Azo compounds, compositions, films, laminates and display devices

Abstract

The present application relates to an azo compound represented by formula (1A). L 1 and L 2 represents a divalent linking group or a single bond. y represents 1 or 2. p and q represent 0 or 1, at least one of which is 1. X represents an oxygen atom or NR 5 5 represents a hydrogen atom or an aliphatic hydrocarbon group. R 12 13 14 represents an aliphatic hydrocarbon group or the like, and can have a polymerizable group. 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 2 3 represents 1,4-phenylene or a divalent sulfur-containing aromatic heterocyclic group. In the case where y is 2, the two Ar 3 may be the same or different.​​​​​

Description

TECHNICAL FIELD

[0001] The present application relates to an azo compound, a composition, a film, a laminate, and a display device. BACKGROUND

[0002] As a polarizing film (optical film) used in liquid crystal display devices and the like, a polarizing film containing a dichroic dye is known. As a dichroic dye, an azo compound having a condensed heterocyclic group is proposed in Patent Literature 1. In addition, a dichroic dye compound having a condensed heterocyclic group whose solubility is improved is proposed in Patent Literature 2.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT LITERATURE

[0005] Patent Literature 1: Japanese Patent Application Laid-Open No. 64-70585

[0006] Patent Literature 2: International Publication No. 2017 / 090668 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, the storage stability of the polarizing film-forming composition containing the azo compound described in Patent Literature 1 is insufficient, and sometimes a defect is generated in the formed film, and a high-quality polarizing film cannot be obtained. In addition, further improvement of the solubility is required for the dichroic dye compound described in Patent Literature 2. An object of the present application is to provide an azo compound capable of forming a high-quality film even when stored for a prescribed time in a state of a composition containing a solvent.

[0009] MEANS FOR SOLVING THE PROBLEMS

[0010] The present application provides the following [1] to [9].

[0011] [1] An azo compound represented by the following formula (1A).

[0012] [Chemical Formula 1]

[0013]

[0014] [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.

[0015] y represents an integer of 1 or 2.

[0016] p and q each independently represent 0 or 1, and at least one of p and q is 1.

[0017] R 12 R 13 and R 14 Each can independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a trialkylsilyloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, or a phenyl group, R. 12 R 13 Or R 14 The hydrogen atoms it contains can be replaced with polymeric groups.

[0018] X represents an oxygen atom or NR. 5 .

[0019] R 5 A group representing an aliphatic hydrocarbon with 1 to 10 hydrogen or carbon atoms can be combined with R. 13 They bond together to form a ring.

[0020] 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-.

[0021] Ar 1 Ar 2 and Ar 3 Each can independently represent a 1,4-phenylene group that may have substituents or a divalent sulfur-containing aromatic heterocyclic group that may have substituents.

[0022] When y is 2, the two Ar 3 They can be the same, or they can be different.

[0023] [2] The azo compound as described in [1] is represented by the following formula (1).

[0024] [Chemical Formula 2]

[0025]

[0026] In formula (1), L represents a divalent linking group or single bond formed by at least one of the groups selected from methylene, oxygen atom and carbonyl.

[0027] y represents an integer of 1 or 2.

[0028] R 1 It represents one group selected from the group consisting of methylamino, ethylamino, dimethylamino, diethylamino, ethylmethylamino, pyrrolyl, oxazolidinyl, piperidinyl, morpholino, methoxy, and ethoxy, wherein the hydrogen atoms of these groups may be replaced by polymerizable groups.

[0029] 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 has a hydrogen atom which can be replaced with a polymerizable group.

[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-.

[0031] Ar 1 , Ar 2 , and Ar 3 each independently represents 1,4-phenylene which can have a substituent, or a divalent sulfur-containing aromatic heterocyclic group which can have a substituent.

[0032] In the case where y is 2, the two Ar 3 may be the same or different.

[0033] [3] The azo compound according to [1] or [2], wherein, in the aforementioned formula (1A) or (1), Q is -N=N-.

[0034] [4] The azo compound according to any one of [1] to [3], wherein, in the aforementioned formula (1A) or (1), at least one of Ar 1 and Ar 2 is a divalent sulfur-containing aromatic heterocyclic group.

[0035] [5] A composition comprising: the azo compound according to any one of [1] to [4]; and a liquid crystalline compound, the aforementioned liquid crystalline compound comprising at least one of a polymerizable liquid crystalline compound and a liquid crystalline high molecular compound.

[0036] [6] The composition according to [5], wherein the aforementioned liquid crystalline compound is a smectic liquid crystalline compound.

[0037] [7] A film using the composition according to [5] or [6] as a forming material.

[0038] [8] A laminate provided with the film according to [7].

[0039] [9] A display device provided with the film according to [7] or the laminate according to [8].

[0040] Effects of the Invention

[0041] According to the present application, it is possible to provide an azo compound capable of forming a high-quality film even when stored for a prescribed period of time in a state of a composition containing a solvent. DETAILED DESCRIPTION

[0042] In the present specification, the term "step" refers not only to an independent step, but also includes a case where the step cannot be clearly distinguished from other steps as long as the desired purpose of the step can be achieved. In addition, in a case where a plurality of substances belonging to each component is present in a composition, the content of each component in the composition refers to the total amount of the plurality of substances present in the composition, unless otherwise specified. Furthermore, as for the upper limit and the lower limit of the numerical range described in the present specification, the numerical values exemplified as the numerical range can be arbitrarily selected and combined, respectively. Hereinafter, the embodiments of the present application will be described in detail. Note that the scope of the present application is not limited to the embodiments described here, and various modifications can be made within the scope of the gist of the present application.

[0043] Azo Compound

[0044] The azo compound according to the present 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)) can be used as a material for forming a polarizing film, for example, as a dichroic dye. That is, the azo compound (1A) can be an effective component constituting a dichroic dye. The azo compound (1A) is excellent in stability as a composition even when stored for a prescribed period of time in a state of a composition containing a solvent, and can form a high-quality film. The stability as a composition means that aggregation, precipitation, or the like of the azo compound (1A) in the composition is suppressed. In addition, the high-quality film can be, for example, a film in which precipitation of the azo compound (1A) is suppressed, or a polarizing film in which generation of orientation defects is suppressed. In addition, the prescribed period of time of storage means, for example, storage for 1 day or more, preferably 5 days or more, at room temperature (25°C).

[0045] [Chemical Formula 3]

[0046]

[0047] 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 14Each can independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a trialkylsilyloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, or a phenyl group, R. 12 R 13 Or R 14 The hydrogen atoms can be replaced with polymerizable groups. X represents an oxygen atom or NR. 5 R 5 A group representing an aliphatic hydrocarbon with 1 to 10 hydrogen or carbon atoms can be combined with R. 13 They bond together 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 can independently represent a 1,4-phenylene group that may have substituents or a divalent sulfur-containing aromatic heterocyclic group that may have substituents. When y is 2, the two Ar groups... 3 They can be the same or different.

[0048] As a result of L 1 or L 2 The divalent linking group, specifically, can be exemplified by alkylene groups having 1 to 4 carbon atoms, alkyloxy groups having 1 to 4 carbon atoms, alkyloxycarbonyl groups having 1 to 4 carbon atoms, carbonyloxyalkylene groups having 1 to 4 carbon atoms, alkylcarbonyloxy groups having 1 to 4 carbon atoms, alkylcarbonylalkylene groups having 1 to 4 carbon atoms, alkylcarbonylcarbonylene groups having 1 to 4 carbon atoms, or carbonylalkylene groups having 1 to 4 carbon atoms. From the viewpoint of the stability of compositions containing azo compounds (1A), in formula (1A), the oxygen atom, and the Ar... 1 The number of groups of atoms directly connected to X (the number of atoms in the main chain) can be 1 to 4, preferably 1 to 3 or 2 to 3. That is, the constituent L... 1 and L 2 The number of atoms can be 1 or more but less than 4, preferably 1 or more but less than 3, or 2 or more but less than 3.

[0049] From the viewpoint of the stability of azo compound (1A), it is preferable to select L1 and L2 in a manner that formula (1A) does not contain oxygen-oxygen bonds or oxygen-nitrogen bonds. That is, when p=1, L 1 It can be represented by the following equation (2). In addition, when q = 1, L 2 It can be represented by the following formula (2a).

[0050] [Chemical Formula 4]

[0051]

[0052] In Formula (2), x represents an integer of 0 to 4. P represents a single bond, or one group selected from the group consisting of -0-, -OC(=0)-, and -C(=0)0-. In the case where P is a single bond, -0-, or -OC(=0)-, x represents an integer of 1 to 4. P is preferably a single bond or -0-. In the case where P is -C(=0)0-, x is an integer of 0 to 4, preferably 1, 2, or 3, more preferably 2. In the case where P is a single bond, -0-, or -OC(=0)-, x is preferably 2 or 3, more preferably 2.

