WO2023276668A1 - Compound, composition, film, laminate, and display device - Google Patents

Compound, composition, film, laminate, and display device Download PDF

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Publication number
WO2023276668A1
WO2023276668A1 PCT/JP2022/023927 JP2022023927W WO2023276668A1 WO 2023276668 A1 WO2023276668 A1 WO 2023276668A1 JP 2022023927 W JP2022023927 W JP 2022023927W WO 2023276668 A1 WO2023276668 A1 WO 2023276668A1
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Prior art keywords
group
compound
carbon atoms
liquid crystal
hydrogen bond
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PCT/JP2022/023927
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French (fr)
Japanese (ja)
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京佑 ▲高▼橋
有弘 八代
雅也 中野
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住友化学株式会社
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Priority to CN202280041321.9A priority Critical patent/CN117480417A/en
Priority to KR1020247000263A priority patent/KR20240026988A/en
Publication of WO2023276668A1 publication Critical patent/WO2023276668A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to compounds, compositions, films, laminates and display devices.
  • An object of the present invention is to provide a compound having a high dichroic ratio, a composition containing the compound, a film formed from the composition, a laminate comprising the film, and a light-emitting device comprising the laminate.
  • the present invention provides the following [1] to [12].
  • [1] A composition containing a compound represented by the following formula (1) and a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound.
  • n represents the integer of 1 or 2.
  • Ar 1 , Ar 2 and Ar 3 each independently represent an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group. At least one of Ar 1 , Ar 2 and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond.
  • R 1 represents an alkylamino group optionally having a polymerizable group.
  • R 2 is an alkanediyl group having 4 to 20 carbon atoms, an alkane having 2 to 20 carbon atoms at least one group selected from the group consisting of a diyloxy group, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediylcarbonyl group having 2 to 20 carbon atoms and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms; show.
  • R 2 represents a cyclic or linear group having 2 to 20 carbon atoms capable of forming a hydrogen bond with the hydroxyl group.
  • R3 represents a polymerizable group or a hydrogen atom.
  • n 2
  • two Ar 2 may be the same or different.
  • [2] The composition according to [1], wherein the polymerizable liquid crystal compound is a polymerizable smectic liquid crystal compound, and the liquid crystalline polymer compound is a smectic liquid crystalline polymer compound.
  • A The composition according to [1] or [2], wherein the polymerizable liquid crystal compound contains a compound represented by the following formula (A).
  • m represents an integer of 1 to 3.
  • X 1 , X 2 and X 3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. When m is 2 or 3, multiple X 1 may be the same or different. At least three selected from the group consisting of X 1 , X 2 and X 3 represent a divalent hydrocarbon 6-membered ring group.
  • Y 1 , Y 2 , W 1 and W 2 each independently represent a single bond or a divalent linking group. When m is 2 or 3, a plurality of Y 1 may be the same or different.
  • V 1 and V 2 each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms.
  • At least one of -CH 2 - constituting the alkanediyl group may be replaced with -O-, -CO-, -S- or -NH-.
  • U 1 and U 2 each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group.
  • [6] A compound represented by the following formula (1a).
  • k represents an integer of 1 or 2.
  • Ar 11 , Ar 12 and Ar 13 each independently represent an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group. At least one of Ar 11 and Ar 12 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond.
  • R 11 represents an alkylamino group optionally having a polymerizable group.
  • R 12 is an alkanediyl group having 4 to 20 carbon atoms, an alkane having 2 to 20 carbon atoms at least one group selected from the group consisting of a diyloxy group, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms; represents When Ar 11 has a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 12 , R 12 represents a cyclic or linear group having 2 to 20 carbon atoms capable of forming a hydrogen bond with the hydroxyl group.
  • R13 represents a polymerizable group or a hydrogen atom.
  • two Ar 12 may be the same or different.
  • [7] The compound of [6], which has 1 hydroxyl group capable of forming an intramolecular hydrogen bond.
  • Ar 11 , Ar 12 and Ar 13 are optionally substituted 1,4-phenylene groups.
  • Ar 11 has a hydroxyl group that can form an intramolecular hydrogen bond with R 13
  • [10] A film formed from the composition according to any one of [1] to [5].
  • [11] A laminate comprising the film according to [10].
  • [12] A display device comprising the laminate according to [11].
  • a compound having a high dichroic ratio it is possible to provide a compound having a high dichroic ratio, a composition containing the compound, a film formed from the composition, a laminate comprising the film, and a light-emitting device comprising the laminate.
  • the term "process” is not only an independent process, but even if it cannot be clearly distinguished from other processes, it is included in this term as long as the intended purpose of the process is achieved.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition.
  • the upper and lower limits of the numerical ranges described herein can be arbitrarily selected and combined.
  • the composition according to this embodiment contains the compound represented by formula (1) and a liquid crystalline compound.
  • the liquid crystal compound includes at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound.
  • the composition is used, for example, as a material for forming a polarizing film. That is, the composition may be a composition for forming a polarizing film.
  • a polarizing plate provided with a polarizing film obtained using the composition as a forming material can exhibit a high dichroic ratio (DR).
  • At least one of Ar 1 , Ar 2 and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. It is thought that the number of rings will increase in , and the interaction with the host compound will improve. It is believed that this increases the dichroic ratio (DR) of the polarizing film containing the compound represented by formula (1).
  • DR dichroic ratio
  • Ar 1 , Ar 2 and Ar 3 each independently represent an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group, preferably a substituent represents a 1,4-phenylene group which may have
  • the divalent sulfur-containing heterocyclic group includes a benzothiazoldiyl group, a thienothiazoldiyl group and a thiazoldiyl group, preferably a benzothiazoldiyl group.
  • the substituents on Ar 1 , Ar 2 and Ar 3 may be at least one selected from the group consisting of halogen atoms, hydroxyl groups, methyl groups and methoxy groups, preferably fluorine atoms, chlorine atoms, hydroxyl groups and methyl groups. or a methoxy group, more preferably a fluorine atom or a hydroxy group.
  • the number of substituents in Ar 1 , Ar 2 and Ar 3 is each independently, for example, 0, 1 or 2, preferably 0 or 1.
  • At least one of Ar 1 , Ar 2 and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond.
  • a hydroxyl group capable of forming an intramolecular hydrogen bond is preferably present in at least one of Ar 1 and Ar 2 , and more preferably present in at least Ar 1 .
  • Functional groups with which hydroxyl groups can form intramolecular hydrogen bonds may exist adjacently on the same ring. That is, the hydroxyl group preferably forms an intramolecular hydrogen bond with a functional group present at its ortho position, and it is also preferred to form a 6-membered cyclic intramolecular hydrogen bond.
  • a functional group with which a hydroxyl group can form an intramolecular hydrogen bond may be, for example, a functional group other than an azo group.
  • the compound represented by formula (1) has a hydroxyl group capable of forming an intramolecular hydrogen bond in at least one of Ar 1 and Ar 2 , and the hydroxyl group is the azo group connecting Ar 1 and Ar 2 and R 2 . It preferably forms an intramolecular hydrogen bond with at least one, and more preferably has at least a hydroxyl group capable of forming an intramolecular hydrogen bond in Ar 1 and the hydroxyl group forms an intramolecular hydrogen bond with R 2 .
  • the number of hydroxyl groups capable of forming an intramolecular hydrogen bond in the compound represented by formula (1) may be, for example, one.
  • R 1 represents an alkylamino group optionally having a polymerizable group.
  • the alkylamino group in R 1 may be a monoalkylamino group or a dialkylamino group, preferably a dialkylamino group.
  • the alkylamino group for R 1 includes a dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, diisopropylamino group, monomethylamino group, monoethylamino group, monopropylamino group, monoisopropylamino group, pyrrolidyl group, piperidyl group, morpholinyl group, oxazolidinyl group, etc., and may be at least one selected from the group consisting of these.
  • the alkylamino group for R 1 is preferably a dimethylamino group or a diethylamino group.
  • At least one hydrogen atom of the alkylamino group represented by R 1 may be substituted with a polymerizable group.
  • the polymerizable group include (meth)acrylate group ((meth)acryloyloxy group), vinylphenyl group, vinyl group, and epoxy group.
  • the polymerizable group is preferably a radically polymerizable group, and more preferably a (meth)acrylate group.
  • R 1 has a polymerizable group, the number thereof is, for example, 1 or 2, preferably 1.
  • R 2 is a cyclic or linear group having 2 to 20 carbon atoms capable of forming an intramolecular hydrogen bond with a hydroxyl group, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, or an alkanediylcarbonyl group having 2 to 20 carbon atoms. group, an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, an alkanediylcarbonyloxy group having 2 to 20 carbon atoms, etc., and at least It is preferred that one species is included.
  • R 2 is an alkanediyl having 4 to 20 carbon atoms.
  • alkanediyloxy group having 2 to 20 carbon atoms, alkanediyloxycarbonyl group having 2 to 20 carbon atoms, alkanediylcarbonyl group having 2 to 20 carbon atoms and alkanediylcarbonyloxy group having 2 to 20 carbon atoms represents at least one group selected from
  • alkanediyl groups having 4 to 20 carbon atoms include n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl and n-octyl groups. , n-nonyl group, n-decyl group, etc. Formed by removing one hydrogen atom from a linear or branched (unsubstituted) alkyl group having 4 to 20 carbon atoms and alkanediyl groups.
  • the alkanediyl group preferably has 4 to 16 carbon atoms, more preferably 4 to 12 carbon atoms.
  • One or more hydrogen atoms constituting the alkyl group having 4 to 20 carbon atoms may be substituted with a halogen atom (eg, fluorine atom), hydroxy group, amino group or substituted amino group.
  • the substituted amino group includes, for example, one or two alkyl groups having 1 to 20 carbon atoms such as N-methylamino group, N-ethylamino group, N,N-dimethylamino group and N,N-diethylamino group. and an amino group substituted with a group.
  • haloalkyl groups having 4 to 20 carbon atoms such as fluorobutyl group and octafluorobutyl group
  • hydroxybutyl group and hydroxypentyl hydroxyalkyl groups having 4 to 20 carbon atoms such as hydroxyhexyl groups
  • unsubstituted amino groups such as aminobutyl groups and 2-(N,N-dimethylamino)butyl groups; and the like.
  • alkanediyloxy group having 2 to 20 carbon atoms examples include ethoxy group, n-propoxy group, isopropyloxy group, n-butoxy group, isobutyloxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, unsubstituted linear or branched chain having 2 to 2 carbon atoms such as neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group
  • An alkanediyloxy group formed by removing one hydrogen atom from an alkoxy group of 20 can be mentioned.
  • the alkanediyloxy group preferably has 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms.
  • One or more hydrogen atoms constituting the alkoxy group having 2 to 20 carbon atoms may be substituted with a halogen atom (eg, fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent.
  • a halogen atom eg, fluorine atom
  • Amino groups having substituents are the same as described above.
  • haloalkoxy groups having 2 to 20 carbon atoms such as tetrafluoroethoxy group and octafluorobutoxy group; 2-hydroxyethoxy group; A hydroxyalkoxy group having 2 to 20 carbon atoms such as; an alkoxy group having 2 to 20 carbon atoms having an unsubstituted or substituted amino group such as an aminoethoxy group and a 2-(N,N-dimethylamino)ethoxy group mentioned.
  • alkanediyloxycarbonyl group having 2 to 20 carbon atoms examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyl
  • An alkanediyloxycarbonyl group formed by removing one hydrogen atom from an unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms such as an oxycarbonyl group can be mentioned.
  • One or more hydrogen atoms constituting the alkoxycarbonyl group having 2 to 20 carbon atoms may be substituted with a halogen atom (e.g., fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent.
  • a halogen atom e.g., fluorine atom
  • Amino groups having substituents are the same as described above.
  • the alkoxycarbonyl group in which one or more hydrogen atoms are replaced with a halogen atom, a hydroxy group, an amino group, or the like includes carbon atoms such as a fluoroethoxycarbonyl group, a trifluoroethoxycarbonyl group, a tetrafluoroethoxycarbonyl group, and an octafluorobutoxycarbonyl group.
  • Haloalkoxycarbonyl groups of numbers 2 to 20 can be mentioned.
  • alkanediylcarbonyl groups having 2 to 20 carbon atoms include acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, tert-butylcarbonyl group and n-pentylcarbonyl group. group, isopentylcarbonyl group, neopentylcarbonyl group, n-hexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, n-nonylcarbonyl group, n-decylcarbonyl group, etc.
  • alkanediylcarbonyl group formed by removing one hydrogen atom from an alkanoyl group of 20 can be mentioned.
  • the alkanediyl portion of the alkanediylcarbonyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms.
  • One or more hydrogen atoms constituting the alkanoyl group having 2 to 20 carbon atoms may be substituted with a halogen atom (eg, fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent.
  • a halogen atom eg, fluorine atom
  • Amino groups having substituents are the same as described above.
  • the alkanoyl group in which one or more hydrogen atoms are substituted with a halogen atom, a hydroxy group, or the like includes 2 to 2 carbon atoms such as a fluoroethoxycarbonyl group, a trifluoroethoxycarbonyl group, a tetrafluoroethylcarbonyl group, an octafluorobutylcarbonyl group, and the like. Twenty haloacyl groups are mentioned.
  • the alkanediylcarbonyloxy group having 2 to 20 carbon atoms includes acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, tert-butyl carbonyloxy group, n-pentylcarbonyloxy group, isopentylcarbonyloxy group, neopentylcarbonyloxy group, n-hexylcarbonyloxy group, n-heptylcarbonyloxy group, n-octylcarbonyloxy group, n-nonylcarbonyloxy group , an alkanediylcarbonyloxy group formed by removing one hydrogen atom from an unsubstituted alkanoyloxy group having 2 to 20 carbon atoms such as n-decylcarbonyloxy group.
  • One or more hydrogen atoms constituting an alkanoyloxy group having 2 to 20 carbon atoms may be substituted with a halogen atom (eg, a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent.
  • a halogen atom eg, a fluorine atom
  • Amino groups having substituents are the same as described above.
  • Examples of the alkanoyloxy group in which one or more hydrogen atoms are substituted with a halogen atom, a hydroxy group, etc. include haloacyloxy groups having 2 to 20 carbon atoms such as a tetrafluoroethylcarbonyloxy group and an octafluorobutylcarbonyloxy group. .
  • R * represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the alkyl group having 1 to 6 carbon atoms includes methyl group, ethyl group, butyl group and hexyl group. etc.
  • Substituted alkyl groups having -O- or -NR * - inserted between carbon atoms include a 2-ethoxyethyl group, a 2-(2-ethoxyethoxy)ethyl group, and a 2-[2-(ethylamino)ethyl) amino] ethyl group and the like.
  • R 2 is a cyclic or chain C 2 to 20 group capable of forming an intramolecular hydrogen bond with the hydroxyl group. represents a group.
  • R 2 may preferably be a chain group having 2 to 20 carbon atoms capable of forming an intramolecular hydrogen bond with a hydroxyl group.
  • the cyclic group represented by R 2 and capable of forming an intramolecular hydrogen bond with a hydroxyl group includes a 2-pyrrolidinediyl group, a 2-piperidinediyl group, a 2-pyrimidinediyl group, a 2-thiazoldiyl group and a 2-thiazolinediyl group. group, 2-oxazolediyl group, 2-oxazolinediyl group, etc., and preferably contains at least one selected from the group consisting of these.
  • a cyclic group capable of forming an intramolecular hydrogen bond with a hydroxyl group may have a substituent.
  • substituents include halogen atoms (eg, fluorine atoms), hydroxy groups, amino groups optionally having substituents, alkoxy groups, alkyl groups, alkylcarbonyl groups, and the like.
  • halogen atoms eg, fluorine atoms
  • hydroxy groups e.g., hydroxypropyl groups
  • amino groups optionally having substituents alkoxy groups, alkyl groups, alkylcarbonyl groups, and the like.
  • alkyl moiety it may have from 1 to 10 carbon atoms, for example.
  • Examples of the chain group represented by R 2 and capable of forming an intramolecular hydrogen bond with a hydroxyl group include an alkanediyloxycarbonyl group having 2 to 20 carbon atoms and an alkanediylcarbonyl group having 2 to 20 carbon atoms. It is preferable to include at least one selected from the group consisting of these.
  • the alkanediyloxycarbonyl group having 2 to 20 carbon atoms and the alkanediylcarbonyl group having 2 to 20 carbon atoms are as described above.
  • R3 represents a polymerizable group or a hydrogen atom.
  • examples of the polymerizable group represented by R 3 include (meth)acrylate group ((meth)acryloyloxy group), vinylphenyl group, vinyl group and epoxy group.
  • the polymerizable group is preferably a radically polymerizable group, and more preferably a (meth)acrylate group.
  • n 1 or 2; When n is 2, two Ar 2 may be the same or different.
  • At least one of Ar 1 , Ar 2 and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond.
  • the number of hydroxyl groups capable of forming an intramolecular hydrogen bond in the compound represented by Formula (1) may be, for example, one. Examples of intramolecular hydrogen bonds in the compound represented by formula (1) are shown below, but the present invention is not limited to these embodiments.
  • Ar 1 , Ar 2 and Ar 3 are 1,4-phenylene groups for convenience, but are not limited to this.
  • R21 represents an alkanediyl group having 2 to 20 carbon atoms.
  • Ar 3 has a hydroxyl group capable of forming an intramolecular hydrogen bond
  • the hydroxyl group on Ar 3 may form, for example, a 6-membered cyclic intramolecular hydrogen bond with the azo group connecting Ar 2 and Ar 3 .
  • the mode of intramolecular hydrogen bonding is preferably any one of (a) to (e), more preferably any one of (a) to (d), ( Either a) or (c) is more preferred.
  • the presence or absence of intramolecular hydrogen bonding can be determined by measuring 1 H-NMR.
  • 1 H-NMR 1 H-NMR.
  • the chemical shift of hydroxyl groups forming intramolecular hydrogen bonds may be, for example, 9.0 ppm or more and 18.0 ppm or less, preferably 10.0 ppm or more, in deuterated chloroform (CDCl 3 ).
  • the chemical shift of hydroxyl groups is greatly affected by the polarity of the measurement solvent. Specifically, in a highly polar solvent (eg, DMSO-d 6 ), it shifts to the low magnetic field side. However, when hydroxyl groups form hydrogen bonds, the influence of the measurement solvent is reduced.
  • the difference between the chemical shift of the hydroxyl group forming the intramolecular hydrogen bond in a highly polar solvent (eg DMSO-d 6 ) and the chemical shift in a low polar solvent (eg CDCl 3 ) is, for example, 1.0 ppm or less. may be present, and may be 0.5 ppm or less.
  • the compound represented by formula (1) may have a maximum absorption wavelength ( ⁇ max) of, for example, 350 nm or more and 650 nm or less, preferably 380 nm or more and 600 nm or less.
  • the maximum absorption wavelength is measured at room temperature (eg, 25° C.) for a chloroform solution of the compound represented by formula (1).
  • the maximum absorption wavelength of the compound represented by formula (1) for example, the skeleton structures of Ar 1 , Ar 2 and Ar 3 , the substituents of Ar 1 , Ar 2 and Ar 3 , n, R 1 and the like are appropriately selected. can be adjusted to a desired wavelength.
  • the compound represented by formula (1) is at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-56).
  • at least one selected from the group consisting of compounds represented by any of formulas (1-1) to (1-46) is more preferred, and any of formulas (1-1) to (1-31)
  • At least one selected from the group consisting of compounds represented by is more preferable, and at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-20) is particularly preferred.
  • the compound represented by formula (1) can be manufactured by appropriately applying a conventionally known synthesis method.
  • it can be constructed by converting an aromatic amine compound having a primary amino group into a diazonium salt with sodium nitrite or the like and diazo-coupling it with an aromatic compound.
  • an azo structure including a thiazole structure can be constructed, for example, with reference to the description in J. Mol. Struct., 2011, 987, 158.
  • a compound in which R 3 is an alkanediyloxy group can be produced as a compound having a desired alkanediyloxy group, for example, by applying an SN2 substitution reaction to a precursor having a hydroxy group.
  • Conventionally known reaction conditions may be appropriately applied to the SN2 substitution reaction, and for example, the description in J. Am. Chem. Soc., 2008, 130, 13079 may be referred to.
  • Concrete examples include conditions for condensation in the presence of an esterifying condensing agent in a solvent.
  • a compound having a hydroxyl group at Ar 1 , Ar 2 or Ar 3 is demethylated with reference to the literature on the demethylation reaction of a salicylic acid-type methoxy group (for example, (Chem. Commun. 2010, 46, 9019-9021.)).
  • the conditions using a demethylating agent in a solvent can be mentioned.
  • Solvents include aprotic polar solvents, whether it is a single solvent or a mixed solvent, Aprotic polar solvents include amide solvents, lactone solvents, nitrogen-containing aromatic solvents, sulfoxide solvents, etc.
  • Amide solvents include N,N-dimethylacetamide, N-methyl -pyrrolidone, N-methylcaprolactam, N,N-dimethylformamide, N,N-diethylformamide, N,N-diethylacetamide, N-methylpropionamide, dimethylimidazolidinone, etc.
  • Lactone solvents include: Examples include ⁇ -butyl lactone, ⁇ -butyl lactone, etc.
  • Nitrogen-containing aromatic solvents include pyridine, quinoline, etc.
  • Sulfoxide solvents include dimethyl sulfoxide, methylphenyl sulfoxide, etc.
  • Preferred examples include amide solvents such as N-methyl-2-pyrrolidone, nitrogen-containing aromatic solvents such as pyridine, etc.
  • a mixed solvent of N-methyl-2-pyrrolidone and pyridine is more preferable.
  • Lithium salt is preferably used as the demethylating agent, and lithium chloride is more preferable.
  • the reaction temperature is, for example, in the range of 0° C. to 200° C., preferably in the range of 20° C. to 150° C., More preferably, the temperature is in the range of 50° C. to 120° C.
  • the reaction mixture is cooled to room temperature, and a poor solvent such as hydrochloric acid or water is added dropwise for precipitation to obtain a demethylated product.
  • the hydroxyl group in the synthetic intermediate inhibits the desired reaction
  • the hydroxyl group is appropriately protected, and the protecting group is removed after the reaction to perform the desired reaction.
  • Common protective groups such as acetyl groups and silyl groups can be used.
  • Known reaction conditions can be used for protection and deprotection.
  • the reaction time in the method for producing the compound represented by formula (1) is determined by appropriately sampling the reaction mixture during the reaction, and measuring the degree of disappearance of the starting compound by known analytical means such as liquid chromatography and gas chromatography. It can also be determined by confirming the degree of production of the compound represented by (1).
  • the compound represented by formula (1) can be isolated by known methods such as recrystallization, reprecipitation, extraction and various types of chromatography, or by appropriately combining these operations.
  • the composition may further contain at least one dye compound other than the compound represented by formula (1), such as a dichroic dye.
  • dye compounds include azo dyes such as monoazo dyes, bisazo dyes, trisazo dyes, tetrakis azo dyes, and stilbene azo dyes, and at least one selected from the group consisting of these is preferred.
  • the composition may contain one type of other dye compound alone, or may contain two or more types in combination.
  • the other dye compound contained in the composition preferably has a maximum absorption wavelength in a wavelength range different from that of the compound represented by formula (1).
  • the composition when used as a coating-type polarizing plate material, preferably contains a combination of three or more dichroic dyes, including the compound represented by formula (1), and three or more azo dyes. It is more preferred to include a combination of When the composition contains a combination of three or more dye compounds having different maximum absorption wavelengths, for example, a film formed from the composition can absorb the entire visible light range.
  • the content thereof is preferably 50 parts by mass or less, and 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the solid content of the composition.
  • the range is more preferable, and the range of 0.1 parts by mass or more and 5 parts by mass or less is even more preferable. Within the above range, it is possible to sufficiently disperse other dye compounds.
  • the composition contains, in addition to the compound represented by Formula (1), a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound.
  • the composition may contain either one of the polymerizable liquid crystal compound and the liquid crystal polymer compound, or may contain both of them.
  • Two or more kinds of polymerizable liquid crystal compounds and liquid crystalline polymer compounds may be included in the composition.
  • the liquid crystalline polymer compound may constitute either a thermotropic liquid crystal polymer or a lyotropic liquid crystal polymer.
  • the liquid crystalline polymer compound preferably constitutes a thermotropic liquid crystal type polymer in that the film thickness can be precisely controlled.
  • Liquid crystals are classified into smectic liquid crystals, nematic liquid crystals, and cholesteric liquid crystals according to the structure of the molecular alignment in the liquid crystal state.
  • smectic liquid crystals are preferably used for polarizing films. Therefore, the polymerizable liquid crystal compound is preferably a polymerizable smectic liquid crystal compound, and the liquid crystalline polymer compound is preferably a smectic liquid crystalline polymer compound.
  • a polarizing film with a high degree of alignment order can be formed.
  • the liquid crystal state exhibited by the polymerizable liquid crystal compound and the liquid crystalline polymer compound is preferably a smectic phase (smectic liquid crystal state). state) is more preferable.
  • the higher order smectic phase includes smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase and smectic L phase.
  • smectic B phase, smectic F phase and smectic I phase are more preferable.
  • a polarizing film with a high degree of orientational order provides a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement.
  • a Bragg peak means a peak derived from a periodic plane structure of molecular orientation.
  • the periodic interval (ordered period) of the polarizing film obtained from the composition is preferably 0.3 nm or more and 0.6 nm or less.
  • the polymerizable liquid crystal compound or liquid crystalline polymer compound may be a polymerizable smectic liquid crystal compound or a smectic liquid crystalline polymer compound that exhibits a Bragg peak derived from a higher-order structure in X-ray diffraction measurement.
  • a polymerizable liquid crystal compound is a compound that has at least one polymerizable group in the molecule and can exhibit a liquid crystal phase by being aligned.
  • the polymerizable liquid crystal compound is preferably a compound capable of exhibiting a liquid crystal phase by being aligned alone.
  • a polymerizable group means a functional group that can participate in a polymerization reaction, and is preferably a radically polymerizable group.
  • the polymerizable liquid crystal compound is not particularly limited as long as it has at least one polymerizable group and preferably exhibits smectic liquid crystallinity, and known polymerizable liquid crystal compounds can be used.
  • the polymerizable liquid crystal compound is preferably, for example, a compound represented by the following formula (A) (hereinafter also referred to as “polymerizable liquid crystal compound (A)”).
  • k is an integer of 1 to 3.
  • X 1 , X 2 and X 3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. When k is 2 or 3, multiple X1's may be the same or different. At least three selected from the group consisting of X 1 , X 2 and X 3 represent a divalent hydrocarbon 6-membered ring group.
  • Y 1 , Y 2 , W 1 and W 2 each independently represent a single bond or a divalent linking group. When k is 2 or 3, Y 1 may be the same or different.
  • V 1 and V 2 each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms.
  • At least one -CH 2 - constituting the alkanediyl group may be substituted with -O-, -CO-, -S- or -NH-.
  • U 1 and U 2 each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group.
  • the divalent aromatic group for X 1 , X 2 and X 3 includes 1,4-phenylene group, 1,4-naphthylene group (naphthalene-1,4-diyl group) and the like.
  • the divalent alicyclic hydrocarbon group includes cyclohexane-1,4-diyl group and the like.
  • At least one of the divalent aromatic group and the divalent alicyclic hydrocarbon group in X 1 , X 2 and X 3 may have a substituent. Examples of substituents include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group and n-butyl group, cyano groups and halogen atoms.
  • At least one —CH 2 — constituting a divalent alicyclic hydrocarbon group may be substituted with —O—, —S— or —NR—.
  • R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • the divalent hydrocarbon 6-membered ring groups for X 1 , X 2 and X 3 include optionally substituted 1,4-phenylene group, optionally substituted cyclohexane-1, 4-diyl group and the like.
  • the divalent aromatic group for X 1 , X 2 and X 3 is preferably an optionally substituted 1,4-phenylene group, more preferably an unsubstituted 1,4-phenylene group.
  • the divalent alicyclic hydrocarbon group is preferably an optionally substituted cyclohexane-1,4-diyl group, more preferably an optionally substituted trans-cyclo Xane-1,4-diyl group, more preferably unsubstituted trans-cyclohexane-1,4-diyl group.
  • Y 1 and Y 2 each independently represent a single bond or a divalent linking group.
  • R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Y 2 is preferably -CH 2 CH 2 - or -CH 2 O-.
  • W1 and W2 each independently represent a single bond or a divalent linking group.
  • W 1 and W 2 are each independently preferably a single bond or -O-.
  • V 1 and V 2 each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms. At least one of -CH 2 - constituting the alkanediyl group may be replaced with -O-, -CO-, -S- or -NH-.
  • the alkanediyl groups represented by V 1 and V 2 include methylene, ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane- 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,1-diyl and icosane-1,20-diyl groups.
  • V 1 and V 2 are preferably alkanediyl groups having 2 to 12 carbon atoms, more preferably alkanediyl groups having 6 to 12 carbon atoms.
  • substituents optionally possessed by the optionally substituted alkanediyl group having 1 to 20 carbon atoms include a cyano group and a halogen atom.
  • the alkanediyl group is preferably an unsubstituted alkanediyl group, more preferably an unsubstituted and linear alkanediyl group.
