bond or -O-. When P is -C(=O)O-, x is an integer of 0 to 4, preferably 1, 2, or 3, and more preferably 2. When P is a single bond, -O-, or -OC(=O)-, x is preferably 2 or 3, and more preferably 2.

[0015] In formula (2a), z represents an integer of 0 to 4. 1 represents a single bond, -C(=O)- or -C(=O)O-. However, P 1 When is a single bond or -C(=O)O-, z represents an integer of 1 to 4. 1 is preferably a single bond or -O-. When P is -C(=O)-, z is an integer from 0 to 4, preferably 1, 2 or 3, more preferably 2. P 1 When is a single bond or —O—, z is preferably 2 or 3, and more preferably 2.

[0016] R 12 , R 13 and R 14 R each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a trialkylsiloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, or a phenyl group. 12 , R 13 and R 14 represents preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a phenyl group, and more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0017] R 12 , R13 or R 14 The aliphatic hydrocarbon group, alkyloxy group, trialkylsiloxy group, trialkylsilyl group, or phenyl group represented by the formula (I) may each independently have a substituent. 12 , R 13 or R 14 Examples of the substituent in R include a polymerizable group, a halogen atom (such as a fluorine atom or a chlorine atom), a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group. 12 , R 13 or R 14 When has substituents, the total number thereof is, for example, 1 to 10, and preferably 1 to 6.

[0018] R 12 , R 13 or R 14 In the aliphatic hydrocarbon group, alkyloxy group, trialkylsiloxy group, trialkylsilyl group, or phenyl group represented by the formula (I), at least one hydrogen atom may be substituted with a polymerizable group. Examples of the polymerizable group include a (meth)acrylate group ((meth)acryloyloxy group), a styryl group (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 12 , R 13 or R 14 is substituted with a polymerizable group, the total number thereof is, for example, 1 or 2, and preferably 1.

[0019] R 12 , R 13 or R 14The number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is preferably 1 to 8, more preferably 1 to 6. The aliphatic hydrocarbon group may be either branched or linear. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. Specific examples of the alkyl group include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, tert-butyl groups, hexyl groups, 2,3-dimethyl-2-butyl groups (1,1,2-trimethylpropyl groups), and octyl groups. R 12 , R 13 and R 14 At least one of R is preferably a branched aliphatic hydrocarbon group, more preferably a branched alkyl group. The branched aliphatic hydrocarbon group has, for example, 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms. 12 , R 13 and R 14 The total number of carbon atoms contained in may be, for example, 3 or more and 24 or less, preferably 6 or more and 18 or less, and more preferably 6 or more and 16 or less.

[0020] R 12 , R 13 or R 14 The number of carbon atoms in the alkyloxy group represented by the formula (I) is preferably 1 to 8, or 1 to 6. The alkyl group portion of the alkyloxy group may be either branched or linear. 12 , R 13 and R 14 At least one of the R groups in formula (1A) is preferably a branched alkyloxy group. The branched alkyloxy group has, for example, 3 to 8 carbon atoms, and preferably 3 to 6 carbon atoms. 12 , R 13 and R 14 The total number of carbon atoms contained in may be, for example, 3 or more and 12 or less, and preferably 6 or more and 12 or less, or 6 or more and 10 or less. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and a hexyloxy group.

[0021] R 12 , R 13 or R 14 The number of carbon atoms in the alkyl portion of the trialkylsiloxy group or trialkylsilyl group represented by the formula (I) is 1 to 6, preferably 1 to 5, or 1 to 4. The total number of carbon atoms in the alkyl portion of the trialkylsiloxy group or trialkylsilyl group is preferably 3 to 8, or 3 to 6. Specific examples of the trialkylsiloxy group include a trimethylsilyloxy group, a triethylsilyloxy group, and a tert-butyldimethylsilyloxy group. Furthermore, examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.

[0022] X is an oxygen atom or NR 5 Represents R 5 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms. 5 The number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is preferably 1 to 8, or 1 to 6. The aliphatic hydrocarbon group may be either branched or linear. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. Specific examples of the alkyl group include methyl groups, ethyl groups, and propyl groups. In addition, R 5 is R 13 may be bonded to each other to form a ring. 5 and R 13 When R and R are bonded to each other to form a ring, q is preferably 0. The ring formed may be a nitrogen-containing aliphatic ring, and the number of members thereof may be, for example, 5 or 6. 5 and R 13 Examples of the ring formed by bonding together include a pyrrolidyl group, a piperidyl group, an oxazolidinyl group, and a morpholyl group.

