Composition, film, laminate, and display device

Abstract

This invention relates to a composition comprising a compound of formula (1), a compound of formula (2) with a maximum absorption wavelength of 550 nm to 650 nm, and a liquid crystal compound. n and m are 1 or 2. R 1 and R 3 Indicates a substituent. R 2 and R 4 Indicates alkylamino, alkoxy, or alkylthio. P represents a single bond, -OC(=O)-, -C(=O)O-, -NHC(=O)-, -C(=O)NH-, -C≡C-, -CH=CH-, -CH=N-, -N=N-, or N=CH-. Ar 1 Ar 2 and Ar 3 Ar represents a 1,4-phenylene or a divalent sulfur-containing aromatic heterocyclic group. 1 and Ar 2 At least one of Ar is fluorinated. 4 Ar 5 and Ar 6 It represents 1,4-phenylene, naphthyl, or divalent sulfur-containing aromatic heterocyclic groups.

Description

Technical Field

[0001] This invention relates to compositions, films, laminates, and display devices. Background Technology

[0002] For displays such as image display panels, there is a continuous demand for thinner designs, and further thinning is also required for polarizing plates and polarizers, which are one of their components. To address such demands, for example, a thin host-guest polarizer has been proposed, which has a polarizing film comprising a polymerizable liquid crystal compound and a pigment compound that displays dichroism (see, for example, Patent Documents 1 and 2).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Publication No. 2007-510946

[0006] Patent Document 2: Japanese Patent Application Publication No. 2013-37353 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] In host-guest polarizers containing multiple pigments, the dichroic ratio in the wavelength range of 570 nm to 700 nm is sometimes reduced due to light degradation of the polarizing film. The object of this invention is to provide a composition capable of forming a polarizing film that suppresses the reduction in dichroic ratio in the wavelength range of 570 nm to 700 nm.

[0009] Methods for solving problems

[0010] The present invention provides the following [1] to [8].

[0011] [1] A composition comprising a first compound represented by formula (1), a second compound represented by formula (2), and a liquid crystal compound, wherein the second compound has a maximum absorption wavelength in a wavelength range of 550 nm to 650 nm, and the liquid crystal compound comprises at least one of a polymeric liquid crystal compound and a liquid crystal polymer compound.

[0012] [Chemical Formula 1]

[0013]

[0014] In equations (1) and (2), n and m each independently represent 1 or 2.

[0015] R 1 and R 3 Each substituent can be represented independently.

[0016] R 2 and R 4 Each can be independently represented by one group selected from the group consisting of alkylamino, alkoxy, and alkylthio groups, wherein the hydrogen atoms of these groups can be replaced by polymerizable groups.

[0017] P represents a single bond, or at least one group selected from the group consisting of -OC(=O)-, -C(=O)O-, -NHC(=O)-, -C(=O)NH-, -C≡C-, -CH=CH-, -CH=N-, -N=N- and -N=CH-.

[0018] Ar 1 Ar 2 and Ar 3 Each can independently represent a 1,4-phenylene or a divalent sulfur-containing aromatic heterocyclic group having at least one of the following as substituents: halogen atom, hydroxyl, methyl and methoxy group.

[0019] Ar 1 and Ar 2 At least one of them has a fluorine atom as a substituent. Among them, in Ar 2 It has fluorine atoms and contains two Ar atoms. 2 In the case of at least one Ar 2 It only needs to have fluorine atoms.

[0020] Ar 4 Ar 5 and Ar 6 Each can independently represent a 1,4-phenylene, naphthyl, or divalent sulfur-containing aromatic heterocyclic group that may have at least one of the following as a substituent: a halogen atom, a hydroxyl group, a methyl group, or a methoxy group.

[0021] When n is 2, there are 2 Ar 2 P and P can be the same or different.

[0022] When m is 2, there are 2 Ar 5 They can be the same, or they can be different.

[0023] [2] The composition as described in [1], wherein, in the aforementioned formula (2), Ar 4 Ar 5 and Ar 6 At least one of them represents a divalent sulfur-containing aromatic heterocyclic group.

[0024] [3] The composition as described in [1] or [2], wherein, in the aforementioned formula (2), Ar 4 Ar 5 and Ar 6At least one of them represents thieno[2,3-d]thiazole-2,5-dimethyl.

[0025] [4] The composition of any one of [1] to [3], wherein in the aforementioned formula (1), P represents a single bond or at least one group selected from the group consisting of -OC(=O)-, -C(=O)O-, -NHC(=O)-, -C(=O)NH- and -N=N-.

[0026] [5] The composition of any one of [1] to [4], wherein the aforementioned liquid crystal compound is a smectic liquid crystal compound.

[0027] [6] A membrane which uses the composition of any one of [1] to [5] as the forming material.

[0028] [7] A laminate having the membrane described in [6].

[0029] [8] A display device having the laminate described in [7].

[0030] Invention Effects

[0031] According to the present invention, a composition can be provided that can form a reduced-suppressed polarizing film with a dichroism ratio in a wavelength range of 570 nm to 700 nm. Detailed Implementation

[0032] In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from others, as long as they achieve the desired purpose of the process. Furthermore, regarding the content of each component in the composition, if multiple substances belonging to each component are present in the composition, unless otherwise specified, the term refers to the total amount of those substances present in the composition. Hereinafter, embodiments of the present invention will be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without prejudice to the spirit of the invention.

[0033] <Composition>

[0034] The composition according to this embodiment includes a first compound represented by formula (1), a second compound represented by formula (2), and a liquid crystal compound. The second compound has a maximum absorption wavelength in the wavelength range of 550 nm to 650 nm, and the liquid crystal compound includes at least one of a polymeric liquid crystal compound and a liquid crystal polymer compound. The composition can be used as, for example, a polarizing film forming material. That is, the composition can be a polarizing film forming composition. The lightfastness of a polarizing plate equipped with a polarizing film obtained by using the composition as a forming material is improved, and the decrease in dichroism ratio associated with light degradation in the wavelength range of 570 nm to 700 nm can be suppressed.

[0035] Compound 1

[0036] The composition comprises at least one of the first compounds. The first compound has a structure represented by formula (1), in Ar 1 and Ar 2 At least one of the compounds contains a fluorine atom as a substituent. Therefore, the first compound is considered to exhibit excellent lightfastness. Because the first compound exhibits excellent lightfastness, it is believed that the disorder of the orientation of the pigment compounds caused by photodegradation in a polarizing film formed from the composition, for example, can be suppressed, and the decrease in the dichroic ratio from the second compound in the wavelength range of 570 nm to 700 nm can be suppressed. It should be noted that the second compound, in a solution state, has a maximum absorption wavelength in the wavelength range of 550 nm to 650 nm, but it is believed that by forming a polarizing film, the absorption wavelength shifts towards the longer wavelength side.

[0037] [Chemical Formula 2]

[0038]

[0039] In equation (1), R 1 Indicates a substituent. R 1 The substituent represented can be, for example, a substituent comprising at least an alkylene group, or a substituent obtained by adding a hydrogen atom or a polymeric group to a divalent group formed by adding at least one of the groups selected from alkylene, alkenyl, oxygen, sulfur, carbonyl, and dialkylsilanediyl groups. As R 1 Examples of substituents include alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio, alkoxyalkylene, alkoxycarbonyl, alkylcarbonyloxy, alkoxycarbonylalkyleneoxycarbonyl, alkylcarbonyloxyalkylene, trialkylsilylalkylene, trialkylsilylalkyleneoxy, etc., and at least one can be selected from the group consisting of them. Additionally, R 1The substituent can be a nitro, cyano, perfluoroalkyl, or other haloalkyl group, a halogen atom, or at least one selected from the group consisting of these. In one embodiment, R 1 The substituent may be selected from at least one group consisting of alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio, alkoxyalkylene, alkoxycarbonyl, alkylcarbonyloxy, alkoxycarbonylalkyleneoxycarbonyl, alkylcarbonyloxyalkylene, trialkylsilyloxyalkylene, trialkylsilyloxyalkyleneoxy, nitro, cyano, haloalkyl, and halogen atoms.

[0040] R 1 The alkyl group represented by the substituent can be either straight-chain or branched. R 1 The substituent may contain alkyl groups with 1 to 12 carbon atoms, preferably 1 to 10, and more preferably 1 to 8. R 1 The substituent may contain alkylene groups with 1 to 12 carbon atoms, preferably 1 to 10, and more preferably 1 to 8.

[0041] As R 1 Specific examples of alkyl groups included in the substituents include, for example, methyl, ethyl, propyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 2-methylbutyl, 3-methylbutyl, hexyl, 1,1-dimethyl-2-methylpropyl, heptyl, 1-ethylpentyl, octyl, 1-ethylhexyl, 2-ethylhexyl, nonyl, 3,7-dimethyloctyl, etc. As R 1 Specific examples of alkylene groups included in the substituents include, for example, methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, cyclohexane-1,4-diyl, etc.

[0042] R 1 At least one of the hydrogen atoms in the indicated substituent can be replaced by a polymerizable group. Examples of polymerizable groups include (meth)acrylate ((meth)acryloyloxy), vinylphenyl, vinyl, and epoxy groups. The polymerizable group is preferably a free radical polymerizable group, and (meth)acrylate is preferred. 1 When polymerizable groups are present, the number of such groups is, for example, one or two, preferably one.

[0043] R 2 This indicates a group selected from the group consisting of alkylamino, alkoxy, and alkylthio groups, preferably alkylamino or alkoxy. The alkylamino group can be a monoalkylamino or dialkylamino, preferably dialkylamino. R 2More preferably, it is dimethylamino, diethylamino, ethylmethylamino, pyrrolyl, piperidinyl, morpholinyl, oxazolyl, methoxy, or ethoxy. 2 At least one of the hydrogen atoms in the indicated group can be replaced by a polymerizable group. R 2 When polymerizable groups are present, the number of such groups is, for example, one or two, preferably one.

[0044] 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. Examples of divalent sulfur-containing aromatic heterocyclic groups include benzothiazolidine, thienothiazolidine, and thiazolidine, with benzothiazolidine being preferred. 1 Ar 2 and Ar 3 The substituents can be at least one selected from the group consisting of halogen atoms, hydroxyl groups, methyl groups, and methoxy groups, preferably fluorine atoms, chlorine atoms, hydroxyl groups, methyl groups, or methoxy groups, and more preferably fluorine atoms or hydroxyl groups. 1 Ar 2 and Ar 3 The substituents in each are independently, for example, 0, 1 or 2, preferably 0 or 1.

[0045] Ar 1 and Ar 2 At least one of them has a fluorine atom as a substituent. That is, Ar 1 and Ar 2 At least one of them can have a fluorine atom as a substituent in Ar 2 It has fluorine atoms as substituents and contains two Ar atoms. 2 In the case of at least one Ar 2 It only requires the presence of a fluorine atom as a substituent. Ar 1 and Ar 2 The total number of fluorine atoms in it is, for example, 1 to 4, preferably 1 to 3, or 1 or 2. Ar 1 and Ar 2 The fluorine atom in Ar can be substituted at a meta position relative to the azo group, for example. 1 and Ar 2 At least one of them can have a hydroxyl group in addition to a fluorine atom. The fluorine atom and the hydroxyl group can react with Ar. 1 and Ar 2 One of them can be replaced, or Ar can be replaced. 1 and Ar 2 Each is substituted. It is believed that the fluorine atom and the hydroxyl group exhibit the same degree of size and electronegativity, and therefore can similarly improve the lightfastness of the first compound.

