WO2024043261A1 - Azo compound or salt thereof, and polarizing film, polarizing plate and liquid crystal display device comprising same - Google Patents

Azo compound or salt thereof, and polarizing film, polarizing plate and liquid crystal display device comprising same Download PDF

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Publication number
WO2024043261A1
WO2024043261A1 PCT/JP2023/030256 JP2023030256W WO2024043261A1 WO 2024043261 A1 WO2024043261 A1 WO 2024043261A1 JP 2023030256 W JP2023030256 W JP 2023030256W WO 2024043261 A1 WO2024043261 A1 WO 2024043261A1
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group
formula
azo compound
polarizing
groups
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PCT/JP2023/030256
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French (fr)
Japanese (ja)
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陵太郎 森田
悠衣 横山
大地 藤原
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日本化薬株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/23—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/08—Disazo dyes from a coupling component "C" containing directive hydroxyl and amino groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/16—Trisazo dyes
    • C09B31/22—Trisazo dyes from a coupling component "D" containing directive hydroxyl and amino groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/30—Other polyazo dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to novel azo compounds or salts thereof, and polarizing films, polarizing plates, and liquid crystal display devices containing them.
  • a polarizing plate that has a light transmission/shielding function is a basic component of a display device such as a liquid crystal display (LCD), along with a liquid crystal that has a light switching function.
  • LCD liquid crystal display
  • the fields of application of this LCD range from small devices such as calculators and watches in the early days to notebook computers, word processors, liquid crystal projectors, liquid crystal televisions, car navigation systems, and indoor and outdoor measuring instruments. It can also be applied to lenses having a polarizing function, and has been applied to sunglasses with improved visibility and, in recent years, polarized glasses compatible with 3D televisions and the like.
  • polarizing plates As the above-mentioned applications of polarizing plates are widespread, they are used under a wide range of conditions from low to high temperatures, low to high humidity, and low to high light levels, so they have high polarizing performance and high durability. There is a need for a polarizing plate that has the following characteristics.
  • polarizing plates are produced by dyeing or impregnating a film of polyvinyl alcohol or its derivatives with iodine or a dichroic dye, stretching and orienting the film, or by removing hydrochloric acid from a polyvinyl chloride film or dehydrating a polyvinyl alcohol film. Manufactured by generating and orienting. These are substances that greatly affect the polarization characteristics and durability of the polarizing plate.
  • An iodine-based polarizing film using iodine has excellent polarizing performance, but is sensitive to water and heat, and has problems with its durability when used for long periods of time in high temperature and high humidity conditions.
  • methods such as treating with formalin or an aqueous solution containing boric acid and using a polymer film with low moisture permeability as a protective film have been considered, but the effects are not sufficient.
  • dye-based polarizing films using dyes have better moisture resistance and heat resistance than iodine-based polarizing films, but generally do not have sufficient polarizing performance.
  • Dye-based neutral gray polarizing plates are generally manufactured by combining multiple types of dyes, but the polarizing performance of dye-based neutral gray polarizing plates is not sufficient, and two-color polarizing plates with good polarization performance for each color used are used. It was necessary to develop a sex dye.
  • Examples of the dye-based polarizing film described above include dye-based polarizing films using water-soluble azo compounds described in Patent Documents 1 to 3, and recently, in order to improve the performance of dichroic dyes, Although the 1-naphthol-3-sulfonic acid derivative described in Patent Document 2 has been developed, sufficient polarization properties have not yet been obtained, and further improvement in performance has been desired.
  • One of the objects of the present invention is to provide a dichroic dye, a polarizing film, and a polarizing plate having excellent polarization performance
  • another object of the present invention is to provide a dichroic dye, a polarizing film, and a polarizing plate having excellent polarization performance.
  • the objective is to provide a neutral gray polarizing plate with less color bleeding.
  • another object of the present invention is to provide a high-performance polarizing plate having excellent polarizing performance and durability (heat resistance, moisture resistance, or light resistance), and to make this possible, novel
  • the purpose of this invention is to provide a dichroic dye (azo compound).
  • the present invention relates to the following [1] to [9].
  • Azo compound or its salt represented by the following formula (1) (In formula (1), Ar represents a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a heterocycle which may have a substituent, and A is any substituent. ).
  • the azo compound or salt thereof of the present invention is useful as a dye for polarizing films.
  • the polarizing film and polarizing plate of the present invention have excellent polarizing performance.
  • the polarizing plate having a neutral gray color according to the present invention exhibits a high-performance achromatic color without orthogonal color leakage in the wavelength region of the visible light region.
  • the polarizing film and polarizing plate of the present invention have excellent polarizing performance (transmittance, contrast) and durability (moisture resistance, heat resistance, light resistance).
  • an "azo compound or a salt thereof” may be simply referred to as an "azo compound” unless it clearly represents a free form.
  • a "substituent” may include a hydrogen atom, a hydrogen atom may be referred to as a “substituent” for convenience.
  • the term “may have a substituent” means that the term “may have a substituent” also includes the case where the compound does not have a substituent.
  • a phenyl group which may have a substituent includes a simple unsubstituted phenyl group and a phenyl group having a substituent.
  • lower in the lower alkyl group, lower alkoxy group, etc. in the present application refers to a group having 1 to 4 carbon atoms (C 1 -C 4 ), preferably 1 to 3 (C 1 -C 3 ) . ).
  • the azo compound or salt thereof of the present invention has a 1-naphthol-3-sulfonic acid derivative substituted with an isoindolyl group represented by the following formula (1).
  • Ar represents a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a heterocycle which may have a substituent, and A is any substituent. (indicates the group)
  • Ar represents a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a heterocycle which may have a substituent, and A is any substituent. Indicates the group.
  • Examples of the above-mentioned optional substituents and the optional substituent represented by A include a diazenyl group, a heterocyclic amino group, a condensed heterocyclic amino group, an alkyl group, an alkoxy group, an aryloxy group, Alkylcarbonylamino group, arylcarbonylamino group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylcarbonyl group, arylcarbonyl group, alkylcarbamoyl group, arylcarbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonylamino group, Arylsulfonylamino group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkylureido
  • heterocyclic amino group examples include a 5- or 6-membered heterocyclic amino group containing 1 to 3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom.
  • heterocyclic amino groups include, for example, 5-membered heteroalicyclic amino groups such as pyrrolidinylamino, tetrahydrofurylamino, tetrahydrothiophen-2-ylamino, and tetrahydrothiophen-3-ylamino; 6-membered heteroalicyclic amino groups such as piperidinylamino, piperazinylamino, dioxan-2-ylamino, morpholinylamino, thiomorpholinylamino; 5-membered aromatic heterocyclic amino groups such as pyrrole amino, pyrazole amino, imidazolamino, triazole amino, furylamino, thiophen-2-ylamino, thi
  • the above condensed heterocyclic amino group includes one benzene ring in a 5- or 6-membered heterocyclic group containing 1 to 3 heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms.
  • Examples include a condensed 5- or 6-membered ring heterocyclic amino group.
  • condensed heterocyclic amino groups include, for example, A condensed heteroalicyclic amino group in which the heterocyclic moiety is a 5-membered alicyclic structure such as phthalanylamino; A fused-ring type heteroalicyclic amino group in which the heterocyclic moiety is a 6-membered alicyclic structure such as benzopyranyl amino;
  • the heterocyclic moiety is aromatic, such as benzopyrrolamino, benzopyrazoleamino, benzimidazolamino, benzotriazoleamino, benzofuranylamino, benzothiophen-2-ylamino, benzothiophen-3-ylamino, benzoxazoleamino, benzothiazoleamino, etc.
  • heterocyclic moiety is a 6-membered aromatic ring, such as quinolinylamino, cinnolinylamino, phthalazinylamino, quinazolinylamino, and quinoxalinylamino.
  • the heterocyclic moiety is preferably an aromatic ring.
  • the heteroatom constituting the heterocycle is preferably selected from nitrogen atoms and sulfur atoms.
  • alkyl group examples include linear, branched or cyclic alkyl groups, preferably C 1 -C 10 alkyl groups.
  • C 1 -C 10 alkyl groups include, for example: Straight chain C 1 -C 10 alkoxy groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; Branched C such as isopropyl, isobutyl, sec-butyl, t-butyl, isoamyl, t-amyl, isohexyl, t-hexyl, isoheptyl, t-heptyl, isooctyl, t-octyl, 2-ethylhexyl, isononyl, isodecyl, etc.
  • 3 -C 10 alkyl group examples include cyclic C 3 -C 7 alkoxy groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Among these, linear or branched alkoxy groups are preferred, and linear or branched C 1 -C 4 alkyl groups are more preferred.
  • alkoxy group examples include linear, branched or cyclic alkoxy groups, preferably C 1 -C 10 alkoxy groups.
  • C 1 -C 10 alkoxy groups include, for example: Straight chain C 1 -C 10 alkoxy groups such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptoxy, n-octyloxy, n-nonyloxy, n-decyloxy; Branched chains such as isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isoamyloxy, t-amyloxy, isohexyloxy, t-hexyloxy, isoheptoxy, t-heptoxy, isooctyloxy, t-octyloxy, 2-ethylhexyloxy, isononyloxy, isodesyloxy,
  • a C 3 -C 10 alkoxy group or examples include cyclic C 3 -C 7 alkoxy groups such as cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, and cycloheptoxy.
  • linear or branched alkoxy groups are preferred, and linear or branched C 1 -C 4 alkoxy groups are more preferred.
  • the alkoxy group may be an alkoxy group having a substituent, for example, a C 1 -C 4 alkoxy group having a sulfo group.