[0023] The azo compound represented by formula (1A) may preferably satisfy p=1 and q=0 in order to further increase the dichroic ratio, and more preferably may be an azo compound represented by the following formula (1) (hereinafter also referred to as azo compound (1)):

[0024] [ka]

[0025] In formula (1), L represents a divalent linking group formed from at least one selected from the group consisting of a methylene group (-CH2-), an oxygen atom (-O-), and a carbonyl group (-C(=O)-), or a single bond. Specific examples of the divalent linking group represented by L include an alkylene group having 1 to 4 carbon atoms, an alkyleneoxy group having 1 to 4 carbon atoms, an alkyleneoxycarbonyl group having 1 to 4 carbon atoms, an alkylenecarbonyloxy group having 1 to 4 carbon atoms, and an alkylenecarbonyl group having 1 to 4 carbon atoms. From the viewpoint of stability as a composition of azo compound (1), in formula (1), the oxygen atom and Ar 1 The number of atomic groups directly linking L (the number of atoms in the main chain) may be 1 or more and 4 or less, preferably 1 or more and 3 or less, or 2 or more and 3 or less. That is, the number of atoms constituting L excluding hydrogen atoms and carbonyl oxygen may be 1 or more and 4 or less, preferably 1 or more and 3 or less, or 2 or more and 3 or less. The divalent linking group represented by L may be represented, for example, by the following formula (2), and the azo compound (1) may be represented by the following formula (1a).

[0026] [ka]

[0027] In formulas (2) and (1a), x represents an integer of 0 to 4. P represents a single bond or a group selected from the group consisting of -O-, -OC(=O)-, and -C(=O)O-. However, when P is a single bond, -O-, or -OC(=O)-, x represents an integer of 1 to 4. P is preferably a single bond or -O-. When P is -C(=O)O-, x is an integer of 0 to 4, preferably 1, 2, or 3, and more preferably 2. When P is a single bond, -O-, or -OC(=O)-, x is an integer of 1 to 4, preferably 2 or 3, and more preferably 2.

[0028] In formulas (1A), (1) and (1a), y represents an integer of 1 or 2. When y is 2, two Ar 3 may be the same or different.

[0029] In formulas (1) and (1a), R 1 R represents one group selected from the group consisting of methylamino, ethylamino, dimethylamino, diethylamino, ethylmethylamino, pyrrolidyl, oxazolyl, oxazolidinyl, piperidyl, morpholino, methoxy, and ethoxy. 1 is preferably a dimethylamino group, a diethylamino group, an ethylmethylamino group, a methoxy group or an ethoxy group, and more preferably a dimethylamino group or a diethylamino group. 1 At least one of the hydrogen atoms of the 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 styryl 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.

[0030] Q represents a single bond or one group selected from the group consisting of -OC(=O)-, -C(=O)O-, -C≡C-, -CH=CH-, -N=N-, -NHC(=O)- and -C(=O)NH-. Q is preferably a single bond, -OC(=O)- or -N=N-, more preferably -N=N-.

[0031] Ar 1 , Ar 2 and Ar 3 Each independently represents a 1,4-phenylene group which may have a substituent or a divalent sulfur-containing aromatic heterocyclic group which may have a substituent. Examples of sulfur-containing aromatic heterocyclic groups include a thiazolediyl group, a benzothiazolediyl group, and a thienothiazolediyl group. Of these, a benzothiazolediyl group or a thienothiazolediyl group is preferred, a thienothiazolediyl group is more preferred, and a thieno[2,3-d]thiazole-2,5-diyl group is even more preferred. Ar 1 and Ar 2 At least one of the groups is preferably a divalent sulfur-containing aromatic heterocyclic group which may have a substituent, more preferably a benzothiazolediyl group or a thienothiazolediyl group, and even more preferably Ar 2 is a benzothiazolediyl group or a thienothiazolediyl group, and particularly preferably Ar 2 is a thienothiazolediyl group. 1 , Ar 2 and Ar 3 Examples of the substituent in Ar include a halogen atom, a hydroxy group, a methyl group, and a methoxy group, and are preferably a fluorine atom, a chlorine atom, a hydroxy group, a methyl group, or a methoxy group, more preferably a fluorine atom, a chlorine atom, a hydroxy group, or a methyl group, and even more preferably a fluorine atom, a chlorine atom, or a methyl group. 1 , Ar 2 and Ar 3 The number of substituents in each group is independently 0, 1 or 2, and preferably 0 or 1.