[0046] P represents a single bond, or at least one group selected from the group consisting of -OC(=O)-, -C(=O)O-, -NHC(=O)-, -C(=O)NH-, -C≡C-, -CH=CH-, -CH=N-, -N=N-, and -N=CH-. P is preferably -OC(=O)-, -C(=O)O-, -NHC(=O)-, -C(=O)NH-, or -N=N-, more preferably -OC(=O)-, -NHC(=O)-, or -N=N-.

[0047] n represents 1 or 2. When n is 2, there are 2 Ar... 2 And P can be the same or different. That is, 2 Ar 2 Each can be the same or different. In addition, each of the two Ps can be the same or different.

[0048] The first compound may have a maximum absorption wavelength (λmax) in a wavelength range different from, for example, the maximum absorption wavelength of the second compound described later. The maximum absorption wavelength of the first compound may be, for example, 350 nm to 600 nm, and preferably 380 nm to 550 nm. The maximum absorption wavelength is determined at room temperature (e.g., 25°C) for a chloroform solution of the first compound. For example, the maximum absorption wavelength of the first compound can be determined by appropriately selecting Ar... 1 Ar 2 and Ar 3 skeleton structure, Ar 1 Ar 2 and Ar 3 Substituents, n, R 2 Adjust it to the desired wavelength.

[0049] Specific examples of the first compound include compounds represented by formulas (1-1) to (1-70) below, but the invention is not limited thereto. In the following specific examples, Et represents ethyl and n-Bu represents n-butyl.

[0050] [Chemical Formula 3]

[0051]

[0052] [Chemical Formula 4]

[0053]

[0054] [Chemical Formula 5]

[0055]

[0056] [Chemical Formula 6]

[0057]

[0058] [Chemical Formula 7]

[0059]

[0060] [Chemical Formula 8]

[0061]

[0062] [Chemical Formula 9]

[0063]

[0064] From the viewpoint of maintaining the dichroic ratio, the first compound is preferably at least one of the group consisting of compounds represented by any one of formulas (1-1) to (1-51) and (1-60) to (1-70), more preferably at least one of the group consisting of compounds represented by any one of formulas (1-1) to (1-40) and (1-64) to (1-70).

[0065] Compound 2

[0066] The composition comprises at least one of the second compounds. The second compound has the structure represented by formula (2) and has a maximum absorption wavelength in the wavelength range of 550 nm to 650 nm.

[0067] [Chemical Formula 10]

[0068]

[0069] In equation (2), R 3 Indicates a substituent. R 3 The details of the substituents are the same as those of R in equation (1). 1 The substituents are represented similarly. R 4 It indicates that one group is selected from the group consisting of alkylamino, alkoxy, and alkylthio, preferably alkylamino, for example, dialkylamino. R 4 More preferably, it is dimethylamino, diethylamino, ethylmethylamino, pyrrolyl, piperidinyl, morpholinyl, or oxazolyl. 4 At least one of the hydrogen atoms in the indicated group can be replaced by a polymerizable group. R 4 When polymerizable groups are present, the number of such groups is, for example, one or two, preferably one.

[0070] Ar 4 Ar 5 and Ar 6Each can independently represent a 1,4-phenylene group that may have substituents, a naphthyl group that may have substituents, or a divalent sulfur-containing aromatic heterocyclic group that may have substituents. Examples of divalent sulfur-containing aromatic heterocyclic groups include thiazolediyl, benzothiazolediyl, and thienothiazolediyl. Regarding Ar... 4 Ar 5 and Ar 6 Preferably, at least one of the groups represents a divalent sulfur-containing aromatic heterocyclic group, more preferably at least one represents a thienothiazole dimethyl group. Further preferably, Ar... 6 It represents thiophenothiazoldiyl.

[0071] Ar 4 Ar 5 and Ar 6 The naphthyl group can be, for example, naphth-1,4-diyl. In addition, the thiazole diyl group can be thiazole-2,4-diyl or thiazole-2,5-diyl, the benzothiazole diyl group can be benzothiazole-2,5-diyl or benzothiazole-2,6-diyl, and the thienothiazole diyl group can be thieno[2,3-d]thiazole-2,5-diyl.

[0072] Ar 4 Ar 5 and Ar 6 The substituents can be at least one selected from the group consisting of halogen atoms, hydroxyl groups, methyl groups, and methoxy groups, preferably fluorine atoms, chlorine atoms, hydroxyl groups, methyl groups, or methoxy groups, and more preferably fluorine atoms or hydroxyl groups. 4 Ar 5 and Ar 6 The substituents in each are independently, for example, 0, 1 or 2, preferably 0 or 1.

[0073] m represents 1 or 2. When m is 2, there are 2 Ar... 5 They can be the same or different.

[0074] The second compound exhibits a maximum absorption wavelength (λmax) in the wavelength range of 550 nm to 650 nm, preferably in the range of 560 nm to 640 nm, and more preferably in the range of 570 nm to 630 nm. The maximum absorption wavelength is determined at room temperature (e.g., 25°C) for a chloroform solution of the second compound. For example, the maximum absorption wavelength of the second compound can be determined by appropriately selecting Ar... 4 Ar 5 and Ar 6 skeleton structure, Ar 4 Ar 5 and Ar 6 Substituents, n, R 4Adjust it to the desired wavelength.

[0075] Specific examples of the second compound include compounds represented by the following formulas (2-1) to (2-42), but the invention is not limited thereto.

[0076] [Chemical Formula 11]

[0077]

[0078] [Chemical Formula 12]

[0079]

[0080] [Chemical Formula 13]

[0081]

[0082] [Chemical Formula 14]

[0083]

[0084] [Chemical Formula 15]

[0085]

[0086] [Chemical Formula 16]

[0087]

[0088] From the viewpoint of dichroism ratio, the second compound is preferably at least one of the group consisting of compounds represented by any one of formulas (2-1) to (2-32) and (2-40) to (2-42), more preferably at least one of the group consisting of compounds represented by any one of formulas (2-1) to (2-18).

[0089] Regarding the content of the first compound in the composition, for example, it is preferably 50 parts by mass or less, more preferably 0.1 parts by mass or more but less than 10 parts by mass, and even more preferably 0.1 parts by mass or more but less than 5 parts by mass, relative to 100 parts by mass of the solid components of the composition. Within the above range, sufficient dispersion of the first compound can be achieved. Thus, a film containing the composition of the first compound, in which defect generation is sufficiently suppressed, can be obtained efficiently. It should be noted that, in this specification, the term "solid components" refers to the total amount of components after removing volatile components such as solvents from the composition. The composition may contain only one first compound, or it may combine two or more first compounds with different structures. When the composition contains two or more first compounds, they may have different maximum absorption wavelengths.

[0090] Regarding the content of the second compound in the composition, for example, it is preferably 50 parts by mass or less, more preferably 0.1 parts by mass or more but less than 10 parts by mass, and even more preferably 0.1 parts by mass or more but less than 5 parts by mass, relative to 100 parts by mass of the solid components of the composition. Within the above range, sufficient dispersion of the first compound can be achieved. Thus, a film containing the composition of the second compound as a forming material, in which defect generation is sufficiently suppressed, can be obtained efficiently. The composition may contain only one type of second compound, or it may combine two or more second compounds with different structures. When the composition contains two or more second compounds, they may have different maximum absorption wavelengths.

[0091] Regarding the ratio of the first compound to the second compound in the composition, the ratio of the content of the second compound to the content of the first compound can be, for example, 0.5 to 2.0, preferably 0.6 to 1.8 or 0.7 to 1.5.

[0092] Methods for manufacturing compounds 1 and 2

[0093] Compound 1 and Compound 2 can be prepared by appropriately applying conventionally known synthetic methods. Specifically, the azo structure (-N=N-) in Compound 1 and Compound 2 can be constructed, for example, by converting an aromatic amine compound having a primary amino group into a diazonium salt using sodium nitrite or the like, referring to the manufacturing examples described in paragraphs

[0220] to

[0268] of International Publication WO2016 / 136561, thereby diazo-coupled the aromatic compound. Alternatively, the azo structure containing a thiazole structure can be constructed, for example, according to J. Mol. Struct., 2011, 987, 158.

[0094] R 1 R 2 R 3 or R 4 Compounds that are alkoxyl groups can be obtained, for example, by applying S to a precursor having a hydroxyl group. N 2. Substitution reaction to produce a compound having the desired alkoxy group. S N The 2-substitution reaction can be carried out under known reaction conditions, for example, as described in J. Am. Chem. Soc., 2008, 130, 13079.

[0095] When the first or second compound contains -OC(=O)- or C(=O)O-, it can be synthesized, for example, by using a precursor having a carboxyl group and a precursor having a hydroxyl group, referring to Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y.; Ma, D. J. J. G. Chem. 2009, 74(3), 4542-4546, etc., by applying a dehydration condensation reaction. Specifically, for example, conditions under which condensation is carried out in a solvent in the presence of an esterifying condensing agent can be cited.

[0096] When the first or second compound contains -NHC(=O)- or C(=O)NH-, it 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, examples can be given of condensation conditions carried out in a solvent in the presence of an amidating condensing agent.

[0097] When compound 1 or compound 2 has a silyloxy group substituted with an aliphatic hydrocarbon group, it can be synthesized by using a precursor having a hydroxyl group and a halosilane substituted with an aliphatic hydrocarbon group, in the presence of a base, under the conditions of a conventional silylation reaction. N For example, the conditions for the 2-substitution reaction can be found in J. Am. Chem. Soc., 1972, 94, 6190, etc.

[0098] Compounds in which P is -C≡C- can be synthesized, for example, by using a precursor with an ethynyl group (-C≡CH) and a precursor with a halogen atom, and by applying a stalk coupling with a Pd or Cu catalyst.

[0099] Compounds in which P is -C=C- can be synthesized, for example, by using a precursor having a vinyl (-C=CH) group and a precursor having a halogen atom, and by applying the Heck reaction using a Pd catalyst and a phosphorus ligand.

[0100] Compounds in which P is -CH=N- or -N=CH- can be synthesized by subjecting a precursor with a formyl group to a precursor with an amino group via a conventional dehydration condensation reaction.

[0101] Regarding the reaction time in the method for producing the first or second compound, it is also appropriate to sample the reaction mixture during the reaction and use known analytical methods such as liquid chromatography or gas chromatography to confirm the degree of disappearance of the starting compound and the degree of formation of the first or second compound.

[0102] The first or second compound can be extracted from the reaction mixture by known methods such as recrystallization, reprecipitation, extraction, and various chromatographic methods, or by appropriate combinations of these operations.