  • the "C 1 -C 4 alkoxy group having a sulfo group” is preferably a straight chain alkoxy group, and the substitution position of the sulfo group is preferably at the terminal of the alkoxy group. More preferred are 3-sulfopropoxy group and 4-sulfobutoxy group, particularly preferred is 3-sulfopropoxy group.
  • the above aryloxy group is preferably a C 6 -C 12 aryloxy group, and specific examples include phenoxy, naphthyloxy, biphenyloxy and the like.
  • alkylcarbonylamino group examples include linear, branched or cyclic alkylcarbonylamino groups, preferably C 1 -C 10 alkylcarbonylamino groups.
  • Specific examples of the C 1 -C 10 alkylcarbonylamino group include, for example, Methylcarbonylamino (acetylamino), ethylcarbonylamino, n-propylcarbonylamino, n-butylcarbonylamino, n-pentylcarbonylamino, n-hexylcarbonylamino, n-heptylcarbonylamino, n-octylcarbonylamino, n- Straight-chain C 1 -C 10 alkylcarbonylamino groups such as nonylcarbonylamino and n-decylcarbonylamino; Isopropylcarbonylamino, isobutylcarbonylamino, sec-butylcarbony
  • the above arylcarbonylamino group is preferably a C 6 -C 12 arylcarbonylamino group, and specific examples include phenylcarbonylamino (benzoylamino), naphthylcarbonylamino, biphenylcarbonylamino, and the like.
  • the alkylcarbonyloxy group mentioned above includes a linear, branched or cyclic alkylcarbonyloxy group, preferably a C 1 -C 10 alkylcarbonyloxy group.
  • Specific examples of the C 1 -C 10 alkylcarbonyloxy group include, for example, Methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, n-butylcarbonyloxy, n-pentylcarbonyloxy, n-hexylcarbonyloxy, n-heptylcarbonyloxy, n-octylcarbonyloxy, n-nonylcarbonyloxy, a linear C 1 -C 10 alkylcarbonyloxy group such as n-decylcarbonyloxy; Isopropylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, t-butylcarbonyloxy, isoa
  • arylcarbonyloxy group is preferably a C 6 -C 12 arylcarbonyloxy group, and specific examples include phenylcarbonyloxy, naphthylcarbonyloxy, biphenylcarbonyloxy and the like.
  • the alkylcarbonyl group mentioned above includes a straight chain, branched chain or cyclic alkylcarbonyl group, preferably a C 1 -C 10 alkylcarbonyl group.
  • Specific examples of the C 1 -C 10 alkylcarbonyl group include, for example, Straight chain C such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, n-pentylcarbonyl, n-hexylcarbonyl, n-heptylcarbonyl, n-octylcarbonyl, n-nonylcarbonyl, n-decylcarbonyl 1 -C 10 alkylcarbonyl group; Isopropylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, t-butylcarbonyl, isoamylcarbonyl, t-amylcarbonyl, isohex
  • the arylcarbonyl group is preferably a C 6 -C 12 arylcarbonyl group, and specific examples include phenylcarbonyl (benzoyl), naphthylcarbonyl, biphenylcarbonyl, and the like.
  • alkylcarbamoyl group examples include linear, branched, or cyclic monoalkylcarbamoyl groups or dialkylcarbamoyl groups.
  • the monoalkylcarbamoyl group is preferably a mono-C 1 -C 10 alkylcarbamoyl group, and specific examples include, for example, Straight-chain carbamoyl, ethylcarbamoyl, n-propylcarbamoyl, n-butylcarbamoyl, n-pentylcarbamoyl, n-hexylcarbamoyl, n-heptylcarbamoyl, n-octylcarbamoyl, n-nonylcarbamoyl, n-decylcarbamoyl mono C 1 -C 10 alkylcarbamoyl group; Isopropylcarbamoyl, isobutylcarbamoyl, sec-butylcarbamoyl, t-butylcarbamoyl, isoamylcarbamoyl
  • the dialkylcarbamoyl group is preferably a di-C 1 -C 10 alkylcarbamoyl group, and specific examples include, for example, Dimethylcarbamoyl, diethylcarbamoyl, di-n-propylcarbamoyl, di-n-butylcarbamoyl, di-n-pentylcarbamoyl, di-n-hexylcarbamoyl, di-n-heptylcarbamoyl, di-n-octylcarbamoyl, di- Straight-chain di-C 1 -C 10 alkylcarbamoyl groups such as n-nonylcarbamoyl and di-n-decylcarbamoyl; Diisopropylcarbamoyl, diisobutylcarbamoyl, di-sec-butylcarbamoyl, di-t-butylcar
  • Carbamoyl group or Examples include cyclic diC 3 -C 7 alkylcarbamoyl groups having two rings such as dicyclopropylcarbamoyl, dicyclobutylcarbamoyl, dicyclopentylcarbamoyl, dicyclohexylcarbamoyl, and dicycloheptylcarbamoyl.
  • linear or branched dialkylcarbamoyl groups are preferred, and linear dialkylcarbamoyl groups are more preferred.
  • arylcarbamoyl group examples include a monoarylcarbamoyl group and a diarylcarbamoyl group.
  • the monoarylcarbamoyl group is preferably a monoC 6 -C 12 arylcarbamoyl group, and specific examples include phenylcarbamoyl, naphthylcarbamoyl, biphenylcarbamoyl, and the like.
  • the diarylcarbamoyl group is preferably a diC 6 -C 12 arylcarbamoyl group, and specific examples include diphenylcarbamoyl, dinaphthylcarbamoyl, di(biphenyl)carbamoyl, and the like.
  • the alkoxycarbonyl group mentioned above includes a linear, branched or cyclic alkoxycarbonyl group, preferably a C 1 -C 10 alkoxycarbonyl group.
  • C 1 -C 10 alkoxycarbonyl groups include: For example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentoxycarbonyl, n-hexyloxycarbonyl, n-heptoxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, n- Straight chain C 1 -C 10 alkoxycarbonyl groups such as decyloxycarbonyl; Isopropoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl, isoamyloxycarbonyl, t-amyloxycarbonyl, isohexyloxycarbonyl,
  • aryloxycarbonyl group is preferably a C 6 -C 12 aryloxycarbonyl group, and specific examples include phenoxycarbonyl, naphthyloxycarbonyl, biphenyloxycarbonyl and the like.
  • alkylsulfonylamino group examples include linear, branched or cyclic alkylsulfonylamino groups, preferably C 1 -C 10 alkylsulfonylamino groups.
  • Specific examples of the C 1 -C 10 alkylsulfonylamino group include, for example, Methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, n-butylsulfonylamino, n-pentylsulfonylamino, n-hexylsulfonylamino, n-heptylsulfonylamino, n-octylsulfonylamino, n-nonylsulfonylamino, A linear C 1 -C 10 alkylsulfonylamino group such as n-decyls
  • the above arylsulfonylamino group is preferably a C 6 -C 12 arylsulfonylamino group, and specific examples include phenylsulfonylamino, toluenesulfonylamino, naphthylsulfonylamino, biphenylsulfonylamino and the like.
  • alkylsulfamoyl group examples include linear, branched, or cyclic monoalkylsulfamoyl groups or dialkylsulfamoyl groups.
  • the monoalkylsulfamoyl group is preferably a mono-C 1 -C 10 alkylsulfamoyl group, and specific examples include, for example, Methylsulfamoyl, ethylsulfamoyl, n-propylsulfamoyl, n-butylsulfamoyl, n-pentylsulfamoyl, n-hexylsulfamoyl, n-heptylsulfamoyl, n-octylsulfamoyl Straight chain mono C 1 -C 10 alkylsulfamoyl groups such as moyl, n-nonylsulfamoyl, n-decylsulfamoyl; Isopropylsulfamoyl, isobutylsulfamoyl, sec-butylsulfamoyl
  • 3 -C 10 alkylsulfamoyl group examples include cyclic monoC 3 -C 7 alkylsulfamoyl groups such as cyclopropylsulfamoyl, cyclobutylsulfamoyl, cyclopentylsulfamoyl, cyclohexylsulfamoyl, and cycloheptylsulfamoyl.
  • linear or branched monoalkylsulfamoyl groups are preferred, and linear monoalkylsulfamoyl groups are more preferred.
  • the dialkylsulfamoyl group is preferably a di-C 1 -C 10 alkylsulfamoyl group, and specific examples include, for example, Dimethylsulfamoyl, diethylsulfamoyl, di-n-propylsulfamoyl, di-n-butylsulfamoyl, di-n-pentylsulfamoyl, di-n-hexylsulfamoyl, di-n- Straight chain di-C 1 -C 10 alkylsulfamoyl groups such as heptylsulfamoyl, di-n-octylsulfamoyl, di-n-nonylsulfamoyl, di-n-decylsulfamoyl; Diisopropylsulfamoyl, diisobutylsulfamoyl, di-sec-butyls
  • arylsulfamoyl group examples include a monoarylsulfamoyl group and a diarylsulfamoyl group.
  • the monoarylsulfamoyl group is preferably a monoC 6 -C 12 arylsulfamoyl group, and specific examples thereof include phenylsulfamoyl, naphthylsulfamoyl, biphenylsulfamoyl and the like.
  • the diarylsulfamoyl group is preferably a diC 6 -C 12 arylsulfamoyl group, and specific examples include diphenylsulfamoyl, dinaphthylsulfamoyl, di(biphenyl)sulfamoyl, etc. .
  • alkylsulfonyl group examples include linear, branched or cyclic alkylsulfonyl groups, preferably C 1 -C 12 alkylsulfonyl groups.