[0032] R 2 , R3 and R 4 R each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms. 2 , R 3 or R 4 The number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is preferably 1 to 8, or 1 to 6. The aliphatic hydrocarbon group may be either branched or linear. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. Specific examples of the alkyl group include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, tert-butyl groups, hexyl groups, 2,3-dimethyl-2-butyl groups (1,1,2-trimethylpropyl groups), and octyl groups. R 2 , R 3 and R 4 At least one of R is preferably a branched aliphatic hydrocarbon group, more preferably a branched alkyl group. The branched aliphatic hydrocarbon group has, for example, 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms. 2 , R 3 and R 4 The total number of carbon atoms contained in R may be, for example, 3 or more and 24 or less, preferably 6 or more and 18 or less, and more preferably 6 or more and 16 or less. 2 , R 3 or R 4 In the aliphatic hydrocarbon group represented by the formula (I), at least one of the hydrogen atoms may be substituted with a polymerizable group. 2 , R 3 or R 4 When has a polymerizable group, the total number thereof is, for example, 1 or 2, and preferably 1.

[0033] In one embodiment, R 2 , R 3 and R 4 may each independently represent an alkyloxy group having 1 to 10 carbon atoms, a trialkylsiloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, or a phenyl group, and a preferred embodiment thereof is 12 , R13 and R 14 is the same as:

[0034] Specific examples of the azo compound (1A) include compounds represented by the following formulae (1-1) to (1-105), but the present invention is not limited to these.

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] From the viewpoint of stability when made into a composition, azo compound (1A) is preferably at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-81) and (1-93) to (1-105), more preferably at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-67), and particularly preferably at least one selected from the group consisting of compounds represented by any one of formulas (1-1), (1-2), and (1-7) to (1-27).

[0041] The azo compound (1A) may have a maximum absorption wavelength (λmax) in the wavelength range of, for example, 550 nm or more and 650 nm or less. The maximum absorption wavelength of the azo compound (1A) may be preferably 560 nm or more and 640 nm or less, more preferably 570 nm or more and 630 nm or less. The maximum absorption wavelength is measured at room temperature (e.g., 25°C) for a chloroform solution of the azo compound (1A). The maximum absorption wavelength of the azo compound (1A) can be measured, for example, by using Ar 1 , Ar 2 and Ar 3 The skeletal structure of Ar 1 , Ar 2 and Ar 3 Substituents y and R 1 By appropriately selecting the above, it is possible to adjust the wavelength to a desired value.

[0042] The specific structure of the azo compound (1A) improves, for example, its solubility in solvents and its stability as a composition. This can be explained, for example, as follows: The silyloxy group substituted with an aliphatic hydrocarbon group is relatively bulky and polar. This is thought to suppress interactions between the azo compounds (1A), improving their solubility in solvents and enabling them to exhibit good compatibility with the host. Furthermore, the silyloxy group is bonded to the chromophore via the linking group L, which is thought to prevent the orientation of the chromophore from being hindered, thereby maintaining a good dichroic ratio (DR) when forming a polarizing film, for example.

[0043] Method for producing azo compounds Azo compound (1A) can be produced by appropriately applying a conventionally known synthesis method. Specifically, the azo structure (-N=N-) in azo compound (1A) 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 the salt with an aromatic compound, for example, by referring to the production examples described in paragraphs

[0220] to

[0268] of International Publication WO2016 / 136561.

[0044] Azo compound (1A) in which Q is a single bond can be synthesized, for example, by using a precursor having a dihydroxyboryl group or a dialkoxyboryl group and a precursor having a halogen atom and applying Suzuki coupling reaction conditions with reference to Netherton, MR; Fu, GC Org. Lett. 2001, 3 (26), 4295-4298.

[0045] A compound in which Q in azo compound (1A) is -OC(=O)- or C(=O)O- 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 such conditions include condensation in a solvent in the presence of an esterification condensing agent.

[0046] A compound in which Q in the azo compound (1A) is -C≡C- can be synthesized, for example, by applying Sonogashira coupling using a Pd or Cu catalyst from a precursor having an ethynyl group (-C≡CH) and a precursor having a halogen atom.