[0053] In Formula (2a), z represents an integer of 0 to 4. P 1 represents a single bond, -C(=0)-, or -C(=0)0-. In the case where P 1 is a single bond or -C(=0)0-, z represents an integer of 1 to 4. P 1 is preferably a single bond or -0-. In the case where P is -C(=0)-, z is an integer of 0 to 4, preferably 1, 2, or 3, more preferably 2. In the case where P 1 is a single bond or -0-, z is preferably 2 or 3, more preferably 2.

[0054] R 12 , R 13 , and R 14 each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a trialkylsilyloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, or a phenyl group. R 12 , R 13 , and R 14 preferably represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a phenyl group, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0055] The aliphatic hydrocarbon group, the alkoxy group, the trialkylsilyloxy group, the trialkylsilyl group, or the phenyl group represented by R 12 , R 13 , or R 14 may each independently have a substituent. As the substituent in R 12 , R 13 , or R 14 , for example, a polymerizable group, a halogen atom (fluorine atom, chlorine atom, or the like), a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or the like can be given. 12 , R 13 , or R 14The total number of substituents, when present, is, for example, 1 to 10, preferably 1 to 6.

[0056] For the aliphatic hydrocarbon group represented by R 12 , R 13 , or R 14 , at least one hydrogen atom can be replaced with a polymerizable group. As the polymerizable group, for example, a (meth)acryloyloxy group, a styryl group (vinylphenyl group), a vinyl group, an epoxy group, or the like can be mentioned. The polymerizable group is preferably a radical polymerizable group, and a (meth)acryloyloxy group is preferable. R 12 , R 13 , or R 14 , when substituted with a polymerizable group, the total number thereof is, for example, 1 or 2, preferably 1.

[0057] The number of carbon atoms of the aliphatic hydrocarbon group represented by R 12 , R 13 , or R 14 is preferably 1 to 8, further preferably 1 to 6. The aliphatic hydrocarbon group can be either branched or linear. As the aliphatic hydrocarbon group, for example, an alkyl group, an alkenyl group, an alkynyl group, and preferably an alkyl group can be mentioned. As the alkyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a hexyl group, a 2,3-dimethyl-2-butyl group (1,1,2-trimethylpropyl group), an octyl group, and the like can be mentioned. Preferably, at least one of R 12 , R 13 , and R 14 is a branched aliphatic hydrocarbon group, more preferably a branched alkyl group. The number of carbon atoms of the branched aliphatic hydrocarbon group is, for example, 3 to 8, preferably 3 to 6. The total number of carbon atoms contained in R 12 , R 13 , and R 14 in formula (1A) is, for example, 3 or more and 24 or less, preferably 6 or more and 18 or less, further preferably 6 or more and 16 or less.

[0058] The number of carbon atoms of the alkoxy group represented by R 12 , R 13 , or R 14 is preferably 1 to 8, or 1 to 6. The alkyl moiety of the alkoxy group can be either branched or linear. Preferably, at least one of R 12 , R 13 , and R 14 is a branched alkoxy group. The number of carbon atoms of the branched alkoxy group is, for example, 3 to 8, preferably 3 to 6. R 12 , R 13 , and R 14The total number of carbon atoms contained may, for example, be 3 or more and 12 or less, preferably 6 or more and 12 or less, or 6 or more and 10 or less. As the alkyloxy group, specifically, for example, methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, hexyloxy, and the like can be given.

[0059] R 12 , R 13 or R 14 representing a trialkylsilyloxy group or an alkyl moiety of a trialkylsilyl group each has a number of carbon atoms of 1 to 6, preferably 1 to 5, or 1 to 4. The total number of carbon atoms of the alkyl moiety of the trialkylsilyloxy group or the trialkylsilyl group is preferably 3 to 8, or 3 to 6. As the trialkylsilyloxy group, specifically, for example, trimethylsilyloxy, triethylsilyloxy, t-butyldimethylsilyloxy can be given. Further, as the trialkylsilyl group, for example, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl can be given.

[0060] X represents an oxygen atom or NR 5 . R 5 represents a hydrogen atom or an aliphatic hydrocarbon group having a number of carbon atoms of 1 to 10. R 5 represents an aliphatic hydrocarbon group having a number of carbon atoms of 1 to 8, or 1 to 6. The aliphatic hydrocarbon group can be either branched or straight. As the aliphatic hydrocarbon group, for example, an alkyl group, an alkenyl group, an alkynyl group, preferably an alkyl group can be given. As the alkyl group, specifically, methyl, ethyl, propyl can be given. Further, R 5 may be bonded to each other to form a ring. R 13 , when R 5 and R 13 are bonded to each other to form a ring, q is preferably 0. Further, the ring formed can be a nitrogen-containing aliphatic ring having, for example, 5 or 6 members. As the ring formed by R 5 and R 13 bonded to each other, for example, pyrrolidinyl, piperidinyl, oxazolidinyl, morpholinyl, and the like can be given.

[0061] From the aspect of further improving the dichroic ratio, the azo compound represented by formula (1A) can preferably be one in which p = 1 and q = 0, more preferably an azo compound represented by the following formula (1) (hereinafter, also referred to as azo compound (1)).

[0062] [Chemical Formula 5]

[0063]

[0064] 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. As the divalent linking group represented by L, specifically, there can be mentioned 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 alkylene carbonyloxy group having 1 to 4 carbon atoms, an alkylene carbonyl group having 1 to 4 carbon atoms, and the like. From the viewpoint of stability as a composition of the azo compound (1), in formula (1), the oxygen atom and Ar 1 The number of groups of directly connected atoms (the number of atoms of the main chain) can be 1 or more and 4 or less, preferably can be 1 or more and 3 or less, or 2 or more and 3 or less. That is, the number of atoms constituting L other than hydrogen atoms and carbonyl oxygen can be 1 or more and 4 or less, preferably can be 1 or more and 3 or less, or 2 or more and 3 or less. The divalent linking group represented by L can be represented by the following formula (2), for example, and the azo compound (1) can be represented by the following formula (1a).

[0065] [Chemical Formula 6]

[0066]

[0067] In formulae (2) and (1a), x represents an integer of 0 to 4. P represents a single bond, or one group selected from the group consisting of -O-, -OC(=O)-, and -C(=O)O-. Among them, in the case where 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-. In the case where P is -C(=O)O-, x is an integer of 0 to 4, preferably 1, 2, or 3, more preferably 2. In the case where P is a single bond, -O-, or -OC(=O)-, x is an integer of 1 to 4, preferably 2 or 3, more preferably 2.

[0068] In formulae (1A), (1), and (1a), y represents an integer of 1 or 2. In the case where y is 2, two Ar 3 may be the same or different.

[0069] In formulae (1) and (1a), 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 pyrrolidinyl group, an oxazolyl group, an oxazolidinyl group, a piperidinyl group, a morpholino group, a methoxy group, and an ethoxy group. R 1 is preferably a dimethylamino group, a diethylamino group, an ethylmethylamino group, a methoxy group, or an ethoxy group, more preferably a dimethylamino group or a diethylamino group. As R 1At least one of the hydrogen atoms of the group represented by the above formula (1) can be replaced with a polymerizable group. As the polymerizable group, for example, a (meth)acryloyloxy group, a styryl group, a vinyl group, an epoxy group, or the like can be given. The polymerizable group is preferably a radical polymerizable group, and is more preferably a (meth)acryloyloxy group. 1 The number of the polymerizable group is, for example, 1 or 2, and is preferably 1.

[0070] 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-, and is more preferably -N=N-.

[0071] Ar 1 , Ar 2 , and Ar 3 each independently represent a 1,4-phenylene group which can have a substituent, or a divalent sulfur-containing aromatic heterocyclic group which can have a substituent. As the sulfur-containing aromatic heterocyclic group, for example, a thiazolylene group, a benzothiazolylene group, a thienothiazolylene group, or the like can be given, and is preferably a benzothiazolylene group, or a thienothiazolylene group, and is more preferably a thienothiazolylene group, and is further preferably a thieno[2,3-d]thiazol-2,5-diyl group. Ar 1 , and Ar 2 at least one of which is preferably a divalent sulfur-containing aromatic heterocyclic group which can have a substituent, and is more preferably a benzothiazolylene group, or a thienothiazolylene group, and is further preferably Ar 2 is a benzothiazolylene group, or a thienothiazolylene group, and is particularly preferably Ar 2 is a thienothiazolylene group. As the substituent of Ar 1 , Ar 2 , and Ar 3 , for example, a halogen atom, a hydroxyl group, a methyl group, a methoxy group, or the like can be given, and is preferably a fluorine atom, a chlorine atom, a hydroxyl group, a methyl group, or a methoxy group, and is more preferably a fluorine atom, a chlorine atom, a hydroxyl group, or a methyl group, and is further preferably a fluorine atom, a chlorine atom, or a methyl group. Ar 1 , Ar 2 , and Ar 3 the number of the substituents in each of Ar

[0072] R 2 , R 3 , and R 4 each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms. As R 2 , R 3 , or R 4The aliphatic hydrocarbon group represented preferably has 1 to 8 carbon atoms, or 1 to 6. The aliphatic hydrocarbon group can be branched or linear. Examples of aliphatic hydrocarbon groups include alkyl, alkenyl, and ynyl groups, with alkyl being preferred. Specifically, examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, 2,3-dimethyl-2-butyl(1,1,2-trimethylpropyl), and octyl. R is preferred. 2 R 3 and R 4 At least one of the groups is 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. R in formula (1) or formula (1a) 2 R 3 and R 4 The total number of carbon atoms contained can be, for example, 3 to 24, preferably 6 to 18, and more preferably 6 to 16. Regarding R... 2 R 3 or R 4 For the aliphatic hydrocarbon group represented, at least one hydrogen atom can be replaced by a polymeric group. R 2 R 3 or R 4 When polymerizable groups are present, the total number is, for example, 1 or 2, preferably 1.