[0103] The composition may further include other pigment compounds besides the first and second compounds, such as at least one dichroic pigment. Examples of other pigment compounds include monoazo pigments, diazo pigments, triazo pigments, tetraazo pigments, iridozo pigments, and other azo pigments, preferably at least one selected from the group consisting of them. The composition may contain one other pigment compound alone or in combination of two or more. For example, when used as a coating polarizing plate material, the other pigment compounds included in the composition preferably have a maximum absorption wavelength in a wavelength range different from that of the first and second compounds. For example, when used as a coating polarizing plate material, the composition preferably includes the first and second compounds and combines to include three or more dichroic pigments, more preferably combining to include three or more azo pigments. By combining three or more pigment compounds with different maximum absorption wavelengths in the composition, absorption in the entire visible light domain can be achieved, for example, using a film formed from the composition.

[0104] When the composition contains other pigment compounds, their content is preferably 50 parts by mass or less relative to 100 parts by mass of the solid components of the composition, more preferably in the range of 0.1 parts by mass to 10 parts by mass, and even more preferably in the range of 0.1 parts by mass to 5 parts by mass. If it is within the above range, the dispersion of other pigment compounds can be sufficiently achieved.

[0105] Liquid crystal compounds

[0106] In addition to the first compound and the second compound, the composition also contains a liquid crystal compound, which comprises at least one of a polymeric liquid crystal compound and a liquid crystal polymer. The composition may contain only one of the polymeric liquid crystal compound and the liquid crystal polymer, or it may contain both. Furthermore, the composition may contain two or more types of polymeric liquid crystal compounds and liquid crystal polymers. By including at least one of the polymeric liquid crystal compound and the liquid crystal polymer in the composition, a composition in which the first compound and the second compound are dispersed in the liquid crystal compound can be formed.

[0107] The liquid crystal polymer can be either a thermotropic liquid crystal polymer or a lyotropic liquid crystal polymer. From the perspective of enabling precise film thickness control, the liquid crystal polymer is preferably a thermotropic liquid crystal polymer.

[0108] Liquid crystals can be classified into smectic liquid crystals, nematic liquid crystals, and cholesteric liquid crystals based on the molecular arrangement in their liquid crystal state. Among these, smectic liquid crystals are preferred for polarizing film applications. Therefore, polymerizable liquid crystal compounds are preferably polymerizable smectic liquid crystal compounds, and liquid crystal polymeric compounds are preferably smectic liquid crystal polymeric compounds.

[0109] By using a polymeric liquid crystal compound exhibiting smectic liquid crystal properties and a polymeric compound exhibiting smectic liquid crystal properties, a polarizing film with high orientation order can be formed. The liquid crystal state exhibited by the polymeric liquid crystal compound and the liquid crystal polymeric compound is preferably a smectic phase (smectic liquid crystal state), and from the viewpoint of achieving higher orientation order, a higher-order smectic phase (higher-order smectic liquid crystal state) is more preferred. Here, the higher-order smectic phase refers to smectic phases B, D, E, F, G, H, I, J, K, and L, among which smectic phases B, F, and I are more preferred. The polarizing film with high orientation order can obtain Bragg peaks originating from higher-order structures such as hexagonal phases and crystalline phases in X-ray diffraction measurements. A Bragg peak refers to a peak originating from a planar periodic structure of molecular orientation. The periodic interval (order period) of the polarizing film obtained from the composition is preferably 0.3 nm or more and 0.6 nm or less. Polymerizable liquid crystal compounds or liquid crystal polymers can be polymerizable smectic liquid crystal compounds or smectic liquid crystal polymers that exhibit Bragg peaks originating from higher-order structures in X-ray diffraction measurements.

[0110] Polymerized liquid crystal compounds

[0111] A polymerizable liquid crystal compound is a compound having at least one polymerizable group within its molecule and capable of exhibiting a liquid crystal phase through orientation. Preferably, a polymerizable liquid crystal compound is a compound capable of exhibiting a liquid crystal phase through orientation alone. A polymerizable group refers to a functional group capable of participating in a polymerization reaction, preferably a free radical polymerizable group.

[0112] As for the polymerizable liquid crystal compound, there is no particular limitation as long as it is a liquid crystal compound having at least one polymerizable group and preferably exhibiting smectic liquid crystal properties, and known polymerizable liquid crystal compounds can be used. Specifically, as a polymerizable liquid crystal compound, for example, a compound represented by the following formula (A) (hereinafter also referred to as "polymerizable liquid crystal compound (A)") is preferred.

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

[0114] In equation (A), k is an integer from 1 to 3. 1 X 2 and X 3 Each X independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. When k is 2 or 3, multiple X... 1 They can be the same or different. Choose freely (X). 1 X 2 and X 3 The group consists of at least three 6-membered cyclic hydrocarbon groups that represent a divalent valence. 1 Y 2 W 1 and W 2 Each independently represents a single bond or a divalent linker. When k is 2 or 3, Y... 1 They can be the same or different. V 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 of them independently represents a polymeric group or a hydrogen atom, and at least one of them represents a polymeric group.

[0115] As X 1 X 2 and X 3 Examples of divalent aromatic groups in this context include 1,4-phenylene and 1,4-naphthylene (naphthalene-1,4-diyl). 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 a substituent. 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 or phenyl group with 1 to 6 carbon atoms.

[0116] As X 1 X 2 and X 3Examples of divalent 6-membered cyclic hydrocarbon 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 can independently represent 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 of the groups consisting of N. Here, R a and R b Each can be independently represented as an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. 1 Preferably, it is -CH2CH2-, -(C=O)O-, or a single bond. 2 Preferably -CH2CH2- or -CH2O-.

[0119] W 1 and W 2 Each independently represents a single bond or a divalent linker. A divalent linker is, for example, at least one selected from the group consisting of -O-, -S-, -(C=O)O-, and -O(C=O)O-. 1 and W 2 Each is preferably a single bond or -O-.

[0120] V 1 and V 2 Each of the above-mentioned alkane diesters can independently represent alkane diesters having 1 to 20 carbon atoms. At least one of the -CH2- groups constituting the aforementioned alkane diesters can be replaced by -O-, -CO-, -S-, or -NH-.

[0121] As V 1 and V 2Examples of alkane diyl groups include 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. 1 and V 2 Preferably, it is an alkane diester with 2 to 12 carbon atoms, more preferably an alkane diester with 6 to 12 carbon atoms.

[0122] Examples of substituents that may be present in an alkane diene having 1 to 20 carbon atoms include cyano groups and halogen atoms. The alkane diene is preferably an unsubstituent alkane diene, more preferably an unsubstituent alkane diene that is linear in shape.

[0123] U 1 and U 2 Each of the following independently represents a polymeric group or a hydrogen atom, and at least one of them represents a polymeric group. U 1 and U 2 Preferably, it contains polymerizable groups. U is preferred. 1 and U 2 All are polymerizable groups, preferably all are free radical polymerizable groups. U 1 The polymerizable group represented by U 2 The polymerizable groups represented may be different from each other, but are preferably groups of the same kind. As U 1 and U 2 The polymerizable groups in the text can be the same groups exemplified above as those present in polymerizable liquid crystal compounds. Among them, U... 1 and U 2 The polymerizable group represented is preferably selected from at least one of the group consisting of vinyloxy, acryloyloxy, methacryloyloxy, oxetylpropyl and oxetylbutyl, more preferably acryloyloxy.

[0124] Specific examples of polymerizable liquid crystal compounds (A) include compounds represented by formulas (A-1) to (A-17). When the polymerizable liquid crystal compound (A) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably in the trans form.

[0125] [Chemical Formula 17]

[0126]

[0127] [Chemical Formula 18]

[0128]

[0129] [Chemical Formula 19]

[0130]

[0131] The polymerizable liquid crystal compound (A) is preferably at least one compound selected from the group consisting of compounds represented by any one of formulas (A-2), (A-3), (A-4), (A-5), (A-6), (A-7), (A-8), (A-13), (A-14), (A-15), (A-16), and (A-17). The polymerizable liquid crystal compound (A) may be used alone or in combination of two or more compounds.

[0132] Polymerizable liquid crystal compounds (A) can be manufactured, for example, by methods described in known documents such as Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996) and Japanese Patent No. 4719156.

[0133] Liquid crystal polymers

[0134] The liquid crystal polymer can be a compound obtained by polymerizing the aforementioned polymeric liquid crystal compound (hereinafter also referred to as a polymer of the polymeric liquid crystal compound), or other liquid crystal polymers, preferably a polymer of the aforementioned polymeric liquid crystal compound.

[0135] The polymer of the aforementioned polymerizable liquid crystal compound can use two or more of the aforementioned polymerizable liquid crystal compounds as raw material monomers. Alternatively, the polymer of the aforementioned polymerizable liquid crystal compound may also contain monomers other than the aforementioned polymerizable liquid crystal compounds as raw material monomers.

[0136] Relative to the total amount of structural units derived from the aforementioned polymeric liquid crystal compound constituting the polymeric liquid crystal compound, the content of the aforementioned polymeric liquid crystal compound in the polymeric liquid crystal compound is generally 1 mol% or more and 100 mol% or less. From the viewpoint of improving the orientation of the aforementioned polymeric liquid crystal compound, it is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

[0137] Other liquid crystal polymers mentioned above include those having liquid crystal groups. Examples of polymers forming the parent backbone include polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyalkylene ethers and polyvinyl alcohol; polymethacrylates; polyacrylates; and so on. These polymers have liquid crystal groups. Among these, polymethacrylates and polyacrylates having liquid crystal groups are preferred.

[0138] The aforementioned other liquid crystal polymers may contain two or more liquid crystal groups. These liquid crystal groups may be contained in the main chain of the polymer forming the parent skeleton, in the side chain of the polymer forming the parent skeleton, or in both the main chain and side chain of the polymer forming the parent skeleton. Examples of liquid crystal groups include groups formed by removing one hydrogen atom from a compound having at least two six-membered ring hydrocarbon structures, or groups formed by removing two hydrogen atoms from the compound.

[0139] Relative to the total amount of structural units of the polymeric compound constituting the parent skeleton of the aforementioned other liquid crystal polymeric compounds, the content of liquid crystal groups in the aforementioned other liquid crystal polymeric compounds is generally 1 mol% or more and 100 mol% or less. From the viewpoint of improving the orientation of the aforementioned other liquid crystal polymeric compounds, it is preferably 30 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

[0140] When two or more polymerizable liquid crystal compounds are combined in the composition, it is preferable that at least one of them is a polymerizable liquid crystal compound (A), and more preferably that two or more of them are polymerizable liquid crystal compounds (A). By combining two or more polymerizable liquid crystal compounds, the liquid crystal phase can sometimes be temporarily maintained even at temperatures below the liquid crystal-crystallization phase transition temperature. The total content of polymerizable liquid crystal compound (A) in the composition is preferably 40% by mass or more, more preferably 60% by mass or more, and all polymerizable liquid crystal compounds may be polymerizable liquid crystal compound (A). If the content of polymerizable liquid crystal compound (A) is within the above range, the polymerizable liquid crystal compounds are easily arranged with a high degree of orientation order, and the first compound and the second compound are oriented accordingly, thereby obtaining a polarizing film with excellent polarization performance.