[0047] A compound in which Q in the azo compound (1A) is -C=C- can be synthesized, for example, by applying a Heck reaction using a Pd catalyst and a phosphorus ligand, using a precursor having an ethenyl group (-C=CH) and a precursor having a halogen atom.

[0048] Azo compound (1A) in which Q is -NHC(=O)- or C(=O)NH- can be synthesized, for example, by applying a dehydration condensation reaction using a precursor having a carboxy group and a precursor having an amino group. Specifically, for example, condensation can be performed in a solvent in the presence of an amidation condensing agent.

[0049] The silyloxy group substituted with an aliphatic hydrocarbon group in the azo compound (1A) can be synthesized by applying general silylation reaction conditions to a precursor having a hydroxyl group and a halogenated silane substituted with an aliphatic hydrocarbon group in the presence of a base. N For the conditions of the displace- ment reaction, see, for example, J. Am. Chem. Soc., 1972, 94, 6190.

[0050] The reaction time in the method for producing azo compound (1A) 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 azo compound (1A), etc., by known analytical means such as liquid chromatography or gas chromatography.

[0051] After the reaction, the azo compound (1A) 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.

[0052] <Dichroic dye> The dichroic dye contains at least one azo compound (1A) as an active ingredient. By including the azo compound (1A), the dichroic dye can form a polarizing film in which the occurrence of alignment defects is suppressed. The dichroic dye may contain only one azo compound (1A) or may contain a combination of two or more azo compounds (1A) with different structures. When the dichroic dye contains two or more azo compounds (1A), they may have different maximum absorption wavelengths. Furthermore, the dichroic dye may contain, in addition to the azo compound (1A), other dye compounds other than the azo compound (1A). The other dye compounds will be described later.

[0053] <Composition> The composition of this embodiment contains at least one azo compound (1A) and a liquid crystalline compound containing at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound. The composition is used, for example, as a material for forming a polarizing film. That is, the composition may be a composition for forming a polarizing film. A polarizing film obtained using the composition as a forming material is a high-quality polarizing film that maintains an excellent dichroic ratio while suppressing the occurrence of alignment defects. By containing the azo compound (1A) as a dichroic dye, the composition can form a polarizing film that is excellent in stability as a composition even after storage for a predetermined period of time and suppresses the occurrence of alignment defects.

[0054] The content of the azo compound (1A) in the composition is, for example, 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, per 100 parts by mass of the solid content of the composition. Within the above range, the azo compound (1A) can be sufficiently dispersed. This allows for efficient production of a film containing the azo compound (1A) as a forming material, with sufficient suppression of defect formation. In this specification, the solid content refers to the total amount of components in the composition excluding volatile components such as solvents. The composition may contain only one type of azo compound (1A) or a combination of two or more types with different structures. When the composition contains two or more types of azo compounds (1A), they may have different maximum absorption wavelengths.

[0055] The composition may further contain at least one other dye compound besides the azo compound (1A), 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 these groups is preferred. The composition may contain one or more of the other dye compounds alone or 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 azo compound (1A). 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 azo compound (1A), 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.

[0056] 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.

[0057] 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 azo compound (1A). The composition may contain both a polymerizable liquid crystalline compound and a liquid crystalline polymer compound, and the composition may contain two or more types of each of the polymerizable liquid crystalline compound and the liquid crystalline polymer compound. By including at least one of the polymerizable liquid crystalline compound and the liquid crystalline polymer compound in the composition, it is possible to form a composition in which the azo compound (1A) is dispersed in the liquid crystalline compound.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] The azo compound (1A) can exhibit high dichroism even when dispersed among dense molecular chains formed from at least one compound of a smectic liquid crystal polymerizable liquid crystal compound and a smectic liquid crystal polymer compound. Therefore, a composition containing a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound, particularly a liquid crystal compound containing at least one of a smectic liquid crystal polymerizable liquid crystal compound and a smectic liquid crystal polymer compound, and the azo compound (1A) can provide a polarizing film in which the occurrence of alignment defects is suppressed and which has a high dichroic ratio.

[0062] 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.