[0073] In one approach, R 2 R 3 and R 4 Each of these can independently represent an alkyloxy group having 1 to 10 carbon atoms, a trialkylsilyloxy group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, or a phenyl group, preferably in the manner of R. 12 R 13 and R 14 same.

[0074] Specific examples of azo compounds (1A) include compounds represented by the following formulas (1-1) to (1-105), but the invention is not limited to these.

[0075] [Chemical Formula 7]

[0076]

[0077] [Chemical Formula 8]

[0078]

[0079] [Chemical Formula 9]

[0080]

[0081] [Chemical Formula 10]

[0082]

[0083] [Chemical Formula 11]

[0084]

[0085] From the viewpoint of stability from the time of production of the composition, the azo compound (1A) is preferably at least one kind selected from the group consisting of the compounds represented by any one of the formulae (1-1) to (1-81) and (1-93) to (1-105), more preferably at least one kind selected from the group consisting of the compounds represented by any one of the formulae (1-1) to (1-67), and particularly preferably at least one kind selected from the group consisting of the compounds represented by any one of the formulae (1-1), (1-2), and (1-7) to (1-27).

[0086] The azo compound (1A) can have an absorption maximum wavelength (λmax) in a wavelength range of 550 nm or more and 650 nm or less, for example. The absorption maximum wavelength of the azo compound (1A) can be preferably 560 nm or more and 640 nm or less, and more preferably 570 nm or more and 630 nm or less. The absorption maximum wavelength is measured for a chloroform solution of the azo compound (1A) at room temperature (for example, 25°C). The absorption maximum wavelength of the azo compound (1A) can be adjusted to a desired wavelength by appropriately selecting the skeleton structure of Ar 1 , Ar 2 , and Ar 3 , the substituents in Ar 1 , Ar 2 , and Ar 3 , y, R 1 , and the like.

[0087] The azo compound (1A) has a specific structure, whereby the solubility stability in a solvent is improved, for example, and the stability as a composition is improved. This can be considered as follows, for example. The aliphatic hydrocarbon group-substituted silyloxy group has a large volume and has polarity. It is considered that the interaction between the azo compounds (1A) is inhibited, the solubility stability in a solvent is improved, and good compatibility with a host can be exhibited. It is also considered that by bonding the silyloxy group to the chromophore via the linking group L, the orientation of the chromophore is not hindered, and in the case of forming a polarizing film, for example, a good dichroic ratio (DR) can be maintained.

[0088] Method for producing azo compound

[0089] The azo compound (1A) can be produced by appropriately applying a synthesis method known heretofore. Specifically, the azo structure (-N=N-) in the azo compound (1A) can be constructed, for example, by converting an aromatic amine compound having a primary amino group into a diazonium salt with sodium nitrite or the like, and subjecting it to diazo coupling with an aromatic compound, with reference to the description of the production examples in

[0220] to

[0268] of International Publication WO 2016 / 136561, and the like.

[0090] The compound in which Q in the azo compound (1A) is a single bond can be synthesized, for example, by using a precursor having a dihydroxyborane group or a dialkoxyborane group, and a precursor having a halogen atom, with reference to Netherton, M. R.; Fu, G. C. Org. Lett. 2001, 3(26), 4295-4298., and the like, and applying the reaction conditions of Suzuki coupling.

[0091] The compound in which Q in the azo compound (1A) is -OC(=O)- or C(=O)O- can be synthesized, for example, by using a precursor having a carboxyl group, and a precursor having a hydroxyl group, with reference to Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y.; Ma, D. J. Org. Chem. 2009, 74(3), 4542-4546., and the like, and applying a dehydration condensation reaction. Specifically, for example, there can be mentioned a condition in which condensation is performed in a solvent in the presence of an esterification condensing agent.

[0092] The compound in which Q in the azo compound (1A) is -C≡C- can be synthesized, for example, by using a precursor having an ethynyl group (-C≡CH), and a precursor having a halogen atom, and applying Sonogashira coupling with a Pd, Cu catalyst

[0093] The compound in which Q in the azo compound (1A) is -C=C- can be synthesized, for example, by using a precursor having a vinyl group (-C=CH), and a precursor having a halogen atom, and applying Heck reaction with a Pd catalyst, a phosphorus ligand

[0094] The compound in which Q in the azo compound (1A) is -NHC(=O)- or C(=O)NH- can be synthesized, for example, by using a precursor having a carboxyl group, and a precursor having an amino group, and applying a dehydration condensation reaction. Specifically, for example, there can be mentioned a condition in which condensation is performed in a solvent in the presence of an amidation condensing agent.

[0095] The aliphatic hydrocarbon group-substituted silyloxy group in the azo compound (1A) can be synthesized by using a precursor having a hydroxyl group and an aliphatic hydrocarbon group-substituted halosilane in the presence of a base, applying the conditions of a general silylation reaction. N 2The conditions of the substitution reaction can be found, for example, in J. Am. Chem. Soc, 1972, 94, 6190, and the like.

[0096] The reaction time in the production method of the azo compound (1A) can also be determined by, for example, sampling the reaction mixture at an appropriate reaction intermediate, and confirming the disappearance degree of the starting compound, the generation degree of the azo compound (1A), and the like, using a known analysis means such as liquid chromatography, gas chromatography, and the like.

[0097] The azo compound (1A) can be taken out from the reaction mixture after the reaction by a known method such as recrystallization, reprecipitation, extraction, and various chromatographies, or by appropriately combining these operations.

[0098] <Dichroic dye>

[0099] The dichroic dye contains at least one azo compound (1A) as an effective component. By containing the azo compound (1A) in the dichroic dye, a polarizing film in which the generation of orientation defects is suppressed can be formed. The dichroic dye can contain only one azo compound (1A), or can contain two or more kinds of azo compounds (1A) in combination. In the case where the dichroic dye contains two or more kinds of azo compounds (1A), they can have mutually different maximum absorption wavelengths. In addition, the dichroic dye can contain, in addition to the azo compound (1A), another dye compound other than the azo compound (1A). The other dye compound will be described later.

[0100] <Composition>

[0101] The composition of the present embodiment contains: at least one azo compound (1A); and a liquid crystalline compound, the aforementioned liquid crystalline compound containing at least one of a polymerizable liquid crystalline compound and a liquid crystalline high molecular compound. The composition is used, for example, as a forming material for a polarizing film. That is, the composition can be a polarizing film-forming composition. The polarizing film obtained by using the composition as a forming material is a high-quality polarizing film that maintains an excellent dichroic ratio and in which the generation of orientation defects is suppressed. The composition is excellent in stability as a composition even after being stored for a prescribed time by containing the azo compound (1A) as a dichroic dye, and a polarizing film in which the generation of orientation defects is suppressed can be formed.

[0102] The content of the azo compound (1A) in the composition is preferably 50 parts by mass or less, more preferably in the range of 0.1 parts by mass or more and 10 parts by mass or less, and further preferably in the range of 0.1 parts by mass or more and 5 parts by mass or less, with respect to 100 parts by mass of the solid content of the composition. If it is within the above range, dispersion of the azo compound (1A) can be sufficiently performed. Thus, a film in which the azo compound (1A) is used as a forming material and in which defect generation is sufficiently suppressed can be efficiently obtained. Note that, in the present specification, the solid content refers to the total amount of the components after removal of volatile components such as solvents from the composition. The composition can contain only one azo compound (1A), or two or more kinds of azo compounds (1A) having different structures in combination. In the case where the composition contains two or more kinds of azo compounds (1A), they can have different maximum absorption wavelengths from each other.

[0103] The composition can further contain at least one other coloring compound than the azo compound (1A), such as a dichroic dye. As the other coloring compound, for example, monoazo dyes, disazo dyes, triazo dyes, tetrazo dyes, stilbazolazo dyes, and the like can be given, and at least one selected from the group consisting of them is preferable. The composition can contain one other coloring compound alone, or two or more kinds in combination. In the case of use as a coating-type polarizing plate material, for example, the other coloring compound contained in the composition preferably has a maximum absorption wavelength in a wavelength range different from that of the azo compound (1A). In the case of use as a coating-type polarizing plate material, for example, the composition preferably contains the azo compound (1A) and further contains three or more kinds of dichroic dyes in combination, and more preferably three or more kinds of azo dyes in combination. By containing three or more kinds of coloring compounds having different maximum absorption wavelengths in combination, for example, it is possible to obtain absorption in the entire visible light region using a film formed from the composition.