[0141] From the viewpoint of improving the orientation of the polymerizable liquid crystal compound and the liquid crystal polymer, the total content of the polymerizable liquid crystal compound and the liquid crystal polymer in the composition is, for example, 50 parts by mass or more, preferably 70 parts by mass or more and 99.9 parts by mass or less, more preferably 70 parts by mass or more and 99.5 parts by mass or less, further preferably 80 parts by mass or more and 99 parts by mass or less, particularly preferably 80 parts by mass or more and 94 parts by mass or less, and even more preferably 80 parts by mass or more and 90 parts by mass or less.

[0142] Relative to the total amount of 100 parts by mass of the polymerizable liquid crystal compound and the liquid crystal polymer compound, the total content of the first compound and the second compound in the composition is generally 0.1 parts by mass or more and 50 parts by mass or less, preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 5 parts by mass or less. If the total content of the first compound and the second compound relative to the total amount of the polymerizable liquid crystal compound and the liquid crystal polymer compound is 50 parts by mass or less, the orientation disorder of the polymerizable liquid crystal compound, the liquid crystal polymer compound, and the first and second compounds is less, and there is a tendency to obtain a polarizing film with high orientation order.

[0143] polymers

[0144] The composition may include a polymeric compound in addition to the first compound, the second compound, and the polymeric liquid crystal compound. By including a polymeric compound in the composition, the first compound and the second compound are often easily dispersed in the composition. There are no particular limitations on the polymeric compound that can be included in the composition, as long as it can disperse the first compound and the second compound. From the viewpoint of easily and uniformly dispersing the first compound and the second compound, acrylic polymers such as polymethyl methacrylate (PMMA) are preferred. Alternatively, the polymeric compound may be a polymer obtained by polymerizing the polymeric liquid crystal compound described above. The weight-average molecular weight of the polymeric compound, converted to polystyrene, is, for example, 10,000 to 200,000, preferably 20,000 to 150,000.

[0145] When the composition contains a polymeric compound, its content can be appropriately selected according to the purpose, etc. The content of the polymeric compound is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less, relative to 100 parts by mass of the solid components of the composition.

[0146] The composition preferably also includes a liquid medium such as a solvent and a polymerization initiator, and may further include photosensitizers, polymerization inhibitors, leveling agents, etc., as needed.

[0147] solvent

[0148] The solvent is preferably one that can completely dissolve the first compound, the second compound, the polymerizable liquid crystal compound, the liquid crystal polymer, and the polymer. Furthermore, a solvent that is inactive for the polymerization reaction of the polymerizable liquid crystal compound is preferred.

[0149] Examples of solvents include alcohol solvents, ester solvents, ketone solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, nitrile solvents, ether solvents, and chlorinated solvents. One of these solvents may be used, or two or more may be used in combination.

[0150] When the composition contains a solvent, the solvent content is preferably 50% by mass or more and 98% by mass or less relative to the total amount of the composition. In other words, the solid component content in the composition is preferably 2% by mass or more and 50% by mass or less. If the solid component content is 50% by mass or less, the viscosity of the composition becomes lower, and the film obtained from the composition, for example, has a generally uniform thickness, and there is a tendency for unevenness to occur in the film. The content of the solid component can be determined with consideration of the thickness of the film to be manufactured.

[0151] Polymerization initiator

[0152] A polymerization initiator is a compound capable of initiating a polymerization reaction of a polymerizable liquid crystal compound. From the perspective of initiating polymerization reactions at lower temperature conditions, a photopolymerization initiator is preferred. Specifically, photopolymerization initiators capable of generating active free radicals or acids through the action of light are examples, with photopolymerization initiators that generate free radicals through the action of light being preferred.

[0153] Examples of polymerization initiators include benzoin compounds, benzophenone compounds, alkyl phenyl ketone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts. The polymerization initiator can be appropriately selected from known polymerization initiators depending on the purpose, etc. Furthermore, a single polymerization initiator can be used, or two or more can be used in combination.

[0154] When the composition contains a polymerization initiator, its content can be appropriately determined according to the type and amount of the polymerizable liquid crystal compound contained in the composition. The content of the polymerization initiator relative to 100 parts by mass of the polymerizable liquid crystal compound 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, for example, 30% by mass or less, 10% by mass or less, or 8% by mass or less. Furthermore, relative to 100 parts by mass of the polymerizable liquid crystal compound, the content of the polymerization initiator is preferably 0.001 parts by mass or more and 30 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 8 parts by mass or less. If the content of the polymerization initiator is within the above range, polymerization can be carried out without disturbing the orientation of the polymerizable liquid crystal compound.

[0155] Photosensitizer

[0156] When the composition contains a photopolymerization initiator, it is preferable that the composition also contains at least one photosensitizer. By including both a photopolymerization initiator and a photosensitizer in the composition, there is a tendency for the polymerization reaction of the polymerizable liquid crystal compound to be further promoted. Examples of such photosensitizers include xanthonone compounds such as xanthonone and thioxanthonone; anthracene compounds such as anthracene and alkoxy-substituted anthracene; phenothiazine and rubrene; and so on. One photosensitizer may be used alone, or two or more may be used in combination.

[0157] When the composition contains a photosensitizer, the content of the photosensitizer in the composition may be appropriately determined according to the type and amount of the photopolymerization initiator and the polymerizable liquid crystal compound. The content of the photosensitizer in the composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0158] Polymerization inhibitor

[0159] The composition may contain at least one polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, alkoxylated hydroquinone, alkoxylated catechol (e.g., butylated catechol), pyrogallol, and free radical scavengers such as 2,2,6,6-tetramethylpiperidine-1-oxo radical; thiophenols; β-naphthylamines and β-naphthols; and so on. By including a polymerization inhibitor in the composition, the extent of polymerization of the polymerizable liquid crystal compound can be controlled.

[0160] When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0161] Leveling agent

[0162] The composition may include at least one leveling agent. The leveling agent has the function of adjusting the flowability of the composition and making the coating obtained by applying the composition smoother; specifically, surfactants are examples. Preferably, the leveling agent is at least one selected from the group consisting of leveling agents mainly composed of polyacrylate compounds and leveling agents mainly composed of compounds containing fluorine atoms. One leveling agent may be used alone, or two or more may be used in combination.

[0163] When the composition includes a leveling agent, the leveling agent content is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.05 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystal polymer. If the leveling agent content is within the aforementioned range, it is easier to achieve horizontal orientation of the polymerizable liquid crystal compound and the liquid crystal polymer, and there is a tendency to avoid unevenness and obtain a smoother film (e.g., a polarizing film).

[0164] If the leveling agent content is within the above range, it is easy to achieve horizontal orientation of the polymerizable liquid crystal compound and the liquid crystal polymer compound, and there is a tendency for the obtained film to become smoother. If the leveling agent content exceeds the above range relative to the polymerizable liquid crystal compound and the liquid crystal polymer compound, there is a tendency for unevenness to occur in the obtained film.

[0165] antioxidants

[0166] The composition may include an antioxidant. There is no particular limitation on the antioxidant, as long as the composition achieves the effects of the present invention, and known antioxidants may be used. From the viewpoint of having a high inhibitory effect on the photodegradation of the first and second compounds, the antioxidant is preferably a so-called primary antioxidant that captures free radicals and thus prevents auto-oxidation. Therefore, the antioxidant included in the composition is more preferably at least one selected from the group consisting of phenolic compounds, alicyclic alcohols, and amines. An antioxidant may be used alone or in combination of two or more.

[0167] Relative to 100 parts by weight of the composition, the content of the antioxidant in the composition is preferably 0.1 parts by weight or more and 15 parts by weight or less, more preferably 0.3 parts by weight or more, even more preferably 0.5 parts by weight or more, more preferably 12 parts by weight or less, and even more preferably 10 parts by weight or less. If the content of the antioxidant is at or above the lower limit, the photodegradation of the first compound and the second compound can be more effectively suppressed. Furthermore, if the content of the antioxidant is below the upper limit, the orientation of the polymerizable liquid crystal compound is less likely to be disturbed, and a higher suppression effect on the photodegradation of the first compound and the second compound can be expected.

[0168] The composition may contain other additives besides those mentioned above. Examples of other additives include mold release agents, stabilizers, colorants such as bluing agents, flame retardants, and lubricants. When the composition contains other additives, the content of the other additives is preferably greater than 0% and less than 20% by mass, and more preferably greater than 0% and less than 10% by mass, relative to the solid components of the composition.

[0169] The composition can be manufactured using conventional methods for preparing compositions. For example, it can be prepared by mixing and stirring a first compound, a second compound, a liquid crystal compound, and additives such as antioxidants and leveling agents as needed.

[0170] <membrane>

[0171] The film involved in this embodiment can be a film containing a first compound and a second compound as forming materials, or a film obtained by using a composition containing a first compound, a second compound, and a liquid crystal compound as forming materials. A film formed from the composition can be formed by applying the composition to a substrate and then performing film formation. Furthermore, if the composition contains a polymerizable liquid crystal compound, a film containing a cured product obtained by polymerizing the polymerizable liquid crystal compound can be formed by applying the composition to a substrate, performing film formation, then polymerizing the polymerizable liquid crystal compound and curing it.

[0172] The composition can form a film, such as a polarizing film, in which the reduction of dichroism ratio caused by light degradation in the wavelength range of 570 nm to 700 nm is suppressed. Therefore, the film according to this embodiment includes a polarizing film with excellent dichroism ratio maintenance formed from a composition comprising a first compound, a second compound, and a liquid crystal compound. Furthermore, the composition can form a film with high orientation order, such as a polarizing film. Therefore, the film according to this embodiment includes a polarizing film with high orientation order formed from a composition comprising a first compound, a second compound, and a liquid crystal compound.

[0173] Here, for polarizing films with high orientation order, Bragg peaks originating from higher-order structures such as hexagonal phases and crystalline phases can be obtained in X-ray diffraction measurements. Therefore, for polarizing films formed from compositions, it is preferable that the polymeric liquid crystal compound or liquid crystal polymer is oriented in a manner that displays Bragg peaks in X-ray diffraction measurements, and more preferably that the molecules of the polymeric liquid crystal compound or liquid crystal polymer are oriented in a "horizontal orientation" along the direction of light absorption. Such a high degree of orientation order as displaying Bragg peaks can be achieved by controlling the type of polymeric liquid crystal compound or liquid crystal polymer used, the amount of the first compound, and the second compound.

[0174] Regarding the first and second compounds and the liquid crystal compound constituting the composition for forming the film, as described above.

[0175] Membranes can be manufactured, for example, by a method that includes the following steps.

[0176] Step A: Forming a coating film comprising a composition containing a first compound, a second compound, a liquid crystal compound, and a solvent;

[0177] Step B: Remove at least a portion of the solvent from the aforementioned coating;

[0178] Step C: The temperature is raised above the temperature at which the liquid crystal compound transitions to a liquid phase, and then cooled to transform the liquid crystal compound into a smectic phase (smectic liquid crystal state); and

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

[0180] The coating film of the composition can be formed, for example, by coating the composition onto a substrate, an alignment film (described later), or the like. Alternatively, the composition can be directly coated onto the retardation film or other layers constituting the polarizing plate.