  • Specific examples of the C 1 -C 12 alkylsulfonyl group include, for example, Methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl, n-pentylsulfonyl, n-hexylsulfonyl, n-heptylsulfonyl, n-octylsulfonyl, n-nonylsulfonyl, n-decylsulfonyl, n-undecyl Straight chain C 1 -C 12 alkylsulfonyl groups such as sulfonyl and n-dode
  • arylsulfonyl group is preferably a C 6 -C 12 arylsulfonyl group, and specific examples include phenylsulfonyl, naphthylsulfonyl, biphenylsulfonyl and the like.
  • the alkylthio group mentioned above includes a linear, branched or cyclic alkylthio group, preferably a C 1 -C 10 alkylthio group.
  • C 1 -C 10 alkylthio groups include, for example: Straight chain C 1 - C 10 alkylthio groups such as methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio; Isopropylthio, isobutylthio, sec-butylthio, t-butylthio, isoamylthio, t-amylthio, isohexylthio, t-hexylthio, isoheptylthio, t-
  • arylthio group is preferably a C 6 -C 12 arylthio group, and specific examples include phenylthio, naphthylthio, biphenylthio and the like.
  • alkylureido group examples include linear, branched, or cyclic monoalkylureido groups or dialkylureido groups.
  • the monoalkylureido group is preferably a mono-C 1 -C 10 alkylureido group, and specific examples include, for example, Linear mono-C such as methylureido, ethylureido, n-propylureido, n-butylureido, n-pentylureido, n-hexylureido, n-heptylureido, n-octylureido, n-nonylureido, n-decylureido 1 -C 10 alkylureido group; Isopropylureido, isobutylureido, sec-butylureido, t-butylureido, isoamylureido, t-amylureido, isohexylureido, t-hexylure
  • the dialkylureido group is preferably a di-C 1 -C 10 alkylureido group, and specific examples include, for example: Dimethylureido, diethylureido, di-n-propylureido, di-n-butylureido, di-n-pentylureido, di-n-hexylureido, di-n-heptylureido, di-n-octylureido, di- Straight-chain diC 1 -C 10 alkylureido groups such as n-nonylureido and di-n-decylureido; Diisopropylureido, diisobutylureido, di-sec-butylureido, di-t-butylureido, diisoamylureido, di-t-amylureido, diisohexy
  • Examples include cyclic diC 3 -C 7 alkylureido groups having two rings such as dicyclopropylureido, dicyclobutylureido, dicyclopentylureido, dicyclohexylureido, and dicycloheptylureido.
  • linear or branched dialkylureido groups are preferred, and linear dialkylureido groups are more preferred.
  • the above aryl ureido group includes a monoarylureido group or a diarylureido group.
  • the monoarylureido group is preferably a monoC 6 -C 12 arylureido group, and specific examples include phenylureido, naphthylureido, biphenylureido, and the like.
  • the diarylureido group is preferably a diC 6 -C 12 arylureido group, and specific examples include diphenylureido, dinaphthylureido, di(biphenyl)ureido, and the like.
  • the alkoxycarbonylamino group mentioned above includes a linear, branched or cyclic alkoxycarbonylamino group, preferably a C 1 -C 10 alkoxycarbonylamino group.
  • Specific examples of the C 1 -C 10 alkoxycarbonylamino group include, for example, Methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, n-butoxycarbonylamino, n-pentoxycarbonylamino, n-hexyloxycarbonylamino, n-heptoxycarbonylamino, n-octyloxycarbonylamino, n- Straight-chain C 1 -C 10 alkoxycarbonylamino groups such as nonyloxycarbonylamino and n-decyloxycarbonylamino; Isopropoxycarbonylamino, isobutoxycarbonylamino, sec-butoxycarbonylamino, t
  • 3 -C 10 alkoxycarbonylamino group examples include cyclic C 3 -C 7 alkoxycarbonylamino groups such as cyclopropoxycarbonylamino, cyclobutoxycarbonylamino, cyclopentoxycarbonylamino, cyclohexyloxycarbonylamino, and cycloheptoxycarbonylamino.
  • cyclic C 3 -C 7 alkoxycarbonylamino groups such as cyclopropoxycarbonylamino, cyclobutoxycarbonylamino, cyclopentoxycarbonylamino, cyclohexyloxycarbonylamino, and cycloheptoxycarbonylamino.
  • linear or branched alkoxycarbonylamino groups are preferred, and linear alkoxycarbonylamino groups are more preferred.
  • the aryloxycarbonylamino group is preferably a C 6 -C 12 aryloxycarbonylamino group, and specific examples include phenylcarbonylamino, naphthylcarbonylamino, biphenylcarbonylamino, and the like.
  • alkylamino group examples include linear, branched, or cyclic monoalkylamino groups or dialkylamino groups.
  • the monoalkylamino group is preferably a mono-C 1 -C 10 alkylamino group, and specific examples include, for example, Linear mono-Cs such as methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, and n-decylamino 1 -C 10 alkylamino group; Isopropylamino, isobutylamino, sec-butylamino, t-butylamino, isoamylamino, t-amylamino, isohexylamino, t-hexylamino, isoheptylamino, t-heptylamino, isooctylamino, t-oct
  • the dialkylamino group is preferably a di-C 1 -C 10 alkylamino group, and specific examples include, for example, Dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, di-n-pentylamino, di-n-hexylamino, di-n-heptylamino, di-n-octylamino, di-n - straight-chain di-C 1 -C 10 alkylamino groups such as nonylamino and di-n-decylamino; Diisopropylamino, diisobutylamino, di-sec-butylamino, di-t-butylamino, diisoamylamino, di-t-amylamino, diisohexylamino, di-t-hexylamino, diisoheptylamino, di-t - Branched di-C 3
  • Examples include cyclic diC 3 -C 7 alkylamino groups having two rings such as dicyclopropylamino, dicyclobutylamino, dicyclopentylamino, dicyclohexylamino, and dicycloheptylamino.
  • linear or branched dialkylamino groups are preferred, and linear dialkylamino groups are more preferred.
  • Examples of the above arylamino group include a monoarylamino group and a diarylamino group.
  • the monoarylamino group is preferably a mono-C 6 -C 12 arylamino group, and specific examples include phenylamino (anilino), naphthylamino, biphenylamino, and the like.
  • the diarylamino group is preferably a di-C 6 -C 12 arylamino group, and specific examples include diphenylamino, dinaphthylamino, di(biphenyl)amino, and the like.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom, a chlorine atom, or a bromine atom being preferred.
  • A include, for example, a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkoxy group having a sulfo group, a nitro group, and a sulfo group.
  • Ar represents a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a heterocycle which may have a substituent;
  • Examples include a 5- or 6-membered heterocycle containing 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms.
  • heterocycles include, for example, Five-membered alicyclic heterocycles such as pyrrolidine, tetrahydrofuran, and tetrahydrothiophene; 6-membered alicyclic heterocycles such as piperidine, piperazine, dioxane, morpholine, thiomorpholine; Aromatic hetero5-membered rings such as pyrrole, pyrazole, imidazole, triazole, furan, thiophene, oxazole, thiazole; Aromatic 6-membered heterocycles such as pyridine, pyrazine, pyridazine, triazine; A condensed aliphatic heterocycle in which the heterocyclic moiety is a 5-membered alicyclic structure such as phthalane, indoline, isoindoline; A condensed aromatic heterocycle in which the heterocyclic moiety is a 5-membered aromatic ring such as benzopyrrol
  • R 1 to R 8 each independently represent an arbitrary substituent, m represents 0 or 1, and n represents 0 or 1.
  • the ring structure drawn by a solid line and a broken line represents a phenyl (phenylene) group or a naphthyl (naphthylene) group.
  • R 1 to R 8 each independently represent an arbitrary substituent, and examples of the arbitrary substituent include the same substituent as the optional substituent in the formula (1). However, it is selected independently of the optional substituents in formula (1). Further, m represents 0 or 1, n represents 0 or 1, and preferably n is 0. Preferred R 1 to R 8 are each independently a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a halogen atom, a carboxy group, a sulfo group, or a C 1 -C 4 group having a sulfo group. is an alkoxy group, an amino group, an acetylamino group, or a benzoylamino group which may have a substituent.
  • the azo compound represented by the formula (2) is more preferably represented by the following formula (3).
  • R 1 to R 6 each independently represent an arbitrary substituent, and m represents 0 or 1.
  • R 1 to R 6 each represent the same meaning as in formula (2).
  • m represents 0 or 1. More preferably, m is 0, and R 1 to R 6 (R 1 to R 4 ) are each independently a hydrogen atom, a C 1 to C 4 alkyl group, a C 1 to C 4 alkoxy group, a halogen atom, These include a carboxyl group, a sulfo group, a C 1 -C 4 alkoxy group having a sulfo group, an amino group, an acetylamino group, and a benzoylamino group which may have a substituent.
  • the "C 1 -C 4 alkyl group” includes, for example, straight chain alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, sec- Examples include branched alkyl groups such as a butyl group and tert-butyl group, and unsaturated hydrocarbon groups such as a vinyl group.
  • Examples of the "C 1 -C 4 alkoxy group" in formulas (2) and (3) include methoxy group, ethoxy group, propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, etc. Can be mentioned.
  • the "C 1 -C 4 alkoxy group having a sulfo group” is preferably a straight chain alkoxy group, and the substitution position of the sulfo group is preferably at the terminal of the alkoxy group. More preferred are 3-sulfopropoxy group and 4-sulfobutoxy group, particularly preferred is 3-sulfopropoxy group.
  • the "benzoylamino group which may have a substituent” is not particularly limited as a substituent, but is preferably a water-soluble group, such as a carboxy group. , a sulfo group is more preferable.
  • the azo compound represented by the above formula (1) or its salt can be easily produced by performing known diazotization and coupling according to the usual method for producing azo dyes as described in Non-Patent Document 1.