[0104] In the case where the composition contains the other coloring compound, the content thereof is preferably 50 parts by mass or less, more preferably in the range of 0.1 parts by mass or more and 10 parts by mass or less, and further preferably in the range of 0.1 parts by mass or more and 5 parts by mass or less, with respect to 100 parts by mass of the solid content of the composition. If it is within the above range, dispersion of the other coloring compound can be sufficiently performed.

[0105] The composition contains, in addition to the azo compound (1A), a liquid-crystalline compound containing at least one of a polymerizable liquid-crystalline compound and a liquid-crystalline high-molecular compound. The composition can contain both the polymerizable liquid-crystalline compound and the liquid-crystalline high-molecular compound, and the composition can contain two or more of each of the polymerizable liquid-crystalline compound and the liquid-crystalline high-molecular compound. By containing at least one of the polymerizable liquid-crystalline compound and the liquid-crystalline high-molecular compound, the composition can be formed in which the azo compound (1A) is dispersed in the liquid-crystalline compound.

[0106] The liquid-crystalline high-molecular compound can be a compound constituting a thermotropic liquid-crystalline polymer or a compound constituting a lyotropic liquid-crystalline polymer. From the viewpoint of enabling dense film thickness control, the liquid-crystalline high-molecular compound is preferably a compound constituting a thermotropic liquid-crystalline polymer.

[0107] As a classification of liquid crystals, depending on the structure of molecular arrangement in the liquid crystal state, there are smectic liquid crystals, nematic liquid crystals, and cholesteric liquid crystals. Among these, in the application to a polarizing film, a smectic liquid crystal can be preferably used. Therefore, the polymerizable liquid-crystalline compound is preferably a polymerizable smectic liquid-crystalline compound, and the liquid-crystalline high-molecular compound is preferably a smectic liquid-crystalline high-molecular compound.

[0108] By using a polymerizable liquid-crystalline compound exhibiting a smectic liquid-crystalline property and a liquid-crystalline high-molecular compound exhibiting a smectic liquid-crystalline property, a polarizing film having a high degree of orientation order can be formed. The liquid crystal state exhibited by the polymerizable liquid-crystalline compound and the liquid-crystalline high-molecular compound is preferably a smectic phase (a smectic liquid crystal state), and more preferably a high-order smectic phase (a high-order smectic liquid crystal state) from the viewpoint of enabling a higher degree of orientation order. Here, the high-order smectic phase refers to a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, and a smectic L phase, and more preferably a smectic B phase, a smectic F phase, and a smectic I phase. A polarizing film having a high degree of orientation order gives a Bragg peak derived from a high-order structure such as a hexagonal phase, a crystal phase in X-ray diffraction measurement. The Bragg peak refers to a peak derived from a planar periodic structure of molecular orientation. The periodic interval (order period) possessed by a polarizing film obtained from the composition is preferably 0.3 nm or more and 0.6 nm or less. The polymerizable liquid-crystalline compound or the liquid-crystalline high-molecular compound can be a polymerizable smectic liquid-crystalline compound or a smectic liquid-crystalline high-molecular compound that exhibits a Bragg peak derived from a high-order structure in X-ray diffraction measurement.

[0109] The azo compound (1A) can exhibit high dichroism even in a state of being dispersed in a tight intermolecular chain formed by at least one of a polymerizable liquid crystalline compound and a liquid crystalline high molecular compound having a smectic liquid crystallinity. Therefore, a polarizing film in which generation of orientation defects is suppressed and dichroism is high can be provided by a combination of a liquid crystalline compound containing at least one of a polymerizable liquid crystalline compound and a liquid crystalline high molecular compound, particularly a liquid crystalline compound containing at least one of a polymerizable liquid crystalline compound having a smectic liquid crystallinity and a liquid crystalline high molecular compound having a smectic liquid crystallinity, and the azo compound (1A).

[0110] Polymerizable liquid crystalline compound

[0111] The polymerizable liquid crystalline compound refers to a compound having at least one polymerizable group in a molecule and capable of exhibiting a liquid crystal phase by performing orientation. The polymerizable liquid crystalline compound is preferably a compound capable of exhibiting a liquid crystal phase by performing orientation alone. The polymerizable group refers to a functional group capable of participating in a polymerization reaction, and is preferably a radical polymerizable group.

[0112] As the polymerizable liquid crystalline compound, any compound having at least one polymerizable group and preferably exhibiting a smectic liquid crystallinity can be used without particular limitation, and known polymerizable liquid crystalline compounds can be used. As the polymerizable liquid crystalline compound, specifically, for example, a compound represented by the following formula (A) (hereinafter, also referred to as "polymerizable liquid crystalline compound (A)") can be preferably mentioned.

[0113] U 1 -V 1 -W 1 -(X 1 -Y 1 ) m -X 2 -Y 2 -X 3 -W 2 -V 2 -U 2 (A)

[0114] In formula (A), m is an integer of 1 to 3. X 1 , X 2 , and X 3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. In the case where m is 2 or 3, X 1 may be the same as or different from each other. At least three of X 1 , X 2 , and X 3 represent a divalent hydrocarbon 6-membered ring group. Y 1 , Y 2 , and W1 and W 2 Each independently represents a single bond or a divalent linker. When m is 2 or 3, Y... 1 They can be the same or different. 1 and V 2 Each of these groups independently represents an alkane diene with 1 to 20 carbon atoms that may have substituents. At least one of the -CH2- groups constituting the alkane diene may be replaced by -O-, -CO-, -S-, or -NH-. U 1 and U 2 Each can independently represent a polymeric group or a hydrogen atom, with at least one representing a polymeric group.

[0115] As X 1 X 2 and X 3 Examples of divalent aromatic groups in [the compound name] include 1,4-phenylene and 1,4-naphthylene. Examples of divalent alicyclic hydrocarbon groups include cyclohexane-1,4-diyl. 1 X 2 and X 3 At least one of the divalent aromatic group and the divalent alicyclic hydrocarbon group may have substituents. Examples of substituents include alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, and n-butyl, cyano groups, and halogen atoms. At least one of the -CH2- groups constituting the divalent alicyclic hydrocarbon group may be replaced by -O-, -S-, or -NR-. Here, R represents an alkyl group with 1 to 6 carbon atoms or a phenyl group.

[0116] As X 1 X 2 and X 3 Examples of divalent hydrocarbon 6-membered cyclic groups include 1,4-phenylene, which may have substituents, and cyclohexane-1,4-diyl, which may have substituents.

[0117] X 1 X 2 and X 3 The divalent aromatic group is preferably a 1,4-phenylene group that may have a substituent, more preferably an unsubstituted 1,4-phenylene group. Furthermore, the divalent alicyclic hydrocarbon group is preferably a cyclohexane-1,4-diyl group that may have a substituent, more preferably a trans-cyclohexane-1,4-diyl group that may have a substituent, and even more preferably an unsubstituted trans-cyclohexane-1,4-diyl group.

[0118] Y 1 and Y 2 Each group independently represents a single bond or a divalent linker. Examples of divalent linkers include -CH2CH2-, -CH2O-, -(C=O)O-, -O(C=O)O-, -N=N-, and -CR. a=CR b -C≡C-, and -CR a at least one selected from the group consisting of =N-, -C≡C-, and -CR a and R b each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y 1 is preferably -CH2CH2-, -(C=O)O-, or a single bond. Y 2 is preferably -CH2CH2- or -CH2O-.

[0119] W 1 and W 2 each 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-. W 1 and W 2 each independently is preferably a single bond or -O-.

[0120] V 1 and V 2 each independently represents an alkane-diyl group having 1 to 20 carbon atoms which can have a substituent. At least one of -CH2- constituting the aforementioned alkane-diyl group can be replaced with -O-, -CO-, -S-, or -NH-.

[0121] As the alkane-diyl group represented by V 1 and V 2 , methylene, ethylene, propane-1, 3-diyl, butane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, decane-1, 10-diyl, tetradecane-1, 1-diyl, and eicosane-1, 20-diyl. V 1 and V 2 is preferably an alkane-diyl group having 2 to 12 carbon atoms, and more preferably an alkane-diyl group having 6 to 12 carbon atoms.

[0122] As the substituent which the alkane-diyl group having 1 to 20 carbon atoms which can have a substituent optionally has, a cyano group and a halogen atom can be mentioned. The alkane-diyl group is preferably an alkane-diyl group having no substituent, and more preferably an alkane-diyl group having no substituent and being linear.

[0123] U 1 and U 2 each independently represents a polymerizable group or a hydrogen atom, at least one of which represents a polymerizable group. U 1 and U 2 is preferably a polymerizable group. Preferably U 1 and U 2are each a polymerizable group, preferably a radical polymerizable group. U 1 the polymerizable groups represented by U 2 the polymerizable groups represented by U 1 and U 2 the polymerizable groups in U 1 and U 2 the polymerizable groups represented by U are 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, more preferably an acryloyloxy group.