[0063] 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)"). U 1 -V 1 -W 1 -(X 1 -Y 1 ) m -X 2 -Y 2 -X 3 -W 2 -V 2 -U 2 (A)

[0064] In formula (A), m is an integer of 1 to 3. X 1 , X 2 and X 3each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. When m is 2 or 3, X 1 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 m 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.

[0065] 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. Examples of the divalent alicyclic hydrocarbon group in X include a cyclohexane-1,4-diyl group. 1 , X 2 and X 3 At 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.

[0066] X 1 , X 2 and X 3Examples 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.

[0067] 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.

[0068] 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—.

[0069] 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—.

[0070] 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-.

[0071] 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.

[0072] 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.

[0073] 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. 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 2Examples 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.

[0074] 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.

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] When two or more polymerizable liquid crystal compounds are combined in a composition, it is preferable that at least one of them is polymerizable liquid crystal compound (A), and more preferably, two or more of them are polymerizable liquid crystal compounds (A). Combining two or more polymerizable liquid crystal compounds may temporarily maintain a liquid crystal phase 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 polymerizable liquid crystal compounds (A). When the content of the polymerizable liquid crystal compound (A) is within the above range, the polymerizable liquid crystal compounds are likely to align with a high degree of orientational order, and the compound represented by formula (1A) is oriented along this order, resulting in a polarizing film with excellent polarization performance.

[0087] 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.

[0088] The content of the azo compound (1A) 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 content of the azo compound (1A) relative to the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound is 50 parts by mass or less, the orientation of the polymerizable liquid crystal compound, the liquid crystalline polymer compound, and the azo compound (1A) tends to be less disordered, and a polarizing film with a high degree of orientational order tends to be obtained.

[0089] polymer compound The composition may further contain a polymer compound in addition to the azo compound (1A), the polymerizable liquid crystal compound, and the liquid crystalline polymer compound. The inclusion of a polymer compound in the composition may facilitate the dispersion of the azo compound (1A) in the composition. The polymer compound that may be contained in the composition is not particularly limited as long as it can disperse the azo compound (1A). Acrylic polymers such as polymethyl methacrylate (PMMA) are preferred because they facilitate uniform dispersion of the azo compound (1A). 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, in terms of polystyrene, is, for example, 10,000 to 200,000, preferably 20,000 to 150,000.

[0090] 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.

[0091] 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.

[0092] solvent The solvent is preferably a solvent that can completely dissolve the azo compound (1A), the polymerizable liquid crystal compound, the liquid crystalline polymer compound, and the polymer compound, and is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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 highly inhibiting the photodegradation of the azo compound (1A), 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.

[0106] The content of the antioxidant in the composition is preferably 0.1 to 15 parts by mass, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less, 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 azo compound (1A) can be more effectively suppressed. On the other hand, 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 higher effect of suppressing photodegradation of the azo compound (1A) can be expected.

[0107] 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.

[0108] The composition can be produced by a conventionally known method for preparing a composition, for example, by mixing and stirring the azo compound (1A), a liquid crystal compound, and, if necessary, additives such as an antioxidant and a leveling agent.

[0109] <Membrane> The film according to this embodiment may be a film containing azo compound (1A) as a forming material, or may be a film obtained by using a composition containing azo compound (1A) 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.

[0110] The composition can 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 azo compound (1A) and a liquid crystalline compound and having a high degree of orientational order.

[0111] 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, the polymerizable liquid crystal compound or liquid crystalline polymer compound has a "horizontal orientation" in which the molecules are oriented in the direction of light absorption. 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 azo compound (1A), and the like.

[0112] The azo compound (1A) and the liquid crystal compound constituting the composition used to form the film are as described above.

[0113] The membrane can be produced, for example, by a method including the following steps. Step A: forming a coating film of a composition containing the azo compound (1A), 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).

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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:

[0125] 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.

[0126] 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.

[0127] 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.

[0128] <Laminate> The laminate according to this embodiment may comprise a film containing the azo compound (1A) as a forming material, or may comprise a film made of a composition containing the azo compound (1A) and a liquid crystalline compound. The laminate may comprise a substrate and a film containing the azo compound (1A) as a forming material disposed on the substrate, or may comprise a substrate, an alignment film disposed on the substrate, and a film made of the azo compound (1A) as a forming material disposed on the alignment film. The film containing the azo compound (1A) as a forming material may constitute a polarizing film. The substrate may also be a retardation film. The laminate may constitute, for example, a polarizing plate. The laminate can be produced, for example, by forming a film on a substrate according to the above-mentioned film production method.