  • aromatic amines represented by the following formula (A) are diazotized by a known method as described in Non-Patent Document 1, and primary coupled with aromatic amines represented by the following formula (B), and the aromatic amines represented by the following formula A monoazoamino compound represented by (C) is obtained.
  • R 1 to R 4 each have the same meaning as in formula (1).
  • this monoazoamino compound (C) is diazotized by a known method as described in Non-Patent Document 1, and is subjected to secondary coupling with an aromatic amine of the following formula (D) to form the monoazoamino compound (C) with the following formula (E).
  • the disazoamino compound shown is obtained.
  • R 1 to R 6 each represent the same meaning as in formula (1).
  • formula (E) is diazotized by a known method as described in Non-Patent Document 1, and coupled with a 1-naphthol-3-sulfonic acid derivative substituted with an isoindolyl group represented by the following formula (F). By doing so, an azo compound of formula (2) is obtained.
  • the diazotization step is carried out by a conventional method of mixing a nitrite such as sodium nitrite with an aqueous solution or suspension of a mineral acid such as hydrochloric acid or sulfuric acid of the diazo component, or a neutral or weakly alkaline solution of the diazo component. This is done by adding nitrite to an aqueous solution and mixing it with mineral acid.
  • the appropriate temperature for diazotization is -10 to 40°C.
  • the coupling step with aromatic amines is carried out by mixing an acidic aqueous solution such as hydrochloric acid or acetic acid with each of the above diazo liquids under acidic conditions at a temperature of -10 to 40°C and a pH of 2 to 7.
  • the monoazo compound and disazo compound obtained by coupling can be used as they are, or they can be precipitated by acid precipitation or salting out and then filtered out, or they can proceed to the next step as a solution or suspension. If the monoazo compound or disazo compound obtained by coupling is poorly soluble and forms a suspension, it can be filtered and used as a press cake in the next coupling step.
  • the coupling reaction between the diazotized product of the disazo compound and the naphthol represented by formula (F) is carried out at a temperature of -10 to 40°C and a pH of 7 to 10 under neutral to alkaline conditions. After the reaction is completed, the precipitate is precipitated by salting out and taken out by filtration. If purification is required, salting out may be repeated or precipitation may be performed from water using an organic solvent. Examples of organic solvents used for purification include water-soluble organic solvents such as alcohols such as methanol and ethanol, and ketones such as acetone.
  • aromatic amine represented by formula (A) which is the starting material for synthesizing the azo compound represented by formula (2) or its salt is a substituted naphthylamine compound, for example, 2-aminonaphthalene- 6-sulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-4,6, 8-trisulfonic acid, 2-aminonaphthalene-3,6,8-trisulfonic acid, 2-amino-1-hydroxy-naphthalene-6-sulfonic acid, 3-amino-1-hydroxy-naphthalene-6-sulfonic acid , 2-amino-8-hydroxy-naphthalene-6-sulfonic acid, 3-amino-8-hydroxy-naphthalene-6-sulfonic acid, 2-amino-1,8-d
  • 2-aminonaphthalene-6,8-disulfonic acid 2-aminonaphthalene-5,7-disulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, and 2-aminonaphthalene-3,6,8-trisulfonic acid. It is sulfonic acid.
  • aromatic amine represented by formula (A) which is the starting material for synthesizing the azo compound represented by formula (2) or its salt is a substituted phenylamine compound, for example, 4-sulfoaniline , 3-sulfoaniline, 2-sulfoaniline, 2,4-disulfoaniline, 2,5-disulfoaniline, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 5-aminoisophthalic acid , 2-aminoterephthalic acid, 4-aminophthalic acid, 4-nitro-2-sulfoaniline, 2-nitro-4-sulfoaniline, 4-methoxy-2-sulfoaniline, 2-methoxy-4-sulfoaniline, 4- Chloro-3-sulfoaniline, 4-chloro-3-carboxyaniline, 4-(3-sulfopropoxy)aniline, 4-(4-aminobenzoylamido)benzene-1,3-
  • 4-sulfoaniline 4-aminobenzoic acid, 2,4-disulfoaniline, 4-(4-aminobenzoylamide)benzene-1,3-disulfonic acid, 5-(4-aminobenzoylamide)benzene- It is a 1,3-dicarboxylic acid.
  • aromatic amines represented by formula (B) and formula (D), which are the starting materials for synthesizing the azo compound represented by formula (2) or its salt are substituted phenylamine compounds,
  • aniline 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 3-methylaniline, 3-ethylaniline, 3-propylaniline, 3-butylaniline, 2,5-dimethylaniline , 2,5-diethylaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-propoxyaniline, 2-butoxyaniline, 3-methoxyaniline, 3-ethoxyaniline, 3-propoxyaniline, 3-butoxyaniline, 2- Methoxy-5-methylaniline, 2,5-dimethoxyaniline, 3,5-dimethylaniline, 2,6-dimethylaniline, 3,5-dimethoxyaniline, 2-chloroaniline, 3-chloroaniline, 3-(2- Amino-4-methylphenoxy)propan
  • aromatic amines represented by formula (B) and formula (D), which are the starting materials for synthesizing the azo compound represented by formula (2) or its salt are substituted naphthylamine compounds, for example, , 1-amino-6-naphthalenesulfonic acid, 1-amino-7-naphthalenesulfonic acid, 1-amino-2-methoxy-6-naphthalenesulfonic acid, 1-amino-2-methoxy-7-naphthalenesulfonic acid, 1 -Amino-2-ethoxy-6-naphthalenesulfonic acid, 1-amino-2-ethoxy-7-naphthalenesulfonic acid, 1-amino-5-hydroxy-7-naphthalenesulfonic acid, etc., but are limited to these. It's not a thing.
  • azo compound represented by the formula (1) or its salt Specific examples of the azo compound represented by the formula (1) or its salt are listed below. Note that the azo compound is expressed in the form of a free acid.
  • the azo compound represented by the above formula (1) may be in the form of a free acid or a salt, or may be a salt of a metal ion or an ammonium ion.
  • metal ions include alkali metal ions such as lithium ions, sodium and potassium ions, alkaline earth metal ions such as calcium ions and magnesium ions.
  • ammonium ions include ammonium ion, methylammonium ion, dimethylammonium ion, triethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, triethanolammonium ion, etc. . More specifically, for example, in the case of a free acid, use sulfonic acid (-SO 3 H), in the case of sodium ion, use sodium sulfonate (-SO 3 Na), and in the case of ammonium ion, use ammonium sulfonate (-SO 3 H). 3NH 4 ).
  • the polarizing film of the present invention contains an azo compound represented by the above formula (1) or a salt thereof as a dichroic dye.
  • the polarizing film may be a neutral gray polarizing film or a color polarizing film, and preferably a neutral gray polarizing film.
  • neutral gray refers to a state in which two polarizing films are stacked so that their orientation directions are perpendicular to each other (hereinafter also referred to as "orthogonal position"). This means that there is less wavelength light leakage (color leakage).
  • the polarizing film of the present invention contains an azo compound represented by the above formula (1) or a salt thereof as a dichroic dye, or a combination of two or more kinds, and if necessary, the azo compound represented by the above formula (1) or a salt thereof.
  • the composition may further contain one or more organic dyes other than the azo compound.
  • organic dyes are not particularly limited, but are dyes with high dichroism that have absorption characteristics in a wavelength range different from the absorption wavelength range of the azo compound represented by the above formula (1) or its salt. is preferred.
  • Other organic dyes include, for example, C. Ai. direct. Yellow 12, C. Ai. direct. Yellow 28, C. Ai. direct. Yellow 44, C. Ai. direct. Orange 26, C. Ai. direct.
  • Orange 39 C. Ai. direct. Orange 71, C. Ai. direct. Orange 107, C. Ai. direct. Red 2, C. Ai. direct. Red 31, C. Ai. direct. Red 79, C. Ai. direct. Red 81, C. Ai. direct. Red 247, C. Ai. direct. Blue 69, C. Ai. direct. Green 80, and Sea. Ai. direct.
  • Typical examples include Green 59 and the dyes described in Non-Patent Document 2, but depending on the purpose, it is preferable to use dyes developed for polarizing plates such as those described in Patent Documents 1 to 4. . These organic dyes are used as free acids, alkali metal salts (for example, Na salts, K salts, Li salts), ammonium salts, or salts of amines.
  • the types of organic dyes to be blended will differ depending on whether the intended polarizing film is a neutral gray polarizing film, a color polarizing film for liquid crystal projectors, or another color polarizing film.
  • the blending ratio is not particularly limited, but in general, the total amount of at least one or more other organic dyes is 0.01 parts by mass of the azo compound of formula (1) or its salt. It is preferably used in a range of 100 parts by mass, more preferably 0.1 to 10 parts by mass.
  • the type and blending ratio of other organic dyes used in combination are adjusted so that the resulting polarizing film has less color leakage in the visible light wavelength range. .
  • the intended polarizing film is a color polarizing film
  • a specific polarizing film is used so that the resulting polarizing film has a high single-plate average light transmittance in a specific wavelength range and a low average light transmittance in the orthogonal position.
  • the type and blending ratio of other organic dyes used in combination are adjusted so that the single plate has an average light transmittance of 39% or more in the wavelength range and an orthogonal average light transmittance of 0.4% or less. .
  • a dichroic dye containing an azo compound represented by the above formula (1) or a salt thereof and, if necessary, other dyes is applied to a polarizing film base material (simply referred to as a "base material"). ) can be produced by incorporating and orienting it by a known method.
  • the polarizing film base material is preferably a polymer film, and more preferably a film made of polyvinyl alcohol resin or a derivative thereof.