  • U 1 and U 2 each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group.
  • U 1 and U 2 are preferably polymerizable groups. Both U 1 and U 2 are preferably polymerizable groups, and preferably both are radically polymerizable groups.
  • the polymerizable group represented by U1 and the polymerizable group represented by U2 may be different from each other, but are preferably of the same type.
  • the polymerizable groups for U 1 and U 2 the same polymerizable groups as those previously exemplified as the polymerizable groups possessed by the polymerizable liquid crystal compound can be mentioned.
  • the polymerizable group represented by U 1 and U 2 is preferably at least one selected from the group consisting of a vinyloxy group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group, and an acryloyloxy group is more preferred.
  • polymerizable liquid crystal compound (A) examples include compounds represented by the following formulas (A-1) to (A-17).
  • the polymerizable liquid crystal compound (A) has a cyclohexane-1,4-diyl group
  • the cyclohexane-1,4-diyl group is preferably trans-type.
  • the polymerizable liquid crystal compound (A) has formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A- 7), represented by any of formula (A-8), formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17) At least one selected from the group consisting of compounds is preferred.
  • the polymerizable liquid crystal compound (A) may be used alone or in combination of two or more.
  • the polymerizable liquid crystal compound (A) can be produced, for example, by the method described in known documents such as Lub et al. Recl. Trav. Chim. can.
  • the liquid crystalline polymer compound may be a compound obtained by polymerizing the above polymerizable liquid crystal compound (hereinafter also referred to as a polymer of a polymerizable liquid crystal compound), or other high liquid crystal compound. It may be a molecular compound, preferably a polymer of the polymerizable liquid crystal compound.
  • Two or more of the polymerizable liquid crystal compounds may be used as raw material monomers for the polymer of the polymerizable liquid crystal compound. Further, the polymer of the polymerizable liquid crystal compound may contain monomers other than the polymerizable liquid crystal compound as raw material monomers.
  • the content of the polymerizable liquid crystal compound in the polymer of the polymerizable liquid crystal compound is usually 1 mol with respect to the total amount of structural units derived from the polymerizable liquid crystal compound constituting the polymer of the polymerizable liquid crystal compound. % or more and 100 mol % or less, preferably 30 mol % or more and 100 mol % or less from the viewpoint of increasing the orientation of the polymer of the polymerizable liquid crystal compound, and 50 mol % or more and 100 mol % or less. more preferably 80 mol % or more and 100 mol % or less.
  • the other liquid crystalline polymer compounds include polymer compounds having a liquid crystalline group.
  • the polymer compound serving as the backbone includes polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyalkylene ethers, polyvinyl alcohols; polymethacrylic acid esters; has a liquid crystalline group.
  • polymethacrylic acid esters and polyacrylic acid esters having a liquid crystalline group are preferable.
  • the other liquid crystalline polymer compound may contain two or more types of liquid crystalline groups.
  • the liquid crystalline group may be contained in the main chain of the polymer compound serving as the backbone, may be contained in the side chain of the polymer compound serving as the backbone, or may be included in the main chain of the polymer compound serving as the backbone. Both chains and side chains may be included.
  • the liquid crystalline group includes a group formed by removing one hydrogen atom from a compound having at least two hydrocarbon six-membered ring structures, or a group formed by removing two hydrogen atoms from the compound. mentioned.
  • the content ratio of the liquid crystalline group in the other liquid crystalline polymer compound is usually 1 mol with respect to the total amount of structural units constituting the polymer compound serving as the base skeleton of the other liquid crystalline polymer compound. % or more and 100 mol % or less, preferably 30 mol % or more and 100 mol % or less, and 50 mol % or more and 100 mol % or less from the viewpoint of increasing the orientation of the other liquid crystalline polymer compound. and more preferably 80 mol % or more and 100 mol % or less.
  • the polymerizable liquid crystal compound (A) When two or more types of polymerizable liquid crystal compounds are combined in the composition, at least one of them is preferably the polymerizable liquid crystal compound (A), and two or more of them are the polymerizable liquid crystal compounds (A). is more preferable.
  • the total content of the polymerizable liquid crystal compound (A) contained in the composition is preferably 40% by mass or more, more preferably 60% by mass, based on the total mass of all polymerizable liquid crystal compounds in the composition. As described above, all polymerizable liquid crystal compounds may be the polymerizable liquid crystal compound (A).
  • the polymerizable liquid crystal compound (A) When the content of the polymerizable liquid crystal compound (A) is within the above range, the polymerizable liquid crystal compound is easily arranged with a high degree of alignment order, and the compound represented by the formula (1) is aligned along it, resulting in excellent A polarizing film having excellent polarizing performance can be obtained.
  • the total content of the polymerizable liquid crystal compound and the liquid crystalline polymer compound in the composition is 100 parts by mass of the solid content of the composition from the viewpoint of increasing the orientation of the polymerizable liquid crystal compound and the liquid crystalline polymer compound.
  • it is 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, and still more preferably 80 parts by mass or more and 99 parts by mass. It is not more than 80 parts by mass and not more than 94 parts by mass, and more preferably not less than 80 parts by mass and not more than 90 parts by mass.
  • the total content of the compound represented by formula (1) in the composition is usually 0.1 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound. or less, preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass be.
  • the total content of the compound represented by formula (1) with respect to the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound is 50 parts by mass or less, the polymerizable liquid crystal compound, the liquid crystalline polymer compound and the formula
  • a polarizing film having a high degree of orientational order can be obtained with less disorder in the orientation of the compound represented by (1).
  • the composition may further contain a polymer compound in addition to the compound represented by Formula (1) and the polymerized liquid crystalline compound.
  • the compound represented by Formula (1) may be easily dispersed in the composition.
  • the polymer compound that the composition may contain is not particularly limited as long as it can disperse the compound represented by formula (1).
  • An acrylic polymer such as polymethyl methacrylate (PMMA) is preferable because the compound represented by Formula (1) can be uniformly dispersed.
  • the polymer compound may be a polymer compound obtained by polymerizing the polymerizable liquid crystal compound described above.
  • the polystyrene equivalent weight average molecular weight of the polymer compound is, for example, 10,000 or more and 200,000 or less, preferably 20,000 or more and 150,000 or less.
  • the composition contains a polymer compound
  • its content can be appropriately selected according to the purpose.
  • the content of the polymer compound is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and preferably 3.0 parts by mass or less with respect to 100 parts by mass of the solid content of the composition. More preferred.
  • the composition preferably further contains a liquid medium such as a solvent and a polymerization initiator, and may further contain a photosensitizer, a polymerization inhibitor, a leveling agent, etc., if necessary.
  • the solvent is preferably a solvent capable of completely dissolving the compound represented by Formula (1), the polymerizable liquid crystal compound, the liquid crystal polymer compound, and the polymer compound. Moreover, the solvent is preferably inert to the polymerization reaction of the polymerizable liquid crystal compound.
  • solvents examples include alcohol solvents, ester solvents, ketone solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, nitrile solvents, ether solvents, and chlorine-containing solvents. These solvents may be used alone or in combination of two or more.
  • the content of the solvent is preferably 50% by mass or more and 98% by mass or less with respect to the total amount of the composition.
  • the content of solids in the composition is preferably 2% by mass or more and 50% by mass or less.
  • the viscosity of the composition is low, and the thickness of a film obtained from the composition, for example, a film, tends to be substantially uniform and unevenness in the film tends to be less likely to occur.
  • the content of such solids can be determined in consideration of the thickness of the film to be produced.
  • the polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound.
  • the polymerization initiator is preferably a photopolymerization initiator because the polymerization reaction can be initiated under lower temperature conditions.
  • photopolymerization initiators capable of generating active radicals or acids by the action of light may be mentioned, and among these, photopolymerization initiators capable of generating radicals by the action of light are preferred.
  • polymerization initiators examples include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts.
  • the polymerization initiator can be appropriately selected from known polymerization initiators according to the purpose and the like.
  • a polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
  • the composition contains a polymerization initiator
  • its content may 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 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 with respect to 100 parts by mass of the polymerizable liquid crystal compound, For example, it is 30% by mass or less, 10% by mass or less, or 8% by mass or less.
  • 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, with respect to 100 parts by mass of the polymerizable liquid crystal compound. Part by mass or more and 8 parts by mass or less is more preferable.
  • the content of the polymerizable initiator is within the above range, polymerization can be carried out without disturbing the alignment of the polymerizable liquid crystal compound.
  • the composition may preferably contain at least one photosensitizer.
  • the composition contains a photopolymerization initiator and a photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound tends to be further accelerated.
  • the photosensitizer include xanthone compounds such as xanthone and thioxanthone; anthracene compounds such as anthracene and alkoxy-substituted anthracene; phenothiazine and rubrene;
  • a photosensitizer can be used individually by 1 type or in combination of 2 or more types.
  • the content of the photosensitizer in the composition may be appropriately determined according to the types and amounts 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 with respect to 100 parts by mass of the polymerizable liquid crystal compound. or less, more preferably 0.5 parts by mass or more and 8 parts by mass or less.
  • the composition may contain at least one polymerization inhibitor.
  • polymerization inhibitors include radical scavengers such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (eg, butylcatechol), pyrogallol, and 2,2,6,6-tetramethyl-1-piperidinyloxy radical.
  • radical scavengers such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (eg, butylcatechol), pyrogallol, and 2,2,6,6-tetramethyl-1-piperidinyloxy radical.
  • thiophenols ⁇ -naphthylamines and ⁇ -naphthols
  • the degree of progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled.
  • 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 100 parts by mass of the polymerizable liquid crystal compound. It is 0.5 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 8 parts by mass or less.
  • the composition may comprise at least one leveling agent.
  • the leveling agent has the function of adjusting the fluidity of the composition and making the coating film obtained by applying the composition more flat, and specifically includes surfactants.
  • the leveling agent is preferably at least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component.
  • a leveling agent can be used individually by 1 type or in combination of 2 or more types.
  • the content of the leveling agent is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound. and more preferably 0.05 parts by mass or more and 3 parts by mass or less.
  • the content of the leveling agent is within the above range, the polymerizable liquid crystal compound and the liquid crystalline polymer compound are easily horizontally aligned, unevenness is less likely to occur, and a smoother film such as a polarizing film tends to be obtained. be.
  • the content of the leveling agent When the content of the leveling agent is within the above range, it is easy to horizontally align the polymerizable liquid crystal compound and the liquid crystal polymer compound, and the resulting film tends to be smoother. If the content of the leveling agent with respect to the polymerizable liquid crystal compound and the liquid crystalline polymer compound exceeds the above range, the resulting film tends to be uneven.
  • the composition may contain an antioxidant.
  • the antioxidant is not particularly limited as long as the composition can exhibit the effects of the present invention, and known antioxidants can be used.
  • the antioxidant is preferably a so-called primary antioxidant that has a radical-scavenging and autoxidation-preventing action from the viewpoint of having a high inhibitory effect on photodegradation of the compound represented by formula (1). Therefore, the antioxidant contained in the composition is more preferably at least one selected from the group consisting of phenol compounds, alicyclic alcohol compounds and amine compounds. Antioxidants may be used alone or in combination of two or more.
  • the content of the antioxidant in the composition is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.3 parts by mass or more, and still more preferably 0.1 part by mass or more, based on 100 parts by mass of the composition. It is 5 parts by mass or more, more preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less.
  • the content of the antioxidant is at least the above lower limit, photodegradation of the compound represented by formula (1) can be more effectively suppressed.
  • the content of the antioxidant is equal to or less than the above upper limit, the orientation of the polymerizable liquid crystal compound is more difficult to disturb, and a higher inhibitory effect on photodegradation of the compound represented by formula (1) is expected. can.
  • the composition may contain additives other than those mentioned above.
  • Other additives include, for example, release agents, stabilizers, colorants such as bluing agents, flame retardants, and lubricants.
  • the content of the other additives is preferably more than 0% and 20% by mass or less, more preferably 0%, based on the solid content of the composition. is 10% by mass or less.
  • the composition can be produced by a conventionally known composition preparation method. For example, it can be prepared by mixing and stirring the compound represented by Formula (1), the liquid crystalline compound, and, if necessary, additives such as an antioxidant and a leveling agent.
  • k represents an integer of 1 or 2.
  • two Ar 12 may be the same or different.
  • Ar 11 , Ar 12 and Ar 13 each independently represent an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group. At least one of Ar 11 and Ar 12 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. Details of Ar 11 , Ar 12 and Ar 13 are the same as Ar 1 , Ar 2 and Ar 3 in Formula (1), and preferred embodiments are also the same.
  • R 11 represents an alkylamino group optionally having a polymerizable group.
  • the details of R 11 are the same as those of R 1 in Formula (1), and the preferred embodiments are also the same.
  • R 12 is a cyclic or chain-like group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, or an alkanediylcarbonyl group having 2 to 20 carbon atoms, which is capable of forming an intramolecular hydrogen bond with a hydroxyl group; , an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, and the like, and at least one selected from the group consisting of these is preferably included.
  • the details of R 12 are the same as those of R 2 in Formula (1), and the preferred embodiments are also the same.
  • R13 represents a polymerizable group or a hydrogen atom.
  • the details of R 13 are the same as those of R 3 in Formula (1), and the preferred embodiments are also the same.
  • the film according to the present embodiment may be a film containing the compound represented by formula (1) as a forming material, or a composition containing the compound represented by formula (1) and a liquid crystalline compound as a forming material. It may be a film obtained as A film made of the composition may be formed by applying the composition to a substrate to form a film. Further, when the composition contains a polymerizable liquid crystal compound, a film containing a cured product obtained by polymerizing the polymerizable liquid crystal compound is obtained by applying the composition to a substrate, forming a film, and then applying the polymerizable liquid crystal compound. may be formed by polymerizing and curing the
  • the composition can form a film with a high dichroic ratio, such as a polarizing film. Therefore, the film according to the present embodiment is a polarizing film formed from a composition containing a compound represented by formula (1) and a liquid crystalline compound, and includes a polarizing film having a high dichroic ratio. do.
  • the composition can also form films with a high degree of orientational order, such as polarizing films. Therefore, the film according to the present embodiment is a polarizing film formed from a composition containing a compound represented by formula (1) and a liquid crystalline compound, and includes a polarizing film with a high degree of orientational order. do.
  • a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase is obtained in X-ray diffraction measurement. Therefore, in the polarizing film formed from the composition, it is preferable that the polymerizable liquid crystal compound or the liquid crystalline polymer compound is oriented so as to exhibit a Bragg peak in X-ray diffraction measurement, and polymerized in the direction of light absorption. It is more preferable to be "horizontal alignment" in which the molecules of the liquid crystal compound or the liquid crystal polymer compound are aligned.
  • a high degree of orientational order exhibiting a Bragg peak can be realized by controlling the type of polymerizable liquid crystal compound or liquid crystalline polymer compound used, the amount of the compound represented by formula (1), and the like.
  • the compound represented by Formula (1) and the liquid crystalline compound constituting the composition used to form the film are as described above.
  • the membrane can be produced, for example, by a method including the following steps.
  • Step A forming a coating film of a composition containing a compound represented by formula (1), a liquid crystalline compound, and a solvent
  • Step B removing at least a portion of the solvent from the coating
  • Step C raising the temperature to a temperature at which the liquid crystalline compound transitions to a liquid phase or higher, and then lowering the temperature to cause the liquid crystalline compound to undergo a phase transition to a smectic phase (smectic liquid crystal state);
  • Step D as necessary. and polymerizing the polymerizable liquid crystal compound while maintaining the smectic phase (smectic liquid crystal state).
  • Formation of a coating film of the composition can be carried out, for example, by coating the composition on a base material, an alignment film described later, or the like.
  • the composition may be directly applied onto the retardation film or other layer that constitutes the polarizing plate.
  • the base material is usually a transparent base material.
  • the base material When the base material is not placed on the display surface of the display element, for example, when a laminate obtained by removing the base material from the film is placed on the display surface of the display element, the base material does not have to be transparent.
  • a transparent base material means a base material having transparency that can transmit light, particularly visible light, and transparency means a light transmittance of 80% or more over a wavelength range of 380 nm or more and 780 nm or less. It means a characteristic.
  • a translucent resin base material is mentioned as a specific transparent base material.
  • the properties required for the base material differ depending on the composition of the film, but usually a base material with as little retardation as possible is preferable.
  • the substrate having the smallest possible retardation include cellulose ester films having no retardation, such as Zero Tack (Konica Minolta Opto Co., Ltd.) and Z Tack (Fuji Film Co., Ltd.).
  • An unstretched cyclic olefin resin substrate is also preferred.
  • the surface of the substrate on which no film is laminated may be subjected to hard coat treatment, antireflection treatment, antistatic treatment, or the like.
  • the thickness of the substrate is usually 5 ⁇ m or more and 300 ⁇ m or less, preferably 20 ⁇ m or more and 200 ⁇ m or less, more preferably 20 ⁇ m or more and 100 ⁇ m or less. If it is at least the above lower limit, a decrease in strength is suppressed, and workability tends to be improved.
  • Examples of methods for applying the composition to a substrate or the like include coating methods such as a spin coating method, extrusion method, gravure coating method, die coating method, bar coating method and applicator method, and printing methods such as a flexographic method. method.
  • the coating film obtained from the composition is removed by drying or the like to form a dry coating film.
  • a dry coating film is formed by drying the coating film under conditions in which the polymerizable liquid crystal compound is not polymerized. Examples of the method for drying the coating film include a natural drying method, a ventilation drying method, a heat drying method, a reduced pressure drying method, and the like.
  • the temperature is raised to a temperature higher than the temperature at which the liquid-crystalline compound undergoes phase transition to the liquid phase, and then the temperature is lowered to cause the liquid-crystalline compound to phase-transition to the smectic phase (smectic liquid crystal state).
  • a phase transition may be carried out after removing the solvent in the coating film, or may be carried out simultaneously with the removal of the solvent.
  • the composition contains a polymerizable liquid crystal compound
  • a film containing a cured product of the polymerizable liquid crystal compound is formed by polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound.
  • a photopolymerization method is preferable as the polymerization method.
  • the light irradiated to the dry coating film includes the type of photopolymerization initiator contained in the dry coating film, the type of polymerizable liquid crystal compound (especially the type of polymerizable group possessed by the polymerizable liquid crystal compound), and its It is selected appropriately according to the amount.
  • ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that a widely used photopolymerization apparatus in the field can be used. It is preferable to select the types of the polymerizable liquid crystal compound, the photopolymerization initiator, etc. contained in the composition.
  • the polymerization temperature can also be controlled by irradiating light while cooling the dry coating film with an appropriate cooling means during polymerization.
  • a patterned film can also be obtained by performing masking or development during photopolymerization.
  • Examples of the light source of the active energy ray 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, and wavelength ranges. LED light sources, chemical lamps, black light lamps, microwave excited mercury lamps, metal halide lamps, etc., which emit light at 380 nm or more and 440 nm or less.
  • the ultraviolet irradiation intensity may be generally 10 mW/cm 2 or more and 3,000 mW/cm 2 or less.
  • the ultraviolet irradiation intensity is preferably in the wavelength range effective for activation of the photopolymerization initiator.
  • the light irradiation time may be usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and still more preferably 0.1 seconds. Seconds or more and one minute or less. It is preferable that the integrated amount of light when irradiated once or multiple times with such an irradiation intensity of ultraviolet rays is 10 mJ/cm 2 or more and 3,000 mJ/cm 2 or less.
  • the polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of a smectic phase, preferably a higher-order smectic phase, to form a film.
  • the film obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase is different from the conventional host-guest type polarizing film, that is, the film having the liquid crystal state of the nematic phase, due to the action of the dichroic dye. It has the advantage of high polarization performance compared to . Furthermore, there is also the advantage of being superior in strength compared to those coated only with dichroic dyes or lyotropic liquid crystals.
  • the thickness of the film can be appropriately selected according to the display device to which it is applied, and is preferably 0.5 ⁇ m or more and 10 ⁇ m or less, more preferably 1 ⁇ m or more and 5 ⁇ m or less, still more preferably 1 ⁇ m or more and 3 ⁇ m or less.
  • the alignment film When the film is used as a polarizing film, it is preferably formed on an alignment film.
  • the alignment film has an alignment regulating force that aligns the polymerizable liquid crystal compound and the liquid crystalline polymer compound in a desired direction.
  • the alignment film has a solvent resistance that does not dissolve when a composition containing a liquid crystalline compound containing at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound is applied.
  • a material having heat resistance in the heat treatment for alignment of the liquid crystal compound is preferable.
  • Examples of such an alignment film include an alignment film containing an alignment polymer, a photo-alignment film, and a groove alignment film having an uneven pattern or a plurality of grooves on the surface. preferable.
  • the laminate according to the present embodiment may include a film containing the compound represented by formula (1) as a forming material, and a composition containing the compound represented by formula (1) and a liquid crystalline compound.
  • a film as a forming material may be provided.
  • the laminate may comprise a substrate and a film containing the compound represented by formula (1) as a forming material disposed on the substrate, and the substrate and the alignment film disposed on the substrate and a film made of the compound represented by the formula (1) and disposed on the alignment film.
  • a film containing the compound represented by Formula (1) as a forming material may constitute a polarizing film.
  • the substrate may be a retardation film.
  • the laminate can constitute, for example, a polarizing plate.
  • the laminate can be produced, for example, by forming a film on a base material according to the film production method described above.
  • the thickness of the laminate is preferably 10 ⁇ m to 300 ⁇ m, more preferably 20 ⁇ m to 200 ⁇ m, still more preferably 25 ⁇ m to 100 ⁇ m, from the viewpoint of flexibility and visibility of the display device.
  • the thickness of the retardation film can be appropriately selected according to the display device to which it is applied.
  • the display device of this embodiment may include the laminate, and the laminate may be a polarizing plate.
  • a display device can be obtained, for example, by bonding a laminate as a polarizing plate to the surface of the display device via an adhesive layer.
  • a display device is a device having a display element and a device including a light-emitting element or a light-emitting device as a light source.
  • Examples of display devices include liquid crystal displays, organic electroluminescence (EL) displays, inorganic electroluminescence (EL) displays, electron emission displays (e.g., field emission displays (FED), surface field emission displays ( SED)), electronic paper (display device using electronic ink, electrophoretic element, etc.), plasma display device, projection display device (e.g., grating light valve (GLV) display device, digital micromirror device (DMD) display devices), and piezoelectric ceramic displays.
  • the liquid crystal display device includes a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, a projection liquid crystal display device, and the like.
  • These display devices may be display devices that display two-dimensional images, or may be stereoscopic display devices that display three-dimensional images.
  • an organic EL display device and a touch panel display device are preferable, and an organic EL display device is particularly preferable.
  • Example 1 Synthesis of Compound 1-1
  • Compound 1-1-a, Compound 1-1-b and Compound 1-1-c were first synthesized. Subsequently, deacetylation was performed to obtain compound 1-1.
  • N,N-dimethylaniline (0.236 g, 1.95 mmol), sodium acetate (0.320 g, 3.90 mmol), methanol (4.3 mL), and water (4.3 mL) were mixed at 0°C. After cooling to 5° C., the whole amount of the diazo solution prepared earlier was added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature, and the precipitated solid was filtered off to obtain compound 1-1-c (0.282 g, yield 94%).
  • Example 2 Synthesis of Compound 1-2
  • compound 1-2-a was first synthesized, followed by compound 1-2-b and then compound 1-2-c and compound 1.
  • -2-d was synthesized. Subsequently, dehydration-condensation esterification was performed to obtain compound 1-2.
  • N,N-dimethylaniline (9.08 g, 75.0 mmol), sodium acetate (16.4 g, 200 mmol), methanol (67.0 mL) and water (34.0 mL) were mixed and heated at 0°C to 5°C. and the whole amount of the diazo solution prepared earlier was added dropwise. After the dropwise addition was completed, the mixture was stirred at 0° C. to 5° C. for 2 hours, heated to room temperature, and the precipitated solid was separated by filtration and washed with acetonitrile/water to obtain compound 1-2-c (13.9 g, 4 -69% yield based on amino-2-methoxybenzoic acid).
  • the chemical shift of the hydroxyl group in CDCl 3 is 10.98 ppm, reflecting the formation of intramolecular hydrogen bonds.
  • the difference in the chemical shifts (10.78 ppm) of the hydroxyl group protons in CDCl 3 , a low-polar heavy solvent, and in DMSO-d 6 , a highly polar heavy solvent is as small as 0.2 ppm, which also indicates intramolecular hydrogen bonding. It reflects what is forming.
  • Comparative Example 1 Synthesis of Compound C-1
  • the aforementioned Compound 1-2-a was first synthesized. Subsequently, compound C-1 was obtained by dehydration-condensation esterification.
  • the chemical shift of the hydroxyl group in CDCl 3 is 4.77 ppm in C-1, reflecting the lack of formation of intramolecular hydrogen bonds.
  • the difference in the chemical shift (9.64 ppm) of the hydroxyl group proton in the low-polar heavy solvent CDCl 3 and in the high-polar heavy solvent DMSO-d 6 is as large as 4.87 ppm, and the effect of the polarity difference between the heavy solvents is large. I have found it to be greatly received. This also reflects that no hydrogen bond is formed in the molecule.
  • Example 11 Preparation of Composition E11 Containing Compound 1-1
  • Composition E1 was obtained by mixing the following components and stirring at 80° C. for 1 hour.
  • ⁇ Polymerizable liquid crystal compound (A-6) 75 parts by mass
  • ⁇ Polymerizable liquid crystal compound (A-7) 25 parts by mass
  • Compound (1-1) 4.0 parts by mass
  • ⁇ Polymerization initiator 2-dimethylamino-2- Benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan) 6 parts by mass
  • Leveling agent 1.2 parts by mass of polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)
  • Solvent 250 parts by mass of o-xylene
  • the polymerizable liquid crystal compound (A-6) was synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). In accordance with this method, a polymerizable liquid crystal compound (A-7) was produced.
  • Examples 12 and 13 Preparation of Compositions E12 and E13 The compositions of Examples 12 and 13 were prepared in the same manner as in Example 11, except that Compounds 1-2 and 1-64, respectively, were used in place of Compound 1-1. Compositions E12 and E13 were obtained respectively.
  • Comparative Example 1 Preparation of Composition C11 Composition C11 of Comparative Example 11 was obtained in the same manner as in Example 11 except that compound C-1 whose synthesis method was described above was used instead of compound 1-1. .
  • polarizing plate 1 Formation of alignment film A glass substrate was used as a transparent substrate. A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) (composition for forming an alignment layer) is applied onto a glass substrate by spin coating, and after drying, the thickness is A film of 100 nm was formed. Subsequently, the surface of the obtained film was subjected to a rubbing treatment to form an alignment film, thereby obtaining a substrate having an alignment film formed on a glass substrate.
  • polyvinyl alcohol polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.
  • the composition obtained above is applied by a spin coating method, dried by heating on a hot plate at 120 ° C. for 3 minutes, and then quickly brought to 70 ° C. (The temperature at which a smectic liquid crystal phase is exhibited when the temperature is lowered) or less to obtain a laminate having a dry film formed on the alignment film.
  • the dry film is irradiated with ultraviolet rays at an exposure amount of 1000 mJ/cm 2 (365 nm standard), thereby removing the polymerizability contained in the dry film.
  • the liquid crystal compound was polymerized while maintaining the liquid crystal state of the composition, and a polarizing film was formed from the dry film to obtain a polarizing plate.
  • the dichroic ratio of the obtained polarizing plate was measured as follows.
  • the absorbance (A1) in the direction of the transmission axis and the absorbance (A2) in the direction of the absorption axis at the maximum absorption wavelength ( ⁇ max) of the polarizing film of the polarizing plate are measured with a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation), and the polarizing plate is measured. It was measured by the double beam method using a device in which the provided folder was set. The folder was provided with a mesh that cuts the amount of light by 50% on the reference side.
  • a ratio (A2/A1) was calculated from the measured absorbance (A1) in the direction of the transmission axis and absorbance (A2) in the direction of the absorption axis, and was defined as the dichroic ratio (DR). Table 1 shows the results.
  • a polarizing plate provided with a film containing a composition containing the compound represented by formula (1) as a forming material can achieve a high dichroic ratio.

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Abstract

Provided is a composition comprising a compound represented by formula (1) and a liquid crystal compound. (In the formula , n is 1 or 2. Ar1, Ar2, and Ar3 each represent a 1,4-phenylene group or the like, and at least one of these has a hydroxyl group that can form a hydrogen bond in the molecule. R1 represents an alkylamino group. When Ar1 does not have a hydroxyl group that can form a hydrogen bond in the molecule, or has said hydroxyl group at the ortho position of an azo group, R2 represents an alkanediyl group, an alkanediyloxy group, an alkanediyloxycarbonyl group, an alkanediylcarbonyl group, or an alkanediylcarbonyloxy group. When Ar1 has, at the ortho position of R2, a hydroxyl group that can form a hydrogen bond in the molecule, R2 represents cyclic or chain group that can form a hydrogen bond with said hydroxyl group. R3 represents a polymerizable group or a hydrogen atom.

Description

化合物、組成物、膜、積層体および表示装置Compounds, compositions, films, laminates and display devices
　本発明は、化合物、組成物、膜、積層体および表示装置に関する。 The present invention relates to compounds, compositions, films, laminates and display devices.