[0129] 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.

[0130] 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.

[0131] <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 an 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]

[0132] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0133] Compound (1-1-a) and compound (1-3-a) were synthesized by a known diazo coupling method.

[0134] Synthesis Example 1: Synthesis of Compound (1-1) Compound (1-1-a) (0.139 g, 0.299 mmol) and imidazole (0.061 g, 0.90 mmol) were dissolved in N,N-dimethylformamide (5.0 mL) and cooled to 0°C. Chlorotriethylsilane (0.095 g, 0.63 mmol) was added, and the mixture was allowed to warm to room temperature and stirred for 5 hours. Water was added to the reaction vessel, and the precipitated solid was filtered off and washed with methanol. The resulting solid was purified by silica gel column chromatography using chloroform as a developing solvent to obtain compound (1-1) (0.130 g, 75% yield).

[0135] [ka]

[0136] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.95(d, 2H), 7.91(s, 1H), 7.80(d, 2H), 7.33(d, 2H), 6. 75(d, 2H), 3.85(t, 2H), 3.52(q, 4H), 2.91(t, 2H), 1.28(t, 6H), 0.93(t, 9H), 0.57(q, 6H) UV-visible light spectrum: λmax = 593 nm (in chloroform)

[0137] Synthesis Example 2: Synthesis of Compound (1-2) Compound (1-1-a) (0.139 g, 0.299 mmol) and imidazole (0.061 g, 0.90 mmol) were dissolved in N,N-dimethylformamide (5.0 mL) and cooled to 0°C. Chlorodimethylthexylsilane (0.112 g, 0.626 mmol) was added, and the mixture was allowed to warm to room temperature and stirred for 5 hours. Water was added to the reaction vessel, and the precipitated solid was filtered off and washed with methanol. The resulting solid was purified by silica gel column chromatography using chloroform as a developing solvent to obtain compound (1-2) (0.130 g, 75% yield).

[0138] [ka]

[0139] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.95(d, 2H), 7.91(s, 1H), 7.80(d, 2H), 7.33(d, 2H), 6.75(d, 2H), 3.84( t, 2H), 3.52(q, 4H), 2.88(t, 2H), 1.63-1.58(m, 1H), 1.28(t, 6H), 0.86(m, 6H), 0.82(m, 6H), 0.03(s, 6H) UV-visible light spectrum: λmax = 592 nm (in chloroform)

[0140] Synthesis Example 3: Synthesis of Compound 1-3 Compound (1-3-a) (1.127 g, 2.501 mmol) and imidazole (0.256 g, 3.76 mmol) were dissolved in tetrahydrofuran (25.0 mL) and cooled to 0°C. Chlorodimethylthexylsilane (0.492 g, 2.77 mmol) was added, and the mixture was allowed to warm to room temperature and stirred for 5 hours. Water was added to the reaction vessel, and the precipitated solid was filtered off and washed with methanol. The resulting solid was purified by silica gel column chromatography using chloroform as a developing solvent to obtain compound (1-3) (0.690 g, 47% yield).

[0141] [ka]

[0142] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.95(d, 2H), 7.91(s, 1H), 7.80(d, 2H), 7.33(d, 2H), 6.75(d, 2H) ), 4.80(s, 2H), 3.52(q, 4H), 1.69(sep, 1H), 1.28(t, 6H), 0.93(m, 6H), 0.89(m, 6H), 0.16(s, 6H) UV-visible light spectrum: λmax = 593 nm (in chloroform)

[0143] Synthesis Example 4: Synthesis of Compound (1-93) Compound (1-1-a) (0.500 g, 1.05 mmol) and imidazole (0.219 g, 3.20 mmol) were dissolved in N,N-dimethylformamide (10.5 mL) and cooled to 0 °C. tert-butyldiphenylchlorosilane (0.596 g, 2.10 mmol) was added, and the mixture was allowed to warm to room temperature and stirred for 5 hours. Water was added to the reaction vessel, 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 to obtain compound (1-93) (0.614 g, 82% yield).