[0181] The substrate is typically a transparent substrate. It should be noted that when the substrate is not disposed on the display surface of the display element, for example, when a laminate obtained by removing the substrate from a film is disposed on the display surface of the display element, the substrate may also be opaque. A transparent substrate refers to a substrate that allows light, especially visible light, to pass through. Transparency is defined as a transmittance of 80% or more relative to light in the wavelength range of 380 nm to 780 nm. A specific example of a transparent substrate is a light-transmitting resin substrate.

[0182] Examples of resins constituting the light-transmitting resin substrate include polyolefins; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; cellulose ester; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide; and polyphenylene ether. From the viewpoint of ease of acquisition and transparency, polyethylene terephthalate, polymethacrylate, cellulose ester, cyclic olefin resin, or polycarbonate are preferred.

[0183] The required properties of the substrate vary depending on the film composition, but a substrate with minimal phase difference is generally preferred. Examples of substrates with minimal phase difference include cellulose ester films such as Zero tack (Konica Minolta Opto Co., Ltd.) and Ztack (Fujifilm Corporation), which do not exhibit phase difference. Unstretched cyclic olefin resin substrates are also preferred. Hard coating, anti-reflective treatment, and antistatic treatment can be applied to the surface of the unlaminated substrate.

[0184] The thickness of the substrate is typically 5 μm to 300 μm, preferably 20 μm to 200 μm, and more preferably 20 μm to 100 μm. If it is above or below the aforementioned lower limit, the reduction in strength is suppressed, and there is a tendency for processability to improve.

[0185] Examples of methods for coating a composition onto a substrate include known methods such as spin coating, extrusion, gravure coating, die coating, doctor blade coating, coating machine, and printing methods such as flexographic printing.

[0186] Next, at least a portion of the solvent contained in the coating film obtained from the composition is removed by drying or the like, thereby forming a dried coating film. Alternatively, if the coating film contains a polymerizable liquid crystal compound, a dried coating film is formed by drying under conditions where the polymerizable liquid crystal compound does not polymerize. Examples of drying methods for the aforementioned coating film include natural drying, ventilation drying, heat drying, and reduced pressure drying.

[0187] Furthermore, to induce the liquid crystal compound to transform into a liquid phase, the temperature is raised above the temperature at which the liquid crystal compound transforms into a liquid phase, and then cooled to induce the liquid crystal compound to transform into a smectic phase (smectic liquid crystal state). This phase transformation can be performed after the solvent in the coating is removed, or it can be performed simultaneously with the removal of the solvent.

[0188] When the composition contains a polymerizable liquid crystal compound, the polymerizable liquid crystal compound is polymerized while maintaining its smectic liquid crystal state to form a cured film containing the polymerizable liquid crystal compound. Photopolymerization is preferred as the polymerization method. In photopolymerization, the light irradiating the dried coating film can be appropriately selected based on the type of photopolymerization initiator contained in the dried coating film, the type of polymerizable liquid crystal compound (especially the type of polymeric groups possessed by the polymerizable liquid crystal compound), and their amount. Specific examples include light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, and gamma rays, and active electron beams. From the perspective of easy control of the polymerization reaction and the use of devices widely used in this field as photopolymerization apparatus, ultraviolet light is preferred. It is preferable to select the polymerizable liquid crystal compound and the type of photopolymerization initiator in the composition in advance in a manner that allows photopolymerization to be carried out using ultraviolet light. Furthermore, during polymerization, the light irradiation can be performed while the dried coating film is cooled using a suitable cooling method, thereby controlling the polymerization temperature. If the polymerization of polymerizable liquid crystal compounds is carried out at a lower temperature by employing such a cooling method, a suitable film can be formed even when using a substrate with low heat resistance. During photopolymerization, patterned films can also be obtained by masking, development, etc.

[0189] Examples of light sources for the aforementioned active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, LED light sources that emit light in a wavelength range of 380nm to 440nm, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.

[0190] Ultraviolet radiation intensity can typically be 10 mW / cm 2 Above 3,000 mW / cm 2 The intensity of ultraviolet irradiation is preferably within the wavelength range effective for activating the photopolymerization initiator. The irradiation time is typically 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and even more preferably 0.1 seconds to 1 minute. When irradiated once or multiple times at this intensity, the cumulative light intensity is preferably 10 mJ / cm². 2 Above 3,000 mJ / cm 2 the following.

[0191] Photopolymerization is performed to polymerize a polymerizable liquid crystal compound while maintaining a smectic phase, preferably a high-order smectic phase, to form a film. The film obtained by polymerizing the polymerizable liquid crystal compound while maintaining the smectic phase also incorporates a dichroic pigment, thus exhibiting higher polarization performance compared to conventional host-guest polarizing films, i.e., films formed from a nematic phase liquid crystal state. Furthermore, it possesses superior strength compared to films coated only with dichroic pigments or lyotropic liquid crystals.

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

[0193] When the film is used as a polarizing film, it is preferably formed on an alignment film. An alignment film is a film with orientation control capabilities that allows a polymeric liquid crystal compound and a liquid crystal polymer compound to be aligned in a desired direction. Preferably, the alignment film has solvent resistance, preventing dissolution from coatings containing a composition comprising at least one of a polymeric liquid crystal compound and a liquid crystal polymer compound, and also has heat resistance for solvent removal and heat treatment during the alignment of the polymeric liquid crystal compound. Examples of such alignment films include alignment films containing an oriented polymer, photo-alignment films, and grooved alignment films with raised or recessed patterns or multiple grooves on their surface. From the viewpoint of accuracy and quality of the alignment angle, a photo-alignment film is preferred.

[0194] <Layered Body>

[0195] The laminate according to this embodiment may include a film containing a first compound and a second compound as forming materials, or it may include a film containing a composition containing the first compound, the second compound, and a liquid crystal compound as forming materials. The laminate may include a substrate and a film containing the first compound and the second compound as forming materials disposed on the substrate, or it may include a substrate, an alignment film disposed on the substrate, and a film containing the first compound and the second compound as forming materials disposed on the alignment film. The film containing the first compound and the second compound as forming materials can constitute a polarizing film. Alternatively, the substrate may be a retardation film. The laminate may, for example, constitute a polarizing plate. The laminate may, for example, be manufactured by forming a film on a substrate according to the film manufacturing method described above.

[0196] From the viewpoint of the flexibility and visual recognizability of the display device, the thickness of the laminate is preferably 10 μm or more and 300 μm or less, more preferably 20 μm or more and 200 μm or less, and even more preferably 25 μm or more and 100 μm or less.

[0197] When the laminate has a phase retardation film as a substrate, the thickness of the phase retardation film can be appropriately selected according to the display device to which it is applied.

[0198] <Display Device>

[0199] The display device of this embodiment includes the aforementioned laminate, which can be a polarizing plate. The display device can be obtained, for example, by attaching the laminate, which serves as the polarizing plate, to the surface of the display device via an adhesive layer. A display device is a device having display elements, and a device that includes a light-emitting element or light-emitting device as a light source. Examples of display devices include liquid crystal display devices, organic electroluminescent (EL) display devices, inorganic electroluminescent (EL) display devices, electron emission display devices (e.g., field emission display devices (FED), surface field emission display devices (SED)), electronic paper (display devices using electronic ink, electrophoretic elements, etc.), plasma display devices, projection display devices (e.g., grating light valve (GLV) display devices, display devices with digital micromirror devices (DMD), and piezoelectric ceramic displays, etc.). Liquid crystal display devices include any of the following: transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct-viewing liquid crystal display devices, and projection liquid crystal display devices. These display devices can be display devices for displaying two-dimensional images or stereoscopic display devices for displaying three-dimensional images. In particular, organic EL display devices and touch panel display devices are preferred as display devices, and organic EL display devices are especially preferred.

[0200] <Dichromatic pigments>

[0201] The dichroic pigment comprises at least one of the first compound and at least one of the second compound as active ingredients. By including the first compound and the second compound in the dichroic pigment, a polarizing film can be formed that suppresses the decrease in dichroism ratio in the wavelength range of 570 nm to 700 nm associated with light degradation. The dichroic pigment may contain only one of the first compound and one of the second compound, or it may contain two or more compounds with different structures. In addition, when the dichroic pigment contains two or more of the first compound or the second compound, they may have different maximum absorption wavelengths. Furthermore, the dichroic pigment may contain other pigment compounds besides the first compound and the second compound. Regarding other pigment compounds, as described above.

[0202] Example

[0203] The present invention will be specifically described below through examples, but the present invention is not limited to these examples. It should be noted that, unless otherwise specified, "parts" and "%" are based on mass.

[0204] Synthesis Example 1: Synthesis of Compound (1-1)

[0205] To synthesize compound (1-1), compound (1-1-a) was first synthesized. Then, dehydration condensation esterification was performed to obtain compound (1-1).

[0206] Synthesis of compound (1-1-a)

[0207] A mixture of 4-amino-2-fluorobenzoic acid (7.76 g, 50.0 mmol), 35% hydrochloric acid (13.2 mL, 150 mmol), and water (100 mL) was cooled to 0°C to 5°C, and a solution of sodium nitrite (3.55 g, 51.5 mmol) in water (6.5 mL) was added dropwise. The mixture was then stirred for 30 minutes while maintaining the temperature at 0°C to 5°C to prepare a diazo solution. Separately, a mixture of N,N-dimethylaniline (9.10 g, 75.1 mmol), sodium acetate (16.4 g, 200 mmol), methanol (67.0 mL), and water (33.0 mL) was cooled to 0°C to 5°C, and the entire volume of the previously prepared diazo solution was added dropwise. After the addition was complete, the mixture was heated to room temperature, and the precipitated solid was separated by filtration to obtain compound (1-1-b) (14.0 g, yield 97%).

[0208] [Chemical Formula 20]

[0209]

[0210] Synthesis of compound (1-1)

[0211] Compound (1-1-a) (0.717 g, 2.50 mmol), 4-n-octyloxyphenol (0.617 g, 2.78 mmol), DMAP (abbreviation for N,N-dimethylaminopyridine, 32.6 mg, 0.267 mmol), and tetrahydrofuran (25.0 mL) were mixed, and EDC·HCl (abbreviation for 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 0.719 g, 3.75 mmol) was added. The reaction solution was stirred at room temperature for 3 days. Water was added to the reaction solution, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid was purified by silica gel column chromatography with chloroform as the developing solvent to give compound (1-1) (0.701 g, yield 51%).

[0212] [Chemical Formula 21]

[0213]

[0214] 1H-NMR (400MHz, CDCl3): δ (ppm) = 8.19 (dd, 1H), 7.94-7.90 (m, 2H), 7.73 (dd, 1H), 7.63 (dd, 1H), 7.17-7.13 (m, 2H), 6.95-6.9 1(m, 2H), 6.79-6.75(m, 2H), 3.96(t, 2H), 3.13(s, 6H), 1.79(quin, 2H), 1.50-1.43(m, 2H), 1.40-1.25(m, 8H), 0.90(t, 3H).