　画像表示パネル等のディスプレイに対して薄型化の継続的な要求が存在しており、その構成要素の１つである偏光板、偏光子等に対してもさらなる薄型化が要求されている。このような要求に対して、例えば、重合性液晶化合物と二色性を示す色素化合物とを含む偏光膜を備える薄型のホストゲスト型偏光子が提案されている（例えば、特許文献１および２参照）。 There is a continuous demand for thinner displays such as image display panels, and there is also a demand for further thinning of polarizing plates, polarizers, etc., which are one of the components. In response to such demands, for example, a thin host-guest polarizer having a polarizing film containing a polymerizable liquid crystal compound and a dye compound exhibiting dichroism has been proposed (see, for example, Patent Documents 1 and 2). ).
特表２００７－５１０９４６号公報Japanese Patent Publication No. 2007-510946 特開２０１３－３７３５３号公報JP 2013-37353 A
　ホストゲスト型偏光子においては、二色比のさらなる向上が求められている。本発明の目的は、二色比の高い化合物、その化合物を含む組成物、その組成物から形成される膜、その膜を備える積層体、その積層体を備える発光装置を提供することにある。 Further improvement in the dichroic ratio is required for host-guest polarizers. An object of the present invention is to provide a compound having a high dichroic ratio, a composition containing the compound, a film formed from the composition, a laminate comprising the film, and a light-emitting device comprising the laminate.
　本発明は下記［１］から［１２］を提供する。
［１］　下記式（１）で表される化合物と、重合性液晶化合物および液晶性の高分子化合物の少なくとも一方を含む液晶性化合物とを含む組成物。 The present invention provides the following [1] to [12].
[1] A composition containing a compound represented by the following formula (1) and a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound.
Figure JPOXMLDOC01-appb-C000004
 ［式（１）中、ｎは、１または２の整数を表す。
　Ａｒ１、Ａｒ２およびＡｒ３は、それぞれ独立に、置換基を有していてもよい、１，４－フェニレン基または含硫黄複素環基を表す。Ａｒ１、Ａｒ２およびＡｒ３の少なくとも１つは、分子内水素結合を形成し得る水酸基を少なくとも１つ有する。
　Ｒ１は、重合性基を有していてもよいアルキルアミノ基を表す。
　Ａｒ１が分子内水素結合を形成し得る水酸基を、有さないか、またはアゾ基のオルト位に有する場合、Ｒ２は、炭素数４から２０のアルカンジイル基、炭素数２から２０のアルカンジイルオキシ基、炭素数２から２０のアルカンジイルオキシカルボニル基、炭素数２から２０のアルカンジイルカルボニル基および炭素数２から２０のアルカンジイルカルボニルオキシ基からなる群より選択される少なくとも１つの基を表す。
　Ａｒ１が分子内水素結合を形成し得る水酸基をＲ２のオルト位に有する場合、Ｒ２は、その水酸基と水素結合を形成し得る環状または鎖状である炭素数２から２０の基を表す。

　Ｒ３は、重合性基または水素原子を表す。
　ｎが２である場合、２つのＡｒ２は互いに同一であっても相異なっていてもよい。］
［２］　前記重合性液晶化合物が重合性スメクチック液晶化合物であり、前記液晶性の高分子化合物がスメクチック液晶性の高分子化合物である［１］に記載の組成物。
［３］　前記重合性液晶化合物が、下記式（Ａ）で表される化合物を含む［１］または［２］に記載の組成物。
Figure JPOXMLDOC01-appb-C000004
 [In formula (1), n represents the integer of 1 or 2.
Ar 1 , Ar 2 and Ar 3 each independently represent an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group. At least one of Ar 1 , Ar 2 and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond.
R 1 represents an alkylamino group optionally having a polymerizable group.
When Ar 1 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond or has a hydroxyl group ortho to the azo group, R 2 is an alkanediyl group having 4 to 20 carbon atoms, an alkane having 2 to 20 carbon atoms at least one group selected from the group consisting of a diyloxy group, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediylcarbonyl group having 2 to 20 carbon atoms and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms; show.
When Ar 1 has a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 2 , R 2 represents a cyclic or linear group having 2 to 20 carbon atoms capable of forming a hydrogen bond with the hydroxyl group. .

R3 represents a polymerizable group or a hydrogen atom.
When n is 2, two Ar 2 may be the same or different. ]
[2] The composition according to [1], wherein the polymerizable liquid crystal compound is a polymerizable smectic liquid crystal compound, and the liquid crystalline polymer compound is a smectic liquid crystalline polymer compound.
[3] The composition according to [1] or [2], wherein the polymerizable liquid crystal compound contains a compound represented by the following formula (A).
Figure JPOXMLDOC01-appb-C000005
 ［式（Ａ）中、ｍは１から３の整数を表す。
　Ｘ１、Ｘ２およびＸ３は、それぞれ独立に、２価の芳香族基または２価の脂環式炭化水素基を表す。ｍが２または３である場合、複数あるＸ１は互いに同一であっても相異なっていてもよい。Ｘ１、Ｘ２およびＸ３からなる群から選択される少なくとも３つが２価の炭化水素６員環基を表す。
　Ｙ１、Ｙ２、Ｗ１およびＷ２は、それぞれ独立に、単結合または２価の連結基を表す。ｍが２または３である場合、複数あるＹ１は互いに同一であっても相異なっていてもよい。
　Ｖ１およびＶ２は、それぞれ独立に、置換基を有していてもよい炭素数１から２０のアルカンジイル基を表す。前記アルカンジイル基を構成する－ＣＨ２－の少なくとも１つは、－Ｏ－、－ＣＯ－、－Ｓ－または－ＮＨ－に置き換わっていてもよい。
　Ｕ１およびＵ２は、それぞれ独立に、重合性基または水素原子を表し、少なくとも一方は重合性基を表す。］
［４］　前記式（１）で表される化合物は、分子内水素結合を形成し得る水酸基数が１である［１］から［３］のいずれかに記載の組成物。
［５］　上記式（１）で表される化合物は、Ｒ３と分子内水素結合し得る水酸基をＡｒ１に有するか、または－Ｎ＝Ｎ－と分子内で水素結合し得る水酸基をＡｒ２に有する［１］から［４］のいずれかに記載の組成物。
［６］　下記式（１ａ）で表される化合物。
Figure JPOXMLDOC01-appb-C000005
 [In the formula (A), m represents an integer of 1 to 3.
X 1 , X 2 and X 3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. When m is 2 or 3, multiple X 1 may be the same or different. At least three selected from the group consisting of X 1 , X 2 and X 3 represent a divalent hydrocarbon 6-membered ring group.
Y 1 , Y 2 , W 1 and W 2 each independently represent a single bond or a divalent linking group. When m is 2 or 3, a plurality of Y 1 may be the same or different.
V 1 and V 2 each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms. At least one of -CH 2 - constituting the alkanediyl group may be replaced with -O-, -CO-, -S- or -NH-.
U 1 and U 2 each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group. ]
[4] The composition according to any one of [1] to [3], wherein the compound represented by formula (1) has one hydroxyl group capable of forming an intramolecular hydrogen bond.
[5] The compound represented by the above formula (1) has a hydroxyl group capable of forming an intramolecular hydrogen bond with R 3 in Ar 1 , or a hydroxyl group capable of forming an intramolecular hydrogen bond with -N=N- in Ar 2 The composition according to any one of [1] to [4].
[6] A compound represented by the following formula (1a).
Figure JPOXMLDOC01-appb-C000006
 ［式（１ａ）中、ｋは、１または２の整数を表す。
　Ａｒ１１、Ａｒ１２およびＡｒ１３は、それぞれ独立に、置換基を有していてもよい１，４－フェニレン基又は含硫黄複素環基を表す。Ａｒ１１およびＡｒ１２の少なくとも一方は、分子内水素結合を形成し得る水酸基を少なくとも１つ有する。　
　Ｒ１１は、重合性基を有していてもよいアルキルアミノ基を表す。
　Ａｒ１１が分子内水素結合を形成し得る水酸基を、有さないか、またはアゾ基のオルト位に有する場合、Ｒ１２は、炭素数４から２０のアルカンジイル基、炭素数２から２０のアルカンジイルオキシ基、炭素数２から２０のアルカンジイルオキシカルボニル基、炭素数２から２０のアルカンジイルオキシカルボニル基および炭素数２から２０のアルカンジイルカルボニルオキシ基からなる群より選択される少なくとも１つの基を表す。
　Ａｒ１１が分子内水素結合を形成し得る水酸基をＲ１２のオルト位に有する場合、Ｒ１２は、その水酸基と水素結合を形成し得る環状または鎖状である炭素数２から２０の基を表す。
　Ｒ１３は、重合性基または水素原子を表す。
　ｋが２である場合、２つのＡｒ１２は互いに同一であっても相異なっていてもよい。］
［７］　分子内水素結合を形成し得る水酸基数が１である［６］に記載の化合物。
［８］　Ａｒ１１、Ａｒ１２およびＡｒ１３は、置換基を有していてもよい１，４－フェニレン基である［６］または［７］に記載の化合物。
［９］　Ｒ１３と分子内水素結合を形成し得る水酸基をＡｒ１１に有するか、または－Ｎ＝Ｎ－と分子内で水素結合し得る水酸基をＡｒ１２に有する［６］から［８］のいずれかに記載の化合物。
［１０］　［１］から［５］のいずれかに記載の組成物を形成材料とする膜。
［１１］　［１０］に記載の膜を含む積層体。
［１２］　［１１］に記載の積層体を備える表示装置。
Figure JPOXMLDOC01-appb-C000006
 [In Formula (1a), k represents an integer of 1 or 2.
Ar 11 , Ar 12 and Ar 13 each independently represent an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group. At least one of Ar 11 and Ar 12 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond.
R 11 represents an alkylamino group optionally having a polymerizable group.
When Ar 11 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond or has a hydroxyl group ortho to the azo group, R 12 is an alkanediyl group having 4 to 20 carbon atoms, an alkane having 2 to 20 carbon atoms at least one group selected from the group consisting of a diyloxy group, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms; represents
When Ar 11 has a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 12 , R 12 represents a cyclic or linear group having 2 to 20 carbon atoms capable of forming a hydrogen bond with the hydroxyl group. .
R13 represents a polymerizable group or a hydrogen atom.
When k is 2, two Ar 12 may be the same or different. ]
[7] The compound of [6], which has 1 hydroxyl group capable of forming an intramolecular hydrogen bond.
[8] The compound according to [6] or [7], wherein Ar 11 , Ar 12 and Ar 13 are optionally substituted 1,4-phenylene groups.
[9] Ar 11 has a hydroxyl group that can form an intramolecular hydrogen bond with R 13 , or Ar 12 has a hydroxyl group that can form an intramolecular hydrogen bond with -N=N- of [6] to [8] A compound according to any one of the above.
[10] A film formed from the composition according to any one of [1] to [5].
[11] A laminate comprising the film according to [10].
[12] A display device comprising the laminate according to [11].
　本発明によれば、二色比の高い化合物、その化合物を含む組成物、その組成物から形成される膜、その膜を備える積層体、その積層体を備える発光装置を提供することができる。 According to the present invention, it is possible to provide a compound having a high dichroic ratio, a composition containing the compound, a film formed from the composition, a laminate comprising the film, and a light-emitting device comprising the laminate.
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。また組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。さらに本明細書に記載される数値範囲の上限及び下限は、当該数値を任意に選択して組み合わせることが可能である。以下、本発明の実施形態について詳細に説明する。なお、本発明の範囲はここで説明する実施の形態に限定されるものではなく、本発明の趣旨を損なわない範囲で種々の変更をすることができる。 In this specification, the term "process" is not only an independent process, but even if it cannot be clearly distinguished from other processes, it is included in this term as long as the intended purpose of the process is achieved. . In addition, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. Furthermore, the upper and lower limits of the numerical ranges described herein can be arbitrarily selected and combined. BEST MODE FOR CARRYING OUT THE INVENTION 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 here, and various modifications can be made without departing from the gist of the present invention.
＜組成物＞
　本実施形態にかかる組成物は、式（１）で表される化合物と、液晶性化合物とを含む。液晶性化合物は、重合性液晶化合物および液晶性の高分子化合物の少なくとも一方を含む。組成物は、例えば偏光膜の形成材料として用いられる。すなわち組成物は、偏光膜形成用組成物であってよい。組成物を形成材料として得られる偏光膜を備える偏光板は、高い二色比（ＤＲ）を示すことができる。 <Composition>
The composition according to this embodiment contains the compound represented by formula (1) and a liquid crystalline compound. The liquid crystal compound includes at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound. The composition is used, for example, as a material for forming a polarizing film. That is, the composition may be a composition for forming a polarizing film. A polarizing plate provided with a polarizing film obtained using the composition as a forming material can exhibit a high dichroic ratio (DR).
　式（１）で表される化合物は、Ａｒ１、Ａｒ２およびＡｒ３の少なくとも１つが、分子内水素結合を形成し得る水酸基を少なくとも１つ有することで、例えば、分子内水素結合により擬似的に環が増えることになり、ホスト化合物との相互作用が向上すると考えられる。これにより、式（１）で表される化合物を含む偏光膜における二色比（ＤＲ）が高くなると考えられる。 In the compound represented by formula (1), at least one of Ar 1 , Ar 2 and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. It is thought that the number of rings will increase in , and the interaction with the host compound will improve. It is believed that this increases the dichroic ratio (DR) of the polarizing film containing the compound represented by formula (1).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（１）中、Ａｒ１、Ａｒ２およびＡｒ３は、それぞれ独立に、置換基を有していてもよい、１，４－フェニレン基または含硫黄複素環基を表し、好ましくは、置換基を有していてもよい１，４－フェニレン基を表す。２価の含硫黄複素環基としては、ベンゾチアゾールジイル基、チエノチアゾールジイル基およびチアゾールジイル基が挙げられ、好ましくはベンゾチアゾールジイル基である。 In formula (1), Ar 1 , Ar 2 and Ar 3 each independently represent an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group, preferably a substituent represents a 1,4-phenylene group which may have The divalent sulfur-containing heterocyclic group includes a benzothiazoldiyl group, a thienothiazoldiyl group and a thiazoldiyl group, preferably a benzothiazoldiyl group.
　Ａｒ１、Ａｒ２およびＡｒ３における置換基は、ハロゲン原子、水酸基、メチル基およびメトキシ基からなる群から選択される少なくとも１種であってよく、好ましくはフッ素原子、塩素原子、水酸基、メチル基またはメトキシ基であり、より好ましくはフッ素原子またはヒドロキシ基である。Ａｒ１、Ａｒ２およびＡｒ３における置換基数は、それぞれ独立に、例えば０、１または２であり、好ましくは０または１である。 The substituents on Ar 1 , Ar 2 and Ar 3 may be at least one selected from the group consisting of halogen atoms, hydroxyl groups, methyl groups and methoxy groups, preferably fluorine atoms, chlorine atoms, hydroxyl groups and methyl groups. or a methoxy group, more preferably a fluorine atom or a hydroxy group. The number of substituents in Ar 1 , Ar 2 and Ar 3 is each independently, for example, 0, 1 or 2, preferably 0 or 1.
　Ａｒ１、Ａｒ２およびＡｒ３の少なくとも１つは、分子内水素結合を形成し得る水酸基を少なくとも１つ有する。分子内水素結合を形成し得る水酸基は、Ａｒ１およびＡｒ２の少なくとも一方に存在することが好ましく、少なくともＡｒ１に存在することがより好ましい。 At least one of Ar 1 , Ar 2 and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. A hydroxyl group capable of forming an intramolecular hydrogen bond is preferably present in at least one of Ar 1 and Ar 2 , and more preferably present in at least Ar 1 .
　水酸基が分子内水素結合を形成し得る官能基は、同一環上に隣接して存在していてよい。すなわち、水酸基はそのオルト位に存在する官能基と分子内水素結合を形成することが好ましく、６員環状の分子内水素結合を形成することもまた好ましい。水酸基が分子内水素結合を形成し得る官能基としては、水酸基、メトキシ基、アゾ基、カルボニル基、オキシカルボニル基（－ＯＣ（＝Ｏ）－）、カルボニルオキシ基（－Ｃ（＝Ｏ）Ｏ－）、２－ピロリジンジイル基、２－ピペリジンジイル基、２－ピリミジンジイル基、２－チアゾールジイル基、２－チアゾリンジイル基、２－オキサゾールジイル基、２－オキサゾリンジイル基等を挙げることができる。水酸基が分子内水素結合を形成し得る官能基は、例えば、アゾ基以外の官能基であってよい。 Functional groups with which hydroxyl groups can form intramolecular hydrogen bonds may exist adjacently on the same ring. That is, the hydroxyl group preferably forms an intramolecular hydrogen bond with a functional group present at its ortho position, and it is also preferred to form a 6-membered cyclic intramolecular hydrogen bond. Examples of functional groups in which a hydroxyl group can form an intramolecular hydrogen bond include a hydroxyl group, a methoxy group, an azo group, a carbonyl group, an oxycarbonyl group (-OC(=O)-), a carbonyloxy group (-C(=O)O -), 2-pyrrolidinediyl group, 2-piperidinediyl group, 2-pyrimidinediyl group, 2-thiazolinediyl group, 2-thiazolinediyl group, 2-oxazolinediyl group, 2-oxazolinediyl group, and the like. . A functional group with which a hydroxyl group can form an intramolecular hydrogen bond may be, for example, a functional group other than an azo group.
　式（１）で表される化合物は、分子内水素結合を形成し得る水酸基をＡｒ１およびＡｒ２の少なくとも一方に有し、その水酸基がＡｒ１とＡｒ２を連結するアゾ基およびＲ２の少なくとも１つと分子内水素結合を形成することが好ましく、分子内水素結合を形成し得る水酸基を少なくともＡｒ１に有し、その水酸基がＲ２と分子内水素結合を形成することがより好ましい。式（１）で表される化合物における分子内水素結合を形成し得る水酸基の数は、例えば１であってよい。水酸基がＲ２と分子内水素結合を形成する場合、Ｒ２は－ＯＣ（＝Ｏ）－、カルボニル基、２－ピロリジンジイル基、２－ピペリジンジイル基、２－ピリミジンジイル基、２－チアゾールジイル基、２－チアゾリンジイル基、２－オキサゾールジイル基または２－オキサゾリンジイル基を含むことが好ましく、少なくとも－ＯＣ（＝Ｏ）－またはカルボニル基を含むことがより好ましく、炭素数２から２０のアルカンジイルオキシカルボニル基または炭素数２から２０のアルカンジイルカルボニル基であることがさらに好ましい。 The compound represented by formula (1) has a hydroxyl group capable of forming an intramolecular hydrogen bond in at least one of Ar 1 and Ar 2 , and the hydroxyl group is the azo group connecting Ar 1 and Ar 2 and R 2 . It preferably forms an intramolecular hydrogen bond with at least one, and more preferably has at least a hydroxyl group capable of forming an intramolecular hydrogen bond in Ar 1 and the hydroxyl group forms an intramolecular hydrogen bond with R 2 . The number of hydroxyl groups capable of forming an intramolecular hydrogen bond in the compound represented by formula (1) may be, for example, one. When a hydroxyl group forms an intramolecular hydrogen bond with R2 , R2 is -OC(=O)-, a carbonyl group, a 2-pyrrolidinediyl group, a 2-piperidinediyl group, a 2-pyrimidinediyl group, a 2-thiazoldiyl group. group, 2-thiazolinediyl group, 2-oxazolinediyl group or 2-oxazolinediyl group, more preferably at least --OC(=O)-- or carbonyl group, alkane having 2 to 20 carbon atoms More preferably, it is a diyloxycarbonyl group or an alkanediylcarbonyl group having 2 to 20 carbon atoms.
　Ｒ１は、重合性基を有していてもよいアルキルアミノ基を表す。Ｒ１におけるアルキルアミノ基は、モノアルキルアミノ基またはジアルキルアミノ基であってよく、好ましくはジアルキルアミノ基である。Ｒ１におけるアルキルアミノ基としては、ジメチルアミノ基、ジエチルアミノ基、エチルメチルアミノ基、ジプロピルアミノ基、ジイソプロピルアミノ基、モノメチルアミノ基、モノエチルアミノ基、モノプロピルアミノ基、モノイソプロピルアミノ基、ピロリジル基、ピペリジル基、モルホリニル基、オキサゾリジニル基等を挙げることでき、これらからなる群から選択される少なくとも１種であってよい。Ｒ１におけるアルキルアミノ基は、好ましくはジメチルアミノ基またはジエチルアミノ基である。 R 1 represents an alkylamino group optionally having a polymerizable group. The alkylamino group in R 1 may be a monoalkylamino group or a dialkylamino group, preferably a dialkylamino group. The alkylamino group for R 1 includes a dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, diisopropylamino group, monomethylamino group, monoethylamino group, monopropylamino group, monoisopropylamino group, pyrrolidyl group, piperidyl group, morpholinyl group, oxazolidinyl group, etc., and may be at least one selected from the group consisting of these. The alkylamino group for R 1 is preferably a dimethylamino group or a diethylamino group.
　Ｒ１で表されるアルキルアミノ基が有する水素原子は、その少なくとも１つが重合性基に置換されていてもよい。ここで重合性基としては、例えば、（メタ）アクリレート基（（メタ）アクリロイルオキシ基）、ビニルフェニル基、ビニル基、エポキシ基等を挙げることができる。重合性基は、ラジカル重合性基であることが好ましく、中でも、（メタ）アクリレート基が好ましい。Ｒ１が重合性基を有する場合、その数は、例えば、１または２個であり、好ましくは１個である。 At least one hydrogen atom of the alkylamino group represented by R 1 may be substituted with a polymerizable group. Examples of the polymerizable group include (meth)acrylate group ((meth)acryloyloxy group), vinylphenyl group, vinyl group, and epoxy group. The polymerizable group is preferably a radically polymerizable group, and more preferably a (meth)acrylate group. When R 1 has a polymerizable group, the number thereof is, for example, 1 or 2, preferably 1.
　Ｒ２としては、水酸基と分子内水素結合を形成し得る環状または鎖状である炭素数２から２０の基、炭素数２から２０のアルカンジイルオキシカルボニル基、炭素数２から２０のアルカンジイルカルボニル基、炭素数４から２０のアルカンジイル基、炭素数２から２０のアルカンジイルオキシ基、炭素数２から２０のアルカンジイルカルボニルオキシ基等を挙げることができ、これらからなる群から選択される少なくとも１種を含むことが好ましい。 R 2 is a cyclic or linear group having 2 to 20 carbon atoms capable of forming an intramolecular hydrogen bond with a hydroxyl group, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, or an alkanediylcarbonyl group having 2 to 20 carbon atoms. group, an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, an alkanediylcarbonyloxy group having 2 to 20 carbon atoms, etc., and at least It is preferred that one species is included.
　Ａｒ１が、分子内水素結合を形成し得る水酸基を、有さないか、またはＡｒ１とＡｒ２を連結するアゾ基のオルト位に有する場合、Ｒ２は、炭素数４から２０のアルカンジイル基、炭素数２から２０のアルカンジイルオキシ基、炭素数２から２０のアルカンジイルオキシカルボニル基、炭素数２から２０のアルカンジイルカルボニル基および炭素数２から２０のアルカンジイルカルボニルオキシ基からなる群より選択される少なくとも１つの基を表す。 When Ar 1 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond or has a hydroxyl group ortho to the azo group connecting Ar 1 and Ar 2 , R 2 is an alkanediyl having 4 to 20 carbon atoms. alkanediyloxy group having 2 to 20 carbon atoms, alkanediyloxycarbonyl group having 2 to 20 carbon atoms, alkanediylcarbonyl group having 2 to 20 carbon atoms and alkanediylcarbonyloxy group having 2 to 20 carbon atoms represents at least one group selected from
　炭素数４から２０のアルカンジイル基としては、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基等の無置換の（置換基を有していない）直鎖状又は分枝鎖状の炭素数４から２０のアルキル基から水素原子を１つ取り除いて形成されるアルカンジイル基が挙げられる。アルカンジイル基の炭素数は、４から１６が好ましく、４から１２がより好ましい。 Examples of alkanediyl groups having 4 to 20 carbon atoms include n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl and n-octyl groups. , n-nonyl group, n-decyl group, etc. Formed by removing one hydrogen atom from a linear or branched (unsubstituted) alkyl group having 4 to 20 carbon atoms and alkanediyl groups. The alkanediyl group preferably has 4 to 16 carbon atoms, more preferably 4 to 12 carbon atoms.
　炭素数４から２０のアルキル基を構成する１つ以上の水素原子は、ハロゲン原子（例えば、フッ素原子）、ヒドロキシ基、アミノ基または置換アミノ基で置換されていてもよい。ここで置換アミノ基としては、例えば、Ｎ－メチルアミノ基、Ｎ－エチルアミノ基、Ｎ，Ｎ－ジメチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基等の１つまたは２つの炭素数１から２０のアルキル基で置換されたアミノ基などが挙げられる。１つ以上の水素原子がハロゲン原子、ヒドロキシ基、アミノ基等で置換されたアルキル基としては、フルオロブチル基、オクタフルオロブチル基等の炭素数４から２０のハロアルキル基；ヒドロキシブチル基、ヒドロキシペンチル基、ヒドロキシヘキシル基等の炭素数４から２０のヒドロキシアルキル基；アミノブチル基、２－（Ｎ，Ｎ－ジメチルアミノ）ブチル基等の無置換アミノ基または置換アミノ基を有する炭素数４から２０のアルキル基などが挙げられる。 One or more hydrogen atoms constituting the alkyl group having 4 to 20 carbon atoms may be substituted with a halogen atom (eg, fluorine atom), hydroxy group, amino group or substituted amino group. Here, the substituted amino group includes, for example, one or two alkyl groups having 1 to 20 carbon atoms such as N-methylamino group, N-ethylamino group, N,N-dimethylamino group and N,N-diethylamino group. and an amino group substituted with a group. Alkyl groups in which one or more hydrogen atoms are substituted with halogen atoms, hydroxy groups, amino groups, etc. include haloalkyl groups having 4 to 20 carbon atoms such as fluorobutyl group and octafluorobutyl group; hydroxybutyl group and hydroxypentyl hydroxyalkyl groups having 4 to 20 carbon atoms such as hydroxyhexyl groups; unsubstituted amino groups such as aminobutyl groups and 2-(N,N-dimethylamino)butyl groups; and the like.
　炭素数２から２０のアルカンジイルオキシ基としては、エトキシ基、ｎ－プロポキシ基、イソプロピルオキシ基、ｎ－ブトキシ基、イソブチルオキシ基、ｔｅｒｔ－ブトキシ基、ｎ－ペンチルオキシ基、イソペンチルオキシ基、ネオペンチルオキシ基、ｎ－ヘキシルオキシ基、ｎ－ヘプチルオキシ基、ｎ－オクチルオキシ基、ｎ－ノニルオキシ基、ｎ－デシルオキシ基等の無置換の直鎖状又は分枝鎖状の炭素数２から２０のアルコキシ基から水素原子を１つ取り除いて形成されるアルカンジイルオキシ基が挙げられる。アルカンジイルオキシ基の炭素数は、２から１６が好ましく、２から１２がより好ましい。 Examples of the alkanediyloxy group having 2 to 20 carbon atoms include ethoxy group, n-propoxy group, isopropyloxy group, n-butoxy group, isobutyloxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, unsubstituted linear or branched chain having 2 to 2 carbon atoms such as neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group An alkanediyloxy group formed by removing one hydrogen atom from an alkoxy group of 20 can be mentioned. The alkanediyloxy group preferably has 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms.
　炭素数２から２０のアルコキシ基を構成する１つ以上の水素原子は、ハロゲン原子（例えば、フッ素原子）、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置換されていてもよい。置換基を有するアミノ基は上記と同様である。１つ以上の水素原子がハロゲン原子、ヒドロキシ、アミノ基等で置換されたアルコキシ基としては、テトラフルオロエトキシ基、オクタフルオロブトキシ基等の炭素数２から２０のハロアルコキシ基；２－ヒドロキシエトキシ基等の炭素数２から２０のヒドロキシアルコキシ基；アミノエトキシ基、２－（Ｎ，Ｎ－ジメチルアミノ）エトキシ基等の無置換または置換基を有するアミノ基を有する炭素数２から２０のアルコキシ基が挙げられる。 One or more hydrogen atoms constituting the alkoxy group having 2 to 20 carbon atoms may be substituted with a halogen atom (eg, fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent. Amino groups having substituents are the same as described above. Alkoxy groups in which one or more hydrogen atoms are substituted with halogen atoms, hydroxy, amino groups, etc. include haloalkoxy groups having 2 to 20 carbon atoms such as tetrafluoroethoxy group and octafluorobutoxy group; 2-hydroxyethoxy group; A hydroxyalkoxy group having 2 to 20 carbon atoms such as; an alkoxy group having 2 to 20 carbon atoms having an unsubstituted or substituted amino group such as an aminoethoxy group and a 2-(N,N-dimethylamino)ethoxy group mentioned.