  • polarizing film base materials include polyvinyl alcohol resins or those modified with olefins such as ethylene and propylene, and unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, and maleic acid. Can be mentioned.
  • a film made of polyvinyl alcohol resin or a derivative thereof is preferably used from the viewpoint of dye adsorption and orientation.
  • the thickness of the polarizing film base material is usually 10 to 100 ⁇ m, preferably about 20 to 80 ⁇ m.
  • a method of dyeing the polymer film is usually adopted to incorporate the azo compound of formula (1) or its salt. Staining is performed, for example, as follows. First, a dye bath is prepared by dissolving the azo compound represented by the above formula (1) or a salt thereof and, if necessary, other organic dyes in water. The dye concentration in the dye bath is not particularly limited, but is usually selected from a range of about 0.001 to 10% by mass. Further, a dyeing aid may be used if necessary, and for example, it is preferable to use Glauber's salt at a concentration of about 0.1 to 10% by mass. Dyeing can be carried out by immersing the polymer film in the dye bath thus prepared for, for example, 1 to 10 minutes. The dyeing temperature is preferably about 30 to 80°C.
  • the orientation of the azo compound represented by the above formula (1) or its salt is performed by stretching a polymer film dyed with a dichroic dye.
  • the stretching ratio is generally 2 to 9 times, preferably 3 to 8 times, and more preferably 4 to 7 times.
  • any known method such as a wet method or a dry method may be used. Stretching of the polymer film may optionally be carried out before dyeing. In this case, the water-soluble dye is oriented at the time of dyeing.
  • the oriented polymer film containing a water-soluble dye is subjected to post-treatment such as boric acid treatment by a known method, if necessary. Such post-treatment is performed for the purpose of improving the light transmittance and polarization degree of the polarizing film.
  • the conditions for the boric acid treatment vary depending on the type of polymer film used and the type of dye used, but generally the boric acid concentration of the boric acid aqueous solution is, for example, 0.1 to 15% by mass, preferably 1 to 10% by mass.
  • the treatment temperature is 30 to 80°C, preferably 40 to 75°C, and the treatment is carried out by immersion for 0.5 to 10 minutes.
  • a fixing treatment may also be performed using an aqueous solution containing a cationic polymer compound.
  • polarizing film of the present invention includes, for example, liquid crystal projectors, calculators, watches, notebook computers, word processors, liquid crystal televisions, car navigation systems, indoor and outdoor measuring instruments and displays, and lenses and glasses.
  • the polarizing film made using the dye of the present invention (hereinafter also referred to as “dye-based polarizing film”) is different from the polarizing film made using iodine (hereinafter also referred to as "iodine-based polarizing film”). It has comparable high polarization performance and excellent durability. Therefore, it is particularly suitable for applications that require high polarization performance and durability, such as various liquid crystal displays for in-vehicle and outdoor displays (e.g., industrial instrument displays and wearable applications), and liquid crystal projectors. be.
  • the polarizing plate of the present invention (hereinafter also referred to as "dye-based polarizing plate”) can be obtained by laminating a transparent protective film on one or both sides of the polarizing film of the present invention.
  • the polarizing plate of the present invention has excellent polarizing performance and durability (moisture resistance, heat resistance, light resistance).
  • the material for forming the transparent protective film is preferably a material with excellent optical transparency and mechanical strength, such as cellulose acetate film, acrylic film, tetrafluoroethylene/hexafluoropropylene copolymer, etc. Examples include fluorine-based films, films made of polyester resins, polyolefin resins, or polyamide-based resins.
  • the transparent protective film is preferably a triacetyl cellulose (TAC) film or a cycloolefin film.
  • the thickness of the protective film is usually preferably 40 to 200 ⁇ m.
  • An adhesive can be used to bond the polarizing film and protective film of the present invention together.
  • adhesives that can be used include polyvinyl alcohol adhesives, urethane emulsion adhesives, acrylic adhesives, and polyester-isocyanate adhesives, with polyvinyl alcohol adhesives being preferred.
  • a transparent protective layer may be further provided on the surface of the polarizing plate of the present invention.
  • the transparent protective layer include an acrylic-based or polysiloxane-based hard coat layer, a urethane-based protective layer, and the like.
  • an antireflection layer AR layer
  • the AR layer can be formed by vapor deposition or sputtering of a substance such as silicon dioxide or titanium oxide, or by thinly applying a fluorine-based substance.
  • the dye-based polarizing plate further includes a support.
  • the dye-based polarizing plate can also be used as an elliptically polarizing plate by pasting a retardation plate on the surface.
  • the polarizing plate of the present invention may be either a neutral gray polarizing plate or a color polarizing plate depending on the purpose.
  • the neutral gray polarizing plate of the present invention has a neutral color, has little orthogonal color leakage in the polarization region of the visible light region, has excellent polarization performance, and also suppresses discoloration and deterioration of polarization performance even under high temperature and high humidity conditions. It has high durability and is suitable for use in vehicles or outdoor displays.
  • a neutral gray polarizing plate for automotive use or outdoor display is a polarizing plate composed of the polarizing film of the present invention and a transparent protective film, and an AR layer is provided in order to further improve the single light transmittance.
  • a plate is preferable, and a polarizing plate with an AR layer and a support, in which both an AR layer and a support such as a transparent resin are attached, is more preferable.
  • the AR layer can be provided on one or both sides of the polarizing plate.
  • the support is preferably provided on one side of the polarizing plate, and may be provided directly on the polarizing plate, or a polarizing plate with an AR layer (AR layer/polarizing plate/AR layer) may be provided on the support. .
  • the polarizing plate with an AR layer and a support preferably includes an AR layer/polarizing plate/AR layer/support in this order.
  • the support preferably has a flat surface for attaching a polarizing plate, and since it is used for optical purposes, it is preferably a transparent substrate.
  • Transparent substrates can be broadly divided into inorganic substrates and organic substrates, including inorganic substrates such as soda glass, borosilicate glass, crystal substrates, sapphire substrates, and spinel substrates, as well as acrylic, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, and Examples include organic substrates such as cycloolefin polymers, and organic substrates are preferred.
  • the thickness and size of the transparent substrate may be any desired size.
  • Color polarizing plates have excellent polarization performance and do not cause discoloration or deterioration of polarization performance even under high temperature and high humidity conditions, so they are suitable for use in liquid crystal projectors and display devices such as in-vehicle and outdoor displays.
  • the color polarizing plate for liquid crystal projectors has brightness and excellent polarization performance, and the required wavelength range of the polarizing plate (A.
  • the average light transmittance of a single plate is 39% or more, the average light transmittance in the orthogonal position is 0.4% or less, more preferably the single plate average light transmittance in the required wavelength range of the polarizing plate is 41% or more, and the average light transmittance in the orthogonal position is 0. .3% or less, more preferably 0.2% or less. More preferably, the single-plate average light transmittance in the required wavelength range of the polarizing plate is 42% or more, and the average light transmittance in the orthogonal position is 0.1% or less.
  • the average light transmittance of a single plate is a specific wavelength range when natural light is incident on a single polarizing plate (hereinafter also simply referred to as a "polarizing plate") that is not provided with an AR layer or a support such as a transparent glass plate. This is the average value of light transmittance at .
  • the orthogonal average light transmittance is the average value of the light transmittance in a specific wavelength region when natural light is incident on two polarizing plates stacked so that their orientation directions are orthogonal to each other.
  • Polarizing films used for color polarizing plates for automobiles or outdoor displays are similar to neutral gray polarizing plates, even if dye-based polarizing plates are provided with a protective layer or an AR layer and a support as necessary. good.
  • a color polarizing plate with a support can be obtained, for example, by applying a transparent adhesive (adhesive) to the flat surface of the support, and then attaching a dye-based polarizing plate to the coated surface.
  • a dye-based polarizing plate may be coated with a transparent adhesive (adhesive), and then a support may be attached to the coated surface.
  • the adhesive pressure-sensitive adhesive
  • the retardation plate side is usually attached to a support to form a stacking order of dye-based polarizing plate/retardation plate/support.
  • the polarizing plate side may be attached to the support and the stacking order may be retardation plate/polarizing plate/support.
  • the display device of the present invention includes the polarizing film or polarizing plate of the present invention.
  • the display device include a liquid crystal display device or an organic electronics display device, for example, for displays such as calculators, watches, notebook computers, word processors, liquid crystal televisions, car navigation systems, and indoor and outdoor measuring instruments and indicators, In particular, it is suitably used for various displays that require high polarization performance and durability, such as in-vehicle or outdoor displays (for example, display applications for industrial instruments and wearable applications).
  • the dye-based polarizing film or dye-based polarizing plate provided in the display device is preferably neutral gray.
  • a dye-based polarizing plate is arranged on either or both of the incident side and the output side of the liquid crystal cell.
  • the dye-based polarizing plate may or may not be in contact with the liquid crystal cell, but from the viewpoint of durability, it is preferably not in contact with the liquid crystal cell.
  • the liquid crystal cell can be used as a support for the dye-based polarizing plate.
  • the dye-based polarizing plate is not in contact with the liquid crystal cell, it is preferable to use a dye-based polarizing plate provided with a support other than the liquid crystal cell.
  • the polarizing plate side of the dye-based polarizing plate is placed on the liquid crystal cell side, and the support side is placed on the liquid crystal cell side. It is preferable to arrange it on the light source side.
  • the incident side of the liquid crystal cell refers to the light source side, and the opposite side is referred to as the output side.
  • a liquid crystal cell included in a liquid crystal display device is, for example, an active matrix type, and is formed by sealing liquid crystal between a transparent substrate on which electrodes and TFTs are formed and a transparent substrate on which a counter electrode is formed. It is preferable.