[0124] As specific examples of the polymerizable liquid crystalline compound (A), there can be mentioned compounds represented by the following Formulas (A-1) to (A-17). In the case where the polymerizable liquid crystalline compound (A) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans type.

[0125] [Chemical Formula 12]

[0126]

[0127] [Chemical Formula 13]

[0128]

[0129] [Chemical Formula 14]

[0130]

[0131] Among them, the polymerizable liquid crystalline compound (A) is preferably at least one selected from the group consisting of a compound represented by any one of Formula (A-2), Formula (A-3), Formula (A-4), Formula (A-5), Formula (A-6), Formula (A-7), Formula (A-8), Formula (A-13), Formula (A-14), Formula (A-15), Formula (A-16), and Formula (A-17). The polymerizable liquid crystalline compound (A) can be used alone as one kind, or two or more kinds in combination.

[0132] The polymerizable liquid crystalline compound (A) can be produced, for example, by the method described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), Japanese Patent No. 4719156, and the like.

[0133] Liquid crystalline polymer compound

[0134] The liquid-crystalline polymer compound can be a compound obtained by polymerizing the aforementioned polymerizable liquid-crystalline compound (hereinafter, also referred to as a polymer of the polymerizable liquid-crystalline compound), or can be another liquid-crystalline polymer compound, and is preferably a polymer of the aforementioned polymerizable liquid-crystalline compound.

[0135] The polymer of the aforementioned polymerizable liquid-crystalline compound can be obtained using two or more of the aforementioned polymerizable liquid-crystalline compounds as raw monomers. In addition, the polymer of the aforementioned polymerizable liquid-crystalline compound can contain another monomer other than the aforementioned polymerizable liquid-crystalline compound as a raw monomer.

[0136] The content ratio of the aforementioned polymerizable liquid-crystalline compound in the polymer of the aforementioned polymerizable liquid-crystalline compound is usually 1 mol% or more and 100 mol% or less, and from the viewpoint of improving the alignment properties of the polymer of the aforementioned polymerizable liquid-crystalline compound, it is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and further preferably 80 mol% or more and 100 mol% or less, with respect to the total amount of the structural units derived from the aforementioned polymerizable liquid-crystalline compound constituting the polymer of the aforementioned polymerizable liquid-crystalline compound.

[0137] As the aforementioned other liquid-crystalline polymer compound, a polymer compound having a liquid-crystalline group can be given. For example, as a polymer compound serving as a parent skeleton, a polyolefin such as polyethylene or polypropylene; a cyclic olefin resin such as a norbornene polymer; a polyalkylene ether, a polyvinyl alcohol; a polymethacrylate; a polyacrylate; and the like, which have a liquid-crystalline group, can be given. Among them, a polymethacrylate or a polyacrylate having a liquid-crystalline group is preferable.

[0138] The aforementioned other liquid-crystalline polymer compound can contain two or more liquid-crystalline groups. The liquid-crystalline group can be contained in the main chain of the polymer compound serving as a parent skeleton, can be contained in the side chain of the polymer compound serving as a parent skeleton, or can be contained in both the main chain and the side chain of the polymer compound serving as a parent skeleton. As the liquid-crystalline group, a group formed by removing one hydrogen atom from a compound having at least two hydrocarbon 6-membered ring structures, or a group formed by removing two hydrogen atoms from the compound, can be given.

[0139] The content ratio of the liquid-crystalline group in the aforementioned other liquid-crystalline polymer compound is usually 1 mol% or more and 100 mol% or less, and from the viewpoint of improving the alignment properties of the aforementioned other liquid-crystalline polymer compound, it is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and further preferably 80 mol% or more and 100 mol% or less, with respect to the total amount of the structural units of the polymer compound serving as a parent skeleton constituting the aforementioned other liquid-crystalline polymer compound.

[0140] In the case where two or more polymerizable liquid crystal compounds are combined in the composition, at least one of them is preferably 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, there is a case where the liquid crystal phase can be temporarily maintained even at a temperature below the liquid crystal-crystalline phase transition temperature. The content of the polymerizable liquid crystal compound (A) contained in the composition, in total, is preferably 40% by mass or more, and more preferably 60% by mass or more, relative to the total mass of all the polymerizable liquid crystal compounds in the composition, and all the polymerizable liquid crystal compounds can be the polymerizable liquid crystal compound (A). If the content of the polymerizable liquid crystal compound (A) is within the above range, the polymerizable liquid crystal compound is easily arranged with a high alignment order, and the compound represented by formula (1A) is oriented therewith, and thus a polarizing film having excellent polarizing properties can be obtained.

[0141] From the viewpoint of improving the alignment properties of the polymerizable liquid crystal compound and the liquid-crystalline high molecular compound, the combined content of the polymerizable liquid crystal compound and the liquid-crystalline high molecular compound in the composition is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 99.9% by mass or less, relative to 100 parts by mass of the solid content of the composition, and is more preferably 70% by mass or more and 99.5% by mass or less, further preferably 80% by mass or more and 99% by mass or less, particularly preferably 80% by mass or more and 94% by mass or less, and more further preferably 80% by mass or more and 90% by mass or less.

[0142] The content of the azo compound (1A) in the composition is generally 0.1 parts by mass or more and 50 parts by mass or less, preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.1 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid-crystalline high molecular compound. If the content of the azo compound (1A) relative to the total amount of the polymerizable liquid crystal compound and the liquid-crystalline high molecular compound is 50 parts by mass or less, the alignment of the polymerizable liquid crystal compound, the liquid-crystalline high molecular compound, and the azo compound (1A) is less disturbed, and there is a tendency that a polarizing film having a high alignment order can be obtained.

[0143] High molecular compound

[0144] The composition can contain a high molecular compound in addition to the azo compound (1A), the polymerizable liquid crystal compound, and the liquid-crystalline high molecular compound. By containing a high molecular compound, the azo compound (1A) is easily dispersed in the composition. The high molecular compound that can be contained in the composition is not particularly limited as long as it can disperse the azo compound (1A). From the viewpoint of easily uniformly dispersing the azo compound (1A), an acrylic polymer such as polymethyl methacrylate (PMMA) is preferred. In addition, the high molecular compound can be a high molecular compound obtained by polymerizing the aforementioned polymerizable liquid crystal compound. The weight average molecular weight of the high molecular compound, in terms of polystyrene, is, for example, 10,000 or more and 200,000 or less, preferably 20,000 or more and 150,000 or less.

[0145] When the composition contains a high molecular compound, the content thereof can be appropriately selected depending on the purpose or the like. The content of the high molecular compound is preferably in the range of 10 parts by mass or less, more preferably 5.0 parts by mass or less, and further preferably 3.0 parts by mass or less, relative to 100 parts by mass of the solid content of the composition.

[0146] The composition preferably further contains a liquid medium such as a solvent and a polymerization initiator, and can further contain a photosensitizer, a polymerization inhibitor, a leveling agent, or the like as needed.

[0147] Solvent

[0148] The solvent is preferably a solvent that can completely dissolve the azo compound (1A), the polymerizable liquid crystal compound, the liquid-crystalline high molecular compound, and the high molecular compound. In addition, it is preferred to be a solvent that is inactive to the polymerization reaction of the polymerizable liquid crystal compound.

[0149] As the solvent, an alcohol solvent, an ester solvent, a ketone solvent, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a nitrile solvent, an ether solvent, a chlorine-containing solvent, or the like can be exemplified. These solvents can be used alone or in combination with two or more.

[0150] When the composition contains a solvent, the content ratio 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 ratio of the solid content in the composition is preferably 2% by mass or more and 50% by mass or less. If the solid content is 50% by mass or less, the viscosity of the composition is lowered, and the thickness of the film obtained from the composition, for example, becomes substantially uniform, and there is a tendency that unevenness is less likely to occur in the film. The content ratio of the solid content can be determined in consideration of the thickness of the film to be produced.

[0151] Polymerization initiator

[0152] The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound. From the aspect of being able to initiate the polymerization reaction at a lower temperature condition, the polymerization initiator is preferably a photopolymerization initiator. Specifically, a photopolymerization initiator capable of generating a reactive radical or acid by the action of light can be cited, of which a photopolymerization initiator generating a radical by the action of light is preferred.

[0153] As the polymerization initiator, benzoin compounds, benzophenone compounds, alkyl phenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts, and the like can be cited. The polymerization initiator can be appropriately selected from known polymerization initiators according to the purpose or the like. In addition, the polymerization initiator can be used alone or in combination with two or more.

[0154] The content of the polymerization initiator in the case where the composition contains the polymerization initiator is appropriately determined according to the kind and the 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 mass% or less, 10 mass% or less, or 8 mass% or less, with respect to 100 parts by mass of the polymerizable liquid crystal compound. In addition, 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 further preferably 0.1 parts by mass or more and 8 parts by mass or less, with respect to 100 parts by mass of the polymerizable liquid crystal compound. If the content of the polymerization initiator is within the above range, the polymerization can be performed without disordering the alignment of the polymerizable liquid crystal compound.