　炭素数２から２０のアルカンジイルオキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、ｎ－プロポキシカルボニル基、イソプロポキシカルボニル基、ｎ－ブトキシカルボニル基、イソブトキシカルボニル基、ｔｅｒｔ－ブトキシカルボニル基、ｎ－ペンチルオキシカルボニル基、イソペンチルオキシカルボニル基、ネオペンチルオキシカルボニル基、ｎ－ヘキシルオキシカルボニル基、ｎ－ヘプチルオキシカルボニル基、ｎ－オクチルオキシカルボニル基、ｎ－ノニルオキシカルボニル基、ｎ－デシルオキシカルボニル基等の無置換の炭素数２から２０のアルコキシカルボニル基から水素原子を１つ取り除いて形成されるアルカンジイルオキシカルボニル基が挙げられる。アルカンジイルオキシカルボニル基のアルカンジイル部分の炭素数は、１から１６が好ましく、１から１２がより好ましい。 Examples of the alkanediyloxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyl An alkanediyloxycarbonyl group formed by removing one hydrogen atom from an unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms such as an oxycarbonyl group can be mentioned. The alkanediyl portion of the alkanediyloxycarbonyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms.
　炭素数２から２０のアルコキシカルボニル基を構成する１つ以上の水素原子は、ハロゲン原子（例えば、フッ素原子）、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置換されていてもよい。置換基を有するアミノ基は上記と同様である。１つ以上の水素原子がハロゲン原子、ヒドロキシ基、アミノ基等で置き換わったアルコキシカルボニル基としては、フルオロエトキシカルボニル基、トリフルオロエトキシカルボニル基、テトラフルオロエトキシカルボニル基、オクタフルオロブトキシカルボニル基等の炭素数２から２０のハロアルコキシカルボニル基が挙げられる。 One or more hydrogen atoms constituting the alkoxycarbonyl group having 2 to 20 carbon atoms may be substituted with a halogen atom (e.g., fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent. Amino groups having substituents are the same as described above. The alkoxycarbonyl group in which one or more hydrogen atoms are replaced with a halogen atom, a hydroxy group, an amino group, or the like includes carbon atoms such as a fluoroethoxycarbonyl group, a trifluoroethoxycarbonyl group, a tetrafluoroethoxycarbonyl group, and an octafluorobutoxycarbonyl group. Haloalkoxycarbonyl groups of numbers 2 to 20 can be mentioned.
　炭素数２から２０のアルカンジイルカルボニル基としては、アセチル基、エチルカルボニル基、ｎ－プロピルカルボニル基、イソプロピルカルボニル基、ｎ－ブチルカルボニル基、イソブチルカルボニル基、ｔｅｒｔ－ブチルカルボニル基、ｎ－ペンチルカルボニル基、イソペンチルカルボニル基、ネオペンチルカルボニル基、ｎ－ヘキシルカルボニル基、ｎ－ヘプチルカルボニル基、ｎ－オクチルカルボニル基、ｎ－ノニルカルボニル基、ｎ－デシルカルボニル基等の無置換の炭素数２から２０のアルカノイル基から水素原子を１つ取り除いて形成されるアルカンジイルカルボニル基が挙げられる。アルカンジイルカルボニル基のアルカンジイル部分の炭素数は、１から１６が好ましく、１から１２がより好ましい。 Examples of alkanediylcarbonyl groups having 2 to 20 carbon atoms include acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, tert-butylcarbonyl group and n-pentylcarbonyl group. group, isopentylcarbonyl group, neopentylcarbonyl group, n-hexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, n-nonylcarbonyl group, n-decylcarbonyl group, etc. unsubstituted from 2 carbon atoms An alkanediylcarbonyl group formed by removing one hydrogen atom from an alkanoyl group of 20 can be mentioned. The alkanediyl portion of the alkanediylcarbonyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms.
　炭素数２から２０のアルカノイル基を構成する１つ以上の水素原子は、ハロゲン原子（例えば、フッ素原子）、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置換されていてもよい。置換基を有するアミノ基は上記と同様である。１つ以上の水素原子がハロゲン原子、ヒドロキシ基等で置換されたアルカノイル基としては、フルオロエトキシカルボニル基、トリフルオロエトキシカルボニル基、テトラフルオロエチルカルボニル基、オクタフルオロブチルカルボニル基等の炭素数２から２０のハロアシル基が挙げられる。 One or more hydrogen atoms constituting the alkanoyl group having 2 to 20 carbon atoms may be substituted with a halogen atom (eg, fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent. Amino groups having substituents are the same as described above. The alkanoyl group in which one or more hydrogen atoms are substituted with a halogen atom, a hydroxy group, or the like includes 2 to 2 carbon atoms such as a fluoroethoxycarbonyl group, a trifluoroethoxycarbonyl group, a tetrafluoroethylcarbonyl group, an octafluorobutylcarbonyl group, and the like. Twenty haloacyl groups are mentioned.
　炭素数２から２０のアルカンジイルカルボニルオキシ基としては、アセチルオキシ基、エチルカルボニルオキシ基、ｎ－プロピルカルボニルオキシ基、イソプロピルカルボニルオキシ基、ｎ－ブチルカルボニルオキシ基、イソブチルカルボニルオキシ基、ｔｅｒｔ－ブチルカルボニルオキシ基、ｎ－ペンチルカルボニルオキシ基、イソペンチルカルボニルオキシ基、ネオペンチルカルボニルオキシ基、ｎ－ヘキシルカルボニルオキシ基、ｎ－ヘプチルカルボニルオキシ基、ｎ－オクチルカルボニルオキシ基、ｎ－ノニルカルボニルオキシ基、ｎ－デシルカルボニルオキシ基等の無置換の炭素数２から２０のアルカノイルオキシ基から水素原子を１つ取り除いて形成されるアルカンジイルカルボニルオキシ基が挙げられる。アルカンジイルカルボニルオキシ基のアルカンジイル部分の炭素数は、１から１６が好ましく、１から１２がより好ましい。 The alkanediylcarbonyloxy group having 2 to 20 carbon atoms includes acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, tert-butyl carbonyloxy group, n-pentylcarbonyloxy group, isopentylcarbonyloxy group, neopentylcarbonyloxy group, n-hexylcarbonyloxy group, n-heptylcarbonyloxy group, n-octylcarbonyloxy group, n-nonylcarbonyloxy group , an alkanediylcarbonyloxy group formed by removing one hydrogen atom from an unsubstituted alkanoyloxy group having 2 to 20 carbon atoms such as n-decylcarbonyloxy group. The alkanediyl portion of the alkanediylcarbonyloxy group preferably has 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms.
　炭素数２から２０のアルカノイルオキシ基を構成する１つ以上の水素原子は、ハロゲン原子（例えば、フッ素原子）、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置換されていてもよい。置換基を有するアミノ基は上記と同様である。１つ以上の水素原子がハロゲン原子、ヒドロキシ基等で置換されたアルカノイルオキシ基としては、テトラフルオロエチルカルボニルオキシ基、オクタフルオロブチルカルボニルオキシ基等の炭素数２から２０のハロアシルオキシ基が挙げられる。 One or more hydrogen atoms constituting an alkanoyloxy group having 2 to 20 carbon atoms may be substituted with a halogen atom (eg, a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent. Amino groups having substituents are the same as described above. Examples of the alkanoyloxy group in which one or more hydrogen atoms are substituted with a halogen atom, a hydroxy group, etc. include haloacyloxy groups having 2 to 20 carbon atoms such as a tetrafluoroethylcarbonyloxy group and an octafluorobutylcarbonyloxy group. .
　炭素数４から２０のアルキル基、炭素数２から２０のアルコキシ基、炭素数２から２０のアルコキシカルボニル基、炭素数２から２０のアルカノイル基または炭素数２から２０のアルカノイルオキシ基を構成するアルキル基部分を構成する－ＣＨ２－の少なくとも１つは、－Ｏ－および－ＮＲ＊－の少なくとも１つで置換されていてもよい。ここでＲ＊は、水素原子または炭素数１から６、好ましくは炭素数１から４のアルキル基を表わし、炭素数１から６のアルキル基としては、メチル基、エチル基、ブチル基、ヘキシル基などが挙げられる。炭素原子間に－Ｏ－または－ＮＲ＊－が挿入された置換アルキル基としては、２－エトキシエチル基、２－（２－エトキシエトキシ）エチル基、２－［２－（エチルアミノ）エチル）アミノ］エチル基等が挙げられる。 an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or an alkanoyloxy group having 2 to 20 carbon atoms; At least one of —CH 2 — constituting the group moiety may be substituted with at least one of —O— and —NR * —. Here, R * represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the alkyl group having 1 to 6 carbon atoms includes methyl group, ethyl group, butyl group and hexyl group. etc. Substituted alkyl groups having -O- or -NR * - inserted between carbon atoms include a 2-ethoxyethyl group, a 2-(2-ethoxyethoxy)ethyl group, and a 2-[2-(ethylamino)ethyl) amino] ethyl group and the like.
　Ａｒ１が、分子内水素結合を形成し得る水酸基をＲ２のオルト位に有する場合、Ｒ２は、その水酸基と分子内水素結合を形成し得る環状または鎖状である炭素数２から２０の基を表す。Ｒ２は、好ましくは、水酸基と分子内水素結合を形成し得る鎖状の炭素数２から２０の基であってよい。Ｒ２で表され、水酸基と分子内水素結合を形成し得る環状の基としては、２－ピロリジンジイル基、２－ピペリジンジイル基、２－ピリミジンジイル基、２－チアゾールジイル基、２－チアゾリンジイル基、２－オキサゾールジイル基、２－オキサゾリンジイル基等を挙げることができ、これらからなる群から選択される少なくとも１種を含むことが好ましい。水酸基と分子内水素結合を形成し得る環状の基は、置換基を有していてもよい。置換基としては、ハロゲン原子（例えば、フッ素原子）、ヒドロキシ基、置換基を有していてもよいアミノ基、アルコキシ基、アルキル基、アルキルカルボニル基等を挙げることができる。置換基がアルキル部分を有する場合、その炭素数は、例えば、１から１０であってよい。 When Ar 1 has a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 2 , R 2 is a cyclic or chain C 2 to 20 group capable of forming an intramolecular hydrogen bond with the hydroxyl group. represents a group. R 2 may preferably be a chain group having 2 to 20 carbon atoms capable of forming an intramolecular hydrogen bond with a hydroxyl group. The cyclic group represented by R 2 and capable of forming an intramolecular hydrogen bond with a hydroxyl group includes a 2-pyrrolidinediyl group, a 2-piperidinediyl group, a 2-pyrimidinediyl group, a 2-thiazoldiyl group and a 2-thiazolinediyl group. group, 2-oxazolediyl group, 2-oxazolinediyl group, etc., and preferably contains at least one selected from the group consisting of these. A cyclic group capable of forming an intramolecular hydrogen bond with a hydroxyl group may have a substituent. Examples of substituents include halogen atoms (eg, fluorine atoms), hydroxy groups, amino groups optionally having substituents, alkoxy groups, alkyl groups, alkylcarbonyl groups, and the like. When a substituent has an alkyl moiety, it may have from 1 to 10 carbon atoms, for example.
　Ｒ２で表され、水酸基と分子内水素結合を形成し得る鎖状の基としては、炭素数２から２０のアルカンジイルオキシカルボニル基、炭素数２から２０のアルカンジイルカルボニル基等を挙げることができ、これらからなる群から選択される少なくとも１種を含むことが好ましい。炭素数２から２０のアルカンジイルオキシカルボニル基および炭素数２から２０のアルカンジイルカルボニル基については、既述のとおりである。 Examples of the chain group represented by R 2 and capable of forming an intramolecular hydrogen bond with a hydroxyl group include an alkanediyloxycarbonyl group having 2 to 20 carbon atoms and an alkanediylcarbonyl group having 2 to 20 carbon atoms. It is preferable to include at least one selected from the group consisting of these. The alkanediyloxycarbonyl group having 2 to 20 carbon atoms and the alkanediylcarbonyl group having 2 to 20 carbon atoms are as described above.
　Ｒ３は、重合性基または水素原子を表す。Ｒ３で表される重合性基としては、例えば、（メタ）アクリレート基（（メタ）アクリロイルオキシ基）、ビニルフェニル基、ビニル基、エポキシ基等を挙げることができる。重合性基は、ラジカル重合性基であることが好ましく、中でも、（メタ）アクリレート基が好ましい。 R3 represents a polymerizable group or a hydrogen atom. Examples of the polymerizable group represented by R 3 include (meth)acrylate group ((meth)acryloyloxy group), vinylphenyl group, vinyl group and epoxy group. The polymerizable group is preferably a radically polymerizable group, and more preferably a (meth)acrylate group.
　ｎは１または２を表す。ｎが２の場合、２つのＡｒ２は互いに同一であっても相異なっていてもよい。 n represents 1 or 2; When n is 2, two Ar 2 may be the same or different.
　式（１）で表される化合物は、Ａｒ１、Ａｒ２およびＡｒ３の少なくとも１つに、分子内水素結合を形成し得る水酸基を少なくとも１つ有する。式（１）で表される化合物における分子内水素結合を形成し得る水酸基数は、例えば１であってよい。以下に、式（１）で表される化合物における分子内水素結合の例を示すが、本発明はこれらの態様に限定されるわけではない。以下の例示ではＡｒ１、Ａｒ２およびＡｒ３を便宜的に１，４－フェニレン基としているがこれに限定されない。また、Ｒ２１は炭素数２から２０のアルカンジイル基を表す。 In the compound represented by formula (1), at least one of Ar 1 , Ar 2 and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. The number of hydroxyl groups capable of forming an intramolecular hydrogen bond in the compound represented by Formula (1) may be, for example, one. Examples of intramolecular hydrogen bonds in the compound represented by formula (1) are shown below, but the present invention is not limited to these embodiments. In the following examples, Ar 1 , Ar 2 and Ar 3 are 1,4-phenylene groups for convenience, but are not limited to this. R21 represents an alkanediyl group having 2 to 20 carbon atoms.
（１）分子内水素結合を形成し得る水酸基をＡｒ１に有する場合
　Ａｒ１上の水酸基は、例えば、Ａｒ１とＡｒ２を連結するアゾ基またはＲ２と６員環状の分子内水素結合を形成することができる。Ａｒ１上の水酸基がＲ２と分子内水素結合を形成する態様としては、以下の（ａ）等を例示することができる。また、Ａｒ１上の水酸基がＡｒ１とＡｒ２を連結するアゾ基と分子内水素結合を形成する態様としては、以下の（ｂ）等を例示することができる。 ( 1 ) When Ar 1 has a hydroxyl group capable of forming an intramolecular hydrogen bond can be formed. The following (a) etc. can be illustrated as an aspect in which the hydroxyl group on Ar 1 forms an intramolecular hydrogen bond with R 2 . The following (b) and the like can be exemplified as a mode in which the hydroxyl group on Ar 1 forms an intramolecular hydrogen bond with the azo group connecting Ar 1 and Ar 2 .
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（２）分子内水素結合を形成し得る水酸基をＡｒ２に有する場合
　Ａｒ２上の水酸基は、例えば、Ａｒ１とＡｒ２を連結するアゾ基またはＡｒ２とＡｒ３を連結するアゾ基と６員環状の分子内水素結合を形成することができる。Ａｒ２上の水酸基がＡｒ１とＡｒ２を連結するアゾ基と分子内水素結合を形成する態様としては、以下の（ｃ）等を例示することができる。また、Ａｒ２上の水酸基がＡｒ２とＡｒ３を連結するアゾ基と分子内水素結合を形成する態様としては、以下の（ｄ）等を例示することができる。 ( 2 ) When Ar 2 has a hydroxyl group capable of forming an intramolecular hydrogen bond A membered ring intramolecular hydrogen bond can be formed. The following (c) and the like can be exemplified as an aspect in which the hydroxyl group on Ar 2 forms an intramolecular hydrogen bond with the azo group connecting Ar 1 and Ar 2 . In addition, the following (d) can be exemplified as an aspect in which the hydroxyl group on Ar 2 forms an intramolecular hydrogen bond with the azo group connecting Ar 2 and Ar 3 .
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
（３）分子内水素結合を形成し得る水酸基をＡｒ３に有する場合
　Ａｒ３上の水酸基は、例えば、Ａｒ２とＡｒ３を連結するアゾ基と６員環状の分子内水素結合を形成することができる。具体的には、以下の（ｅ）等を例示することができる。 (3) When Ar 3 has a hydroxyl group capable of forming an intramolecular hydrogen bond The hydroxyl group on Ar 3 may form, for example, a 6-membered cyclic intramolecular hydrogen bond with the azo group connecting Ar 2 and Ar 3 . can be done. Specifically, the following (e) and the like can be exemplified.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　分子内水素結合の態様は、二色比向上の観点から、（ａ）から（ｅ）のいずれかであることが好ましく、（ａ）から（ｄ）のいずれかであることがより好ましく、（ａ）および（ｃ）のいずれかであることがさらに好ましい。 From the viewpoint of improving the dichroic ratio, the mode of intramolecular hydrogen bonding is preferably any one of (a) to (e), more preferably any one of (a) to (d), ( Either a) or (c) is more preferred.
　分子内水素結合の有無は、１Ｈ－ＮＭＲを測定することで判断できる。例えば、https://www.chem-station.com/yukitopics/nmr-analysis.htm、「有機化合物のスペクトルによる同定法（第６版）」（１９９９年、東京化学同人、Ｐ．１６２－１６５）などに記載されているように、水素結合を形成している水酸基のプロトンは、水素結合を形成していない場合に比べて、低磁場側に観測される。分子内水素結合を形成している水酸基の化学シフトは、例えば重クロロホルム（ＣＤＣｌ３）中において、９．０ｐｐｍ以上１８．０ｐｐｍ以下であってよく、好ましくは１０．０ｐｐｍ以上であってよい。 The presence or absence of intramolecular hydrogen bonding can be determined by measuring 1 H-NMR. For example, https://www.chem-station.com/yukitopics/nmr-analysis.htm, "Spectral identification of organic compounds (6th edition)" (1999, Tokyo Kagaku Dojin, pp. 162-165) , etc., the protons of hydroxyl groups forming hydrogen bonds are observed on the lower magnetic field side than when they do not form hydrogen bonds. The chemical shift of hydroxyl groups forming intramolecular hydrogen bonds may be, for example, 9.0 ppm or more and 18.0 ppm or less, preferably 10.0 ppm or more, in deuterated chloroform (CDCl 3 ).
　また、一般に水酸基の化学シフトは測定溶媒の極性に大きく影響される。具体的には、高極性溶媒（例えばＤＭＳＯ－ｄ６）中では低磁場側に大きくシフトする。しかし、水酸基が水素結合を形成している場合には測定溶媒の影響が小さくなる。分子内水素結合を形成している水酸基の高極性溶媒（例えばＤＭＳＯ－ｄ６）中における化学シフトと、低極性溶媒（例えばＣＤＣｌ３）中における化学シフトとの差分は、例えば１．０ｐｐｍ以下であってよく、０．５ｐｐｍ以下であってよい。 Also, in general, the chemical shift of hydroxyl groups is greatly affected by the polarity of the measurement solvent. Specifically, in a highly polar solvent (eg, DMSO-d 6 ), it shifts to the low magnetic field side. However, when hydroxyl groups form hydrogen bonds, the influence of the measurement solvent is reduced. The difference between the chemical shift of the hydroxyl group forming the intramolecular hydrogen bond in a highly polar solvent (eg DMSO-d 6 ) and the chemical shift in a low polar solvent (eg CDCl 3 ) is, for example, 1.0 ppm or less. may be present, and may be 0.5 ppm or less.
　式（１）で表される化合物は、極大吸収波長（λｍａｘ）は、例えば３５０ｎｍ以上６５０ｎｍ以下であってよく、好ましくは３８０ｎｍ以上６００ｎｍ以下であってよい。極大吸収波長は、式（１）で表される化合物のクロロホルム溶液について、室温（例えば、２５℃）で測定される。式（１）で表される化合物の極大吸収波長は、例えば、Ａｒ１、Ａｒ２およびＡｒ３の骨格構造、Ａｒ１、Ａｒ２およびＡｒ３における置換基、ｎ、Ｒ１等を適宜選択することで所望の波長に調整することができる。 The compound represented by formula (1) may have a maximum absorption wavelength (λmax) of, for example, 350 nm or more and 650 nm or less, preferably 380 nm or more and 600 nm or less. The maximum absorption wavelength is measured at room temperature (eg, 25° C.) for a chloroform solution of the compound represented by formula (1). For the maximum absorption wavelength of the compound represented by formula (1), for example, the skeleton structures of Ar 1 , Ar 2 and Ar 3 , the substituents of Ar 1 , Ar 2 and Ar 3 , n, R 1 and the like are appropriately selected. can be adjusted to a desired wavelength.
　式（１）で表される化合物の具体例としては、以下の式（１－１）から式（１－７８）で表される化合物が挙げられるが、本発明はこれらに限定されるものではない。 Specific examples of the compound represented by formula (1) include compounds represented by the following formulas (1-1) to (1-78), but the present invention is not limited thereto. No.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（１）で表される化合物は、二色比向上の観点から、式（１－１）から（１－５６）のいずれかで表される化合物からなる群から選択される少なくとも１種が好ましく、式（１－１）から（１－４６）のいずれかで表される化合物からなる群から選択される少なくとも１種がより好ましく、式（１－１）から（１－３１）のいずれかで表される化合物からなる群から選択される少なくとも１種がさらに好ましく、式（１－１）から（１－２０）のいずれかで表される化合物からなる群から選択される少なくとも１種が特に好ましい。 From the viewpoint of improving the dichroic ratio, the compound represented by formula (1) is at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-56). Preferably, at least one selected from the group consisting of compounds represented by any of formulas (1-1) to (1-46) is more preferred, and any of formulas (1-1) to (1-31) At least one selected from the group consisting of compounds represented by is more preferable, and at least one selected from the group consisting of compounds represented by any one of formulas (1-1) to (1-20) is particularly preferred.
式（１）で表される化合物の製造方法
　式（１）で表される化合物は従来公知の合成方法を適宜適用することで製造することができる。具体的に、式（１）で表される化合物におけるアゾ構造（－Ｎ＝Ｎ－）は、例えば、国際公開ＷＯ２０１６／１３６５６１号の段落［０２２０］から［０２６８］の製造例の記載等を参考に、１級アミノ基を有する芳香族アミン化合物を亜硝酸ナトリウムなどでジアゾニウム塩に変換し、芳香族化合物とジアゾカップリングさせることで構築することができる。また、チアゾール構造を含むアゾ構造は、例えば、J. Mol. Struct., 2011, 987,158.の記載を参照して構築することができる。 Method for Producing Compound Represented by Formula (1) The compound represented by formula (1) can be manufactured by appropriately applying a conventionally known synthesis method. Specifically, for the azo structure (-N=N-) in the compound represented by formula (1), for example, refer to the description of the production examples in paragraphs [0220] to [0268] of International Publication WO2016/136561. Alternatively, it can be constructed by converting an aromatic amine compound having a primary amino group into a diazonium salt with sodium nitrite or the like and diazo-coupling it with an aromatic compound. Also, an azo structure including a thiazole structure can be constructed, for example, with reference to the description in J. Mol. Struct., 2011, 987, 158.
　Ｒ３がアルカンジイルオキシ基である化合物は、例えば、ヒドロキシ基を有する前駆体にＳＮ２置換反応を適用することで所望のアルカンジイルオキシ基を有する化合物として製造することができる。ＳＮ２置換反応は、従来公知の反応条件を適宜適用してもよいし、例えば、J. Am. Chem. Soc., 2008, 130, 13079の記載を参照してもよい。 A compound in which R 3 is an alkanediyloxy group can be produced as a compound having a desired alkanediyloxy group, for example, by applying an SN2 substitution reaction to a precursor having a hydroxy group. Conventionally known reaction conditions may be appropriately applied to the SN2 substitution reaction, and for example, the description in J. Am. Chem. Soc., 2008, 130, 13079 may be referred to.
　式（１）で表される化合物が、－ＯＣ（＝Ｏ）－またはＣ（＝Ｏ）Ｏ－を含む場合、例えば、カルボキシ基を有する前駆体と、水酸基を有する前駆体とを用いて、Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y.; Ma, D. J. Org. Chem. 2009, 74 (3), 4542-4546.などを参考にして脱水縮合反応を適用することで合成することができる。具体的には例えば、溶媒中、エステル化縮合剤の存在下で縮合する条件が挙げられる。 When the compound represented by formula (1) contains -OC(=O)- or C(=O)O-, for example, using a precursor having a carboxy group and a precursor having a hydroxyl group, Jiang, L.; Lu, X.; Zhang, H.; Jiang, Y.; Ma, D. J. Org. Chem. 2009, 74 (3), 4542-4546. Can be synthesized by applying. Concrete examples include conditions for condensation in the presence of an esterifying condensing agent in a solvent.
　Ａｒ１、Ａｒ２またはＡｒ３に水酸基を有する化合物は、サリチル酸型メトキシ基の脱メチル化反応の文献（例えば、(Chem. Commun. 2010, 46, 9019-9021.）を参考にして脱メチル化を行うことで水酸基に変換することができる。例えば、溶媒中脱メチル化剤を用いる条件が挙げられる。溶媒としては非プロトン性極性溶媒が挙げられ、単独溶媒であっても混合溶媒であってもよい。非プロトン性極性溶媒としては、アミド系溶媒やラクトン系溶媒、含窒素芳香族系溶媒、スルホキシド系溶媒等が挙げられる。アミド系溶媒としては、Ｎ、Ｎ－ジメチルアセトアミド、Ｎ－メチル－ピロリドン、Ｎ－メチルカプロラクタム、Ｎ、Ｎ－ジメチルホルムアミド、Ｎ、Ｎ－ジエチルホルムアミド、Ｎ、Ｎ－ジエチルアセトアミド、Ｎ－メチルプロピオンアミド、ジメチルイミダゾリジノン等が挙げられる。ラクトン系溶媒としては、γ－ブチルラクトン、β－ブチルラクトン等が挙げられる。含窒素芳香族系溶媒としては、ピリジン、キノリン等が挙げられる。スルホキシド系溶媒としては、ジメチルスルホキシド、メチルフェニルスルホキシド等が挙げられる。なかでも好ましい例としてはＮ－メチル－２－ピロリドンなどのアミド系溶媒、ピリジンなどの含窒素芳香族系溶媒が挙げられる。なかでもＮ－メチル－２－ピロリドン、ピリジンの混合溶媒であることがより好ましい。脱メチル化剤としてはリチウム塩を用いることが好ましく、なかでも塩化リチウムがより好ましい。反応温度は例えば０℃から２００℃の範囲が挙げられ、好ましくは２０℃から１５０℃の範囲であり、より好ましくは５０℃から１２０℃の範囲である。反応終了後室温まで冷却し、塩酸、水などの貧溶媒を滴下して析出させることで、脱メチル化した生成物を得ることができる。 A compound having a hydroxyl group at Ar 1 , Ar 2 or Ar 3 is demethylated with reference to the literature on the demethylation reaction of a salicylic acid-type methoxy group (for example, (Chem. Commun. 2010, 46, 9019-9021.)). can be converted to a hydroxyl group by performing.For example, the conditions using a demethylating agent in a solvent can be mentioned.Solvents include aprotic polar solvents, whether it is a single solvent or a mixed solvent, Aprotic polar solvents include amide solvents, lactone solvents, nitrogen-containing aromatic solvents, sulfoxide solvents, etc. Amide solvents include N,N-dimethylacetamide, N-methyl -pyrrolidone, N-methylcaprolactam, N,N-dimethylformamide, N,N-diethylformamide, N,N-diethylacetamide, N-methylpropionamide, dimethylimidazolidinone, etc. Lactone solvents include: Examples include γ-butyl lactone, β-butyl lactone, etc. Nitrogen-containing aromatic solvents include pyridine, quinoline, etc. Sulfoxide solvents include dimethyl sulfoxide, methylphenyl sulfoxide, etc. Among them, Preferred examples include amide solvents such as N-methyl-2-pyrrolidone, nitrogen-containing aromatic solvents such as pyridine, etc. Among them, a mixed solvent of N-methyl-2-pyrrolidone and pyridine is more preferable. Lithium salt is preferably used as the demethylating agent, and lithium chloride is more preferable.The reaction temperature is, for example, in the range of 0° C. to 200° C., preferably in the range of 20° C. to 150° C., More preferably, the temperature is in the range of 50° C. to 120° C. After completion of the reaction, the reaction mixture is cooled to room temperature, and a poor solvent such as hydrochloric acid or water is added dropwise for precipitation to obtain a demethylated product.
　式（１）で表される化合物の製造において合成中間体における水酸基が目的の反応を阻害する場合、適宜水酸基を保護し、反応後に保護基を脱離することで目的の反応を行うことができる。保護基としてはアセチル基、シリル基など一般的なものを用いることができる。保護、脱保護の反応条件は公知のものを用いることができる。 In the production of the compound represented by the formula (1), when the hydroxyl group in the synthetic intermediate inhibits the desired reaction, the hydroxyl group is appropriately protected, and the protecting group is removed after the reaction to perform the desired reaction. . Common protective groups such as acetyl groups and silyl groups can be used. Known reaction conditions can be used for protection and deprotection.