[0215] Synthesis Example 2: Synthesis of Compounds (1-2)

[0216] To synthesize compound (1-2), compound (1-2-d) was first synthesized via compounds (1-2-a), (1-2-b), and (1-2-c). Alkylation was then performed to obtain compound (1-2).

[0217] Synthesis of compound (1-2-a)

[0218] A mixture of 4'-aminoacetanilide (7.51 g, 50.0 mmol), 35% hydrochloric acid (6.6 mL, 75 mmol), and water (150 mL) was mixed and cooled to 0°C to 5°C. A solution of sodium nitrite (5.18 g, 75.0 mmol) in water (10.0 mL) was added dropwise. The mixture was then stirred for 60 minutes while maintaining the temperature at 0°C to 5°C, and a solution of sulfamic acid (2.43 g, 25.0 mmol) in water (15.0 mL) was further added dropwise to prepare a diazonium solution. Meanwhile, a mixture of phenol (7.07 g, 75.1 mmol), sodium acetate (12.3 g, 150 mmol), and water (250 mL) was mixed and cooled to 0°C to 5°C. The entire amount of the previously prepared diazonium solution was added dropwise. After the addition was complete, the mixture was heated to room temperature, and the precipitated solid was separated by filtration to obtain compound (1-2-a) (7.58 g, yield 59%).

[0219] [Chemical Formula 22]

[0220]

[0221] Synthesis of compound (1-2-b)

[0222] Compound (1-2-a) (5.11 g, 20.0 mmol), methyl iodoform (14.2 g, 100 mmol), potassium carbonate (8.29 g, 60.0 mmol), and N,N-dimethylacetamide (50 mL) were mixed and heated and stirred at 50 °C for 3 hours. Water was added to the reaction solution, and the precipitated solid was separated by filtration to give compound (1-2-b) (5.04 g, yield 94%).

[0223] [Chemical Formula 23]

[0224]

[0225] Synthesis of compound (1-2-c)

[0226] Compound (1-2-b) (5.39 g, 20.0 mmol), sodium hydroxide (20.0 g, 501 mmol), methanol (20 mL), and water (10 mL) were mixed and heated and stirred at 110 °C for 8 hours. The solid was separated by filtration to give compound (1-2-c) (4.25 g, yield 93%).

[0227] [Chemical Formula 24]

[0228]

[0229] Synthesis of compound (1-2-d)

[0230] Compound (1-2-c) (1.36 g, 6.00 mmol), 35% hydrochloric acid (1.6 mL, 18 mmol), acetic acid (18.0 mL), and water (18.0 mL) were mixed and cooled to 0-5°C. A solution of sodium nitrite (0.433 g, 6.28 mmol) in water (0.80 mL) was added dropwise. The mixture was then stirred for 30 minutes while maintaining the temperature at 0-5°C to prepare a diazonium solution. Separately, 2-fluorophenol (1.02 g, 9.11 mmol), sodium acetate (1.98 g, 24.1 mmol), methanol (24.0 mL), and water (12.0 mL) were mixed and cooled to 0-5°C. The entire amount of the previously prepared diazonium solution was added dropwise. After the addition was complete, the mixture was heated to room temperature and stirred for 5 hours. The precipitated solid was separated by filtration to obtain compound (1-2-d) (1.77 g, yield 84%).

[0231] [Chemical Formula 25]

[0232]

[0233] Synthesis of compounds (1-2)

[0234] Compound (1-2-d) (0.353 g, 1.01 mmol), 1-iodobutane (0.372 g, 2.02 mmol), potassium carbonate (0.424 g, 3.01 mmol), and N,N-dimethylacetamide (5.0 mL) were mixed and heated and stirred at 90 °C for 1 hour. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography with chloroform as the developing solvent, and further purified by reprecipitation from chloroform / methanol to give compound (1-2) (0.302 g, yield 74%).

[0235] [Chemical Formula 26]

[0236]

[0237] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 8.01 (s, 4H), 7.98-7.94 (m, 2H), 7.81-7.78 (m, 1H), 7.73 (dd, 1H), 7.0 9(dd, 1H), 7.06-7.02(m, 2H), 4.14(t, 2H), 3.91(s, 3H), 1.87(quin, 2H), 1.55(sext, 2H), 1.01(t, 3H).

[0238] Synthesis Example 3: Synthesis of Compounds (1-3)

[0239] To synthesize compound (1-3), compound (1-2-c) was used as a starting material to synthesize compound (1-3-a). Alkylation was then performed to obtain compound (1-3).

[0240] Synthesis of compound (1-3-a)

[0241] Compound (1-2-c) (1.64 g, 7.00 mmol), 35% hydrochloric acid (1.85 mL, 21.0 mmol), acetic acid (21.0 mL), and water (21.0 mL) were mixed and cooled to 0-5°C. A solution of sodium nitrite (0.509 g, 7.38 mmol) in water (1.00 mL) was added dropwise. The mixture was then stirred for 30 minutes while maintaining the temperature at 0-5°C to prepare a diazonium solution. Separately, 2,6-difluorophenol (1.40 g, 10.5 mmol), sodium acetate (2.31 g, 28.2 mmol), methanol (28.0 mL), and water (14.0 mL) were mixed and cooled to 0-5°C. The entire amount of the previously prepared diazonium solution was added dropwise. After the addition was complete, the mixture was heated to room temperature and stirred for 5 hours. The precipitated solid was separated by filtration to obtain compound (1-3-a) (2.34 g, yield 91%).

[0242] [Chemical Formula 27]

[0243]

[0244] Synthesis of compounds (1-3)

[0245] Compound (1-3-a) (0.368 g, 1.00 mmol), 1-iodobutane (0.372 g, 2.02 mmol), potassium carbonate (0.423 g, 3.00 mmol), and N,N-dimethylacetamide (5.0 mL) were mixed and heated and stirred at 100 °C for 30 minutes. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography with chloroform as the developing solvent, and further purified by reprecipitation from chloroform / methanol to give compound (1-2) (0.309 g, yield 73%).

[0246] [Chemical Formula 28]

[0247]

[0248] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 8.02 (s, 4H), 7.99-7.95 (m, 2H), 7.61-7.54 (m, 2H), 7.0 6-7.02(m, 2H), 4.27(t, 2H), 3.92(s, 3H), 1.80(quin, 2H), 1.53(sext, 2H), 0.99(t, 3H).

[0249] Synthesis Example 4: Synthesis of compounds (1-4)

[0250] To synthesize compound (1-4), compound (1-4-d) was first synthesized via compounds (1-4-a), (1-4-b), and (1-4-c). Alkylation was then performed to obtain compound (1-4).

[0251] Synthesis of compound (1-4-a)

[0252] 3-Fluoro-4-nitroaniline (2.12 g, 13.6 mmol), 35% hydrochloric acid (3.60 mL, 40.8 mmol), acetic acid (13.5 mL), and water (13.5 mL) were mixed and cooled to 0-5°C. A solution of sodium nitrite (5.18 g, 75.0 mmol) in water (10.0 mL) was added dropwise. The mixture was then stirred for 60 minutes while maintaining the temperature at 0-5°C to prepare a diazo solution. Meanwhile, phenol (1.97 g, 20.5 mmol), sodium acetate (4.51 g, 55.0 mmol), and water (27.0 mL) were mixed and cooled to 0-5°C. The entire amount of the previously prepared diazo solution was added dropwise. After the addition was complete, the mixture was heated to room temperature, and the precipitated solid was separated by filtration to obtain compound (1-4-a) (3.44 g, yield 97%).

[0253] [Chemical Formula 29]

[0254]

[0255] Synthesis of compound (1-4-b)

[0256] Compound (1-4-a) (1.57 g, 6.00 mmol), iodoethane (1.88 g, 12.1 mmol), potassium carbonate (2.54 g, 18.0 mmol), and N,N-dimethylacetamide (12.0 mL) were mixed and heated and stirred at 70 °C for 30 minutes. Water was added to the reaction solution, and the precipitated solid was separated by filtration to give compound (1-4-b) (1.67 g, yield 96%).

[0257] [Chemical Formula 30]

[0258]

[0259] Synthesis of compound (1-4-c)

[0260] Compound (1-4-b) (1.62 g, 5.60 mmol), sodium sulfide nonahydrate (2.77 g, 11.3 mmol), ethanol (14 mL), and water (14 mL) were mixed and heated under reflux for 30 minutes. Water was added to the reaction solution, and the precipitated solid was separated by filtration to give compound (1-4-c) (0.981 g, yield 67%).

[0261] [Chemical Formula 31]

[0262]

[0263] Synthesis of compound (1-4-d)

[0264] Compound (1-4-c) (0.908 g, 3.50 mmol), 35% hydrochloric acid (0.95 mL, 11 mmol), acetic acid (11.0 mL), and water (11.0 mL) were mixed and cooled to 0-5°C. A solution of sodium nitrite (0.433 g, 6.28 mmol) in water (0.80 mL) was added dropwise. The mixture was then stirred for 30 minutes while maintaining the temperature at 0-5°C to prepare a diazonium solution. Separately, 2-fluorophenol (0.595 g, 5.30 mmol), sodium acetate (1.16 g, 14.1 mmol), methanol (14.0 mL), and water (7.0 mL) were mixed and cooled to 0-5°C. The entire volume of the previously prepared diazonium solution was added dropwise, and the mixture was stirred for 2 hours while maintaining the temperature at 0-5°C. After cooling to room temperature, the precipitated solid was separated by filtration to obtain compound (1-4-d) (1.17 g, yield 88%).

[0265] [Chemical Formula 32]

[0266]

[0267] Synthesis of compounds (1-4)

[0268] Compound (1-4-d) (0.574 g, 1.50 mmol), 1-iodobutane (0.558 g, 3.03 mmol), potassium carbonate (0.635 g, 4.51 mmol), and N,N-dimethylacetamide (7.5 mL) were mixed and heated and stirred at 100 °C for 1 hour. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography with toluene as the developing solvent, and further purified by reprecipitation from chloroform / methanol to give compound (1-4) (0.373 g, yield 57%).

[0269] [Chemical Formula 33]

[0270]

[0271] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 7.97-7.93 (m, 2H), 7.88 (dd, 1H), 7.83-7.74 (m, 4H), 7.09 (dd, 1H) , 7.04-7.00(m, 2H), 4.17-4.12(m, 4H), 1.87(quin, 2H), 1.55(sext, 2H), 1.47(t, 3H), 1.01(t, 3H).

[0272] Synthesis Example 5: Synthesis of compounds (1-5)

[0273] To synthesize compound (1-5), compound (1-4-c) was used as a starting material to synthesize compound (1-5-a). Alkylation was then performed to obtain compound (1-5).

[0274] Synthesis of compound (1-5-a)

[0275] Compound (1-4-c) (0.803 g, 3.00 mmol), 35% hydrochloric acid (0.80 mL, 9.1 mmol), acetic acid (9.0 mL), and water (9.0 mL) were mixed and cooled to 0-5°C. A solution of sodium nitrite (0.219 g, 3.17 mmol) in water (0.50 mL) was added dropwise. The mixture was then stirred for 30 minutes while maintaining the temperature at 0-5°C to prepare a diazo solution. Separately, 2,6-difluorophenol (1.40 g, 10.5 mmol), sodium acetate (2.31 g, 28.2 mmol), methanol (28.0 mL), and water (14.0 mL) were mixed and cooled to 0-5°C. The entire volume of the previously prepared diazo solution was added dropwise, and the mixture was stirred for 2 hours while maintaining the temperature at 0-5°C. After cooling to room temperature, the precipitated solid was separated by filtration to obtain compound (1-5-a) (1.04 g, yield 91%).