[0155] Photosensitizer

[0156] In the case where the composition contains the photopolymerization initiator, the composition can preferably contain at least one photosensitizer. By containing the photopolymerization initiator and the photosensitizer in the composition, there is a tendency that the polymerization reaction of the polymerizable liquid crystal compound is further promoted. As the photosensitizer, xanthone compounds such as xanthone and thioxanthone; anthracene compounds such as anthracene and alkoxy-substituted anthracene; phenothiazine and rubrene; and the like can be cited. The photosensitizer can be used alone or in combination with two or more.

[0157] In the case where the composition contains the photosensitizer, the content of the photosensitizer in the composition is appropriately determined according to the kind and the 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 further preferably 0.5 parts by mass or more and 8 parts by mass or less, with respect to 100 parts by mass of the polymerizable liquid crystal compound.

[0158] Polymerization inhibitor

[0159] The composition can contain at least one polymerization inhibitor. As the polymerization inhibitor, for example, there can be mentioned hydroquinone, hydroquinone containing an alkoxy group, catechol containing an alkoxy group (e.g., butyl catechol), pyrogallol, 2,2,6,6-tetramethylpiperidine-1-oxyl radical and the like radical scavengers; thiophenols; β-naphthylamines and β-naphthols; and the like. By including the polymerization inhibitor in the composition, the degree of progress of the polymerization reaction of the polymerizable liquid crystalline compound can be controlled.

[0160] In the case where the composition contains the 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 further 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 crystalline compound.

[0161] Leveling agent

[0162] The composition can contain at least one leveling agent. The leveling agent has a function of adjusting the flowability of the composition and making the coating film obtained by applying the composition more flat, and specifically, there can be mentioned a surfactant. As the leveling agent, at least one selected from the group consisting of a leveling agent in which a polyacrylate compound is a main component and a leveling agent in which a compound containing a fluorine atom is a main component is preferred. The leveling agent can be used alone or in combination of two or more.

[0163] In the case where the composition contains the leveling agent, the content of the leveling agent is preferably 0.05 parts by mass or more and 5 parts by mass or less, and more preferably 0.05 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the total amount of the polymerizable liquid crystalline compound and the liquid crystalline high molecular compound. If the content of the leveling agent is within the above range, the polymerizable liquid crystalline compound and the liquid crystalline high molecular compound are easily horizontally oriented, and there is a tendency that unevenness is less likely to occur and a smoother film (e.g., a polarizing film) is obtained.

[0164] If the content of the leveling agent is within the above range, the polymerizable liquid crystalline compound and the liquid crystalline high molecular compound are easily horizontally oriented, and there is a tendency that the obtained film becomes smoother. If the content of the leveling agent relative to the polymerizable liquid crystalline compound and the liquid crystalline high molecular compound exceeds the above range, there is a tendency that unevenness is easily generated in the obtained film.

[0165] Antioxidant

[0166] The composition can contain an antioxidant. The antioxidant is not particularly limited as long as the composition can exert the effects of the present application, and a known antioxidant can be used. From the viewpoint of having a high inhibitory effect on the photo-degradation of the azo compound (1A), the antioxidant is preferably a so-called primary antioxidant that has a function of preventing auto-oxidation by capturing a radical. Therefore, the antioxidant contained in the composition is more preferably at least one selected from the group consisting of a phenol-based compound, an alicyclic alcohol-based compound, and an amine-based compound. The antioxidant can be used alone as only one kind, or two or more kinds can be used in combination.

[0167] The content of the above-described antioxidant in the composition is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more, and more preferably 12 parts by mass or less, and further preferably 10 parts by mass or less, relative to 100 parts by mass of the composition. If the content of the antioxidant is above the above-described lower limit value, the photo-degradation of the azo compound (1A) can be more effectively inhibited. In addition, if the content of the antioxidant is below the above-described upper limit value, the alignment of the polymerizable liquid crystal compound is less likely to be disturbed, and a higher inhibitory effect on the photo-degradation of the azo compound (1A) can be expected.

[0168] The composition can contain other additives other than the above-described ones. As the other additives, for example, a release agent, a colorant such as a stabilizer, a bluing agent, a flame retardant, and a lubricant can be mentioned. In the case where the composition contains the other additives, the content of the other additives is preferably more than 0% and 20% by mass or less, and more preferably more than 0% and 10% by mass or less, relative to the solid content of the composition.

[0169] The composition can be produced by a method known in the art. For example, the azo compound (1A), the liquid crystal compound, and the additives such as the antioxidant and the leveling agent, which are added as needed, can be mixed and stirred to produce the composition.

[0170] <Membrane>

[0171] The membrane according to the present embodiment can be a membrane containing the azo compound (1A) as a forming material, and can be a membrane obtained by using a composition containing the azo compound (1A) and the liquid crystal compound as a forming material. The membrane formed from the composition can be formed by applying the composition to a substrate and film-forming. In the case where the composition contains the polymerizable liquid crystal compound, a membrane containing a cured product obtained by polymerizing the polymerizable liquid crystal compound can be formed by applying the composition to a substrate, film-forming, and then polymerizing and curing the polymerizable liquid crystal compound.

[0172] The composition can form a film with high orientation order, for example, a polarizing film. Thus, the film according to the present embodiment includes a polarizing film formed from the composition containing the azo compound (1A) and the liquid crystalline compound, and having high orientation order.

[0173] Here, the polarizing film with high orientation order can obtain a Bragg peak derived from a high-order structure such as a hexagonal phase, a crystal phase in X-ray diffraction measurement. Thus, the polarizing film formed from the composition is preferably oriented in a manner that the polymerizable liquid crystalline compound or the liquid crystalline high molecular compound shows a Bragg peak in X-ray diffraction measurement, and more preferably "horizontal orientation" in which the molecules of the polymerizable liquid crystalline compound or the liquid crystalline high molecular compound are oriented in the direction of the absorbed light. As for the high orientation order showing a Bragg peak, it can be achieved by controlling the kind of the polymerizable liquid crystalline compound or the liquid crystalline high molecular compound, the amount of the azo compound (1A), and the like.

[0174] As for the azo compound (1A) and the liquid crystalline compound constituting the composition for forming the film, the above-described matters are applied.

[0175] The film can be manufactured, for example, by a method including the following steps.

[0176] Step A: forming a coating film of a composition containing the azo compound (1A), the liquid crystalline compound, and a solvent;

[0177] Step B: removing at least a part of the solvent from the aforementioned coating film;

[0178] Step C: increasing the temperature to a temperature at which the liquid crystalline compound phase-transitions to a liquid phase or more, and then decreasing the temperature to phase-transition the liquid crystalline compound to a smectic phase (smectic liquid crystal state); and

[0179] Step D: polymerizing the polymerizable liquid crystalline compound as needed, while maintaining the aforementioned smectic phase (smectic liquid crystal state).

[0180] The formation of the coating film of the composition can be performed, for example, by applying the composition on a substrate, an alignment film described later, or the like. Alternatively, the composition can be applied directly on a phase difference film or other layer constituting a polarizing plate.

[0181] The substrate is typically a transparent substrate. Note that the substrate can be non-transparent when the substrate is not disposed on the display surface of a display element, for example, when the laminate after removing the substrate from the film is disposed on the display surface of a display element. The transparent substrate refers to a substrate having transparency that allows light, particularly visible light, to pass through. The transparency refers to a property of having a transmittance of 80% or more for light in the wavelength range of 380 nm to 780 nm. As a specific transparent substrate, a light-transmissive resin substrate can be mentioned.

[0182] As the resin constituting the light-transmissive resin substrate, there can be mentioned polyolefins; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylates; polyacrylates; cellulose esters; polyethylene naphthalate; polycarbonates; polysulfones; polyethersulfones; polyether ketones; polyphenylene sulfide and polyphenylene ether; and the like. From the viewpoint of ease of obtaining and transparency, polyethylene terephthalate, polymethacrylates, cellulose esters, cyclic olefin-based resins or polycarbonates are preferred.

[0183] The properties required of the substrate vary depending on the constitution of the film, and generally a substrate having as little phase difference as possible is preferred. As a substrate having as little phase difference as possible, there can be mentioned cellulose ester films such as Zero Tac (Konica Minolta Opto Co., Ltd.), Z-Tac (Fuji Photo Film Co., Ltd.) and the like which do not have a phase difference. In addition, an unstretched cyclic olefin-based resin substrate is also preferred. Hard coating treatment, anti-reflection treatment, antistatic treatment and the like can be applied to the surface of the substrate which is not laminated with the film.

[0184] The thickness of the substrate is generally 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 it is 20 μm or more, there is a tendency that the decrease in strength is suppressed and the processability becomes good.

[0185] As the method of applying the composition to a substrate or the like, there can be mentioned known methods such as spin coating, extrusion, gravure coating, die coating, bar coating, applicator coating, printing methods such as flexographic printing and the like.