  • Light emitted from a light source such as a cold cathode tube lamp or a white LED passes through a dye-based polarizing plate, then passes through a liquid crystal cell, a color filter, and then a dye-based polarizing plate and is projected onto a display screen.
  • dye-based polarizing plates have brightness, excellent polarization performance, polarization properties, and light resistance
  • liquid crystal display devices are less likely to discolor or deteriorate in polarization performance even in high-temperature, high-humidity conditions such as inside a car or outdoors, making them highly reliable. expensive.
  • Step 1 71.7 parts of commercially available 6-amino-1-naphthol-3-sulfonic acid and 52.5 parts of ⁇ , ⁇ '-dichloro-o-xylene were mixed with 900 parts of water and 150 parts of N-methyl-2-pyrrolidone. The mixture was added to the mixed solution of 50% and reacted at 50° C. for 8 hours while maintaining the pH at 3.0 to 7.5 using a 25% aqueous sodium hydroxide solution. 180 parts of sodium chloride was added to the resulting reaction solution, and the precipitated solid was filtered and dried to obtain 6-(isoindolin-2-yl)-1-naphthol-3-sulfone represented by the following formula (10). 34.1 parts of acid were obtained.
  • Step 2 Add 27.7 parts of commercially available 4-(4-aminophenylazo)benzenesulfonic acid to 300 parts of water, stir and suspend, adjust the pH to 9.0 using 25% sodium hydroxide, and add 40 17.3 parts of aqueous sodium nitrite solution was added. The obtained solution was added dropwise to a mixed solution of 100 parts of water and 42 parts of 35% hydrochloric acid to prepare a diazo liquid. Next, 34.1 parts of 6-(isoindolin-2-yl)-1-naphthol-3-sulfonic acid represented by formula (10) obtained in step 1 was added to 300 parts of water, and 25% water was added. It was dissolved in an aqueous sodium oxide solution to make it slightly alkaline.
  • Example 2 instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, synthesize with reference to Example (n2) of International Publication No. 2021/015188. The procedure was repeated in the same manner as in Example 1, except that 41.8 parts of 5- ⁇ 4-[(4-amino-2-methylphenyl)diazenyl]benzoylamino ⁇ benzene-1,3-dicarboxylic acid, which is an azo compound capable of , 26.0 parts of an azo compound represented by formula (12) (Compound Example 1-38) was obtained.
  • Example 3 instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, it can be synthesized with reference to Example 6 of International Publication No. 2017/146212.
  • Example 4 instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, it can be synthesized with reference to Example 1 of International Publication No. 2021/015188. The procedure was carried out except that 60.6 parts of 4-( ⁇ 4-[(4-amino-6-sulfonaphthalen-1-yl)diazenyl]-6-sulfonaphthalen-1-yl ⁇ diazenyl)benzoic acid, which is an azo compound, was used. In the same manner as in Example 1, 31.0 parts of an azo compound represented by formula (14) (Compound Example 1-49) was obtained.
  • Example 5 It is an azo compound that can be synthesized with reference to US Publication No. 2004/022805 in place of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1.
  • the azo compound represented by formula (15) (Compound Example 1 -24) 27.0 parts were obtained.
  • Example 6 instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, refer to Examples (n2) and (n4) of International Publication No. 2021/015188.
  • Example 7 In place of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, formula (8) of Example 1 of International Publication No. 2010/038379 was used as a reference. 7-( ⁇ 4-[(4-amino-2,5-dimethylphenyl)diazenyl]-2-chloro-5-(3-sulfopropoxy)phenyl ⁇ diazenyl)naphthalene-1, which is an azo compound that can be synthesized. , 3-disulfonic acid 71.2 parts were used in the same manner as in Example 1 to obtain 28.0 parts of an azo compound represented by formula (17) (Compound Example 1-53).
  • Example 8 instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, it can be synthesized with reference to Example 1 of International Publication No. 2012/108169.
  • Example 9 instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, synthesize with reference to Example (n2) of International Publication No. 2021/015188.
  • An azo compound represented by formula (19) was prepared in the same manner as in Example 1 except for using 30.0 parts of 5-[(4-aminobenzoyl)amino]benzene-1,3-dicarboxylic acid, which is an intermediate capable of producing (Compound Example 1-52) 26.0 parts were obtained.
  • Comparative example 12 Comparative Example 11 except that 32.9 parts of 6-benzylamino-1-naphthol-3-sulfonic acid was used in place of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid used in Comparative Example 11. In the same manner as above, 22.5 parts of an azo compound represented by the following formula (112) was obtained.
  • Examples 1 to 9 and Comparative Examples 1 to 16 Preparation of polarizing film
  • a polyvinyl alcohol film with a thickness of 75 ⁇ m was placed in an aqueous solution (dye bath) at 45°C with a concentration of 0.03% of each azo compound obtained in Examples 1 to 9 and Comparative Examples 1 to 16 and 0.1% of Glauber's salt. Soaked for 4 minutes.
  • This film was stretched 5 times in a 3% boric acid aqueous solution at 50° C., washed with water and dried while maintaining tension to obtain a polarizing film.
  • the polarizing films obtained in Examples 1 to 9 and Comparative Examples 1 to 16 were evaluated as follows.
  • the maximum absorption wavelength, parallel polarization transmittance (Ky), and cross polarization transmittance (Kz) of the polarizing film were measured using a spectrophotometer (UH-4150, manufactured by Hitachi, Ltd.).
  • Ky is the transmittance when the absorption axis of the absolute polarizer and the absorption axis of the polarizing film are placed parallel to each other
  • Kz is the transmittance when the absorption axis of the absolute polarizer and the absorption axis of the polarizing film are superimposed in parallel.
  • Table 1 shows the values obtained by measurement and calculation of the polarizing films of Example 1 and Comparative Examples 1 to 10.
  • the polarizing film produced using the azo compound of Example 1 had a high dichroic ratio. Specifically, the polarizing film of Example 1 had a higher dichroic ratio than any of the polarizing films of Comparative Examples 1 to 10. Further, in comparison with Comparative Example 6 and Comparative Example 4, sufficient superiority was shown. Furthermore, since it showed superiority compared to the azo compounds of Comparative Examples 8 and 9, it was shown that having the isoindolyl group according to the present invention contributed to improved performance.
  • Table 2 shows the values obtained by measurement and calculation of the polarizing films of Example 2 and Comparative Examples 11 to 14.
  • Table 2 shows that the polarizing film produced using the azo compound of the present invention in Example 2 had a high dichroic ratio. Specifically, the polarizing film of Example 2 exhibits a dichroic ratio of 45 or more at a single transmittance of approximately 44%, whereas Comparative Examples 11, 12, 13, and 14 all have a dichroic ratio of 45 or more. The ratio was 45 or less, and no compound reaching the performance of the present compound was obtained.
  • Table 3 shows the values obtained by measurement and calculation of the polarizing films of Example 3 and Comparative Example 15.
  • Table 4 also shows values obtained by measurement and calculation of the polarizing films of Example 4 and Comparative Example 16.
  • Tables 3 and 4 show a comparison between the present compound and a compound that has been applied as a blue dye with a maximum absorption wavelength exceeding 600 nm.
  • the present example has a higher dichroic ratio than the comparative example, and has good blue dichroic performance because it has a 1-naphthol-3-sulfonic acid derivative substituted with the isoindolyl group, which is the present compound. It was shown that a color dye can be obtained.
  • Table 5 shows the values obtained by measurement and calculation of the polarizing films of Examples 5 to 9 and Comparative Examples 1 and 2.
  • the polarizing films produced using the azo compounds of Examples 5 to 9 all had high polarization index and dichroic ratio. Specifically, the polarizing films of Examples 5 to 9 exhibit a degree of polarization of 98% or more and a high dichroic ratio at a single transmittance of about 44%, whereas the polarizing films of Examples 5 to 9 exhibit a high dichroic ratio with a polarization degree of 98% or more at a single transmittance of about 44%.
  • the polarizing films of Comparative Examples 1 and 2 which are known as water-soluble dichroic dyes, could not achieve a degree of polarization of 98%.
  • Example 10 Production of neutral gray polarizing plate 0.2% of the compound represented by the formula (13) of Example 3 as the red dye, and 0.0% of the compound of the formula (1-A14) described in Example 6 of International Publication No. 2017/146212 as the blue dye. .3%, C. as an orange dye.
  • Ai. direct. A polyvinyl alcohol film with a thickness of 75 ⁇ m was immersed for 4 minutes in a 45° C. aqueous solution (dye bath) containing 0.2% Orange 39 and 0.1% Glauber's Salt. This film was stretched 5 times in a 3% boric acid aqueous solution at 50° C., washed with water and dried while maintaining tension to obtain a polarizing film.
  • the obtained polarizing film had a single average transmittance of 42% in the wavelength range of 380 nm to 780 nm, and an average transmittance of 0.1% in the orthogonal position, indicating a high degree of polarization.
  • Both sides of this polarizing film are laminated with triacetyl cellulose film (TAC film: manufactured by Fuji Film Co., Ltd., product name TD-80U) via an adhesive of polyvinyl alcohol aqueous solution, and the dye layer is laminated in the order of TAC/polarizing film/TAC.
  • a system polarizing plate neutral gray polarizing plate
  • One side of the obtained neutral gray polarizing plate was attached to glass using an adhesive to prepare a neutral gray polarizing plate measurement sample in which TAC/polarizing film/TAC/glass were laminated in this order.