[0276] [Chemical Formula 34]

[0277]

[0278] Synthesis of compounds (1-5)

[0279] Compound (1-5-a) (0.383 g, 1.00 mmol), 1-iodobutane (0.373 g, 2.03 mmol), potassium carbonate (0.423 g, 3.00 mmol), and N,N-dimethylacetamide (5.0 mL) were mixed and heated and stirred at 100 °C for 30 minutes. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography with toluene as the developing solvent, and further purified by reprecipitation from chloroform / methanol to give compound (1-5) (0.218 g, 50% yield).

[0280] [Chemical Formula 35]

[0281]

[0282] 1H-NMR (400MHz, CDCl3): δ (ppm) = 7.97-7.84 (m, 4H), 7.79-7.74 (m, 2H), 7.04-7.00 (m, 2H), 6. 79-6.75(m, 2H), 4.15(q, 2H), 4.05(t, 2H), 1.82(quin, 2H), 1.57-1.46(m, 5H), 1.00(t, 3H).

[0283] Synthesis Example 6: Synthesis of Compounds (1-64)

[0284] Compound (1-64) was obtained by dehydration condensation esterification using compound (1-1-a) as a starting material.

[0285] Synthesis of compounds (1-64)

[0286] Compound (1-1-a) (0.288 g, 1.00 mmol), 4-n-butylphenol (0.183 g, 1.22 mmol), DMAP (15.2 mg, 0.124 mmol), and tetrahydrofuran (10.0 mL) were mixed, and EDC·HCl (0.286 g, 1.49 mmol) was added. The reaction solution was stirred at room temperature for 2 days. Water was added to the reaction solution, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid was purified by silica gel column chromatography with chloroform as the developing solvent to give compound (1-64) (0.248 g, yield 48%).

[0287] [Chemical Formula 36]

[0288]

[0289] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 8.19 (dd, 1H), 7.94-7.90 (m, 2H), 7.73 (dd, 1H), 7.63 (dd, 1H), 7.25-7.22 (m, 2H) , 7.17-7.13(m, 2H), 6.79-6.75(m, 2H), 3.13(s, 6H), 2.64(t, 2H), 1.62(quin, 2H), 1.38(sext, 2H), 0.94(t, 3H).

[0290] Synthesis Example 7: Synthesis of Compounds (1-65)

[0291] Compound (1-65) was obtained by dehydration condensation esterification using compound (1-1-a) as a starting material.

[0292] Synthesis of compounds (1-65)

[0293] Compound (1-1-a) (2.00 g, 6.84 mmol), 4-(trans-4-butylcyclohexyl)phenol (1.95 g, 8.20 mmol), DMAP (84.4 mg, 0.684 mmol), and chloroform (20.0 mL) were mixed and cooled to 0-5 °C. DIC (abbreviation for N,N-diisopropylcarbodiimide, 1.2 mL, 7.5 mmol) was added dropwise. The mixture was then stirred for 2 hours while maintaining the temperature at 0-5 °C, followed by warming to room temperature and stirring for 1.5 hours. The reaction solution was filtered through silica, and the filtrate was concentrated and purified by recrystallization from methanol and chloroform to give compound (1-65) (2.51 g, 73% yield).

[0294] [Chemical Formula 37]

[0295]

[0296] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 8.19 (dd, 1H), 7.94-7.90 (m, 2H), 7.73 (dd, 1H), 7.63 (dd, 1H), 7.28-7.24 (m, 2H), 7.18-7.14 (m, 2H), 6.7 9-6.75 (m, 2H), 3.13 (s, 6H), 2.53-2.46 (m, 1H), 1.94-1.86 (m, 4H), 1.51-1.40 (m, 2H), 1.33-1.21 (m, 7H), 1.11-1.01 (m, 2H), 0.91 (t, 3H).

[0297] Synthesis Example 8: Synthesis of Compounds (1-66)

[0298] To synthesize compound (1-66), compound (1-66-d) was first synthesized via compounds (1-66-a), (1-66-b), and (1-66-c). Alkylation was then performed to obtain compound (1-66).

[0299] Synthesis of compound (1-66-a)

[0300] A diazo solution was prepared by mixing 4-nitroaniline (6.91 g, 50.0 mmol), 35% hydrochloric acid (13.2 mL, 150 mmol), acetic acid (50.0 mL), and water (50.0 mL), cooling the mixture to 0-5°C, and adding a solution of sodium nitrite (3.55 g, 51.5 mmol) in water (6.5 mL) over 20 minutes. Separately, a diazo solution was prepared by mixing phenol (7.22 g, 75.2 mmol), sodium acetate (16.5 g, 202 mmol), and water (100 mL), cooling the mixture to 0-5°C, and adding the entire amount of the previously prepared diazo solution over 20 minutes. After the addition was complete, the mixture was heated to room temperature, and the precipitated solid was separated by filtration to obtain compound (1-66-a) (11.7 g, yield 96%).

[0301] [Chemical Formula 38]

[0302]

[0303] Synthesis of compound (1-66-b)

[0304] Compound (1-66-a) (3.65 g, 15.00 mmol), iodoethane (4.69 g, 30.1 mmol), potassium carbonate (6.35 g, 45.0 mmol), and N,N-dimethylacetamide (30.0 mL) were mixed and heated and stirred at 70 °C for 1 hour. Water was added to the reaction solution, and the precipitated solid was separated by filtration to give compound (1-66-b) (3.98 g, yield 98%).

[0305] [Chemical Formula 39]

[0306]

[0307] Synthesis of compound (1-66-c)

[0308] Compound (1-66-b) (3.80 g, 14.0 mmol), sodium sulfide nonahydrate (6.88 g, 28.1 mmol), ethanol (35 mL), and water (35 mL) were mixed and heated under reflux for 30 minutes. Water was added to the reaction solution, and the precipitated solid was separated by filtration to give compound (1-66-c) (3.06 g, 90% yield).

[0309] [Chemical Formula 40]

[0310]

[0311] Synthesis of compound (1-66-d)

[0312] A diazo solution was prepared by mixing compound (1-66-c) (0.996 g, 4.00 mmol), 35% hydrochloric acid (1.05 mL, 11.9 mmol), acetic acid (12.0 mL), and water (12.0 mL), and cooling to 0-5°C. A solution of sodium nitrite (0.290 g, 4.21 mmol) in water (0.60 mL) was added dropwise over 5 minutes. Meanwhile, a diazo solution was prepared by mixing 3-fluorophenol (0.700 g, 6.12 mmol), sodium acetate (1.41 g, 17.2 mmol), and water (24.0 mL), and cooling to 0-5°C. The entire volume of the previously prepared diazo solution was added dropwise over 5 minutes, and the mixture was stirred for 1 hour while maintaining the temperature at 0-5°C. After cooling to room temperature, the mixture was stirred for another day. The precipitated solid was separated by filtration to obtain compound (1-66-d) (1.32 g, yield 91%).

[0313] [Chemical Formula 41]

[0314]

[0315] Synthesis of compounds (1-66)

[0316] Compound (1-66-d) (0.367 g, 1.01 mmol), 1-iodobutane (0.374 g, 2.03 mmol), potassium carbonate (0.423 g, 3.00 mmol), and N,N-dimethylacetamide (5.0 mL) were mixed and heated and stirred at 100 °C for 30 minutes. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by silica gel column chromatography with chloroform as the developing solvent, and further purified by reprecipitation from chloroform / methanol to give compound (1-66) (0.199 g, yield 47%).

[0317] [Chemical Formula 42]

[0318]

[0319] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 8.05-7.99 (m, 4H), 7.97-7.93 (m, 2H), 7.83 (dd, 1H), 7.04-7.00 (m, 2H), 6.80-6.75(m, 2H), 4.14(q, 2H), 4.04(t, 2H), 1.82(quin, 2H), 1.52(sext, 2H), 1.47(t, 3H), 1.00(t, 3H).

[0320] Synthesis Example 9: Synthesis of Compounds (1-67)

[0321] To synthesize compound (1-67), compound (1-66-c) was used as a starting material to synthesize compound (1-67-a). Alkylation was then performed to obtain compound (1-67).

[0322] Synthesis of compound (1-67-a)

[0323] A diazo solution was prepared by mixing compound (1-66-c) (0.919 g, 3.81 mmol), 35% hydrochloric acid (1.00 mL, 11.3 mmol), acetic acid (3.8 mL), and water (3.8 mL) and cooling to 0-5°C. A solution of sodium nitrite (0.278 g, 4.02 mmol) in water (0.50 mL) was then added dropwise. Conversely, a diazo solution was prepared by mixing 2,5-difluorophenol (0.722 g, 5.44 mmol), sodium acetate (1.26 g, 15.4 mmol), and water (15.0 mL) and cooling to 0-5°C. The entire volume of the previously prepared diazo solution was added dropwise, and the mixture was stirred for one day while maintaining the temperature at 0-5°C. The mixture was then heated to 50°C and stirred for another hour. The precipitated solid was separated by filtration to obtain compound (1-67-a) (1.40 g, 96% yield).

[0324] [Chemical Formula 43]

[0325]

[0326] Synthesis of compounds (1-67)

[0327] Compound (1-67-a) (0.384 g, 1.00 mmol), 1-iodobutane (0.373 g, 2.03 mmol), potassium carbonate (0.431 g, 3.05 mmol), and N,N-dimethylacetamide (10.0 mL) were mixed and heated and stirred at 100 °C for 30 minutes. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified by preparative GPC with chloroform as the mobile phase, and further purified by reprecipitation from chloroform / methanol to give compound (1-67) (0.222 g, 50% yield).

[0328] [Chemical Formula 44]

[0329]

[0330] 1H-NMR (400MHz, CDCl3): δ (ppm) = 8.05-7.99 (m, 4H), 7.97-7.93 (m, 2H), 7.66 (dd, 1H), 7.04-7.00(m, 2H), 6.86(dd, 1H), 4.14(q, 2H), 4.11(t, 2H), 1.87(quin, 2H),

[0331] Synthesis Example 10: Synthesis of Compounds (1-68)

[0332] To synthesize compound (1-68), compound (1-66-a) was used as a starting material, and compound (1-68-b) was synthesized via compound (1-68-a). Alkylation was then performed to obtain compound (1-68).

[0333] Synthesis of compound (1-68-a)

[0334] Compound (1-66-a) (0.973 g, 4.00 mmol), sodium sulfide nonahydrate (2.00 g, 8.14 mmol), ethanol (cmL), and water (4.0 mL) were mixed and heated under reflux for 30 minutes. The reaction solution was then added to a solution of ammonium chloride (1.00 g) in water (50 mL), and the precipitated solid was separated by filtration to give compound (1-68-a) (0.734 g, yield 86%).