　式（１）で表される化合物の製造方法における反応時間は、反応途中の反応混合物を適宜サンプリングし、液体クロマトグラフィー、ガスクロマトグラフィーなどの公知の分析手段により、原料化合物の消失の度合い、式（１）で表される化合物の生成の度合いなどを確認して定めることもできる。 The reaction time in the method for producing the compound represented by formula (1) is determined by appropriately sampling the reaction mixture during the reaction, and measuring the degree of disappearance of the starting compound by known analytical means such as liquid chromatography and gas chromatography. It can also be determined by confirming the degree of production of the compound represented by (1).
　反応後の反応混合物からは、再結晶、再沈殿、抽出および各種クロマトグラフィーといった公知の方法により、或いはこれらの操作を適宜組み合わせることにより、式（１）で表される化合物を取り出すことができる。 From the reaction mixture after the reaction, the compound represented by formula (1) can be isolated by known methods such as recrystallization, reprecipitation, extraction and various types of chromatography, or by appropriately combining these operations.
　組成物は、式（１）で表される化合物以外のその他の色素化合物、例えば二色性色素の少なくとも１種を更に含んでいてもよい。その他の色素化合物としては、例えば、モノアゾ色素、ビスアゾ色素、トリスアゾ色素、テトラキスアゾ色素、スチルベンアゾ色素などのアゾ色素を挙げることができ、これらからなる群から選択される少なくとも１種が好ましい。組成物は、その他の色素化合物を１種単独で含んでいてもよく、２種以上を組み合わせて含んでいてもよい。例えば塗布型偏光板材料として用いる場合では、組成物が含むその他の色素化合物は、式（１）で表される化合物とは異なる波長範囲に極大吸収波長を有することが好ましい。例えば塗布型偏光板材料として用いる場合では、組成物は、式（１）で表される化合物を含めて、３種類以上の二色性色素を組み合わせて含むことが好ましく、３種類以上のアゾ色素を組み合わせて含むことがより好ましい。組成物が極大吸収波長の異なる３種以上の色素化合物を組み合わせて含むことで、例えば、組成物から形成される膜によって可視光全域で吸収を得ることができる。 The composition may further contain at least one dye compound other than the compound represented by formula (1), such as a dichroic dye. Examples of other dye compounds include azo dyes such as monoazo dyes, bisazo dyes, trisazo dyes, tetrakis azo dyes, and stilbene azo dyes, and at least one selected from the group consisting of these is preferred. The composition may contain one type of other dye compound alone, or may contain two or more types in combination. For example, when the composition is used as a coating-type polarizing plate material, the other dye compound contained in the composition preferably has a maximum absorption wavelength in a wavelength range different from that of the compound represented by formula (1). For example, when used as a coating-type polarizing plate material, the composition preferably contains a combination of three or more dichroic dyes, including the compound represented by formula (1), and three or more azo dyes. It is more preferred to include a combination of When the composition contains a combination of three or more dye compounds having different maximum absorption wavelengths, for example, a film formed from the composition can absorb the entire visible light range.
　組成物が、その他の色素化合物を含む場合、その含有量は、組成物の固形分１００質量部に対して、５０質量部以下であることが好ましく、０．１質量部以上１０質量部以下の範囲がより好ましく、０．１質量部以上５質量部以下の範囲がさらに好ましい。上記範囲内であれば、その他の色素化合物の分散が十分に可能になる。 When the composition contains other dye compounds, the content thereof is preferably 50 parts by mass or less, and 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the solid content of the composition. The range is more preferable, and the range of 0.1 parts by mass or more and 5 parts by mass or less is even more preferable. Within the above range, it is possible to sufficiently disperse other dye compounds.
液晶性化合物
　組成物は、式（１）で表される化合物に加えて、重合性液晶化合物および液晶性の高分子化合物の少なくとも１種を含む液晶性化合物を含む。組成物は、重合性液晶化合物および液晶性の高分子化合物の一方のみを含んでいても、両方を含んでいてもよい。また、組成物に含まれる重合性液晶化合物および液晶性の高分子化合物は、それぞれ２種以上であってもよい。組成物が重合性液晶化合物および液晶性の高分子化合物の少なくとも１種を含むことで、式（１）で表される化合物が液晶性化合物に分散した組成物を構成することができる。 Liquid Crystal Compound The composition contains, in addition to the compound represented by Formula (1), a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound. The composition may contain either one of the polymerizable liquid crystal compound and the liquid crystal polymer compound, or may contain both of them. Two or more kinds of polymerizable liquid crystal compounds and liquid crystalline polymer compounds may be included in the composition. By including at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound in the composition, it is possible to constitute a composition in which the compound represented by Formula (1) is dispersed in the liquid crystalline compound.
　液晶性の高分子化合物は、サーモトロピック液晶型ポリマーを構成するものであってもよいし、リオトロピック液晶型ポリマーを構成するものであってもよい。液晶性の高分子化合物は、緻密な膜厚制御が可能な点で、サーモトロピック液晶型ポリマーを構成するものであることが好ましい。 The liquid crystalline polymer compound may constitute either a thermotropic liquid crystal polymer or a lyotropic liquid crystal polymer. The liquid crystalline polymer compound preferably constitutes a thermotropic liquid crystal type polymer in that the film thickness can be precisely controlled.
　液晶の分類としては、液晶状態での分子配列の構造により、スメクチック液晶、ネマチック液晶、コレステリック液晶に分類される。なかでも偏光膜用途においてはスメクチック液晶が好ましく用いられる。したがって、重合性液晶化合物は、重合性スメクチック液晶化合物であることが好ましく、液晶性の高分子化合物は、スメクチック液晶性の高分子化合物であることが好ましい。 Liquid crystals are classified into smectic liquid crystals, nematic liquid crystals, and cholesteric liquid crystals according to the structure of the molecular alignment in the liquid crystal state. Among them, smectic liquid crystals are preferably used for polarizing films. Therefore, the polymerizable liquid crystal compound is preferably a polymerizable smectic liquid crystal compound, and the liquid crystalline polymer compound is preferably a smectic liquid crystalline polymer compound.
　スメクチック液晶性を示す重合性液晶化合物およびスメクチック液晶性を示す高分子化合物を用いることにより、配向秩序度の高い偏光膜を形成することができる。重合性液晶化合物および液晶性の高分子化合物の示す液晶状態は、好ましくはスメクチック相（スメクチック液晶状態）であり、より高い配向秩序度を実現し得る観点から、高次スメクチック相（高次スメクチック液晶状態）であることがより好ましい。ここで、高次スメクチック相とは、スメクチックＢ相、スメクチックＤ相、スメクチックＥ相、スメクチックＦ相、スメクチックＧ相、スメクチックＨ相、スメクチックＩ相、スメクチックＪ相、スメクチックＫ相およびスメクチックＬ相を意味し、これらの中でも、スメクチックＢ相、スメクチックＦ相およびスメクチックＩ相がより好ましい。配向秩序度の高い偏光膜は、Ｘ線回折測定においてヘキサチック相やクリスタル相といった高次構造由来のブラッグピークが得られる。ブラッグピークとは、分子配向の面周期構造に由来するピークを意味する。組成物から得られる偏光膜が有する周期間隔（秩序周期）は、好ましくは０．３ｎｍ以上０．６ｎｍ以下である。重合性液晶化合物または液晶性の高分子化合物は、Ｘ線回折測定において高次構造由来のブラッグピークを示す、重合性スメクチック液晶化合物またはスメクチック液晶性の高分子化合物であってよい。 By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity and a polymer compound exhibiting smectic liquid crystallinity, a polarizing film with a high degree of alignment order can be formed. The liquid crystal state exhibited by the polymerizable liquid crystal compound and the liquid crystalline polymer compound is preferably a smectic phase (smectic liquid crystal state). state) is more preferable. Here, the higher order smectic phase includes smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase and smectic L phase. Among these, smectic B phase, smectic F phase and smectic I phase are more preferable. A polarizing film with a high degree of orientational order provides a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement. A Bragg peak means a peak derived from a periodic plane structure of molecular orientation. The periodic interval (ordered period) of the polarizing film obtained from the composition is preferably 0.3 nm or more and 0.6 nm or less. The polymerizable liquid crystal compound or liquid crystalline polymer compound may be a polymerizable smectic liquid crystal compound or a smectic liquid crystalline polymer compound that exhibits a Bragg peak derived from a higher-order structure in X-ray diffraction measurement.
重合性液晶化合物
　重合性液晶化合物とは、分子内に少なくとも１つの重合性基を有し、配向することによって液晶相を示すことができる化合物である。重合性液晶化合物は、好ましくは単独で配向することによって液晶相を示すことができる化合物である。重合性基とは、重合反応に関与し得る官能基を意味し、ラジカル重合性基であることが好ましい。 Polymerizable Liquid Crystal Compound A polymerizable liquid crystal compound is a compound that has at least one polymerizable group in the molecule and can exhibit a liquid crystal phase by being aligned. The polymerizable liquid crystal compound is preferably a compound capable of exhibiting a liquid crystal phase by being aligned alone. A polymerizable group means a functional group that can participate in a polymerization reaction, and is preferably a radically polymerizable group.
　重合性液晶化合物としては、少なくとも１つの重合性基を有し、好ましくはスメクチック液晶性を示す液晶化合物であれば特に限定されず、公知の重合性液晶化合物を用いることができる。重合性液晶化合物として具体的には、例えば、下記式（Ａ）で表される化合物（以下、「重合性液晶化合物（Ａ）」ともいう）が好ましく挙げられる。 The polymerizable liquid crystal compound is not particularly limited as long as it has at least one polymerizable group and preferably exhibits smectic liquid crystallinity, and known polymerizable liquid crystal compounds can be used. Specifically, the polymerizable liquid crystal compound is preferably, for example, a compound represented by the following formula (A) (hereinafter also referred to as “polymerizable liquid crystal compound (A)”).
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（Ａ）中、ｋは１から３の整数である。Ｘ１、Ｘ２およびＸ３は、各々独立して、２価の芳香族基または２価の脂環式炭化水素基を表す。ｋが２または３である場合、複数のＸ１は互いに同一であっても相異なっていてもよい。Ｘ１、Ｘ２およびＸ３からなる群から選択される少なくとも３つが２価の炭化水素６員環基を表す。Ｙ１、Ｙ２、Ｗ１およびＷ２は、それぞれ独立に、単結合または２価の連結基を表す。ｋが２または３である場合、Ｙ１は互いに同一であっても相異なっていてもよい。Ｖ１およびＶ２は、各々独立して、置換基を有していてもよい炭素数１から２０のアルカンジイル基を表す。アルカンジイル基を構成する－ＣＨ２－の少なくとも１つは、－Ｏ－、－ＣＯ－、－Ｓ－または－ＮＨ－に置換されていてもよい。Ｕ１およびＵ２は、それぞれ独立に、重合性基または水素原子を表し、少なくとも一方は重合性基を表す。 In formula (A), k is an integer of 1 to 3. X 1 , X 2 and X 3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. When k is 2 or 3, multiple X1's may be the same or different. At least three selected from the group consisting of X 1 , X 2 and X 3 represent a divalent hydrocarbon 6-membered ring group. Y 1 , Y 2 , W 1 and W 2 each independently represent a single bond or a divalent linking group. When k is 2 or 3, Y 1 may be the same or different. V 1 and V 2 each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms. At least one -CH 2 - constituting the alkanediyl group may be substituted with -O-, -CO-, -S- or -NH-. U 1 and U 2 each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group.
　Ｘ１、Ｘ２およびＸ３における２価の芳香族基としては、１，４－フェニレン基、１，４－ナフチレン基（ナフタレン－１，４－ジイル基）等が挙げられる。２価の脂環式炭化水素基としては、シクロヘキサン－１，４－ジイル基等が挙げられる。Ｘ１、Ｘ２およびＸ３における２価の芳香族基および２価の脂環式炭化水素基の少なくとも１つは、置換基を有していてもよい。置換基としては、メチル基、エチル基、ｎ－ブチル基等の炭素数１から４のアルキル基、シアノ基、ハロゲン原子などが挙げられる。２価の脂環式炭化水素基を構成する－ＣＨ２－の少なくとも１つは、－Ｏ－、－Ｓ－または－ＮＲ－に置換されていてもよい。ここで、Ｒは、炭素数１から６のアルキル基またはフェニル基を表す。 The divalent aromatic group for X 1 , X 2 and X 3 includes 1,4-phenylene group, 1,4-naphthylene group (naphthalene-1,4-diyl group) and the like. The divalent alicyclic hydrocarbon group includes cyclohexane-1,4-diyl group and the like. At least one of the divalent aromatic group and the divalent alicyclic hydrocarbon group in X 1 , X 2 and X 3 may have a substituent. Examples of substituents include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group and n-butyl group, cyano groups and halogen atoms. At least one —CH 2 — constituting a divalent alicyclic hydrocarbon group may be substituted with —O—, —S— or —NR—. Here, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.
　Ｘ１、Ｘ２およびＸ３における２価の炭化水素６員環基としては、置換基を有していてもよい１，４－フェニレン基、置換基を有していてもよいシクロヘキサン－１，４－ジイル基等が挙げられる。 The divalent hydrocarbon 6-membered ring groups for X 1 , X 2 and X 3 include optionally substituted 1,4-phenylene group, optionally substituted cyclohexane-1, 4-diyl group and the like.
　Ｘ１、Ｘ２およびＸ３における２価の芳香族基は、好ましくは置換基を有していてもよい１，４－フェニレン基であり、より好ましくは無置換の１，４－フェニレン基である。また２価の脂環式炭化水素基は、好ましくは置換基を有していてもよいシクロヘキサン－１，４－ジイル基であり、より好ましくは置換基を有していてもよいトランス－シクロへキサン－１，４－ジイル基であり、さらに好ましくは無換基のトランス－シクロへキサン－１，４－ジイル基である。 The divalent aromatic group for X 1 , X 2 and X 3 is preferably an optionally substituted 1,4-phenylene group, more preferably an unsubstituted 1,4-phenylene group. be. The divalent alicyclic hydrocarbon group is preferably an optionally substituted cyclohexane-1,4-diyl group, more preferably an optionally substituted trans-cyclo Xane-1,4-diyl group, more preferably unsubstituted trans-cyclohexane-1,4-diyl group.
　Ｙ１およびＹ２は、各々独立して単結合または２価の連結基を表す。２価の連結基は、例えば、－ＣＨ２ＣＨ２－、－ＣＨ２Ｏ－、－（Ｃ＝Ｏ）Ｏ－、－Ｏ（Ｃ＝Ｏ）Ｏ－、－Ｎ＝Ｎ－、－ＣＲａ＝ＣＲｂ－、－Ｃ≡Ｃ－および－ＣＲａ＝Ｎ－からなる群から選択される少なくとも１種である。ここでＲａおよびＲｂは、各々独立して、水素原子または炭素数１から４のアルキル基を表す。Ｙ１は、好ましくは－ＣＨ２ＣＨ２－、－（Ｃ＝Ｏ）Ｏ－または単結合である。Ｙ２は、好ましくは－ＣＨ２ＣＨ２－または－ＣＨ２Ｏ－である。 Y 1 and Y 2 each independently represent a single bond or a divalent linking group. Divalent linking groups are, for example, -CH 2 CH 2 -, -CH 2 O-, -(C=O)O-, -O(C=O)O-, -N=N-, -CR a is at least one selected from the group consisting of =CR b -, -C≡C- and -CR a =N-; Here, R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y 1 is preferably -CH 2 CH 2 -, -(C=O)O- or a single bond. Y 2 is preferably -CH 2 CH 2 - or -CH 2 O-.
　Ｗ１およびＷ２は、各々独立して、単結合または２価の連結基を表す。２価の連結基は、例えば、－Ｏ－、－Ｓ－、－（Ｃ＝Ｏ）Ｏ－および－Ｏ（Ｃ＝Ｏ）Ｏ－からなる群から選択される少なくとも１種である。Ｗ１およびＷ２は、各々独立して、好ましくは単結合または－Ｏ－である。 W1 and W2 each independently represent a single bond or a divalent linking group. The divalent linking group is, for example, at least one selected from the group consisting of -O-, -S-, -(C=O)O- and -O(C=O)O-. W 1 and W 2 are each independently preferably a single bond or -O-.
　Ｖ１およびＶ２は、それぞれ独立に、置換基を有していてもよい炭素数１から２０のアルカンジイル基を表す。前記アルカンジイル基を構成する－ＣＨ２－の少なくとも１つは、－Ｏ－、－ＣＯ－、－Ｓ－または－ＮＨ－に置き換わっていてもよい。 V 1 and V 2 each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms. At least one of -CH 2 - constituting the alkanediyl group may be replaced with -O-, -CO-, -S- or -NH-.
　Ｖ１およびＶ２で表されるアルカンジイル基としては、メチレン基、エチレン基、プロパン－１，３－ジイル基、ブタン－１，３－ジイル基、ブタン－１，４－ジイル基、ペンタン－１，５－ジイル基、ヘキサン－１，６－ジイル基、ヘプタン－１，７－ジイル基、オクタン－１，８－ジイル基、デカン－１，１０－ジイル基、テトラデカン－１，１－ジイル基、およびイコサン－１，２０－ジイル基が挙げられる。Ｖ１およびＶ２は、好ましくは炭素数２から１２のアルカンジイル基であり、より好ましくは炭素数６から１２のアルカンジイル基である。 The alkanediyl groups represented by V 1 and V 2 include methylene, ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane- 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,1-diyl and icosane-1,20-diyl groups. V 1 and V 2 are preferably alkanediyl groups having 2 to 12 carbon atoms, more preferably alkanediyl groups having 6 to 12 carbon atoms.
　置換基を有していてもよい炭素数１から２０のアルカンジイル基が任意に有する置換基としては、シアノ基およびハロゲン原子が挙げられる。当該アルカンジイル基は、好ましくは置換基を有していないアルカンジイル基であり、より好ましくは置換基を有しておらず、かつ直鎖状のアルカンジイル基である。 Examples of substituents optionally possessed by the optionally substituted alkanediyl group having 1 to 20 carbon atoms include a cyano group and a halogen atom. The alkanediyl group is preferably an unsubstituted alkanediyl group, more preferably an unsubstituted and linear alkanediyl group.
　Ｕ１およびＵ２は、それぞれ独立に、重合性基または水素原子を表し、少なくとも一方は重合性基を表す。Ｕ１およびＵ２は、好ましくは重合性基である。Ｕ１およびＵ２がともに重合性基であることが好ましく、ともにラジカル重合性基であることが好ましい。Ｕ１で示される重合性基とＵ２で示される重合性基とは、互いに異なっていてもよいが、同じ種類の基であることが好ましい。Ｕ１およびＵ２における重合性基としては、重合性液晶化合物が有する重合性基として先に例示した重合性基と同様のものが挙げられる。中でも、Ｕ１およびＵ２で表される重合性基は、ビニルオキシ基、アクリロイルオキシ基、メタクリロイルオキシ基、オキシラニル基、およびオキセタニル基からなる群から選択される少なくとも１種が好ましく、アクリロイルオキシ基がより好ましい。 U 1 and U 2 each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group. U 1 and U 2 are preferably polymerizable groups. Both U 1 and U 2 are preferably polymerizable groups, and preferably both are radically polymerizable groups. The polymerizable group represented by U1 and the polymerizable group represented by U2 may be different from each other, but are preferably of the same type. As the polymerizable groups for U 1 and U 2 , the same polymerizable groups as those previously exemplified as the polymerizable groups possessed by the polymerizable liquid crystal compound can be mentioned. Among them, the polymerizable group represented by U 1 and U 2 is preferably at least one selected from the group consisting of a vinyloxy group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group, and an acryloyloxy group is more preferred.
　重合性液晶化合物（Ａ）の具体例としては、下記式（Ａ－１）から式（Ａ－１７）で表される化合物が挙げられる。重合性液晶化合物（Ａ）がシクロヘキサン－１，４－ジイル基を有する場合には、そのシクロヘキサン－１，４－ジイル基は、トランス型であることが好ましい。 Specific examples of the polymerizable liquid crystal compound (A) include compounds represented by the following 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 trans-type.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　中でも、重合性液晶化合物（Ａ）は、式（Ａ－２）、式（Ａ－３）、式（Ａ－４）、式（Ａ－５）、式（Ａ－６）、式（Ａ－７）、式（Ａ－８）、式（Ａ－１３）、式（Ａ－１４）、式（Ａ－１５）、式（Ａ－１６）および式（Ａ－１７）のいずれかで表される化合物からなる群から選択される少なくとも１種が好ましい。重合性液晶化合物（Ａ）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Among them, the polymerizable liquid crystal compound (A) has formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A- 7), represented by any of formula (A-8), formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17) At least one selected from the group consisting of compounds is preferred. The polymerizable liquid crystal compound (A) may be used alone or in combination of two or more.
　重合性液晶化合物（Ａ）は、例えば、Lub et al. Recl. Trav. Chim. Pays-Bas,115,321-328(1996)、特許第４７１９１５６号公報等の公知文献に記載の方法により製造することができる。 The polymerizable liquid crystal compound (A) can be produced, for example, by the method described in known documents such as Lub et al. Recl. Trav. Chim. can.
液晶性の高分子化合物
　液晶性の高分子化合物とは、前記重合性液晶化合物を重合させた化合物（以下、重合性液晶化合物の重合体ともいう）であってもよく、その他の液晶性の高分子化合物であってもよく、好ましくは、前記重合性液晶化合物の重合体である。 Liquid crystalline polymer compound The liquid crystalline polymer compound may be a compound obtained by polymerizing the above polymerizable liquid crystal compound (hereinafter also referred to as a polymer of a polymerizable liquid crystal compound), or other high liquid crystal compound. It may be a molecular compound, preferably a polymer of the polymerizable liquid crystal compound.
　前記重合性液晶化合物の重合体は、２種以上の前記重合性液晶化合物を原料モノマーとして用いてもよい。また、前記重合性液晶化合物の重合体は、前記重合性液晶化合物以外のその他のモノマーを原料モノマーとして含んでいてもよい。 Two or more of the polymerizable liquid crystal compounds may be used as raw material monomers for the polymer of the polymerizable liquid crystal compound. Further, the polymer of the polymerizable liquid crystal compound may contain monomers other than the polymerizable liquid crystal compound as raw material monomers.
　前記重合性液晶化合物の重合体における前記重合性液晶化合物の含有割合は、前記重合性液晶化合物の重合体を構成する前記重合性液晶化合物に由来する構成単位の合計量に対して、通常１モル％以上１００モル％以下であり、前記重合性液晶化合物の重合体の配向性を高くするという観点から、３０モル％以上１００モル％以下であることが好ましく、５０モル％以上１００モル％以下であることがより好ましく、８０モル％以上１００モル％以下であることがさらに好ましい。 The content of the polymerizable liquid crystal compound in the polymer of the polymerizable liquid crystal compound is usually 1 mol with respect to the total amount of structural units derived from the polymerizable liquid crystal compound constituting the polymer of the polymerizable liquid crystal compound. % or more and 100 mol % or less, preferably 30 mol % or more and 100 mol % or less from the viewpoint of increasing the orientation of the polymer of the polymerizable liquid crystal compound, and 50 mol % or more and 100 mol % or less. more preferably 80 mol % or more and 100 mol % or less.
　前記その他の液晶性の高分子化合物としては、液晶性基を有する高分子化合物が挙げられる。例えば、母骨格となる高分子化合物としては、ポリエチレン、ポリプロピレンなどのポリオレフィン；ノルボルネンポリマーなどの環状オレフィン樹脂；ポリアルキレンエーテル、ポリビニルアルコール；ポリメタクリル酸エステル；ポリアクリル酸エステル；等が挙げられ、これらの高分子化合物が液晶性基を有する。中でも、液晶性基を有するポリメタクリル酸エステル、ポリアクリル酸エステルが好ましい。 Examples of the other liquid crystalline polymer compounds include polymer compounds having a liquid crystalline group. For example, the polymer compound serving as the backbone includes polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyalkylene ethers, polyvinyl alcohols; polymethacrylic acid esters; has a liquid crystalline group. Among them, polymethacrylic acid esters and polyacrylic acid esters having a liquid crystalline group are preferable.
　前記その他の液晶性の高分子化合物は、２種類以上の液晶性基を含んでいてもよい。液晶性基は、母骨格となる高分子化合物の主鎖に含まれていてもよく、母骨格となる高分子化合物の側鎖に含まれていてもよく、母骨格となる高分子化合物の主鎖および側鎖ともに含まれていてもよい。液晶性基としては、少なくとも２つの炭化水素６員環構造を有する化合物から１個の水素原子を除いて形成される基、または、該化合物から２個の水素原子を除いて形成される基が挙げられる。 The other liquid crystalline polymer compound may contain two or more types of liquid crystalline groups. The liquid crystalline group may be contained in the main chain of the polymer compound serving as the backbone, may be contained in the side chain of the polymer compound serving as the backbone, or may be included in the main chain of the polymer compound serving as the backbone. Both chains and side chains may be included. The liquid crystalline group includes a group formed by removing one hydrogen atom from a compound having at least two hydrocarbon six-membered ring structures, or a group formed by removing two hydrogen atoms from the compound. mentioned.
　前記その他の液晶性の高分子化合物における液晶性基の含有割合は、前記その他の液晶性の高分子化合物の母骨格となる高分子化合物を構成する構成単位の合計量に対して、通常１モル％以上１００モル％以下であり、前記その他の液晶性の高分子化合物の配向性を高くするという観点から、３０モル％以上１００モル％以下であることが好ましく、５０モル％以上１００モル％以下であることがより好ましく、８０モル％以上１００モル％以下であることがさらに好ましい。 The content ratio of the liquid crystalline group in the other liquid crystalline polymer compound is usually 1 mol with respect to the total amount of structural units constituting the polymer compound serving as the base skeleton of the other liquid crystalline polymer compound. % or more and 100 mol % or less, preferably 30 mol % or more and 100 mol % or less, and 50 mol % or more and 100 mol % or less from the viewpoint of increasing the orientation of the other liquid crystalline polymer compound. and more preferably 80 mol % or more and 100 mol % or less.
　組成物において、２種類以上の重合性液晶化合物を組み合わせる場合には、そのうちの少なくとも１種類が重合性液晶化合物（Ａ）であることが好ましく、そのうちの２種類以上が重合性液晶化合物（Ａ）であることがより好ましい。２種類以上の重合性液晶化合物を組み合わせることにより、液晶－結晶相転移温度以下の温度であっても液晶相を一時的に保持することができる場合がある。組成物に含まれる重合性液晶化合物（Ａ）の含有量は、組成物中の全重合性液晶化合物の総質量に対して合計で、好ましくは４０質量％以上であり、より好ましくは６０質量％以上であり、全ての重合性液晶化合物が重合性液晶化合物（Ａ）であってもよい。重合性液晶化合物（Ａ）の含有量が上記範囲内であると、重合性液晶化合物が高い配向秩序度で並びやすく、それに沿って式（１）で表される化合物が配向することにより、優れた偏光性能を有する偏光膜を得ることができる。 When two or more types of polymerizable liquid crystal compounds are combined in the composition, at least one of them is preferably the polymerizable liquid crystal compound (A), and two or more of them are the polymerizable liquid crystal compounds (A). is more preferable. By combining two or more types of polymerizable liquid crystal compounds, it may be possible to temporarily maintain the liquid crystal phase even at a temperature equal to or lower than the liquid crystal-crystal phase transition temperature. The total content of the polymerizable liquid crystal compound (A) contained in the composition is preferably 40% by mass or more, more preferably 60% by mass, based on the total mass of all polymerizable liquid crystal compounds in the composition. As described above, all polymerizable liquid crystal compounds may be the polymerizable liquid crystal compound (A). When the content of the polymerizable liquid crystal compound (A) is within the above range, the polymerizable liquid crystal compound is easily arranged with a high degree of alignment order, and the compound represented by the formula (1) is aligned along it, resulting in excellent A polarizing film having excellent polarizing performance can be obtained.
　組成物における重合性液晶化合物および液晶性の高分子化合物の合計含有割合は、重合性液晶化合物および液晶性の高分子化合物の配向性を高くするという観点から、組成物の固形分１００質量部に対して、例えば５０質量部以上であり、好ましくは７０質量部以上９９．９質量部以下であり、より好ましくは７０質量部以上９９．５質量部以下であり、更に好ましくは８０質量部以上９９質量部以下であり、特に好ましくは８０質量部以上９４質量部以下であり、より更に好ましくは８０質量部以上９０質量部以下である。 The total content of the polymerizable liquid crystal compound and the liquid crystalline polymer compound in the composition is 100 parts by mass of the solid content of the composition from the viewpoint of increasing the orientation of the polymerizable liquid crystal compound and the liquid crystalline polymer compound. On the other hand, for example, it is 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, and still more preferably 80 parts by mass or more and 99 parts by mass. It is not more than 80 parts by mass and not more than 94 parts by mass, and more preferably not less than 80 parts by mass and not more than 90 parts by mass.