[0144] [ka]

[0145] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.93(d, 2H), 7.90(s, 1H), 7.77(d, 2H), 7.57(dd, 4H), 7.46-7.32(m, 6H) , 7.27(d, 2H), 6.74(d, 2H), 3.88(t, 2H), 3.51(q, 4H), 2.90(t, 2H), 1.27(t, 6H), 1.01(t, 9H), 0.57(q, 6H) UV-visible light spectrum: λmax = 592 nm (in chloroform)

[0146] Comparative Synthesis Example 1: Synthesis of Compound (2-1) Compound 1-1-a (0.186 g, 0.400 mmol), N,N-diisopropylcarbodiimide (1.01 g, 8.00 mmol), 4-dimethylaminopyridine (0.012 g, 0.098 mmol), and 2-ethylhexanoic acid (0.149 g, 1.03 mmol) were mixed and stirred at room temperature for 15 hours. A saturated aqueous solution of sodium bicarbonate was added to the reaction vessel, 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 to obtain compound (2-1) (0.049 g, 21% yield).

[0147] [ka]

[0148] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.95(d, 2H), 7.92(s, 1H), 7.82(d, 2H), 7.36(d, 2H), 6.75(d, 2H), 4.36(t, 2H), 3.5 2(q, 4H), 3.03(t, 2H), 2.19(quin, 1H), 1.60(m, 2H) 1.56(m, 2H), 1.54(m, 2H) 1.50(m, 2H), 1.28(t, 6H), 0.84(t, 6H) UV-visible light spectrum: λmax = 594 nm (in chloroform)

[0149] The following compounds (2-2) and (2-3) were synthesized by a known diazo coupling method.

[0150] [ka]

[0151] Example 1: Preparation of composition E1 containing compound (1-1) The following components were mixed and stirred at 90° C. for 1 hour to obtain composition E1. ·Compound (1-1) 4.0 parts by mass ·Polymerizable liquid crystal compound (A-6) 75 parts by mass ·Polymerizable liquid crystal compound (A-8) 25 parts by mass ·Polymerizable non-liquid crystal compound 5 parts by mass Dipentaerythritol hexaacrylate (Manufactured by Daicel Cytec Co., Ltd.) Polymerization initiator 6 parts by mass 2-Dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; BASF Japan) Leveling agent 1.2 parts by mass Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) Solvent: toluene 250 parts by weight

[0152] The structures of the polymerizable liquid crystal compounds are as follows: The polymerizable liquid crystal compounds (A-6) and (A-8) were synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[0153] [ka] TIFF0007752517000022.tif19148

[0154] A polarizing film was formed using the obtained composition E1 as follows. 1. Formation of alignment layer A glass substrate was used as the substrate. A 2% by mass aqueous solution (alignment film polymer composition) of polyvinyl alcohol (Polyvinyl Alcohol 1000, fully saponified, manufactured by Fujifilm 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 layer was formed by rubbing the surface of the obtained film. The rubbing treatment was performed using a semi-automatic rubbing device (product name: LQ-008, manufactured by Joyo Engineering Co., Ltd.) with a cloth (product name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.) under conditions of a pressing depth of 0.15 mm, a rotation speed of 500 rpm, and 16.7 mm / s. This rubbing treatment yielded a laminate (1) in which an alignment film was formed on the glass substrate.

[0155] 2. Formation of polarizing film The resulting composition E1 was applied by spin coating to the alignment layer of the laminate (1), heated and dried on a hot plate at 120°C for 1 minute, and then quickly cooled to room temperature to form a dry coating on the alignment layer. Next, using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.), ultraviolet light was irradiated at an exposure dose of 2000mJ / cm2 (based on 313nm) to polymerize the polymerizable liquid crystal compound contained in the dry coating, forming a polarizing film from the dry coating and obtaining laminate (2). The thickness of the polarizing film was measured using a laser microscope (OLS3000 manufactured by Olympus Corporation) and found to be 1.8µm.

[0156] Example 2 Except for using compound (1-2) instead of compound (1-1), composition E2 was obtained in the same manner as in Example 1. Except for using composition E2 obtained, a laminate (2) having a polarizing film formed thereon was obtained in the same manner as in Example 1.

[0157] Example 3 Except for using compound (1-3) instead of compound (1-1), composition E3 was obtained in the same manner as in Example 1. Except for using composition E3 obtained, a laminate (2) having a polarizing film formed thereon was obtained in the same manner as in Example 1.

[0158] Example 4 Except for using compound (1-93) instead of compound (1-1), composition E4 was obtained in the same manner as in Example 1. Except for using composition E4 obtained, a laminate (2) having a polarizing film formed thereon was obtained in the same manner as in Example 1.