  • the neutral gray polarizing plate obtained in Example 10 had a single average transmittance even after 500 hours at an environmental temperature of 105°C and after 500 hours at an environmental temperature of 80°C and a relative humidity of 90%. There was no change in , and it showed long-term durability even under high temperature and high humidity conditions. Furthermore, the neutral gray polarizing plate of Example 10 showed no change in average transmittance even after 200 hours in a xenon light resistance test (SX-75 manufactured by Suga Test Instruments Co., Ltd.) at 60 W and an environmental temperature of 50°C. The light resistance against long-term exposure to light was also excellent.
  • the neutral gray polarizing plate of Example 10 prepared using the compound of the present invention has excellent polarizing performance and is a high-performance dye-based plate with durability (moisture resistance, heat resistance, light resistance). It was shown to be a polarizing plate.
  • the polarizing film or its polarizing plate produced using the azo compound of the present invention can be provided with a protective layer or a functional layer and a transparent support such as glass, crystal, sapphire, etc. as necessary, and can be used in liquid crystal projectors, calculators, watches, etc. Applicable to notebook computers, word processors, LCD televisions, polarized lenses, polarized glasses, car navigation systems, and indoor and outdoor measuring instruments and displays.
  • the polarizing film or polarizing plate of the present invention can be suitably used for liquid crystal display devices, such as reflective liquid crystal display devices, transflective liquid crystal display devices, and organic electroluminescence devices other than liquid crystal display devices.

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Abstract

An azo compound represented by formula (1) or a salt thereof. (In formula (1), Ar indicates a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a heterocycle which may have a substituent, and A indicates an arbitrary substituent.)

Description

アゾ化合物又はその塩、並びにそれらを含有する偏光膜、偏光板及び液晶表示装置Azo compounds or salts thereof, and polarizing films, polarizing plates, and liquid crystal display devices containing them
　本発明は、新規なアゾ化合物又はその塩、並びにそれらを含有する偏光膜、偏光板及び液晶表示装置に関する。 The present invention relates to novel azo compounds or salts thereof, and polarizing films, polarizing plates, and liquid crystal display devices containing them.
　光の透過・遮へい機能を有する偏光板は、光のスイッチング機能を有する液晶とともに液晶ディスプレイ（Ｌｉｑｕｉｄ　Ｃｒｙｓｔａｌ　Ｄｉｓｐｌａｙ：ＬＣＤ）等の表示装置の基本的な構成要素である。このＬＣＤの適用分野も初期の頃の電卓及び時計等の小型機器から、ノートパソコン、ワープロ、液晶プロジェクター、液晶テレビ、カーナビゲーション、及び屋内外の計測機器等が挙げられる。また偏光機能を有するレンズへの適用も可能であり、視認性の向上したサングラスや、近年では３Ｄテレビなどに対応する偏光メガネなどへの応用がなされている。以上のような偏光板の用途が広範囲に広がっているため、使用条件も低温～高温、低湿度～高湿度、低光量～高光量の幅広い条件で使用されることから、高い偏光性能かつ高い耐久性を有する偏光板が求められている。 A polarizing plate that has a light transmission/shielding function is a basic component of a display device such as a liquid crystal display (LCD), along with a liquid crystal that has a light switching function. The fields of application of this LCD range from small devices such as calculators and watches in the early days to notebook computers, word processors, liquid crystal projectors, liquid crystal televisions, car navigation systems, and indoor and outdoor measuring instruments. It can also be applied to lenses having a polarizing function, and has been applied to sunglasses with improved visibility and, in recent years, polarized glasses compatible with 3D televisions and the like. As the above-mentioned applications of polarizing plates are widespread, they are used under a wide range of conditions from low to high temperatures, low to high humidity, and low to high light levels, so they have high polarizing performance and high durability. There is a need for a polarizing plate that has the following characteristics.
　現在、偏光板はポリビニルアルコール又はその誘導体のフィルムにヨウ素や二色性染料を染色又は含侵せしめて延伸し配向させるか、あるいはポリ塩化ビニルフィルムの脱塩酸又はポリビニルアルコール系フィルムの脱水によりポリエンを生成して配向せしめることによって製造される。これらは、偏光板における偏光特性や耐久性に大きく影響する物質である。ヨウ素を用いたヨウ素系偏光膜は、偏光性能には優れるが、水及び熱に対して弱く、高温、高湿の状態で長時間使用する場合にはその耐久性に問題がある。耐久性を向上させるためにホルマリン、あるいは、ホウ酸を含む水溶液で処理し、また透湿度の低い高分子フィルムを保護膜として用いる方法などが考えられているがその効果は十分とはいえない。 Currently, polarizing plates are produced by dyeing or impregnating a film of polyvinyl alcohol or its derivatives with iodine or a dichroic dye, stretching and orienting the film, or by removing hydrochloric acid from a polyvinyl chloride film or dehydrating a polyvinyl alcohol film. Manufactured by generating and orienting. These are substances that greatly affect the polarization characteristics and durability of the polarizing plate. An iodine-based polarizing film using iodine has excellent polarizing performance, but is sensitive to water and heat, and has problems with its durability when used for long periods of time in high temperature and high humidity conditions. In order to improve durability, methods such as treating with formalin or an aqueous solution containing boric acid and using a polymer film with low moisture permeability as a protective film have been considered, but the effects are not sufficient.
　他方、染料を用いた染料系偏光膜はヨウ素系偏光膜に比べ、耐湿性及び耐熱性は優れるが、一般に偏光性能が十分でない。染料系ニュートラルグレー偏光板は、一般的には複数種の染料を組み合わせて製造されているが、染料系ニュートラルグレー偏光板の偏光性能は十分ではなく、用いられる各色で偏光性能が良好な二色性染料の開発が必要であった。 On the other hand, dye-based polarizing films using dyes have better moisture resistance and heat resistance than iodine-based polarizing films, but generally do not have sufficient polarizing performance. Dye-based neutral gray polarizing plates are generally manufactured by combining multiple types of dyes, but the polarizing performance of dye-based neutral gray polarizing plates is not sufficient, and two-color polarizing plates with good polarization performance for each color used are used. It was necessary to develop a sex dye.
　上記のような染料系偏光膜としては、例えば特許文献１～３に記載されている水溶性アゾ化合物を用いた染料系偏光膜が挙げられ、また最近では二色性染料の性能向上のために特許文献２に記載されている１－ナフトール－３－スルホン酸誘導体の開発がなされているが、まだ十分な偏光特性を得るには至っておらず、更なる高性能化が求められていた。 Examples of the dye-based polarizing film described above include dye-based polarizing films using water-soluble azo compounds described in Patent Documents 1 to 3, and recently, in order to improve the performance of dichroic dyes, Although the 1-naphthol-3-sulfonic acid derivative described in Patent Document 2 has been developed, sufficient polarization properties have not yet been obtained, and further improvement in performance has been desired.
国際公開第２０１７／１４６２１２号公報International Publication No. 2017/146212 国際公開第２０１９／１１７１３１号公報International Publication No. 2019/117131 国際公開第２０２０／０５０３３３号公報International Publication No. 2020/050333 国際公開第２０２１／０１５１８８号公報International Publication No. 2021/015188
　本発明の目的の一つは、優れた偏光性能を有する二色性染料、偏光膜、偏光板を提供することにあり、さらに本発明の他の目的は、可視光領域の波長領域における直交位の色もれが少ないニュートラルグレー偏光板を提供することにある。さらに本発明の他の目的は、優れた偏光性能及び耐久性（耐熱性、耐湿性又は耐光性）を有する高性能な偏光板を提供することにあり、それらを可能にするために必要な新規の二色性染料（アゾ化合物）を提供する事である。 One of the objects of the present invention is to provide a dichroic dye, a polarizing film, and a polarizing plate having excellent polarization performance, and another object of the present invention is to provide a dichroic dye, a polarizing film, and a polarizing plate having excellent polarization performance. The objective is to provide a neutral gray polarizing plate with less color bleeding. Furthermore, another object of the present invention is to provide a high-performance polarizing plate having excellent polarizing performance and durability (heat resistance, moisture resistance, or light resistance), and to make this possible, novel The purpose of this invention is to provide a dichroic dye (azo compound).
　本発明者らは、かかる目的を達成すべく鋭意研究を進めた結果、特定のアゾ化合物又はその塩を含有する偏光膜及び偏光板が、優れた偏光性能、耐久性を有することを見出した。 As a result of intensive research to achieve this objective, the present inventors discovered that polarizing films and polarizing plates containing a specific azo compound or its salt have excellent polarizing performance and durability.
　すなわち本発明は、以下の［１］～［９］に関する。
［１］
　下記式（１）で表されるアゾ化合物又はその塩：
Figure JPOXMLDOC01-appb-C000004
（式（１）中、Ａｒは置換基を有してもよいベンゼン環、置換基を有してもよいナフタレン環、又は置換基を有してもよい複素環を示し、Ａは任意の置換基を示す）。
［２］
　前記式（１）で表されるアゾ化合物が下記式（２）で表される、［１］に記載のアゾ化合物又はその塩：
Figure JPOXMLDOC01-appb-C000005
（式（２）中、Ｒ１～Ｒ８は各々独立に任意の置換基を表し、ｍは０又は１の整数を、またｎは０又は１を示す）。
［３］
　前記式（１）で表されるアゾ化合物が下記式（３）で表される、［１］に記載のアゾ化合物又はその塩：
Figure JPOXMLDOC01-appb-C000006
（上記式（３）中、Ｒ１～Ｒ６は各々独立に任意の置換基を表し、ｍは０又は１を示す）。
［４］
　［１］～［３］のいずれかに記載のアゾ化合物又はその塩を含有する偏光膜。
［５］
　基材を含む、［４］に記載の偏光膜。
［６］
　［１］～［３］のいずれかに記載のアゾ化合物又はその塩以外の有機染料を１種類以上含有する［４］に記載の偏光膜。
［７］
　ニュートラルグレー色を有する［４］に記載の偏光膜。
［８］
　［４］に記載の偏光膜及びその片面又は両面に設けられた透明保護膜を備える偏光板。
［９］
　［４］に記載の偏光膜又は［８］に記載の偏光板を備える表示装置。 That is, the present invention relates to the following [1] to [9].