[0186] Next, at least a part of the solvent contained in the coating film obtained from the composition is removed by drying or the like, whereby a dried coating film is formed. In the case where the polymerizable liquid crystalline compound is contained in the coating film, the dried coating film is formed by performing drying under conditions in which the polymerizable liquid crystalline compound does not polymerize. As the drying method of the coating film, there can be mentioned natural drying, air drying, heating drying, reduced pressure drying and the like.

[0187] Further, in order to make the liquid crystalline compound phase change into a liquid phase, the temperature is raised to a temperature at which the liquid crystalline compound phase changes into a liquid phase or more, and then the temperature is lowered to make the liquid crystalline compound phase change into a smectic phase (smectic liquid crystal state). This phase change can be performed after the removal of the solvent from the coating film, or it can be performed simultaneously with the removal of the solvent.

[0188] 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. As the polymerization method, photopolymerization is preferred. In photopolymerization, as the light to be irradiated to the dried coating film, one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays, active electron beams, and the like are appropriately selected depending on the kind of photopolymerization initiator contained in the dried coating film, the kind of polymerizable liquid crystal compound (particularly, the kind of polymerizable group possessed by the polymerizable liquid crystal compound), and the amount thereof. Among them, from the viewpoint of easy control of the progress of polymerization and the viewpoint that a device widely used in the field as a photopolymerization device can be used, ultraviolet light is preferred, and it is preferred to previously select the kind of polymerizable liquid crystal compound, the kind of photopolymerization initiator, and the like contained in the composition in such a manner that photopolymerization by ultraviolet light is possible. In addition, at the time of polymerization, the polymerization temperature can also be controlled by performing light irradiation while cooling the dried coating film with an appropriate cooling means. If the polymerization of the polymerizable liquid crystal compound is performed at a lower temperature by employing such a cooling means, even if the substrate is made of a material having a low heat resistance, a film can be appropriately formed. At the time of photopolymerization, by performing masking, development, and the like, a patterned film can also be obtained.

[0189] As the light source of the aforementioned active energy ray, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-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 that emits light in the wavelength range of 380 nm or more and 440 nm or less, a chemical lamp, a black light, a microwave-excited mercury lamp, a metal halide lamp, and the like can be given.

[0190] The ultraviolet irradiation intensity can generally be 10 mW / cm 2 3,000 mW / cm 2 or more. The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for the activation of the photopolymerization initiator. The irradiation time of the light can generally be 0.1 seconds or more and 10 minutes or less, preferably 0.1 seconds or more and 5 minutes or less, more preferably 0.1 seconds or more and 3 minutes or less, and further preferably 0.1 seconds or more and 1 minute or less. When irradiation is performed once or a plurality of times at such an ultraviolet irradiation intensity, the cumulative light amount is preferably 10 mJ / cm 2 3,000 mJ / cm 2 or more.

[0191] By performing photopolymerization, the polymerizable liquid crystalline compound is polymerized while maintaining the liquid crystal state as a smectic phase, preferably a high-order smectic phase, to form a film. The film obtained by polymerizing the polymerizable liquid crystalline compound while maintaining the liquid crystal state as a smectic phase also has the advantage of having high polarizing performance due to the action of the dichroic dye, compared to conventional host-guest type polarizing films, i.e., films formed from a nematic liquid crystal state. In addition, the film also has the advantage of being excellent in strength, compared to films formed from only a dichroic dye or a lyotropic liquid crystal.

[0192] The thickness of the film can be appropriately selected depending on the display device or the like to which it is applied, and is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and further preferably 1 μm or more and 3 μm or less.

[0193] When the film is used as a polarizing film, it is preferably formed on an alignment film. The alignment film is a film having an alignment restricting force that causes the polymerizable liquid crystalline compound and the liquid-crystalline high molecular compound to be aligned in a desired direction. As the alignment film, it is preferable to have solvent resistance that does not dissolve due to coating or the like of a composition containing a liquid-crystalline compound (which includes at least one of the polymerizable liquid crystalline compound and the liquid-crystalline high molecular compound), and heat resistance to heat treatment for removing a solvent and aligning the polymerizable liquid crystalline compound. As the alignment film, an alignment film containing an alignment polymer, a photo-alignment film, and a groove alignment film having a concave-convex pattern or a plurality of grooves on the surface can be given, and from the viewpoint of the precision and quality of the alignment angle, a photo-alignment film is preferable.

[0194] <Stacked Body>

[0195] The stacked body according to the present embodiment can have a film containing the azo compound (1A) as a forming material, or a film containing a composition containing the azo compound (1A) and a liquid-crystalline compound as a forming material. The stacked body can have a substrate, and a film containing the azo compound (1A) as a forming material disposed on the substrate, or a substrate, an alignment film disposed on the substrate, and a film containing the azo compound (1A) as a forming material disposed on the alignment film. The film containing the azo compound (1A) as a forming material can constitute a polarizing film. In addition, the substrate can be a phase difference film. The stacked body can constitute, for example, a polarizing plate. The stacked body can be manufactured, for example, by forming a film on a substrate according to the film manufacturing method described above.

[0196] From the viewpoint of the bendability and visual recognition of the display device, the thickness of the stacked body is preferably 10 μm or more and 300 μm or less, more preferably 20 μm or more and 200 μm or less, and further preferably 25 μm or more and 100 μm or less.

[0197] When the layered body has a phase difference film as a base material, the thickness of the phase difference film can be appropriately selected depending on the display device to which the layered body is applied.

[0198] <Display device>

[0199] The display device of the present embodiment has the aforementioned layered body, and the layered body can be a polarizing plate. The display device can be obtained, for example, by adhering the layered body as a polarizing plate to the surface of the display device via an adhesive layer. The display device refers to a device having a display element, and includes a device including a light-emitting element or a light-emitting device as a light-emitting source. As the display device, for example, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, an electron emission display device (for example, a field emission display device (FED), a surface-conduction electron-emitter array (SED)), electronic paper (a display device using electronic ink, an electrophoretic element, or the like), a plasma display device, a projection display device (for example, a grating light valve (GLV) display device, a display device having a digital micromirror device (DMD)), and a piezoelectric ceramic display, or the like can be given. The liquid crystal display device includes any of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, a projection liquid crystal display device, and the like. These display devices can be display devices that display a two-dimensional image, or stereoscopic display devices that display a three-dimensional image. In particular, as the display device, an organic EL display device and a touch panel display device are preferable, and an organic EL display device is particularly preferable.

[0200] <Example>

[0201] Hereinafter, the present application will be specifically described by way of examples, but the present application is not limited to these examples.

[0202] Compound (1-1-a) and compound (1-3-a) were synthesized by a known diazo coupling method.

[0203] Synthesis Example 1: Synthesis of compound (1-1)

[0204] 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), cooled to 0°C, chlorotriethylsilane (0.095 g, 0.63 mmol) was added, and the temperature was returned 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 obtained solid was purified by silica gel column chromatography with chloroform as the developing agent, to obtain compound (1-1) (0.130 g, yield 75%).

[0205] [Chemical Formula 15]

[0206]

[0207] 1 H-NMR (400 MHz, CDC13): 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)

[0208] UV-visible light spectrum: λmax = 593 nm (in chloroform)

[0209] Synthesis Example 2: Synthesis of compound (1-2)

[0210] Compound (1-1-a) (0.139 g, 0.299 mmol), imidazole (0.061 g, 0.90 mmol) were dissolved in N,N-dimethylformamide (5.0 mL), cooled to 0°C, chlorodimethyltert-hexylsilane (0.112 g, 0.626 mmol) was added, and it was returned 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 obtained solid was purified using a silica gel column chromatography with chloroform as the developing agent to obtain compound (1-2) (0.130 g, yield 75%).

[0211] [Chemical Formula 16]

[0212]

[0213] 1 H-NMR (400 MHz, CDC13): 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)

[0214] UV-visible light spectrum: λmax = 592 nm (in chloroform)

[0215] Synthesis Example 3: Synthesis of compound 1-3

[0216] Compound (1-3-a) (1.127 g, 2.501 mmol), imidazole (0.256 g, 3.76 mmol) were dissolved in tetrahydrofuran (25.0 mL), cooled to 0°C, chlorodimethyl-tert-hexylsilane (0.492 g, 2.77 mmol) was added, and the temperature was returned 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 obtained solid was purified by silica gel column chromatography with chloroform as the developing agent to obtain compound (1-3) (0.690 g, yield 47%).

[0217] [Chemical Formula 17]

[0218]

[0219] 1 H-NMR (400 MHz, 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)

[0220] UV-visible light spectrum: λmax= 593 nm (in chloroform)

[0221] Synthesis Example 4: Synthesis of compound (1-93)

[0222] Compound (1-1-a) (0.500 g, 1.05 mmol), imidazole (0.219 g, 3.20 mmol) were dissolved in N,N-dimethylformamide (10.5 mL), cooled to 0°C, tert-butyldiphenylchlorosilane (0.596 g, 2.10 mmol) was added, and the temperature was returned 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 obtained solid was purified by silica gel column chromatography with chloroform as the developing agent to obtain compound (1-93) (0.614 g, yield 82%).