　組成物における式（１）で表される化合物の総含有量は、重合性液晶化合物および液晶性の高分子化合物の合計量１００質量部に対して、通常、０．１質量部以上５０質量部以下であり、好ましくは０．１質量部以上２０質量部以下であり、より好ましくは０．１質量部以上１０質量部以下であり、さらに好ましくは０．１質量部以上、５質量部以下である。重合性液晶化合物および液晶性の高分子化合物の合計量に対する式（１）で表される化合物の総含有量が５０質量部以下であると、重合性液晶化合物、液晶性の高分子化合物および式（１）で表される化合物の配向の乱れが少なく、高い配向秩序度を有する偏光膜を得ることができる傾向がある。 The total content of the compound represented by formula (1) in the composition is usually 0.1 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound. or less, preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass be. When the total content of the compound represented by formula (1) with respect to the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound is 50 parts by mass or less, the polymerizable liquid crystal compound, the liquid crystalline polymer compound and the formula There is a tendency that a polarizing film having a high degree of orientational order can be obtained with less disorder in the orientation of the compound represented by (1).
高分子化合物
　組成物は、式（１）で表される化合物および重合液晶性化合物に加えて、高分子化合物を更に含んでいてもよい。組成物が高分子化合物を含むことで、式（１）で表される化合物が組成物中に分散し易くなる場合がある。組成物が含みうる高分子化合物としては、式（１）で表される化合物を分散可能であれば、特に制限はない。式（１）で表される化合物を均一に分散させやすい点から、ポリメチルメタクリレート（ＰＭＭＡ）などのアクリル系ポリマーが好ましい。また高分子化合物は、既述の重合性液晶化合物を重合した高分子化合物であってもよい。高分子化合物のポリスチレン換算の重量平均分子量は、例えば１万以上２０万以下であり、好ましくは２万以上１５万以下である。 Polymer Compound The composition may further contain a polymer compound in addition to the compound represented by Formula (1) and the polymerized liquid crystalline compound. When the composition contains a polymer compound, the compound represented by Formula (1) may be easily dispersed in the composition. The polymer compound that the composition may contain is not particularly limited as long as it can disperse the compound represented by formula (1). An acrylic polymer such as polymethyl methacrylate (PMMA) is preferable because the compound represented by Formula (1) can be uniformly dispersed. Further, the polymer compound may be a polymer compound obtained by polymerizing the polymerizable liquid crystal compound described above. The polystyrene equivalent weight average molecular weight of the polymer compound is, for example, 10,000 or more and 200,000 or less, preferably 20,000 or more and 150,000 or less.
　組成物が高分子化合物を含む場合、その含有量は、目的等に応じて適宜選択することができる。高分子化合物の含有量は、組成物の固形分１００質量部に対して、１０質量部以下であると好ましく、５．０質量部以下の範囲がより好ましく、３．０質量部以下の範囲がさらに好ましい。 When the composition contains a polymer compound, its content can be appropriately selected according to the purpose. The content of the polymer compound is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and preferably 3.0 parts by mass or less with respect to 100 parts by mass of the solid content of the composition. More preferred.
　組成物は、好ましくは溶剤等の液媒体および重合開始剤をさらに含み、必要に応じて光増感剤、重合禁止剤、レベリング剤等をさらに含んでいてもよい。 The composition preferably further contains a liquid medium such as a solvent and a polymerization initiator, and may further contain a photosensitizer, a polymerization inhibitor, a leveling agent, etc., if necessary.
溶剤
　溶剤は、式（１）で表される化合物、重合性液晶化合物、液晶性の高分子化合物、ならびに高分子化合物を完全に溶解し得る溶剤であることが好ましい。また、重合性液晶化合物の重合反応に不活性な溶剤であることが好ましい。 Solvent The solvent is preferably a solvent capable of completely dissolving the compound represented by Formula (1), the polymerizable liquid crystal compound, the liquid crystal polymer compound, and the polymer compound. Moreover, the solvent is preferably inert to the polymerization reaction of the polymerizable liquid crystal compound.
　溶剤としては、アルコール溶剤、エステル溶剤、ケトン溶剤、脂肪族炭化水素溶剤、芳香族炭化水素溶剤、ニトリル溶剤、エーテル溶剤、塩素含有溶剤等が挙げられる。これら溶剤は、１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。 Examples of solvents include alcohol solvents, ester solvents, ketone solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, nitrile solvents, ether solvents, and chlorine-containing solvents. These solvents may be used alone or in combination of two or more.
　組成物が溶剤を含む場合において、溶剤の含有割合は、組成物の総量に対して５０質量％以上９８質量％以下が好ましい。換言すると、組成物における固形分の含有割合は、２質量％以上５０質量％以下が好ましい。当該固形分が５０質量％以下であると、組成物の粘度が低くなり、組成物から得られる膜、例えば膜の厚みが略均一になり、当該膜にムラが生じ難くなる傾向がある。かかる固形分の含有割合は、製造しようとする膜の厚さを考慮して定めることができる。 When the composition contains a solvent, the content of the solvent is preferably 50% by mass or more and 98% by mass or less with respect to the total amount of the composition. In other words, the content of solids in the composition is preferably 2% by mass or more and 50% by mass or less. When the solid content is 50% by mass or less, the viscosity of the composition is low, and the thickness of a film obtained from the composition, for example, a film, tends to be substantially uniform and unevenness in the film tends to be less likely to occur. The content of such solids can be determined in consideration of the thickness of the film to be produced.
重合開始剤
　重合開始剤は、重合性液晶化合物の重合反応を開始し得る化合物である。重合開始剤は、より低温条件下で重合反応を開始できる点で、光重合開始剤が好ましい。具体的には、光の作用により活性ラジカルまたは酸を発生できる光重合開始剤が挙げられ、中でも、光の作用によりラジカルを発生する光重合開始剤が好ましい。 Polymerization Initiator The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound. The polymerization initiator is preferably a photopolymerization initiator because the polymerization reaction can be initiated under lower temperature conditions. Specifically, photopolymerization initiators capable of generating active radicals or acids by the action of light may be mentioned, and among these, photopolymerization initiators capable of generating radicals by the action of light are preferred.
　重合開始剤としては、ベンゾイン化合物、ベンゾフェノン化合物、アルキルフェノン化合物、アシルホスフィンオキサイド化合物、トリアジン化合物、ヨードニウム塩、およびスルホニウム塩などが挙げられる。重合開始剤は、公知の重合開始剤から目的等に応じて適宜選択することができる。また、重合開始剤は、１種単独または２種以上を組み合わせて使用できる。 Examples of polymerization initiators include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts. The polymerization initiator can be appropriately selected from known polymerization initiators according to the purpose and the like. Moreover, a polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
　組成物が重合開始剤を含有する場合、その含有量は、該組成物に含まれる重合性液晶化合物の種類およびその量に応じて適宜決定すればよい。重合開始剤の含有量は、重合性液晶化合物１００質量部に対して、例えば０．００１質量部以上、０．０１質量部以上、０．１質量部以上または０．５質量部以上であり、例えば３０質量％以下、１０質量％以下または８質量％以下である。また重合開始剤の含有量は、重合性液晶化合物１００質量部に対して、０．００１質量部以上３０質量部以下が好ましく、０．０１質量部以上１０質量部以下がより好ましく、０．１質量部以上８質量部以下がさらに好ましい。重合性開始剤の含有量が上記範囲内であると、重合性液晶化合物の配向を乱すことなく重合させることができる。 When the composition contains a polymerization initiator, its content may 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 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 with respect to 100 parts by mass of the polymerizable liquid crystal compound, For example, it is 30% by mass or less, 10% by mass or less, or 8% by mass or less. 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, with respect to 100 parts by mass of the polymerizable liquid crystal compound. Part by mass or more and 8 parts by mass or less is more preferable. When the content of the polymerizable initiator is within the above range, polymerization can be carried out without disturbing the alignment of the polymerizable liquid crystal compound.
光増感剤
　組成物が光重合開始剤を含有する場合、組成物は、好ましくは光増感剤の少なくとも１種を含有してよい。組成物が光重合開始剤および光増感剤を含有することにより、重合性液晶化合物の重合反応がより促進される傾向がある。当該光増感剤としては、キサントンおよびチオキサントン等のキサントン化合物；アントラセンおよびアルコキシ基置換アントラセン等のアントラセン化合物；フェノチアジンおよびルブレン；などが挙げられる。光増感剤は、１種単独または２種以上を組み合わせて使用できる。 Photosensitizer When the composition contains a photoinitiator, the composition may preferably contain at least one photosensitizer. When the composition contains a photopolymerization initiator and a photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound tends to be further accelerated. Examples of the photosensitizer include xanthone compounds such as xanthone and thioxanthone; anthracene compounds such as anthracene and alkoxy-substituted anthracene; phenothiazine and rubrene; A photosensitizer can be used individually by 1 type or in combination of 2 or more types.
　組成物が光増感剤を含む場合、組成物における光増感剤の含有量は、光重合開始剤および重合性液晶化合物の種類およびその量に応じて適宜決定すればよい。組成物における光増感剤の含有量は、重合性液晶化合物１００質量部に対して、好ましくは０．１質量部以上３０質量部以下であり、より好ましくは０．５質量部以上１０質量部以下であり、さらに好ましくは０．５質量部以上８質量部以下である。 When the composition contains a photosensitizer, the content of the photosensitizer in the composition may be appropriately determined according to the types and amounts 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 with respect to 100 parts by mass of the polymerizable liquid crystal compound. or less, more preferably 0.5 parts by mass or more and 8 parts by mass or less.
重合禁止剤
　組成物は、重合禁止剤の少なくとも１種を含んでいてもよい。重合禁止剤としては、例えば、ハイドロキノン、アルコキシ基含有ハイドロキノン、アルコキシ基含有カテコール（例えばブチルカテコール）、ピロガロール、２，２，６，６－テトラメチル－１－ピペリジニルオキシラジカル等のラジカル捕捉剤；チオフェノール類；β－ナフチルアミン類およびβ－ナフトール類；などが挙げられる。組成物が重合禁止剤を含むことにより、重合性液晶化合物の重合反応の進行度合いを制御することができる。 Polymerization Inhibitor The composition may contain at least one polymerization inhibitor. Examples of polymerization inhibitors include radical scavengers such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (eg, butylcatechol), pyrogallol, and 2,2,6,6-tetramethyl-1-piperidinyloxy radical. thiophenols; β-naphthylamines and β-naphthols; By including a polymerization inhibitor in the composition, the degree of progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled.
　組成物が重合禁止剤を含む場合、組成物における重合禁止剤の含有量は、重合性液晶化合物１００質量部に対して、好ましくは０．１質量部以上３０質量部以下であり、より好ましくは０．５質量部以上１０質量部以下であり、さらに好ましくは０．５質量部以上８質量部以下である。 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 100 parts by mass of the polymerizable liquid crystal compound. It is 0.5 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 8 parts by mass or less.
レベリング剤
　組成物は、レベリング剤の少なくとも１種を含んでいてもよい。レベリング剤は、組成物の流動性を調整し、該組成物を塗布することにより得られる塗膜をより平坦にする機能を有し、具体的には、界面活性剤が挙げられる。レベリング剤としては、ポリアクリレート化合物を主成分とするレベリング剤およびフッ素原子含有化合物を主成分とするレベリング剤からなる群から選ばれる少なくとも１種が好ましい。レベリング剤は、１種単独または２種以上を組み合わせて使用できる。 Leveling Agent The composition may comprise at least one leveling agent. The leveling agent has the function of adjusting the fluidity of the composition and making the coating film obtained by applying the composition more flat, and specifically includes surfactants. The leveling agent is preferably at least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component. A leveling agent can be used individually by 1 type or in combination of 2 or more types.
　組成物がレベリング剤を含む場合、レベリング剤の含有量は、重合性液晶化合物および液晶性の高分子化合物の合計量１００質量部に対して、好ましくは０．０５質量部以上５質量部以下であり、より好ましくは０．０５質量部以上３質量部以下である。レベリング剤の含有量が前記範囲内であると、重合性液晶化合物および液晶性の高分子化合物を水平配向させやすく、かつ、ムラが生じ難く、より平滑な膜、例えば偏光膜を得られる傾向がある。 When the composition contains a leveling agent, the content of the leveling agent is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the liquid crystalline polymer compound. and more preferably 0.05 parts by mass or more and 3 parts by mass or less. When the content of the leveling agent is within the above range, the polymerizable liquid crystal compound and the liquid crystalline polymer compound are easily horizontally aligned, unevenness is less likely to occur, and a smoother film such as a polarizing film tends to be obtained. be.
　レベリング剤の含有量が上記範囲内であると、重合性液晶化合物および液晶性の高分子化合物を水平配向させることが容易であり、かつ、得られる膜がより平滑となる傾向がある。重合性液晶化合物および液晶性の高分子化合物に対するレベリング剤の含有量が上記範囲を超えると、得られる膜にムラが生じ易い傾向がある。 When the content of the leveling agent is within the above range, it is easy to horizontally align the polymerizable liquid crystal compound and the liquid crystal polymer compound, and the resulting film tends to be smoother. If the content of the leveling agent with respect to the polymerizable liquid crystal compound and the liquid crystalline polymer compound exceeds the above range, the resulting film tends to be uneven.
酸化防止剤
　組成物は酸化防止剤を含んでいてもよい。酸化防止剤は、組成物が本発明の効果を発揮し得るものであれば特に限定されず、公知の酸化防止剤を用いることができる。酸化防止剤は、式（１）で表される化合物の光劣化に対する高い抑制効果を有する観点から、ラジカルを捕捉して自動酸化の防止作用を有する、いわゆる一次酸化防止剤が好ましい。したがって、組成物に含まれる酸化防止剤は、フェノール系化合物、脂環式アルコール系化合物およびアミン系化合物からなる群から選択される少なくとも１種であることがより好ましい。酸化防止剤は、１種のみを単独で用いても、２種以上を組み合わせて用いてもよい。 Antioxidant The composition may contain an antioxidant. The antioxidant is not particularly limited as long as the composition can exhibit the effects of the present invention, and known antioxidants can be used. The antioxidant is preferably a so-called primary antioxidant that has a radical-scavenging and autoxidation-preventing action from the viewpoint of having a high inhibitory effect on photodegradation of the compound represented by formula (1). Therefore, the antioxidant contained in the composition is more preferably at least one selected from the group consisting of phenol compounds, alicyclic alcohol compounds and amine compounds. Antioxidants may be used alone or in combination of two or more.
　組成物における上記酸化防止剤の含有量は、組成物１００質量部に対して好ましくは０．１質量部以上１５質量部以下であり、より好ましくは０．３質量部以上、さらに好ましくは０．５質量部以上であり、より好ましくは１２質量部以下であり、さらに好ましくは１０質量部以下である。酸化防止剤の含有量が上記下限値以上であると、式（１）で表される化合物の光劣化をより効果的に抑制することができる。また、酸化防止剤の含有量が上記上限値以下であると、重合性液晶化合物の配向をより乱し難く、かつ、式（１）で表される化合物の光劣化に対するより高い抑制効果を期待できる。 The content of the antioxidant in the composition is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.3 parts by mass or more, and still more preferably 0.1 part by mass or more, based on 100 parts by mass of the composition. It is 5 parts by mass or more, more preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less. When the content of the antioxidant is at least the above lower limit, photodegradation of the compound represented by formula (1) can be more effectively suppressed. In addition, when the content of the antioxidant is equal to or less than the above upper limit, the orientation of the polymerizable liquid crystal compound is more difficult to disturb, and a higher inhibitory effect on photodegradation of the compound represented by formula (1) is expected. can.
　組成物は、上記以外の他の添加剤を含有してよい。他の添加剤としては、例えば、離型剤、安定剤、ブルーイング剤等の着色剤、難燃剤および滑剤などが挙げられる。組成物が他の添加剤を含有する場合、他の添加剤の含有量は、組成物の固形分に対して、０％を超えて２０質量％以下であることが好ましく、より好ましくは０％を超えて１０質量％以下である。 The composition may contain additives other than those mentioned above. Other additives include, for example, 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 more than 0% and 20% by mass or less, more preferably 0%, based on the solid content of the composition. is 10% by mass or less.
　組成物は、従来公知の組成物の調製方法により製造することができる。例えば、式（１）で表される化合物と、液晶性化合物と、必要に応じて酸化防止剤、レベリング剤などの添加剤とを混合、撹拌することにより調製することができる。 The composition can be produced by a conventionally known composition preparation method. For example, it can be prepared by mixing and stirring the compound represented by Formula (1), the liquid crystalline compound, and, if necessary, additives such as an antioxidant and a leveling agent.
＜化合物＞
　本実施形態にかかる化合物は、下記式（１ａ）で表される。 <Compound>
The compound according to this embodiment is represented by the following formula (1a).
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　式（１ａ）中、ｋは、１または２の整数を表す。ｋが２の場合、２つのＡｒ１２は互いに同一であっても相異なっていてもよい。 In formula (1a), k represents an integer of 1 or 2. When k is 2, two Ar 12 may be the same or different.
　Ａｒ１１、Ａｒ１２およびＡｒ１３は、それぞれ独立に、置換基を有していてもよい１，４－フェニレン基又は含硫黄複素環基を表す。Ａｒ１１およびＡｒ１２の少なくとも一方は、分子内水素結合を形成し得る水酸基を少なくとも１つ有する。Ａｒ１１、Ａｒ１２およびＡｒ１３の詳細は、式（１）におけるＡｒ１、Ａｒ２およびＡｒ３のそれぞれと同様であり、好ましい態様も同様である。 Ar 11 , Ar 12 and Ar 13 each independently represent an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group. At least one of Ar 11 and Ar 12 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond. Details of Ar 11 , Ar 12 and Ar 13 are the same as Ar 1 , Ar 2 and Ar 3 in Formula (1), and preferred embodiments are also the same.
　Ｒ１１は、重合性基を有していてもよいアルキルアミノ基を表す。Ｒ１１の詳細は、式（１）におけるＲ１と同様であり、好ましい態様も同様である。 R 11 represents an alkylamino group optionally having a polymerizable group. The details of R 11 are the same as those of R 1 in Formula (1), and the preferred embodiments are also the same.
　Ｒ１２は、水酸基と分子内水素結合を形成し得る環状または鎖状である炭素数２から２０の基、炭素数２から２０のアルカンジイルオキシカルボニル基、炭素数２から２０のアルカンジイルカルボニル基、炭素数４から２０のアルカンジイル基、炭素数２から２０のアルカンジイルオキシ基等を挙げることができ、これらからなる群から選択される少なくとも１種を含むことが好ましい。Ｒ１２の詳細は、式（１）におけるＲ２と同様であり、好ましい態様も同様である。 R 12 is a cyclic or chain-like group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, or an alkanediylcarbonyl group having 2 to 20 carbon atoms, which is capable of forming an intramolecular hydrogen bond with a hydroxyl group; , an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, and the like, and at least one selected from the group consisting of these is preferably included. The details of R 12 are the same as those of R 2 in Formula (1), and the preferred embodiments are also the same.
　Ｒ１３は、重合性基または水素原子を表す。Ｒ１３の詳細は、式（１）におけるＲ３と同様であり、好ましい態様も同様である。 R13 represents a polymerizable group or a hydrogen atom. The details of R 13 are the same as those of R 3 in Formula (1), and the preferred embodiments are also the same.
＜膜＞
　本実施形態にかかる膜は、式（１）で表される化合物を形成材料として含む膜であってもよく、式（１）で表される化合物と液晶性化合物とを含む組成物を形成材料として得られる膜であってもよい。組成物からなる膜は、組成物を基材に付与し、成膜することで形成されてよい。また、組成物が、重合性液晶化合物を含む場合、該重合性液晶化合物を重合させて得られる硬化物を含む膜は、組成物を基材に付与し、成膜した後に該重合性液晶化合物を重合し、硬化させることで形成されてよい。 <Membrane>
The film according to the present embodiment may be a film containing the compound represented by formula (1) as a forming material, or a composition containing the compound represented by formula (1) and a liquid crystalline compound as a forming material. It may be a film obtained as A film made of the composition may be formed by applying the composition to a substrate to form a film. Further, when the composition contains a polymerizable liquid crystal compound, a film containing a cured product obtained by polymerizing the polymerizable liquid crystal compound is obtained by applying the composition to a substrate, forming a film, and then applying the polymerizable liquid crystal compound. may be formed by polymerizing and curing the
　組成物は、二色比の高い膜、例えば偏光膜を形成することができる。したがって、本実施形態にかかる膜は、式（１）で表される化合物と、液晶性化合物とを含んでなる組成物から形成される偏光膜であって、二色比の高い偏光膜を包含する。また、組成物は、配向秩序度の高い膜、例えば偏光膜を形成することができる。したがって、本実施形態にかかる膜は、式（１）で表される化合物と、液晶性化合物とを含んでなる組成物から形成される偏光膜であって、配向秩序度の高い偏光膜を包含する。 The composition can form a film with a high dichroic ratio, such as a polarizing film. Therefore, the film according to the present embodiment is a polarizing film formed from a composition containing a compound represented by formula (1) and a liquid crystalline compound, and includes a polarizing film having a high dichroic ratio. do. The composition can also form films with a high degree of orientational order, such as polarizing films. Therefore, the film according to the present embodiment is a polarizing film formed from a composition containing a compound represented by formula (1) and a liquid crystalline compound, and includes a polarizing film with a high degree of orientational order. do.
　ここで、配向秩序度の高い偏光膜では、Ｘ線回折測定においてヘキサチック相やクリスタル相といった高次構造由来のブラッグピークが得られる。したがって、組成物から形成される偏光膜は、重合性液晶化合物または液晶性の高分子化合物がＸ線回折測定においてブラッグピークを示すように配向していることが好ましく、光を吸収する方向に重合性液晶化合物または液晶性の高分子化合物の分子が配向する「水平配向」であることがより好ましい。ブラッグピークを示すような高い配向秩序度は、用いる重合性液晶化合物または液晶性の高分子化合物の種類、式（１）で表される化合物の量等を制御することにより実現し得る。 Here, in a polarizing film with a high degree of orientational order, a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase is obtained in X-ray diffraction measurement. Therefore, in the polarizing film formed from the composition, it is preferable that the polymerizable liquid crystal compound or the liquid crystalline polymer compound is oriented so as to exhibit a Bragg peak in X-ray diffraction measurement, and polymerized in the direction of light absorption. It is more preferable to be "horizontal alignment" in which the molecules of the liquid crystal compound or the liquid crystal polymer compound are aligned. A high degree of orientational order exhibiting a Bragg peak can be realized by controlling the type of polymerizable liquid crystal compound or liquid crystalline polymer compound used, the amount of the compound represented by formula (1), and the like.
　膜を形成するために用いる組成物を構成する式（１）で表される化合物および液晶性化合物については、既述の通りである。 The compound represented by Formula (1) and the liquid crystalline compound constituting the composition used to form the film are as described above.
　膜は、例えば、以下の工程を含む方法により製造することができる。
　工程Ａ：式（１）で表される化合物と液晶性化合物と溶剤とを含む組成物の塗膜を形成すること、
　工程Ｂ：前記塗膜から溶剤の少なくとも一部を除去すること、
　工程Ｃ：液晶性化合物が液体相に相転移する温度以上まで昇温した後、降温して、該液晶性化合物をスメクチック相（スメクチック液晶状態）に相転移させること、および
　工程Ｄ：必要に応じて、前記スメクチック相（スメクチック液晶状態）を保持したまま、重合性液晶化合物を重合させること。 The membrane can be produced, for example, by a method including the following steps.
Step A: forming a coating film of a composition containing a compound represented by formula (1), a liquid crystalline compound, and a solvent;
Step B: removing at least a portion of the solvent from the coating;
Step C: raising the temperature to a temperature at which the liquid crystalline compound transitions to a liquid phase or higher, and then lowering the temperature to cause the liquid crystalline compound to undergo a phase transition to a smectic phase (smectic liquid crystal state); and Step D: as necessary. and polymerizing the polymerizable liquid crystal compound while maintaining the smectic phase (smectic liquid crystal state).
　組成物の塗膜の形成は、例えば、基材、後述する配向膜などの上に組成物を塗布することにより行うことができる。また、偏光板を構成する位相差フィルム、その他の層上に組成物を直接塗布してもよい。 Formation of a coating film of the composition can be carried out, for example, by coating the composition on a base material, an alignment film described later, or the like. Alternatively, the composition may be directly applied onto the retardation film or other layer that constitutes the polarizing plate.
　基材は通常、透明基材である。なお、基材が表示素子の表示面に設置されないとき、例えば、膜から基材を取り除いた積層体を表示素子の表示面に設置する場合は、基材は透明でなくてもよい。透明基材とは、光、特に可視光を透過し得る透明性を有する基材を意味し、透明性とは、３８０ｎｍ以上７８０ｎｍ以下の波長範囲にわたる光線に対しての透過率が８０％以上となる特性をいう。具体的な透明基材としては、透光性樹脂基材が挙げられる。 The base material is usually a transparent base material. When the base material is not placed on the display surface of the display element, for example, when a laminate obtained by removing the base material from the film is placed on the display surface of the display element, the base material does not have to be transparent. A transparent base material means a base material having transparency that can transmit light, particularly visible light, and transparency means a light transmittance of 80% or more over a wavelength range of 380 nm or more and 780 nm or less. It means a characteristic. A translucent resin base material is mentioned as a specific transparent base material.
　透光性樹脂基材を構成する樹脂としては、ポリオレフィン；環状オレフィン系樹脂；ポリビニルアルコール；ポリエチレンテレフタレート；ポリメタクリル酸エステル；ポリアクリル酸エステル；セルロースエステル；ポリエチレンナフタレート；ポリカーボネート；ポリスルホン；ポリエーテルスルホン；ポリエーテルケトン；ポリフェニレンスルフィドおよびポリフェニレンオキシド等が挙げられる。入手のしやすさや透明性の観点から、ポリエチレンテレフタレート、ポリメタクリル酸エステル、セルロースエステル、環状オレフィン系樹脂またはポリカーボネートが好ましい。 Polyolefin; cyclic olefin resin; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid ester; polyacrylic acid ester; cellulose ester; polyethylene naphthalate; polycarbonate; polyether ketones; polyphenylene sulfides and polyphenylene oxides; From the viewpoint of availability and transparency, polyethylene terephthalate, polymethacrylate, cellulose ester, cyclic olefin resin, or polycarbonate are preferred.
　基材に求められる特性は、膜の構成によって異なるが、通常、位相差性ができるだけ小さい基材が好ましい。位相差性ができるだけ小さい基材としては、ゼロタック（コニカミノルタオプト株式会社）、Ｚタック（富士フイルム株式会社）等の位相差を有しないセルロースエステルフィルム等が挙げられる。また、未延伸の環状オレフィン系樹脂基材も好ましい。膜が積層されていない基材の面には、ハードコート処理、反射防止処理、帯電防止処理等がなされてもよい。 The properties required for the base material differ depending on the composition of the film, but usually a base material with as little retardation as possible is preferable. Examples of the substrate having the smallest possible retardation include cellulose ester films having no retardation, such as Zero Tack (Konica Minolta Opto Co., Ltd.) and Z Tack (Fuji Film Co., Ltd.). An unstretched cyclic olefin resin substrate is also preferred. The surface of the substrate on which no film is laminated may be subjected to hard coat treatment, antireflection treatment, antistatic treatment, or the like.
　基材の厚みは、通常５μｍ以上３００μｍ以下であり、好ましくは２０μｍ以上２００μｍ以下、より好ましくは２０μｍ以上１００μｍ以下である。前記下限値以上であれば強度の低下が抑制され、加工性が良好になる傾向がある。 The thickness of the substrate is usually 5 µm or more and 300 µm or less, preferably 20 µm or more and 200 µm or less, more preferably 20 µm or more and 100 µm or less. If it is at least the above lower limit, a decrease in strength is suppressed, and workability tends to be improved.
　組成物を基材等に塗布する方法としては、スピンコーティング法、エクストルージョン法、グラビアコーティング法、ダイコーティング法、バーコーティング法、アプリケータ法などの塗布法、フレキソ法などの印刷法などの公知の方法が挙げられる。 Examples of methods for applying the composition to a substrate or the like include coating methods such as a spin coating method, extrusion method, gravure coating method, die coating method, bar coating method and applicator method, and printing methods such as a flexographic method. method.
　次いで、組成物から得られた塗膜に含まれる溶剤の少なくとも一部を乾燥等により除去することにより乾燥塗膜が形成される。また、該塗膜中に重合性液晶化合物が含まれる場合、該重合性液晶化合物が重合しない条件で、乾燥をおこなうことにより乾燥塗膜が形成される。前記塗膜の乾燥方法としては、自然乾燥法、通風乾燥法、加熱乾燥、減圧乾燥法等が挙げられる。 Then, at least part of the solvent contained in the coating film obtained from the composition is removed by drying or the like to form a dry coating film. Moreover, when the coating film contains a polymerizable liquid crystal compound, a dry coating film is formed by drying the coating film under conditions in which the polymerizable liquid crystal compound is not polymerized. Examples of the method for drying the coating film include a natural drying method, a ventilation drying method, a heat drying method, a reduced pressure drying method, and the like.