[0335] [Chemical Formula 45]

[0336]

[0337] Synthesis of compound (1-68-b)

[0338] A diazo solution was prepared by mixing compound (1-68-a) (0.103 g, 0.482 mmol), 35% hydrochloric acid (10.15 mL, 1.7 mmol), acetic acid (0.50 mL), and water (0.5 mL), cooling the mixture to 0°C to 5°C, and then adding a solution of sodium nitrite (37.6 mg, 0.545 mmol) in water (0.20 mL). The mixture was stirred at 0°C to 5°C for 1 hour. Separately, a diazo solution was prepared by mixing 2,5-difluorophenol (0.104 g, 0.785 mmol), sodium acetate (0.174 g, 2.12 mmol), and water (2.0 mL), cooling the mixture to 0°C to 5°C, and then adding the entire volume of the previously prepared diazo solution. The mixture was stirred at 0°C to 5°C for 1 day. The temperature was then raised to 40°C and stirred for another 35 hours. The precipitated solid was separated by filtration to obtain compound (1-68-b) (0.122 g, yield 62%).

[0339] [Chemical Formula 46]

[0340]

[0341] Synthesis of compounds (1-68)

[0342] Compound (1-68-b) (0.109 g, 0.308 mmol), 1-iodo-2-methylpropane (0.182 g, 0.987 mmol), potassium carbonate (0.171 g, 1.21 mmol), and N,N-dimethylacetamide (3.0 mL) were mixed and heated and stirred at 100 °C for 2 hours. 1-iodo-2-methylpropane (0.20 mL, 1.74 mmol) was added to the reaction solution, and the mixture was heated and stirred for another 30 minutes. Methanol was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified using preparative GPC with chloroform as the mobile phase, and further purified by reprecipitation from chloroform / methanol to give compound (1-68) (0.0275 g, yield 19%).

[0343] [Chemical Formula 47]

[0344]

[0345] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 8.05-7.99 (m, 4H), 7.97-7.93 (m, 2H), 7.67 (dd, 1H), 7.0 4-7.00 (m, 2H), 3.86 (d, 2H), 3.83 (d, 2H), 2.20 (sept, 1H), 2.14 (sept, 1H), 1.07 (t, 12H).

[0346] According to the manufacturing methods of compounds A-1 and B-1 disclosed in Japanese Patent Application Publication No. 2017-197630, the following compounds (2-1) and (2-2) were synthesized.

[0347] [Chemical Formula 48]

[0348]

[0349] Synthesis Example 11: Synthesis of Compounds (2-8)

[0350] To synthesize compound (2-8), compound (2-8-a) was synthesized via a known diazo coupling method. This was followed by silylation to obtain compound (2-8).

[0351] Compound (2-8-a) (0.139 g, 0.299 mmol) and imidazole (0.061 g, 0.90 mmol) were dissolved in N,N-dimethylformamide (5.0 mL). After cooling to 0 °C, dimethyl tert-hexylchlorosilane (0.112 g, 0.626 mmol) was added, and the mixture was allowed to return to room temperature and stirred for 5 hours. Water was added to the reaction vessel, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid was purified by silica gel column chromatography with chloroform as the developing solvent to give compound (2-8) (0.130 g, 75% yield).

[0352] [Chemical Formula 49]

[0353]

[0354] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 7.95 (d, 2H), 7.91 (s, 1H), 7.80 (d, 2H), 7.33 (d, 2H), 6.75 (d, 2H), 3.84 ( t, 2H), 3.52 (q, 4H), 2.88 (t, 2H), 1.63-1.58 (m, 1H), 1.28 (t, 6H), 0.86 (m, 6H), 0.82 (m, 6H), 0.03 (s, 6H)

[0355] Example 1: Preparation of composition E1 comprising compound (1-1), compound (2-1) and compound (2-2)

[0356] The following ingredients are mixed and stirred at 80°C for 1 hour to obtain composition E1.

[0357]

[0358] Polymerizable liquid crystal compound (A-6)

[0359] [Chemical Formula 50]

[0360]

[0361] Polymerizable liquid crystal compound (A-7)

[0362] [Chemical Formula 51]

[0363]

[0364] It should be noted that the polymerizable liquid crystal compound (A-6) was synthesized using the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). Additionally, the polymerizable liquid crystal compound (A-7) was prepared according to the same method.

[0365] <Examples 2 to 10>: Preparation of compositions E2 to E10

[0366] Instead of compound (1-1), compounds (1-2) to (1-5) and (1-64) to (1-68) were used respectively, and in Examples 6 and 7, 2.0 parts by mass of compound (2-8) was used instead of compounds (2-1) and compound (2-2). Otherwise, the same procedure as in Example 1 was followed to obtain compositions E2 to E10 of Examples 2 to 10.

[0367] <Comparative Examples 1 and 2>: Preparation of Compositions C1 and C2

[0368] Instead of compound (1-1), compounds (3-1) or (3-2) represented by the following formula were used respectively, and the same procedure was followed as in Example 1 to obtain compositions C1 and C2 of Comparative Examples 1 and 2, respectively. It should be noted that compounds (3-1) and (3-2) were synthesized according to the method described in the above synthesis examples.

[0369] [Chemical Formula 52]

[0370]

[0371] <Manufacturing of Polarizing Plates>

[0372] 1. Formation of alignment film

[0373] A glass substrate was used as the transparent substrate. A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) (a composition for forming an alignment layer) was coated onto the glass substrate using a spin coating method. After drying, a film with a thickness of 100 nm was formed. Next, the surface of the obtained film was subjected to a rubbing treatment to form an alignment film, thereby obtaining a substrate with an alignment film formed on the glass substrate.

[0374] 2. Formation of polarizing film

[0375] The composition obtained above is applied to the alignment film of the substrate obtained above by spin coating. After being heated and dried on a heating plate at 120°C for 3 minutes, it is rapidly cooled to below 70°C (the temperature at which a smectic liquid crystal phase is formed during cooling) to obtain a laminate with a dried film formed on the alignment film.

[0376] Next, a UV irradiation device (SPOT CURE SP-7; manufactured by USHIO Inc.) was used, with an exposure dose of 2400 mJ / cm². 2 Under conditions of 365 nm, ultraviolet light is irradiated onto the dried film, thereby causing the polymerizable liquid crystal compound contained in the dried film to polymerize while maintaining the liquid crystal state of the composition, forming a polarizing film from the dried film, and obtaining a polarizing plate.

[0377] <Evaluation>

[0378] The dichroic ratio of the obtained polarizing plate was measured as follows. Using a spectrophotometer (Shimadzu UV-3150, manufactured by Shimadzu Corporation) with a support mounted on the polarizing plate, the absorbance along the transmission axis (A1) and the absorbance along the absorption axis (A2) of the polarizing film in the wavelength range of 570 nm to 700 nm were measured using the double-beam method. A screen with a 50% light cutoff was placed on the reference side of the support. The ratio (A2 / A1) was calculated from the measured absorbance along the transmission axis (A1) and the absorbance along the absorption axis (A2), and this ratio was used as the dichroic ratio (DR0) before the lightfastness test.

[0379] In addition, a protective film (40μm TAC (KONICA MINOLTA Co., Ltd. "KC4UY")) was applied to the surface of the formed polarizing film, and light was irradiated from above under the following conditions to evaluate its lightfastness. The dichroism ratio at the maximum absorption wavelength (λmax) in the range of 570nm to 700nm after the lightfastness test was calculated as the dichroism ratio after the lightfastness test (DR1). The dichroism ratio after the lightfastness test (DR1) was further divided by the dichroism ratio before the anti-contrast test (DR0) to obtain the percentage, which was taken as the dichroism ratio retention rate (%). The results are shown in Table 1. It should be noted that if the dichroism ratio retention rate is greater than 95%, it is judged to be a good polarizing film.

[0380] The light irradiation conditions for the lightfastness test are as follows.

[0381] Equipment used: ATLAS Ci4000

[0382] Light source: Xenon arc lamp

[0383] Exposure conditions: 120W / m 2 (300nm-400nm)

[0384] Test duration: 20 hours

[0385] Exposure level: 8640 kJ / m 2

[0386] Temperature: 65℃.

[0387] [Table 1]

[0388]

[0389] As shown in Table 1, a polarizing plate having a film containing a composition comprising the first compound and the second compound as a forming material can achieve excellent dichroism ratio maintenance.

Claims

1. A composition comprising a first compound represented by formula (1), a second compound represented by formula (2), and a liquid crystal compound, wherein the second compound has a maximum absorption wavelength in the wavelength range of 550 nm to 650 nm, and the liquid crystal compound comprises at least one of a polymeric liquid crystal compound and a liquid crystal polymer compound. The first compound has a maximum absorption wavelength in a wavelength range different from that of the second compound. The liquid crystal compound is a smectic liquid crystal compound. [Chemical Formula 1] In equations (1) and (2), n and m each independently represent 1 or 2; R 1 and R 3 Each substituent can be represented independently; R 2 and R 4 Each of these groups independently represents one group selected from the group consisting of alkylamino, alkoxy, and alkylthio groups, wherein the hydrogen atoms of these groups are optionally replaced by polymerizable groups; P represents a single bond, or at least one group selected from the group consisting of -OC(=O)-, -C(=O)O-, -NHC(=O)-, -C(=O)NH-, -C≡C-, -CH=CH-, -CH=N-, -N=N- and -N=CH-; Ar 1 Ar 2 and Ar 3 Each independently represents a 1,4-phenylene or a divalent sulfur-containing aromatic heterocyclic group optionally having at least one of the substituents selected from the group consisting of halogen atoms, hydroxyl groups, methyl groups and methoxy groups; Ar 1 and Ar 2 At least one of them has a fluorine atom as a substituent; wherein, In Ar 2 It has fluorine atoms and contains two Ar atoms. 2 In the case of at least one Ar 2 It has fluorine atoms; Ar 4 Ar 5 and Ar 6 Each independently represents a 1,4-phenylene, naphthyl or divalent sulfur-containing aromatic heterocyclic group that optionally has at least one of the following as a substituent: a halogen atom, a hydroxyl group, a methyl group and a methoxy group. When n is 2, there are 2 Ar 2 P and P can be the same or different; When m is 2, there are 2 Ar 5 They can be the same or different.

2. The composition of claim 1, wherein, In the above formula (2), Ar 4 Ar 5 and Ar 6 At least one of them represents a divalent sulfur-containing aromatic heterocyclic group.

3. The composition according to claim 1 or 2, wherein, In the above formula (2), Ar 4 Ar 5 and Ar 6 At least one of them represents thieno[2,3-d]thiazole-2,5-dimethyl.

4. The composition according to any one of claims 1 to 3, wherein, In the formula (1), P represents a single bond or at least one group selected from the group consisting of -OC(=O)-, -C(=O)O-, -NHC(=O)-, -C(=O)NH- and -N=N-.

5. A membrane, wherein the composition of any one of claims 1 to 4 is used as the forming material.

6. A laminate comprising the membrane of claim 5.

7. A display device comprising the laminate of claim 6.

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