[0223] [Chemical Formula 18]

[0224]

[0225] 1H-NMR (400 MHz, CDC13): 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)

[0226] UV-visible spectrum: λmax = 592 nm (in chloroform)

[0227] Comparative Synthesis Example 1: Synthesis of Compound (2-1)

[0228] 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), 2-ethylhexanoic acid (0.149 g, 1.03 mmol) were mixed and stirred at room temperature for 15 hours. Saturated aqueous sodium bicarbonate solution was added to the reaction vessel, and the precipitated solid was filtered and washed with methanol. The obtained solid was purified using silica gel column chromatography with chloroform as the developing agent to obtain compound (2-1) (0.049 g, yield 21%).

[0229] [Chemical Formula 19]

[0230]

[0231] 1 H-NMR (400 MHz, CDC13): 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), 3.52 (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)

[0232] UV-visible spectrum: λmax = 594 nm (in chloroform)

[0233] The following compound (2-2) and compound (2-3) were synthesized using a known diazo coupling method.

[0234] [Chemical Formula 20]

[0235]

[0236] Example 1: Preparation of composition E1 containing compound (1-1)

[0237] The following ingredients were mixed and stirred at 90°C for 1 hour, whereby composition E1 was obtained.

[0238]

[0239] The structure of the polymerizable liquid crystal compound is shown below. Note that the polymerizable liquid crystal compounds (A-6), (A-8) were synthesized using the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[0240] [Chemical Formula 21]

[0241]

[0242] Using the obtained composition E1, a polarizing film was formed in the following manner.

[0243] 1. Formation of alignment film

[0244] A glass substrate was used as the substrate. On the glass substrate, a 2 mass% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000, fully saponified type, manufactured by FUJIFILM and Wako Pure Chemical Industries, Ltd.) (alignment film polymer composition) was applied by the spin coating method, and after drying, a film having a thickness of 100 nm was formed. Next, rubbing treatment was performed on the surface of the obtained film, whereby an alignment layer was formed. The rubbing treatment was performed using a semi-automatic rubbing device (trade name: LQ-008 type, manufactured by Jishan Engineering Co., Ltd.) using a cloth (trade name: YA-20-RW, manufactured by Kikugawa Chemical Co., Ltd.) under conditions of a pressure of 0.15 mm, a rotation speed of 500 rpm, and 16.7 mm / s. By this rubbing treatment, a laminate (1) in which an alignment film was formed on a glass substrate was obtained.

[0245] 2. Formation of polarizing film

[0246] The obtained composition E1 was applied to the alignment film of the laminate (1) by the spin coating method, and after heating and drying on a hot plate at 120°C for 1 minute, rapid cooling to room temperature was performed, and a dried film was formed on the alignment layer. Next, using a UV irradiation device (SPOT CURE SP-7; manufactured by USHIO Inc.), ultraviolet rays were irradiated at an exposure amount of 2000 mJ / cm 2 (under the condition of 313 nm), whereby the polymerizable liquid crystal compound contained in the dried film was polymerized, and a polarizing film was formed from the dried film, and a laminate (2) was obtained. The thickness of the polarizing film at this time was measured using a laser microscope (OLS3000 manufactured by Olympus Corporation), and the result was 1.8 μm.

[0247] Example 2

[0248] The same operation as in Example 1 was conducted except that compound (1-2) was used instead of compound (1-1) to obtain a composition E2. The same operation as in Example 1 was conducted except that the obtained composition E2 was used to obtain a laminate (2) on which a polarizing film was formed.

[0249] Example 3

[0250] The same operation as in Example 1 was conducted except that compound (1-3) was used instead of compound (1-1) to obtain a composition E3. The same operation as in Example 1 was conducted except that the obtained composition E3 was used to obtain a laminate (2) on which a polarizing film was formed.

[0251] Example 4

[0252] The same operation as in Example 1 was conducted except that compound (1-93) was used instead of compound (1-1) to obtain a composition E4. The same operation as in Example 1 was conducted except that the obtained composition E4 was used to obtain a laminate (2) on which a polarizing film was formed.

[0253] Comparative Example 1

[0254] The same operation as in Example 1 was conducted except that compound (2-1) was used instead of compound (1-1) to obtain a composition Cl. The same operation as in Example 1 was conducted except that the obtained composition Cl was used to obtain a laminate (2) on which a polarizing film was formed.

[0255] Comparative Example 2

[0256] The same operation as in Example 1 was conducted except that compound (2-2) was used instead of compound (1-1) to obtain a composition C2. The same operation as in Example 1 was conducted except that the obtained composition C2 was used to obtain a laminate (2) on which a polarizing film was formed.

[0257] Comparative Example 3

[0258] The same operation as in Example 1 was conducted except that compound (2-3) was used instead of compound (1-1) to obtain a composition C3. The same operation as in Example 1 was conducted except that the obtained composition C3 was used to obtain a laminate (2) on which a polarizing film was formed.

[0259] < Evaluation >

[0260] Absorbance retention rate

[0261] The storage stability of the composition obtained above was evaluated as follows: Immediately after preparation (within 10 minutes), the composition was diluted with chloroform, and the initial absorbance was measured at the wavelength of maximum absorption in the absorption spectrum. The diluted solution was stored at room temperature (25°C), and the absorbance at the wavelength of maximum absorption was measured again after 1 day and 5 days from the time of preparation. The absorbance obtained after the second measurement was divided by the initial absorbance, and the absorbance retention rate (%) after 1 day and 5 days was calculated, respectively, and evaluated according to the following evaluation criteria. The results are shown in Table 1.

[0262] Evaluation Criteria

[0263] A: Absorbance retention rate is between 70% and 100%.

[0264] B: Absorbance retention rate is above 45% and below 70%.

[0265] C: Absorbance retention rate is less than 45%.

[0266] Evaluation of polarizing film

[0267] The appearance of the polarizing film obtained above was examined visually and under a microscope to check for orientation defects caused by crystal precipitation, and evaluated according to the following evaluation criteria. The results are shown in Table 1.

[0268] Evaluation Criteria

[0269] A: There is no orientation defect; it maintains good orientation.

[0270] B: A slight orientation defect was confirmed, but it can still be used as a polarizing film.

[0271] C: An orientation defect was identified, making it unsuitable for use as a polarizing film.

[0272] The dichroic ratio of the laminate (2) obtained above was determined as follows. Using a spectrophotometer (Shimadzu Corporation UV-3150) equipped with a folder containing the laminate (2), the absorbance (A1) along the transmission axis and the absorbance (A2) along the absorption axis at the maximum absorption wavelength (λmax) of the polarizing film of the laminate (2) were measured using the two-beam method. A grid that intercepts 50% of the light was placed on the reference side of the folder. The ratio (A2 / A1) was calculated based on the measured absorbance (A1) along the transmission axis and the absorbance (A2) along the absorption axis, and was taken as the dichroic ratio (DR). The results are shown in Table 1. Note that - in the table indicates no evaluation.

[0273] [Table 1]

[0274]

[0275] As shown in Table 1, the storage stability of the composition containing the azo compound (1A) is excellent, and a high-quality polarizing film can be formed.

Claims

1. An azo compound, represented by the following formula (1A), [Chemical Formula 1] In equation (1A), L 1 and L 2 Each can independently represent an alkylene group with 1 to 4 carbon atoms or a single bond; y represents 1; p and q each represent 0 or 1 independently, and at least one of p and q is 1; R 12 R 13 and R 14 Each can independently represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, or a phenyl group; X represents an oxygen atom or NR. 5 ; R 5 This represents an aliphatic hydrocarbon group with 1 to 6 hydrogen or carbon atoms, which can be combined with R 13 They bond together to form a ring; Q represents -N = N-; Ar 1 Ar 2 and Ar 3 Each can be independently represented as 1,4-phenylene or divalent thienothiazole dimethyl.

2. The azo compound as claimed in claim 1, which is represented by the following formula (1), [Chemical Formula 2] In formula (1), L represents an alkylene group with 1 to 4 carbon atoms or a single bond; y represents 1; R 1 It indicates that one group is selected from the group consisting of methylamino, ethylamino, dimethylamino, diethylamino, and ethylmethylamino. R 2 R 3 and R 4 Each group independently represents an aliphatic hydrocarbon group with 1 to 6 carbon atoms; Q represents -N = N-; Ar 1 Ar 2 and Ar 3 Each can be independently represented as 1,4-phenylene or divalent thienothiazole dimethyl.

3. The azo compound as described in claim 1 or 2, wherein, Ar 1 and Ar 2 At least one of them is a divalent thienothiazoldiyl group.

4. A composition comprising: an azo compound according to any one of claims 1 to 3; and a liquid crystal compound comprising at least one of a polymeric liquid crystal compound and a liquid crystal polymer compound.

5. The composition of claim 4, wherein, The aforementioned liquid crystal compounds are smectic liquid crystal compounds.

6. A membrane, wherein the composition of claim 4 or 5 is used as the forming material.

7. A laminate comprising the membrane of claim 6.

8. A display device comprising the film of claim 6 or the laminate of claim 7.

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