　さらに、液晶性化合物を液体相に相転移させるため、液晶性化合物が液体相に相転移する温度以上まで昇温した後、降温して液晶性化合物をスメクチック相（スメクチック液晶状態）に相転移させる。かかる相転移は、塗膜中の溶剤除去後に行ってもよいし、溶剤の除去と同時に行ってもよい。 Furthermore, in order to phase-transition the liquid-crystalline compound to the liquid phase, the temperature is raised to a temperature higher than the temperature at which the liquid-crystalline compound undergoes phase transition to the liquid phase, and then the temperature is lowered to cause the liquid-crystalline compound to phase-transition to the smectic phase (smectic liquid crystal state). . Such a phase transition may be carried out after removing the solvent in the coating film, or may be carried out simultaneously with the removal of the solvent.
　組成物が、重合性液晶化合物を含む場合、重合性液晶化合物のスメクチック液晶状態を保持したまま、重合性液晶化合物を重合させることにより、重合性液晶化合物の硬化物を含む膜が形成される。重合方法としては光重合法が好ましい。光重合において、乾燥塗膜に照射する光としては、乾燥塗膜に含まれる光重合開始剤の種類、重合性液晶化合物の種類（特に、重合性液晶化合物が有する重合性基の種類）およびその量に応じて適宜選択される。その具体例としては、可視光、紫外光、赤外光、Ｘ線、α線、β線およびγ線からなる群から選択される１種以上の光、活性電子線等が挙げられる。中でも、重合反応の進行を制御し易い点や、光重合装置として当分野で広範に用いられているものが使用できるという点で、紫外光が好ましく、紫外光によって、光重合可能なように、組成物に含有される重合性液晶化合物、光重合開始剤の種類等を選択しておくことが好ましい。また、重合時に、適切な冷却手段により乾燥塗膜を冷却しながら、光照射することで、重合温度を制御することもできる。このような冷却手段の採用により、より低温で重合性液晶化合物の重合を実施すれば、基材が比較的耐熱性が低いものを用いたとしても、適切に膜を形成できる。光重合の際、マスキングや現像を行うなどによって、パターニングされた膜を得ることもできる。 When the composition contains a polymerizable liquid crystal compound, a film containing a cured product of the polymerizable liquid crystal compound is formed by polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound. A photopolymerization method is preferable as the polymerization method. In photopolymerization, the light irradiated to the dry coating film includes the type of photopolymerization initiator contained in the dry coating film, the type of polymerizable liquid crystal compound (especially the type of polymerizable group possessed by the polymerizable liquid crystal compound), and its It is selected appropriately according to the amount. Specific examples thereof include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays and γ-rays, active electron beams, and the like. Among them, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that a widely used photopolymerization apparatus in the field can be used. It is preferable to select the types of the polymerizable liquid crystal compound, the photopolymerization initiator, etc. contained in the composition. The polymerization temperature can also be controlled by irradiating light while cooling the dry coating film with an appropriate cooling means during polymerization. By adopting such a cooling means and polymerizing the polymerizable liquid crystal compound at a lower temperature, it is possible to appropriately form a film even if a substrate having relatively low heat resistance is used. A patterned film can also be obtained by performing masking or development during photopolymerization.
　前記活性エネルギー線の光源としては、例えば、低圧水銀ランプ、中圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、ハロゲンランプ、カーボンアーク灯、タングステンランプ、ガリウムランプ、エキシマレーザー、波長範囲３８０ｎｍ以上４４０ｎｍ以下で発光するＬＥＤ光源、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ等が挙げられる。 Examples of the light source of the active energy ray 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, and wavelength ranges. LED light sources, chemical lamps, black light lamps, microwave excited mercury lamps, metal halide lamps, etc., which emit light at 380 nm or more and 440 nm or less.
　紫外線照射強度は、通常、１０ｍＷ／ｃｍ２以上３，０００ｍＷ／ｃｍ２以下であってよい。紫外線照射強度は、好ましくは光重合開始剤の活性化に有効な波長領域における強度である。光を照射する時間は、通常０．１秒以上１０分以下であってよく、好ましくは０．１秒以上５分以下、より好ましくは０．１秒以上３分以下、さらに好ましくは０．１秒以上１分以下である。このような紫外線照射強度で１回または複数回照射すると、その積算光量は、１０ｍＪ／ｃｍ２以上３，０００ｍＪ／ｃｍ２以下であることが好ましい。 The ultraviolet irradiation intensity may be generally 10 mW/cm 2 or more and 3,000 mW/cm 2 or less. The ultraviolet irradiation intensity is preferably in the wavelength range effective for activation of the photopolymerization initiator. The light irradiation time may be usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and still more preferably 0.1 seconds. Seconds or more and one minute or less. It is preferable that the integrated amount of light when irradiated once or multiple times with such an irradiation intensity of ultraviolet rays is 10 mJ/cm 2 or more and 3,000 mJ/cm 2 or less.
　光重合を行うことにより、重合性液晶化合物は、スメクチック相、好ましくは高次のスメクチック相の液晶状態を保持したまま重合し、膜が形成される。重合性液晶化合物がスメクチック相の液晶状態を保持したまま重合して得られる膜は、二色性色素の作用にも伴い、従来のホストゲスト型偏光フィルム、すなわち、ネマチック相の液晶状態からなる膜と比較して、偏光性能が高いという利点がある。さらに、二色性色素、またはリオトロピック液晶のみを塗布したものと比較して、強度に優れるという利点もある。 By performing photopolymerization, the polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of a smectic phase, preferably a higher-order smectic phase, to form a film. The film obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase is different from the conventional host-guest type polarizing film, that is, the film having the liquid crystal state of the nematic phase, due to the action of the dichroic dye. It has the advantage of high polarization performance compared to . Furthermore, there is also the advantage of being superior in strength compared to those coated only with dichroic dyes or lyotropic liquid crystals.
　膜の厚みは、適用される表示装置等に応じて適宜選択でき、好ましくは０．５μｍ以上１０μｍ以下、より好ましくは１μｍ以上５μｍ以下、さらに好ましくは１μｍ以上３μｍ以下である。 The thickness of the film can be appropriately selected according to the display device to which it is applied, and is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, still more preferably 1 μm or more and 3 μm or less.
　膜が、偏光膜として使用される場合、配向膜上に形成されることが好ましい。配向膜は、重合性液晶化合物および液晶性の高分子化合物を所望の方向に液晶配向させる、配向規制力を有するものである。配向膜としては、重合性液晶化合物および液晶性の高分子化合物の少なくとも１種を含む液晶性化合物を含有する組成物の塗布等により溶解しない溶剤耐性を有し、また、溶剤の除去や重合性液晶化合物の配向のための加熱処理における耐熱性を有するものが好ましい。かかる配向膜としては、配向性ポリマーを含む配向膜、光配向膜および表面に凹凸パターンや複数の溝を有するグルブ配向膜等が挙げられ、配向角の精度および品質の観点から、光配向膜が好ましい。 When the film is used as a polarizing film, it is preferably formed on an alignment film. The alignment film has an alignment regulating force that aligns the polymerizable liquid crystal compound and the liquid crystalline polymer compound in a desired direction. The alignment film has a solvent resistance that does not dissolve when a composition containing a liquid crystalline compound containing at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound is applied. A material having heat resistance in the heat treatment for alignment of the liquid crystal compound is preferable. Examples of such an alignment film include an alignment film containing an alignment polymer, a photo-alignment film, and a groove alignment film having an uneven pattern or a plurality of grooves on the surface. preferable.
＜積層体＞
　本実施形態にかかる積層体は、式（１）で表される化合物を形成材料として含む膜を備えていてもよく、式（１）で表される化合物と液晶性化合物とを含む組成物を形成材料とする膜を備えていてもよい。積層体は、基材と、基材上に配置される式（１）で表される化合物を形成材料として含む膜とを備えていてよく、基材と、基材上に配置される配向膜と、配向膜上に配置される式（１）で表される化合物を形成材料とする膜とを備えていてよい。式（１）で表される化合物を形成材料として含む膜は、偏光膜を構成してよい。また、基材は位相差フィルムであってもよい。積層体は、例えば、偏光板を構成することができる。積層体は、例えば、上述した膜の製造方法に準じて、基材上に膜を形成することで製造することができる。 <Laminate>
The laminate according to the present embodiment may include a film containing the compound represented by formula (1) as a forming material, and a composition containing the compound represented by formula (1) and a liquid crystalline compound. A film as a forming material may be provided. The laminate may comprise a substrate and a film containing the compound represented by formula (1) as a forming material disposed on the substrate, and the substrate and the alignment film disposed on the substrate and a film made of the compound represented by the formula (1) and disposed on the alignment film. A film containing the compound represented by Formula (1) as a forming material may constitute a polarizing film. Also, the substrate may be a retardation film. The laminate can constitute, for example, a polarizing plate. The laminate can be produced, for example, by forming a film on a base material according to the film production method described above.
　積層体の厚みは、表示装置の屈曲性や視認性の観点から、好ましくは１０μｍ以上３００μｍ以下、より好ましくは２０μｍ以上２００μｍ以下、さらに好ましくは２５μｍ以上１００μｍ以下である。 The thickness of the laminate is preferably 10 μm to 300 μm, more preferably 20 μm to 200 μm, still more preferably 25 μm to 100 μm, from the viewpoint of flexibility and visibility of the display device.
　積層体が基材として位相差フィルムを備える場合、位相差フィルムの厚みは、適用される表示装置に応じて適宜選択できる。 When the laminate has a retardation film as a base material, the thickness of the retardation film can be appropriately selected according to the display device to which it is applied.
＜表示装置＞
　本実施形態の表示装置は、前記積層体を備え、積層体は偏光板であってよい。表示装置は、例えば、粘接着剤層を介して、偏光板としての積層体を表示装置の表面に貼合することにより得ることができる。表示装置とは、表示素子を有する装置であり、発光源として発光素子または発光装置を含む装置である。表示装置としては、例えば、液晶表示装置、有機エレクトロルミネッセンス（ＥＬ）表示装置、無機エレクトロルミネッセンス（ＥＬ）表示装置、電子放出表示装置（例えば、電場放出表示装置（ＦＥＤ）、表面電界放出表示装置（ＳＥＤ））、電子ペーパー（電子インク、電気泳動素子等を用いた表示装置）、プラズマ表示装置、投射型表示装置（例えば、グレーティングライトバルブ（ＧＬＶ）表示装置、デジタルマイクロミラーデバイス（ＤＭＤ）を有する表示装置）、および圧電セラミックディスプレイ等が挙げられる。液晶表示装置は、透過型液晶表示装置、半透過型液晶表示装置、反射型液晶表示装置、直視型液晶表示装置、および投写型液晶表示装置等のいずれも包含する。これらの表示装置は、２次元画像を表示する表示装置であってもよいし、３次元画像を表示する立体表示装置であってもよい。特に、表示装置としては、有機ＥＬ表示装置およびタッチパネル表示装置が好ましく、特に有機ＥＬ表示装置が好ましい。 <Display device>
The display device of this embodiment may include the laminate, and the laminate may be a polarizing plate. A display device can be obtained, for example, by bonding a laminate as a polarizing plate to the surface of the display device via an adhesive layer. A display device is a device having a display element and a device including a light-emitting element or a light-emitting device as a light source. Examples of display devices include liquid crystal displays, organic electroluminescence (EL) displays, inorganic electroluminescence (EL) displays, electron emission displays (e.g., field emission displays (FED), surface field emission displays ( SED)), electronic paper (display device using electronic ink, electrophoretic element, etc.), plasma display device, projection display device (e.g., grating light valve (GLV) display device, digital micromirror device (DMD) display devices), and piezoelectric ceramic displays. The liquid crystal display device includes a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, a projection liquid crystal display device, and the like. These display devices may be display devices that display two-dimensional images, or may be stereoscopic display devices that display three-dimensional images. In particular, as the display device, an organic EL display device and a touch panel display device are preferable, and an organic EL display device is particularly preferable.
　以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、特に断りのない限り、「部」及び「％」は質量基準である。また、「常温」および「ＲＴ」は２３℃である。 The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. "Parts" and "%" are based on mass unless otherwise specified. Also, "normal temperature" and "RT" are 23°C.
実施例１：化合物１－１の合成
　化合物１－１を合成するために、まず化合物１－１－ａ、化合物１－１－ｂおよび化合物１－１－ｃを合成した。続いて脱アセチル化をして化合物１－１を得た。 Example 1 Synthesis of Compound 1-1 In order to synthesize Compound 1-1, Compound 1-1-a, Compound 1-1-b and Compound 1-1-c were first synthesized. Subsequently, deacetylation was performed to obtain compound 1-1.
化合物１－１－ａの合成　
　４－アミノ安息香酸エチル（１．６５ｇ、１０．０ｍｍｏｌ）、３５％塩酸（２．６５ｍＬ，３０．０ｍｍｏｌ）、および水（２５．０ｍＬ）を混合して０℃から５℃に冷却し、そこへ亜硝酸ナトリウム（０．７２４ｇ、１．０５ｍｍｏｌ）の水（１．３ｍＬ）溶液を滴下した。その後、０℃から５℃を保ちながら１時間撹拌し、アミド硫酸（４９．０ｍｇ、０．５０５ｍｍｏｌ）の水（０．３ｍＬ）溶液を加え、ジアゾ液を調製した。一方、３－アミノフェノール（２．１８３ｇ、２０．０ｍｍｏｌ）、酢酸ナトリウム（４．１４ｇ，５０．５ｍｍｏｌ）、および水（７５．０ｍＬ）を混合して０℃から５℃に冷却し、先ほど調製したジアゾ液全量を滴下した。滴下終了後常温まで昇温し１時間撹拌した、析出した固体を濾別して化合物１－１－ａを得た（２．２８ｇ、収率８０％） Synthesis of compound 1-1-a
Ethyl 4-aminobenzoate (1.65 g, 10.0 mmol), 35% hydrochloric acid (2.65 mL, 30.0 mmol), and water (25.0 mL) were mixed and cooled to 0°C to 5°C. A solution of sodium nitrite (0.724 g, 1.05 mmol) in water (1.3 mL) was added dropwise. After that, the mixture was stirred for 1 hour while maintaining the temperature from 0°C to 5°C, and a solution of amidosulfuric acid (49.0 mg, 0.505 mmol) in water (0.3 mL) was added to prepare a diazo solution. Meanwhile, 3-aminophenol (2.183 g, 20.0 mmol), sodium acetate (4.14 g, 50.5 mmol), and water (75.0 mL) were mixed and cooled from 0 ° C. to 5 ° C., The whole amount of the obtained diazo solution was added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature and the mixture was stirred for 1 hour. The precipitated solid was separated by filtration to obtain compound 1-1-a (2.28 g, yield 80%).
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
化合物１－１―ｂの合成
　化合物１－１－ａ（０．８５６ｇ、３．００ｍｍｏｌ）、ＤＭＡＰ（Ｎ，Ｎ－ジメチルアミノピリジンの略。３８．０ｍｇ、０．３０１ｍｍｏｌ）、トリエチルアミン（０．３６５ｇ、３．６１ｍｍｏｌ）、およびクロロホルム（６０．０ｍＬ）を混合して０℃から５℃に冷却し、無水酢酸（０．３６８ｇ、３．６０ｍｍｏｌ）を滴下した。その後、反応溶液を常温まで昇温し、２１時間撹拌した。反応溶液に水を加え分液し、有機層に硫酸マグネシウムを加えて乾燥後、濃縮して得られた固体をクロロホルム／メタノールを展開溶媒としたシリカゲルカラムクロマトグラフィーにて精製し、化合物１－１―ｂを得た（０．２３２ｇ、収率２４％）。 Synthesis of compound 1-1-b Compound 1-1-a (0.856 g, 3.00 mmol), DMAP (abbreviation for N,N-dimethylaminopyridine. 38.0 mg, 0.301 mmol), triethylamine (0.365 g , 3.61 mmol), and chloroform (60.0 mL) were mixed and cooled to 0° C. to 5° C. and acetic anhydride (0.368 g, 3.60 mmol) was added dropwise. After that, the reaction solution was warmed to room temperature and stirred for 21 hours. Water is added to the reaction solution to separate the layers, magnesium sulfate is added to the organic layer, the organic layer is dried, and the solid obtained by concentration is purified by silica gel column chromatography using chloroform/methanol as a developing solvent to give compound 1-1. -b was obtained (0.232 g, 24% yield).
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
化合物１－１―ｃの合成　
　化合物１－１―ｂ（０．２１３ｇ、０．６５１ｍｍｏｌ）、３５％塩酸（０．２０ｍＬ、２．１０ｍｍｏｌ）、酢酸（３．５ｍＬ）および水（０．９ｍＬ）を混合して０℃から５℃に冷却し、そこへ亜硝酸ナトリウム（６７．０ｍｇ、０．９７１ｍｍｏｌ）の水（０．１ｍＬ）溶液を滴下した。その後、０℃から５℃を保ちながら３０分撹拌し、アミド硫酸（３２．０ｍｇ、０．３３０ｍｍｏｌ）の水（０．２ｍＬ）溶液を加え、ジアゾ液を調製した。一方、Ｎ，Ｎ－ジメチルアニリン（０．２３６ｇ、１．９５ｍｍｏｌ）、酢酸ナトリウム（０．３２０ｇ，３．９０ｍｍｏｌ）、メタノール（４．３ｍＬ）、および水（４．３ｍＬ）を混合して０℃から５℃に冷却し、先ほど調製したジアゾ液全量を滴下した。滴下終了後常温まで昇温し、析出した固体を濾別して化合物１－１－ｃを得た（０．２８２ｇ、収率９４％） Synthesis of compound 1-1-c
Compound 1-1-b (0.213 g, 0.651 mmol), 35% hydrochloric acid (0.20 mL, 2.10 mmol), acetic acid (3.5 mL) and water (0.9 mL) were mixed and heated from 0°C to 5°C. After cooling to °C, a solution of sodium nitrite (67.0 mg, 0.971 mmol) in water (0.1 mL) was added dropwise. After that, the mixture was stirred for 30 minutes while maintaining the temperature from 0°C to 5°C, and a solution of amidosulfuric acid (32.0 mg, 0.330 mmol) in water (0.2 mL) was added to prepare a diazo solution. Meanwhile, N,N-dimethylaniline (0.236 g, 1.95 mmol), sodium acetate (0.320 g, 3.90 mmol), methanol (4.3 mL), and water (4.3 mL) were mixed at 0°C. After cooling to 5° C., the whole amount of the diazo solution prepared earlier was added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature, and the precipitated solid was filtered off to obtain compound 1-1-c (0.282 g, yield 94%).
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
化合物１－１の合成
　化合物１－１－ｃ（０．２６０ｇ、０．５６６ｍｍｏｌ）、炭酸カリウム（０．１６２ｇ、１．１７ｍｍｏｌ）、メタノール（５．０ｍＬ）、およびテトラヒドロフラン（５．０ｍＬ）を混合し、常温で４時間撹拌した。反応溶液に塩化アンモニウム水溶液を加え中和し、有機層を濃縮し、酢酸エチルで希釈し水、および食塩水で分液した。有機層に硫酸マグネシウムで乾燥、濃縮して固体を得た。得た固体を、クロロホルムを展開溶媒としたシリカゲルカラムクロマトグラフィーにて精製し、さらにクロロホルム／メタノールからの再沈殿により精製し、化合物１－１を得た（０．１６４ｇ、収率６９％）。 Synthesis of compound 1-1 Mix compound 1-1-c (0.260 g, 0.566 mmol), potassium carbonate (0.162 g, 1.17 mmol), methanol (5.0 mL), and tetrahydrofuran (5.0 mL) and stirred at room temperature for 4 hours. An aqueous ammonium chloride solution was added to the reaction solution for neutralization, and the organic layer was concentrated, diluted with ethyl acetate, and separated with water and brine. The organic layer was dried over magnesium sulfate and concentrated to obtain a solid. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent, and further purified by reprecipitation from chloroform/methanol to obtain compound 1-1 (0.164 g, yield 69%).
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ（ｐｐｍ）＝１３．０７（ｓ，１Ｈ），８．２０（ｄ，２Ｈ），８．０５（ｄ，１Ｈ），７．９５－７．９２（ｍ，４Ｈ），７．５９（ｄｄ，１Ｈ），７．４９（ｄ，１Ｈ），６．７７（ｄ，２Ｈ），４．４３（ｑ，２Ｈ），３．１３（ｓ，６Ｈ）、１．４４（ｔ，３Ｈ）． 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 13.07 (s, 1H), 8.20 (d, 2H), 8.05 (d, 1H), 7.95-7.92 (m, 4H), 7.59 (dd, 1H), 7.49 (d, 1H), 6.77 (d, 2H), 4.43 (q, 2H), 3.13 (s, 6H) , 1.44(t, 3H).
　化合物１－１においてはＣＤＣｌ３中における水酸基の化学シフトが１３．０７ｐｐｍであり、分子内水素結合を形成していることを反映している。 In compound 1-1, the chemical shift of the hydroxyl group in CDCl 3 is 13.07 ppm, reflecting the formation of intramolecular hydrogen bonds.
実施例２：化合物１－２の合成
　化合物１－２を合成するために、まず化合物１－２－ａを合成し、続いて化合物１－２－ｂを経て化合物１－２－ｃおよび化合物１－２－ｄを合成した。続いて脱水縮合エステル化をして化合物１－２を得た。 Example 2 Synthesis of Compound 1-2 In order to synthesize compound 1-2, compound 1-2-a was first synthesized, followed by compound 1-2-b and then compound 1-2-c and compound 1. -2-d was synthesized. Subsequently, dehydration-condensation esterification was performed to obtain compound 1-2.
化合物１－２－ａの合成　
　亜硫酸水素ナトリウム（７８．０ｇ、７５０ｍｍｏｌ）、および水（１５０ｍＬ）を混合し、７０℃まで昇温し３７％ホルムアルデヒド水溶液（４４．３ｍＬ、６００ｍｍｏｌ）を滴下した。全量滴下後、４０℃まで冷却し、アニリン（４５．７ｍＬ、５００ｍｍｏｌ）を１時間で滴下し、９時間撹拌した。０℃まで冷却し、析出した固体を濾別し、化合物１－２－ａを得た（９６．０ｇ、収率１００％）。 Synthesis of compound 1-2-a
Sodium bisulfite (78.0 g, 750 mmol) and water (150 mL) were mixed, heated to 70° C., and 37% formaldehyde aqueous solution (44.3 mL, 600 mmol) was added dropwise. After dropping the entire amount, the mixture was cooled to 40° C., aniline (45.7 mL, 500 mmol) was added dropwise over 1 hour, and the mixture was stirred for 9 hours. After cooling to 0° C., the precipitated solid was filtered off to obtain compound 1-2-a (96.0 g, yield 100%).
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
化合物１－２－ｂの合成　
　４－アミノ－２－メトキシ安息香酸（８．３６ｇ、５０．０ｍｍｏｌ）、３５％塩酸（１３．２ｍＬ、１５０．０ｍｍｏｌ）、および水（１００ｍＬ）を混合して０℃から５℃に冷却し、そこへ亜硝酸ナトリウム（３．６２ｇ、５２．５ｍｍｏｌ）の水（７．０ｍＬ）溶液を滴下した。その後、０℃から５℃を保ちながら４時間撹拌し、ジアゾ液を調製した。一方、化合物１－２－ａ（１５．７ｇ、７５．０ｍｍｏｌ）、および水（２００ｍＬ）を混合して０℃から５℃に冷却し、先ほど調製したジアゾ液全量を滴下した。滴下終了後０℃から５℃で３時間撹拌し、常温まで昇温し１６時間撹拌した。その後、水酸化ナトリウム（２４．０ｇ、６００ｍｍｏｌ）を加え、９０℃まで昇温し２時間撹拌した。常温まで冷却し、塩酸（５２ｍＬ、５８９ｍｍｏｌ）を滴下し、析出した固体を濾別し、さらに水で洗浄して固体である化合物１－２－ｂを得た。精製せずに次のジアゾカップリングに供した。 Synthesis of compound 1-2-b
4-amino-2-methoxybenzoic acid (8.36 g, 50.0 mmol), 35% hydrochloric acid (13.2 mL, 150.0 mmol), and water (100 mL) were mixed and cooled to 0° C. to 5° C., A solution of sodium nitrite (3.62 g, 52.5 mmol) in water (7.0 mL) was added dropwise thereto. Thereafter, the mixture was stirred for 4 hours while maintaining the temperature from 0°C to 5°C to prepare a diazo solution. On the other hand, compound 1-2-a (15.7 g, 75.0 mmol) and water (200 mL) were mixed and cooled from 0° C. to 5° C., and the whole amount of the diazo solution prepared earlier was added dropwise. After completion of dropping, the mixture was stirred at 0° C. to 5° C. for 3 hours, heated to room temperature, and stirred for 16 hours. After that, sodium hydroxide (24.0 g, 600 mmol) was added, and the mixture was heated to 90°C and stirred for 2 hours. After cooling to room temperature, hydrochloric acid (52 mL, 589 mmol) was added dropwise, and the precipitated solid was separated by filtration and washed with water to obtain compound 1-2-b as a solid. It was subjected to the next diazo coupling without purification.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
化合物１－２－ｃの合成
　化合物１－２－ｂに３５％塩酸（８．８ｍＬ、１００．０ｍｍｏｌ）、酢酸（５０．０ｍＬ）、および水（５０．０ｍＬ）を混合して０℃から５℃に冷却し、そこへ亜硝酸ナトリウム（３．６２ｇ、５２．５ｍｍｏｌ）の水（７．０ｍＬ）溶液を滴下した。その後、０℃から５℃を保ちながら１時間撹拌し、ジアゾ液を調製した。一方、Ｎ，Ｎ－ジメチルアニリン（９．０８ｇ、７５．０ｍｍｏｌ）、酢酸ナトリウム（１６．４ｇ、２００ｍｍｏｌ）、メタノール（６７．０ｍＬ）および水（３４．０ｍＬ）を混合して０℃から５℃に冷却し、先ほど調製したジアゾ液全量を滴下した。滴下終了後０℃から５℃で２時間撹拌し、常温まで昇温し析出した固体を濾別し、さらにアセトニトリル／水で洗浄して化合物１－２－ｃを得た（１３．９ｇ、４－アミノ－２－メトキシ安息香酸基準の収率６９％）。 Synthesis of Compound 1-2-c Compound 1-2-b was mixed with 35% hydrochloric acid (8.8 mL, 100.0 mmol), acetic acid (50.0 mL), and water (50.0 mL) to give a reaction temperature of 0° C. to 5° C. After cooling to °C, a solution of sodium nitrite (3.62 g, 52.5 mmol) in water (7.0 mL) was added dropwise. Thereafter, the mixture was stirred for 1 hour while maintaining the temperature from 0°C to 5°C to prepare a diazo solution. Meanwhile, N,N-dimethylaniline (9.08 g, 75.0 mmol), sodium acetate (16.4 g, 200 mmol), methanol (67.0 mL) and water (34.0 mL) were mixed and heated at 0°C to 5°C. and the whole amount of the diazo solution prepared earlier was added dropwise. After the dropwise addition was completed, the mixture was stirred at 0° C. to 5° C. for 2 hours, heated to room temperature, and the precipitated solid was separated by filtration and washed with acetonitrile/water to obtain compound 1-2-c (13.9 g, 4 -69% yield based on amino-2-methoxybenzoic acid).
化合物１－２－ｄの合成
　化合物１－２－ｃ（１３．７ｇ、３４ｍｍｏｌ）、塩化リチウム（４．３２ｇ、１００ｍｍｏｌ）、Ｎ－メチル－２－ピロリドン（６８ｍＬ）、およびピリジン（２２．７ｍＬ）を混合し、１００℃まで昇温して１６時間撹拌した。その後、常温まで冷却し、塩酸（２８ｍＬ，３１７ｍｍｏｌ）を滴下し、析出した固体を濾別し、さらに水で洗浄して化合物１－２－ｄを得た（１５．０ｇ、収率１０４％）。 Synthesis of compound 1-2-d Compound 1-2-c (13.7 g, 34 mmol), lithium chloride (4.32 g, 100 mmol), N-methyl-2-pyrrolidone (68 mL), and pyridine (22.7 mL) were mixed, heated to 100° C. and stirred for 16 hours. Then, it was cooled to room temperature, hydrochloric acid (28 mL, 317 mmol) was added dropwise, and the precipitated solid was filtered off and washed with water to obtain compound 1-2-d (15.0 g, yield 104%). .
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
化合物１－２の合成
　化合物１－２－ｄ（６．３９ｇ、１５．０ｍｍｏｌ）、１－ブタノール（１３．８ｍＬ、１５０ｍｍｏｌ）、ＤＭＡＰ（２．０２ｇ、１６．５ｍｍｏｌ）、およびテトラヒドロフラン（５０．０ｍＬ）を混合し、ＥＤＣ・ＨＣｌ（４．３１ｇ、２２．５ｍｍｏｌ）を加え、反応溶液を５０℃まで昇温し４時間撹拌した。反応溶液に水（１５０ｍＬ）を加え、析出した固体を濾別し、メタノールで洗浄した。得られた固体を、クロロホルムを展開溶媒としたシリカゲルカラムクロマトグラフィーにて精製し、さらにクロロホルム／メタノールからの再沈殿により精製し、化合物１－２を得た（１．９３ｇ、収率２９％）。 Synthesis of compound 1-2 Compound 1-2-d (6.39 g, 15.0 mmol), 1-butanol (13.8 mL, 150 mmol), DMAP (2.02 g, 16.5 mmol), and tetrahydrofuran (50.0 mL) ), EDC.HCl (4.31 g, 22.5 mmol) was added, and the reaction solution was heated to 50° C. and stirred for 4 hours. Water (150 mL) was added to the reaction solution, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent, and further purified by reprecipitation from chloroform/methanol to obtain compound 1-2 (1.93 g, yield 29%). .