[0159] Comparative Example 1 A composition C1 was obtained in the same manner as in Example 1, except that compound (2-1) was used instead of compound (1-1). A laminate (2) having a polarizing film formed thereon was obtained in the same manner as in Example 1, except that the obtained composition C1 was used.

[0160] Comparative Example 2 Except for using compound (2-2) instead of compound (1-1), composition C2 was obtained in the same manner as in Example 1. Except for using the obtained composition C2, a laminate (2) having a polarizing film formed thereon was obtained in the same manner as in Example 1.

[0161] Comparative Example 3 Except for using compound (2-3) instead of compound (1-1), composition C3 was obtained in the same manner as in Example 1. Except for using the obtained composition C3, a laminate (2) having a polarizing film formed thereon was obtained in the same manner as in Example 1.

[0162] <Evaluation> Absorbance maintenance rate The storage stability of the compositions obtained above was evaluated as follows. Immediately after preparation (within 10 minutes), the compositions were diluted with chloroform, and the initial absorbance was measured at the maximum absorption wavelength in the absorption spectrum. The diluted solutions were stored at room temperature (25°C), and the absorbance at the maximum absorption wavelength was measured again one day and five days after preparation. The remeasured absorbance was divided by the initial absorbance to calculate the absorbance retention rate (%) after one day and five days, and evaluated according to the following criteria. The results are shown in Table 1.

[0163] Evaluation criteria A: The absorbance retention rate was 70% or more and 100% or less. B: The absorbance maintenance rate was 45% or more and less than 70%. C: The absorbance retention rate was less than 45%.

[0164] Polarizing film evaluation The appearance of the polarizing film obtained above was observed visually and under a microscope to check for the presence or absence of alignment defects due to crystal precipitation, and was evaluated according to the following criteria. The results are shown in Table 1.

[0165] Evaluation criteria A: There were no alignment defects and good alignment was maintained. B: Slight alignment defects were observed, but the film was suitable for use as a polarizing film. C: Alignment defects were observed, and the film was not suitable for use as a polarizing film.

[0166] The dichroic ratio of the laminate (2) obtained above 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 laminate (2) were measured by the double beam method using a spectrophotometer (Shimadzu Corporation UV-3150) in which a folder containing the laminate (2) was set. A mesh that cuts the amount of light by 50% was installed on the reference side of the folder. 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. Note that - in the table indicates that the value was not evaluated.

[0167] [Table 1]

[0168] As shown in Table 1, the composition containing the azo compound (1A) had excellent storage stability and was capable of forming a high-quality polarizing film.

Claims

1. An azo compound represented by the following formula (1): 【Chemistry 2】 [In formula (1), L represents an alkylene group having 1 to 4 carbon atoms, an alkyleneoxy group having 1 to 4 carbon atoms, an alkyleneoxycarbonyl group having 1 to 4 carbon atoms, an alkylenecarbonyloxy group having 1 to 4 carbon atoms, an alkylenecarbonyl group having 1 to 4 carbon atoms, or a single bond. y represents an integer of 1 or 2; R １ represents one group selected from the group consisting of a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, a pyrrolidyl group, an oxazolidinyl group, a piperidyl group, a morpholino group, a methoxy group, and an ethoxy group, and a hydrogen atom of these groups may be substituted with a polymerizable group. R ２ , R ３ and R ４ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms; R ２ , R ３ or R ４ The hydrogen atoms of may be substituted with polymerizable groups. Q represents a single bond or a group selected from the group consisting of —OC(═O)—, —C(═O)O—, —C≡C—, —CH═CH—, —N═N—, —NHC(═O)— and —C(═O)NH—. Ar 1 and Ar 3 each independently represent a 1,4-phenylene group which may have a substituent, and Ar 2 represents a thiazolediyl group, a benzothiazolediyl group, or a thienothiazolediyl group which may have a substituent, and the substituent is a halogen atom, a hydroxy group, a methyl group, or a methoxy group. When y is 2, two Ar ３ may be the same or different.]

2. 2. The azo compound according to claim 1, wherein Q in the formula (1) is -N=N-.

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

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

5. A film formed from the composition according to claim 3 or 4.

6. A laminate comprising the film of claim 5.

7. A display device comprising the film according to claim 5 or the laminate according to claim 6.

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