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ（ｐｐｍ）＝１０．９８（ｓ，１Ｈ），８．０７（ｄ，２Ｈ），８．０１－７．９８（ｍ，３Ｈ），７．９３（ｄｄ，２Ｈ），７．５２（ｄ，１Ｈ），７．４５（ｄｄ，１Ｈ），６．７８（ｄ，２Ｈ），４．４０（ｔ，２Ｈ），３．１２（ｓ，６Ｈ），１．８１（ｑｕｉｎ、２Ｈ），１．５６－１．４７（ｍ，２Ｈ），１．０１（ｔ，３Ｈ）． 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 10.98 (s, 1H), 8.07 (d, 2H), 8.01-7.98 (m, 3H), 7.93 (dd, 2H), 7.52 (d, 1H), 7.45 (dd, 1H), 6.78 (d, 2H), 4.40 (t, 2H), 3.12 (s, 6H) , 1.81 (quin, 2H), 1.56-1.47 (m, 2H), 1.01 (t, 3H).
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ（ｐｐｍ）＝１０．７８（ｂｒ，１Ｈ），８．０８（ｄ，２Ｈ），７．９９－７．９７（ｍ，３Ｈ），７．８６（ｄ，２Ｈ），７．４８（ｄｄ，１Ｈ），７．４５（ｄ，１Ｈ），６．８８（ｄ，２Ｈ），４．３６（ｔ，２Ｈ），３．１０（ｓ，６Ｈ），１．７４（ｑｕｉｎ，２Ｈ），１．５０－１．４１（ｍ，２Ｈ），０．９６（ｔ，３Ｈ） 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 10.78 (br, 1H), 8.08 (d, 2H), 7.99-7.97 (m, 3H), 7 .86 (d, 2H), 7.48 (dd, 1H), 7.45 (d, 1H), 6.88 (d, 2H), 4.36 (t, 2H), 3.10 (s, 6H), 1.74 (quin, 2H), 1.50-1.41 (m, 2H), 0.96 (t, 3H)
　化合物１－２においてはＣＤＣｌ３中の水酸基の化学シフトが１０．９８ｐｐｍであり、分子内水素結合を形成していることを反映している。また低極性重溶媒であるＣＤＣｌ３中と高極性重溶媒ＤＭＳＯ－ｄ６中での水酸基のプロトンの化学シフト（１０．７８ｐｐｍ）の差は０．２ｐｐｍと小さく、このことも分子内水素結合を形成していることを反映している。 In compound 1-2, the chemical shift of the hydroxyl group in CDCl 3 is 10.98 ppm, reflecting the formation of intramolecular hydrogen bonds. In addition, the difference in the chemical shifts (10.78 ppm) of the hydroxyl group protons in CDCl 3 , a low-polar heavy solvent, and in DMSO-d 6 , a highly polar heavy solvent, is as small as 0.2 ppm, which also indicates intramolecular hydrogen bonding. It reflects what is forming.
実施例３：化合物１－６４の合成
　ジアゾカップリング反応により化合物１－６４を得た。 Example 3: Synthesis of compound 1-64 Compound 1-64 was obtained by diazo coupling reaction.
化合物１－６４の合成
　４－アミノアゾベンゼン－４’－安息香酸ブチル（０．５９５ｇ、２．００ｍｍｏｌ）、酢酸（６．００ｍＬ）、水（６．００ｍＬ）、および３５％塩酸（０．５３０ｍＬ、６．００ｍｍｏｌ）を混合して０℃から５℃に冷却し、そこへ亜硝酸ナトリウム（０．１４６ｇ、２．１１ｍｍｏｌ）の水（０．４ｍＬ）溶液を滴下し、０℃から５℃を保ちながら３０分間撹拌してジアゾ液を調製した。一方、３－（ジメチルアミノ）フェノール（０．４１１ｇ、２．９９ｍｍｏｌ）、酢酸ナトリウム（０．６６２ｇ，８．０７ｍｍｏｌ）、水（５．０ｍＬ）、およびメタノール（７．５ｍＬ）を混合して０℃から５℃に冷却し、先ほど調製したジアゾ液全量を滴下し、０℃から５℃を維持したまま１時間攪拌した。常温まで昇温し、析出した固体を濾別した。得られた固体を、クロロホルム／メタノール（９９：３）を展開溶媒としたシリカゲルカラムクロマトグラフィーにて精製し、さらにクロロホルム／メタノールからの再沈殿により精製し、化合物１－６４を得た（０．１５３ｇ、収率１７％）。 Synthesis of Compound 1-64 Butyl 4-aminoazobenzene-4′-benzoate (0.595 g, 2.00 mmol), acetic acid (6.00 mL), water (6.00 mL), and 35% hydrochloric acid (0.530 mL, 6.00 mmol) was mixed and cooled to 0°C to 5°C, to which a solution of sodium nitrite (0.146 g, 2.11 mmol) in water (0.4 mL) was added dropwise, and the temperature was maintained at 0°C to 5°C. While stirring for 30 minutes, a diazo solution was prepared. Meanwhile, 3-(dimethylamino)phenol (0.411 g, 2.99 mmol), sodium acetate (0.662 g, 8.07 mmol), water (5.0 mL), and methanol (7.5 mL) were mixed to give 0 C. to 5.degree. C., the whole amount of the diazo solution prepared earlier was added dropwise, and the mixture was stirred for 1 hour while maintaining the temperature from 0.degree. C. to 5.degree. The temperature was raised to normal temperature, and the precipitated solid was separated by filtration. The resulting solid was purified by silica gel column chromatography using chloroform/methanol (99:3) as a developing solvent, and further purified by reprecipitation from chloroform/methanol to obtain compound 1-64 (0. 153 g, 17% yield).
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ（ｐｐｍ）＝１５．１４（ｂｒ，１Ｈ），８．２０（ｄ，２Ｈ），８．０５（ｄ，２Ｈ），７．９６（ｄ，２Ｈ），７．８３（ｄ，２Ｈ），７．５２（ｄ，２Ｈ），６．４８（ｄｄ，１Ｈ），６．０５（ｄ，１Ｈ），４．３７（ｔ，２Ｈ），３．１５（ｓ，６Ｈ），１．７９（ｑｕｉｎ，２Ｈ），１．５６―１．４７（ｍ，２Ｈ），１．０１（ｔ，３Ｈ）． 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 15.14 (br, 1H), 8.20 (d, 2H), 8.05 (d, 2H), 7.96 (d, 2H) ), 7.83 (d, 2H), 7.52 (d, 2H), 6.48 (dd, 1H), 6.05 (d, 1H), 4.37 (t, 2H), 3.15 (s, 6H), 1.79 (quin, 2H), 1.56-1.47 (m, 2H), 1.01 (t, 3H).
　化合物１－６４においてはＣＤＣｌ３中の水酸基の化学シフトが１５．１４ｐｐｍであり、分子内水素結合を形成していると推測される。 In compound 1-64, the chemical shift of the hydroxyl group in CDCl 3 is 15.14 ppm, suggesting the formation of intramolecular hydrogen bonds.
比較例１：化合物Ｃ－１の合成
　化合物Ｃ－１を合成するために、まず先述の化合物１－２－ａを合成した。続いて脱水縮合エステル化して化合物Ｃ－１を得た。 Comparative Example 1: Synthesis of Compound C-1 In order to synthesize Compound C-1, the aforementioned Compound 1-2-a was first synthesized. Subsequently, compound C-1 was obtained by dehydration-condensation esterification.
化合物Ｃ－１の合成
　化合物１－２－ａ（０．２９１ｇ、１．０１ｍｍｏｌ）、４－ｎ－ブチルレソルシノール（０．１９９ｇ、１．２０ｍｍｏｌ）、ＤＭＡＰ（７６．０ｍｇ、０．６２２ｍｍｏｌ）、およびテトラヒドロフラン（１０．０ｍＬ）を混合し、ＥＤＣ・ＨＣｌ（０．２３３ｇ、１．２２ｍｍｏｌ）を加え、反応溶液を常温で１８時間撹拌した。反応溶液に水を加え、析出した固体を濾別し、メタノールで洗浄した。得られた固体を、クロロホルムを展開溶媒としたシリカゲルカラムクロマトグラフィーにて精製し、さらに水／メタノールからの再沈殿により精製し、化合物Ｃ－１を得た（０．０６４ｇ、収率１２％）。 Synthesis of Compound C-1 Compound 1-2-a (0.291 g, 1.01 mmol), 4-n-butylresorcinol (0.199 g, 1.20 mmol), DMAP (76.0 mg, 0.622 mmol), and tetrahydrofuran (10.0 mL) were mixed, EDC.HCl (0.233 g, 1.22 mmol) was added and the reaction solution was stirred at ambient temperature for 18 hours. Water was added to the reaction solution, and the precipitated solid was separated by filtration and washed with methanol. The obtained solid was purified by silica gel column chromatography using chloroform as a developing solvent, and further purified by reprecipitation from water/methanol to obtain compound C-1 (0.064 g, yield 12%). .
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ（ｐｐｍ）＝８．１８（ｔ，１Ｈ），７．９２（ｄ，２Ｈ），７．７３（ｄｄ，１Ｈ），７．６３（ｄｄ，１Ｈ），７．１５（ｄ，１Ｈ），６．７９－６．７２（ｍ，４Ｈ），４．７７（ｓ，１Ｈ），３．１４（ｓ，６Ｈ），２．６１（ｔ，２Ｈ），１．６５－１．５７（ｍ，２Ｈ），１．４５－１．３６（ｍ，２Ｈ），０．９６（ｔ，３Ｈ）． 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 8.18 (t, 1H), 7.92 (d, 2H), 7.73 (dd, 1H), 7.63 (dd, 1H) ), 7.15 (d, 1H), 6.79-6.72 (m, 4H), 4.77 (s, 1H), 3.14 (s, 6H), 2.61 (t, 2H) , 1.65-1.57 (m, 2H), 1.45-1.36 (m, 2H), 0.96 (t, 3H).
１Ｈ－ＮＭＲ（４００ＭＨｚ、ＤＭＳＯ－ｄ６）：δ（ｐｐｍ）＝９．６４（ｂｒ，１Ｈ）、８．１９（ｔ，１Ｈ），７．８７（ｄ，２Ｈ），７．７６（ｄｄ，１Ｈ），７．６７（ｄｄ，１Ｈ），７．１１（ｄ，１Ｈ），６．８８（ｄ，２Ｈ），６．６９（ｄ，１Ｈ），６．６４（ｄｄ，１Ｈ），３．１２（ｓ，６Ｈ），１．５３（ｑｕｉｎ，２Ｈ），１．３８－１．２８（ｍ，２Ｈ），０．９１（ｔ，３Ｈ）． 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 9.64 (br, 1H), 8.19 (t, 1H), 7.87 (d, 2H), 7.76 (dd , 1H), 7.67 (dd, 1H), 7.11 (d, 1H), 6.88 (d, 2H), 6.69 (d, 1H), 6.64 (dd, 1H), 3 .12 (s, 6H), 1.53 (quin, 2H), 1.38-1.28 (m, 2H), 0.91 (t, 3H).
　実施例の化合物と異なり、Ｃ－１においてはＣＤＣｌ３中の水酸基の化学シフトが４．７７ｐｐｍであり、分子内水素結合を形成していないことを反映している。また低極性重溶媒であるＣＤＣｌ３中と高極性重溶媒ＤＭＳＯ－ｄ６中での水酸基のプロトンの化学シフト（９．６４ｐｐｍ）の差は４．８７ｐｐｍと大きく、重溶媒の極性差による影響を大きく受けることがわかった。このことも分子内で水素結合を形成していないことを反映している。 Unlike the compounds of the examples, the chemical shift of the hydroxyl group in CDCl 3 is 4.77 ppm in C-1, reflecting the lack of formation of intramolecular hydrogen bonds. In addition, the difference in the chemical shift (9.64 ppm) of the hydroxyl group proton in the low-polar heavy solvent CDCl 3 and in the high-polar heavy solvent DMSO-d 6 is as large as 4.87 ppm, and the effect of the polarity difference between the heavy solvents is large. I have found it to be greatly received. This also reflects that no hydrogen bond is formed in the molecule.
実施例１１：化合物１－１を含む組成物Ｅ１１の調製
　下記の成分を混合し、８０℃で１時間攪拌することで、組成物Ｅ１を得た。
・重合性液晶化合物（Ａ－６）　　７５質量部
・重合性液晶化合物（Ａ－７）　　２５質量部
・化合物（１－１）　　　　　　　４．０質量部
・重合開始剤：　２－ジメチルアミノ－２－ベンジル－１－（４－モルホリノフェニル）ブタン－１－オン（イルガキュア３６９；ＢＡＳＦジャパン社製）
　　　　　　　　　　　　　　　　６質量部
・レベリング剤：ポリアクリレート化合物（ＢＹＫ－３６１Ｎ；ＢＹＫ－Ｃｈｅｍｉｅ社製）　　　　　　　　　　　　　　１．２質量部
・溶剤：ｏ－キシレン　　　　　　２５０質量部 Example 11 Preparation of Composition E11 Containing Compound 1-1 Composition E1 was obtained by mixing the following components and stirring at 80° C. for 1 hour.
・Polymerizable liquid crystal compound (A-6) 75 parts by mass ・Polymerizable liquid crystal compound (A-7) 25 parts by mass ・Compound (1-1) 4.0 parts by mass ・Polymerization initiator: 2-dimethylamino-2- Benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan)
6 parts by mass Leveling agent: 1.2 parts by mass of polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) Solvent: 250 parts by mass of o-xylene
　重合性液晶化合物（Ａ－６） Polymerizable liquid crystal compound (A-6)
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　重合性液晶化合物（Ａ－７） Polymerizable liquid crystal compound (A-7)
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　なお、重合性液晶化合物（Ａ－６）は、Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996)に記載の方法で合成した。また、この方法に準拠して、重合性液晶化合物（Ａ－７）を製造した。 The polymerizable liquid crystal compound (A-6) was synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). In accordance with this method, a polymerizable liquid crystal compound (A-7) was produced.
実施例１２および１３：組成物Ｅ１２およびＥ１３の調製
　化合物１－１の代わりに、化合物１－２および１－６４をそれぞれ用いたこと以外は実施例１１と同様にして、実施例１２および１３の組成物Ｅ１２およびＥ１３をそれぞれ得た。 Examples 12 and 13: Preparation of Compositions E12 and E13 The compositions of Examples 12 and 13 were prepared in the same manner as in Example 11, except that Compounds 1-2 and 1-64, respectively, were used in place of Compound 1-1. Compositions E12 and E13 were obtained respectively.
比較例１：組成物Ｃ１１の調製
　化合物１－１の代わりに、合成法を先述した化合物Ｃ－１を用いたこと以外は実施例１１と同様にして、比較例１１の組成物Ｃ１１を得た。 Comparative Example 1: Preparation of Composition C11 Composition C11 of Comparative Example 11 was obtained in the same manner as in Example 11 except that compound C-1 whose synthesis method was described above was used instead of compound 1-1. .
偏光板の製造
１．配向膜の形成 
　透明基材としてガラス基板を用いた。ガラス基板上に、ポリビニルアルコール（ポリビニルアルコール１０００完全ケン化型、和光純薬工業株式会社製）の２質量％水溶液（配向層形成用組成物）をスピンコート法により塗布し、乾燥後、厚さ１００ｎｍの膜を形成した。続いて、得られた膜の表面にラビング処理を施すことにより配向膜を形成し、ガラス基板上に配向膜が形成された基材を得た。 Production of polarizing plate 1. Formation of alignment film
A glass substrate was used as a transparent substrate. A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) (composition for forming an alignment layer) is applied onto a glass substrate by spin coating, and after drying, the thickness is A film of 100 nm was formed. Subsequently, the surface of the obtained film was subjected to a rubbing treatment to form an alignment film, thereby obtaining a substrate having an alignment film formed on a glass substrate.
２．偏光膜の形成
　上記で得られた基材の配向膜上に、上記で得られた組成物をスピンコート法により塗布し、１２０℃のホットプレート上で３分間加熱乾燥した後、速やかに７０℃（降温時にスメクチック液晶相を示す温度）以下に冷却して、配向膜上に乾燥皮膜が形成された積層体を得た。 2. Formation of polarizing film On the alignment film of the substrate obtained above, the composition obtained above is applied by a spin coating method, dried by heating on a hot plate at 120 ° C. for 3 minutes, and then quickly brought to 70 ° C. (The temperature at which a smectic liquid crystal phase is exhibited when the temperature is lowered) or less to obtain a laminate having a dry film formed on the alignment film.
　次いで、ＵＶ照射装置（ＳＰＯＴ　ＣＵＲＥ　ＳＰ－７；ウシオ電機株式会社製）を用い、紫外線を、露光量１０００ｍＪ／ｃｍ２（３６５ｎｍ基準）で乾燥皮膜に照射することにより、乾燥皮膜に含まれる重合性液晶化合物を、組成物の液晶状態を保持したまま重合させ、乾燥皮膜から偏光膜を形成して偏光板を得た。 Next, using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.), the dry film is irradiated with ultraviolet rays at an exposure amount of 1000 mJ/cm 2 (365 nm standard), thereby removing the polymerizability contained in the dry film. The liquid crystal compound was polymerized while maintaining the liquid crystal state of the composition, and a polarizing film was formed from the dry film to obtain a polarizing plate.
＜評価＞
　得られた偏光板について、以下のようにして二色比の測定を行った。偏光板の偏光膜の極大吸収波長（λmax）における透過軸方向の吸光度（Ａ１）及び吸収軸方向の吸光度（Ａ２）を、分光光度計（島津製作所株式会社製　ＵＶ－３１５０）に、偏光板を備えるフォルダーをセットした装置を用いて、ダブルビーム法で測定した。該フォルダーには、リファレンス側に光量を５０％カットするメッシュを設置した。測定された透過軸方向の吸光度（Ａ１）及び吸収軸方向の吸光度（Ａ２）の値から、比（Ａ２／Ａ１）を算出し、二色比（ＤＲ）とした。結果を表１に示す。 <Evaluation>
The dichroic ratio of the obtained polarizing plate was measured as follows. The absorbance (A1) in the direction of the transmission axis and the absorbance (A2) in the direction of the absorption axis at the maximum absorption wavelength (λmax) of the polarizing film of the polarizing plate are measured with a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation), and the polarizing plate is measured. It was measured by the double beam method using a device in which the provided folder was set. The folder was provided with a mesh that cuts the amount of light by 50% on the reference side. A ratio (A2/A1) was calculated from the measured absorbance (A1) in the direction of the transmission axis and absorbance (A2) in the direction of the absorption axis, and was defined as the dichroic ratio (DR). Table 1 shows the results.
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
　表１から式（１）で表される化合物を含む組成物を形成材料とする膜を備える偏光板は高い二色比を実現できることがわかる。 From Table 1, it can be seen that a polarizing plate provided with a film containing a composition containing the compound represented by formula (1) as a forming material can achieve a high dichroic ratio.

Claims (12)

  1. 　下記式（１）で表される化合物と、重合性液晶化合物および液晶性の高分子化合物の少なくとも一方を含む液晶性化合物とを含む組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式（１）中、ｎは、１または２の整数を表す。
    　Ａｒ１、Ａｒ２およびＡｒ３は、それぞれ独立に、置換基を有していてもよい、１，４－フェニレン基または含硫黄複素環基を表す。Ａｒ１、Ａｒ２およびＡｒ３の少なくとも１つは、分子内水素結合を形成し得る水酸基を少なくとも１つ有する。
    　Ｒ１は、重合性基を有していてもよいアルキルアミノ基を表す。
    　Ａｒ１が分子内水素結合を形成し得る水酸基を、有さないか、またはアゾ基のオルト位に有する場合、Ｒ２は、炭素数４から２０のアルカンジイル基、炭素数２から２０のアルカンジイルオキシ基、炭素数２から２０のアルカンジイルオキシカルボニル基、炭素数２から２０のアルカンジイルカルボニル基および炭素数２から２０のアルカンジイルカルボニルオキシ基からなる群より選択される少なくとも１つの基を表す。
    　Ａｒ１が分子内水素結合を形成し得る水酸基をＲ２のオルト位に有する場合、Ｒ２は、その水酸基と水素結合を形成し得る環状または鎖状である炭素数２から２０の基を表す。
    　Ｒ３は、重合性基または水素原子を表す。
    　ｎが２である場合、２つのＡｒ２は互いに同一であっても相異なっていてもよい。］     A composition comprising a compound represented by the following formula (1) and a liquid crystal compound containing at least one of a polymerizable liquid crystal compound and a liquid crystal polymer compound.
    Figure JPOXMLDOC01-appb-C000001
     [In formula (1), n represents the integer of 1 or 2.
    Ar 1 , Ar 2 and Ar 3 each independently represent an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group. At least one of Ar 1 , Ar 2 and Ar 3 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond.
    R 1 represents an alkylamino group optionally having a polymerizable group.
    When Ar 1 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond or has a hydroxyl group ortho to the azo group, R 2 is an alkanediyl group having 4 to 20 carbon atoms, an alkane having 2 to 20 carbon atoms at least one group selected from the group consisting of a diyloxy group, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediylcarbonyl group having 2 to 20 carbon atoms and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms; show.
    When Ar 1 has a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 2 , R 2 represents a cyclic or linear group having 2 to 20 carbon atoms capable of forming a hydrogen bond with the hydroxyl group. .
    R3 represents a polymerizable group or a hydrogen atom.
    When n is 2, two Ar 2 may be the same or different. ]
  2. 　前記重合性液晶化合物が重合性スメクチック液晶化合物であり、前記液晶性の高分子化合物がスメクチック液晶性の高分子化合物である請求項１に記載の組成物。 The composition according to claim 1, wherein the polymerizable liquid crystal compound is a polymerizable smectic liquid crystal compound, and the liquid crystalline polymer compound is a smectic liquid crystalline polymer compound.
  3. 　前記重合性液晶化合物が、下記式（Ａ）で表される化合物を含む請求項１または２に記載の組成物。
    Figure JPOXMLDOC01-appb-C000002
     ［式（Ａ）中、ｍは１から３の整数を表す。
    　Ｘ１、Ｘ２およびＸ３は、それぞれ独立に、２価の芳香族基または２価の脂環式炭化水素基を表す。ｍが２または３である場合、複数あるＸ１は互いに同一であっても相異なっていてもよい。Ｘ１、Ｘ２およびＸ３からなる群から選択される少なくとも３つが２価の炭化水素６員環基を表す。
    　Ｙ１、Ｙ２、Ｗ１およびＷ２は、それぞれ独立に、単結合または２価の連結基を表す。ｍが２または３である場合、複数あるＹ１は互いに同一であっても相異なっていてもよい。
    　Ｖ１およびＶ２は、それぞれ独立に、置換基を有していてもよい炭素数１から２０のアルカンジイル基を表す。前記アルカンジイル基を構成する－ＣＨ２－の少なくとも１つは、－Ｏ－、－ＣＯ－、－Ｓ－または－ＮＨ－に置き換わっていてもよい。
    　Ｕ１およびＵ２は、それぞれ独立に、重合性基または水素原子を表し、少なくとも一方は重合性基を表す。］     3. The composition according to claim 1, wherein the polymerizable liquid crystal compound contains a compound represented by the following formula (A).
    Figure JPOXMLDOC01-appb-C000002
     [In the formula (A), m represents an integer of 1 to 3.
    X 1 , X 2 and X 3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. When m is 2 or 3, multiple X 1 may be the same or different. At least three selected from the group consisting of X 1 , X 2 and X 3 represent a divalent hydrocarbon 6-membered ring group.
    Y 1 , Y 2 , W 1 and W 2 each independently represent a single bond or a divalent linking group. When m is 2 or 3, a plurality of Y 1 may be the same or different.
    V 1 and V 2 each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms. At least one of -CH 2 - constituting the alkanediyl group may be replaced with -O-, -CO-, -S- or -NH-.
    U 1 and U 2 each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group. ]
  4. 　前記式（１）で表される化合物は、分子内水素結合を形成し得る水酸基数が１である請求項１から３のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 3, wherein the compound represented by formula (1) has one hydroxyl group capable of forming an intramolecular hydrogen bond.
  5. 　上記式（１）で表される化合物は、Ｒ３と分子内水素結合し得る水酸基をＡｒ１に有するか、または－Ｎ＝Ｎ－と分子内で水素結合し得る水酸基をＡｒ２に有する請求項１から４のいずれか１項に記載の組成物。 The compound represented by the above formula (1) has a hydroxyl group capable of forming an intramolecular hydrogen bond with R 3 in Ar 1 , or a hydroxyl group capable of forming an intramolecular hydrogen bond with -N=N- in Ar 2 . Item 5. The composition according to any one of Items 1 to 4.
  6. 　下記式（１ａ）で表される化合物。
    Figure JPOXMLDOC01-appb-C000003
     ［式（１ａ）中、ｋは、１または２の整数を表す。
    　Ａｒ１１、Ａｒ１２およびＡｒ１３は、それぞれ独立に、置換基を有していてもよい１，４－フェニレン基又は含硫黄複素環基を表す。Ａｒ１１およびＡｒ１２の少なくとも一方は、分子内水素結合を形成し得る水酸基を少なくとも１つ有する。　
    　Ｒ１１は、重合性基を有していてもよいアルキルアミノ基を表す。
    　Ａｒ１１が分子内水素結合を形成し得る水酸基を、有さないか、またはアゾ基のオルト位に有する場合、Ｒ１２は、炭素数４から２０のアルカンジイル基、炭素数２から２０のアルカンジイルオキシ基、炭素数２から２０のアルカンジイルオキシカルボニル基、炭素数２から２０のアルカンジイルカルボニル基および炭素数２から２０のアルカンジイルカルボニルオキシ基からなる群より選択される少なくとも１つの基を表す。
    　Ａｒ１１が分子内水素結合を形成し得る水酸基をＲ１２のオルト位に有する場合、Ｒ１２は、その水酸基と水素結合を形成し得る環状または鎖状である炭素数２から２０の基を表す。
    　Ｒ１３は、重合性基または水素原子を表す。
    　ｋが２である場合、２つのＡｒ１２は互いに同一であっても相異なっていてもよい。］     A compound represented by the following formula (1a).
    Figure JPOXMLDOC01-appb-C000003
     [In Formula (1a), k represents an integer of 1 or 2.
    Ar 11 , Ar 12 and Ar 13 each independently represent an optionally substituted 1,4-phenylene group or a sulfur-containing heterocyclic group. At least one of Ar 11 and Ar 12 has at least one hydroxyl group capable of forming an intramolecular hydrogen bond.
    R 11 represents an alkylamino group optionally having a polymerizable group.
    When Ar 11 does not have a hydroxyl group capable of forming an intramolecular hydrogen bond or has a hydroxyl group ortho to the azo group, R 12 is an alkanediyl group having 4 to 20 carbon atoms, an alkane having 2 to 20 carbon atoms at least one group selected from the group consisting of a diyloxy group, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, an alkanediylcarbonyl group having 2 to 20 carbon atoms and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms; show.
    When Ar 11 has a hydroxyl group capable of forming an intramolecular hydrogen bond at the ortho position of R 12 , R 12 represents a cyclic or linear group having 2 to 20 carbon atoms capable of forming a hydrogen bond with the hydroxyl group. .
    R13 represents a polymerizable group or a hydrogen atom.
    When k is 2, two Ar 12 may be the same or different. ]
  7. 　分子内水素結合を形成し得る水酸基数が１である請求項６に記載の化合物。 The compound according to claim 6, wherein the number of hydroxyl groups capable of forming an intramolecular hydrogen bond is 1.
  8. 　Ａｒ１１、Ａｒ１２およびＡｒ１３は、置換基を有していてもよい１，４－フェニレン基である請求項６または７に記載の化合物。 8. The compound according to claim 6 or 7, wherein Ar 11 , Ar 12 and Ar 13 are optionally substituted 1,4-phenylene groups.
  9. 　Ｒ１３と分子内水素結合を形成し得る水酸基をＡｒ１１に有するか、または－Ｎ＝Ｎ－と分子内で水素結合し得る水酸基をＡｒ２に有する請求項６から８のいずれか１項に記載の化合物。 9. Any one of claims 6 to 8, wherein Ar 11 has a hydroxyl group capable of forming an intramolecular hydrogen bond with R 13 , or Ar 2 has a hydroxyl group capable of forming an intramolecular hydrogen bond with -N=N- Compound as described.
  10. 　請求項１から５のいずれか１項に記載の組成物を形成材料とする膜。 A film using the composition according to any one of claims 1 to 5 as a forming material.
  11. 　請求項１０に記載の膜を含む積層体。 A laminate comprising the film according to claim 10.
  12. 　請求項１１に記載の積層体を備える表示装置。 A display device comprising the laminate according to claim 11.
PCT/JP2022/023927 2021-06-30 2022-06-15 Compound, composition, film, laminate, and display device WO2023276668A1 (en)

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