[1]
Azo compound or its salt represented by the following formula (1):
Figure JPOXMLDOC01-appb-C000004
(In formula (1), Ar represents a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a heterocycle which may have a substituent, and A is any substituent. ).
[2]
The azo compound or a salt thereof according to [1], wherein the azo compound represented by the formula (1) is represented by the following formula (2):
Figure JPOXMLDOC01-appb-C000005
(In formula (2), R 1 to R 8 each independently represent an arbitrary substituent, m represents an integer of 0 or 1, and n represents 0 or 1).
[3]
The azo compound or a salt thereof according to [1], wherein the azo compound represented by the formula (1) is represented by the following formula (3):
Figure JPOXMLDOC01-appb-C000006
(In the above formula (3), R 1 to R 6 each independently represent an arbitrary substituent, and m represents 0 or 1).
[4]
A polarizing film containing the azo compound or salt thereof according to any one of [1] to [3].
[5]
The polarizing film according to [4], which includes a base material.
[6]
The polarizing film according to [4], which contains one or more organic dyes other than the azo compound or salt thereof according to any one of [1] to [3].
[7]
The polarizing film according to [4], which has a neutral gray color.
[8]
A polarizing plate comprising the polarizing film according to [4] and a transparent protective film provided on one or both sides thereof.
[9]
A display device comprising the polarizing film according to [4] or the polarizing plate according to [8].
　本発明のアゾ化合物又はその塩は偏光膜用の染料として有用である。一態様において本発明の偏光膜及び偏光板は、優れた偏光性能を有する。一態様において、本発明のニュートラルグレー色を有する偏光板は、可視光領域の波長領域における直交位の色もれがない高性能な無彩色を示す。一態様において、本発明の偏光膜及び偏光板は、優れた偏光性能（透過率、コントラスト）及び耐久性（耐湿性、耐熱性、耐光性）を有する。 The azo compound or salt thereof of the present invention is useful as a dye for polarizing films. In one aspect, the polarizing film and polarizing plate of the present invention have excellent polarizing performance. In one aspect, the polarizing plate having a neutral gray color according to the present invention exhibits a high-performance achromatic color without orthogonal color leakage in the wavelength region of the visible light region. In one embodiment, the polarizing film and polarizing plate of the present invention have excellent polarizing performance (transmittance, contrast) and durability (moisture resistance, heat resistance, light resistance).
　本明細書及び特許請求の範囲において、明確に遊離形態を表すものである場合を除き、「アゾ化合物又はその塩」を単に「アゾ化合物」と称することもある。
　本明細書及び特許請求の範囲において、「置換基」には水素原子を含んでもよいため、水素原子を便宜上「置換基」として説明することもある。「置換基を有してもよい」とは、置換基を有していない場合も含まれることを意味する。例えば、「置換基を有してもよいフェニル基」は、非置換の単なるフェニル基と、置換基を有するフェニル基を含む。また、本願の低級アルキル基、低級アルコキシ基などの「低級」とは特に記載がなければ、炭素原子数が１～４（Ｃ１－Ｃ４）、好ましくは１～３（Ｃ１－Ｃ３）であることを示す。 In this specification and claims, an "azo compound or a salt thereof" may be simply referred to as an "azo compound" unless it clearly represents a free form.
In this specification and claims, since a "substituent" may include a hydrogen atom, a hydrogen atom may be referred to as a "substituent" for convenience. The term "may have a substituent" means that the term "may have a substituent" also includes the case where the compound does not have a substituent. For example, "a phenyl group which may have a substituent" includes a simple unsubstituted phenyl group and a phenyl group having a substituent. In addition, unless otherwise specified, "lower" in the lower alkyl group, lower alkoxy group, etc. in the present application refers to a group having 1 to 4 carbon atoms (C 1 -C 4 ), preferably 1 to 3 (C 1 -C 3 ) . ).
　本発明のアゾ化合物又はその塩は、下記式（１）で表されるイソインドリル基が置換した１－ナフトール－３－スルホン酸誘導体を有する。
Figure JPOXMLDOC01-appb-C000007
（式（１）中、Ａｒは置換基を有してもよいベンゼン環、置換基を有してもよいナフタレン環、又は置換基を有してもよい複素環を示し、Ａは任意の置換基を示す。） The azo compound or salt thereof of the present invention has a 1-naphthol-3-sulfonic acid derivative substituted with an isoindolyl group represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000007
(In formula (1), Ar represents a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a heterocycle which may have a substituent, and A is any substituent. (indicates the group)
　上記式（１）中、Ａｒは置換基を有してもよいベンゼン環、置換基を有してもよいナフタレン環、又は置換基を有してもよい複素環を示し、Ａは任意の置換基を示す。前述の有してもよい置換基、及びＡで示される任意の置換基としては、例えば、ジアゼニル基、複素環アミノ基、縮環型複素環アミノ基、アルキル基、アルコキシ基、アリールオキシ基、アルキルカルボニルアミノ基、アリールカルボニルアミノ基、アルキルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルカルボニル基、アリールカルボニル基、アルキルカルバモイル基、アリールカルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルスルファモイル基、アリールスルファモイル基、アルキルスルホニル基、アリールスルホニル基、アルキルチオ基、アリールチオ基、アルキルウレイド基、アリールウレイド基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルアミノ基、アリールアミノ基、ヒドロキシ基（－ＯＨ）、シアノ基（－ＣＮ）、ニトロ基（－ＮＯ２）、メルカプト基（－ＳＨ）、ハロゲン原子、カルボキシ基（－ＣＯ２Ｈ）、スルホ基（－ＳＯ３Ｈ）、アミノ基（－ＮＨ２）、水素原子等が挙げられる。
　後述するように、Ａｒとしての「置換基を有してもよいベンゼン環」又は「置換基を有してもよいナフタレン環」として、式（２）又は（３）中の相当する箇所の構造であってもよい。 In the above formula (1), Ar represents a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a heterocycle which may have a substituent, and A is any substituent. Indicates the group. Examples of the above-mentioned optional substituents and the optional substituent represented by A include a diazenyl group, a heterocyclic amino group, a condensed heterocyclic amino group, an alkyl group, an alkoxy group, an aryloxy group, Alkylcarbonylamino group, arylcarbonylamino group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylcarbonyl group, arylcarbonyl group, alkylcarbamoyl group, arylcarbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonylamino group, Arylsulfonylamino group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkylureido group, arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, Alkylamino group, arylamino group, hydroxy group (-OH), cyano group (-CN), nitro group (-NO 2 ), mercapto group (-SH), halogen atom, carboxy group (-CO 2 H), sulfonate Examples include a group (-SO 3 H), an amino group (-NH 2 ), and a hydrogen atom.
As described later, as Ar, "benzene ring which may have a substituent" or "naphthalene ring which may have a substituent", the structure at the corresponding position in formula (2) or (3) It may be.
　上記複素環アミノ基としては、窒素原子、酸素原子及び硫黄原子からなる群から選択される１～３つのヘテロ原子を含む、５又は６員環の複素環アミノ基が挙げられる。このような複素環アミノ基の具体例としては、例えば、
　ピロリジニルアミノ、テトラヒドロフリルアミノ、テトラヒドロチオフェン－２－イルアミノ、テトラヒドロチオフェン－３－イルアミノ等の５員複素脂環式アミノ基；
　ピペリジニルアミノ、ピペラジニルアミノ、ジオキサン－２－イルアミノ、モルホリニルアミノ、チオモルホリニルアミノ等の６員複素脂環式アミノ基；
　ピロールアミノ、ピラゾールアミノ、イミダゾールアミノ、トリアゾールアミノ、フリルアミノ、チオフェン－２－イルアミノ、チオフェン－３－イルアミノ、オキサゾールアミノ、チアゾールアミノ等の５員芳香族複素環式アミノ基；又は、
　ピリジルアミノ、ピラジルアミノ、ピリダジニルアミノ、トリアジニルアミノ等の６員芳香族複素環式アミノ基等が挙げられる。
　前記複素環基は、複素環部分が芳香族環であることが好ましい。また、複素環を構成するヘテロ原子としては窒素原子、及び硫黄原子から選択されることが好ましい。 Examples of the above-mentioned heterocyclic amino group include a 5- or 6-membered heterocyclic amino group containing 1 to 3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples of such heterocyclic amino groups include, for example,
5-membered heteroalicyclic amino groups such as pyrrolidinylamino, tetrahydrofurylamino, tetrahydrothiophen-2-ylamino, and tetrahydrothiophen-3-ylamino;
6-membered heteroalicyclic amino groups such as piperidinylamino, piperazinylamino, dioxan-2-ylamino, morpholinylamino, thiomorpholinylamino;
5-membered aromatic heterocyclic amino groups such as pyrrole amino, pyrazole amino, imidazolamino, triazole amino, furylamino, thiophen-2-ylamino, thiophen-3-ylamino, oxazole amino, thiazole amino; or,
Examples include 6-membered aromatic heterocyclic amino groups such as pyridylamino, pyradyl amino, pyridazinylamino, and triazinylamino.
In the heterocyclic group, the heterocyclic moiety is preferably an aromatic ring. Furthermore, the heteroatom constituting the heterocycle is preferably selected from nitrogen atoms and sulfur atoms.
　上記縮環型複素環アミノ基としては、窒素原子、酸素原子及び硫黄原子からなる群から選択される１～３つのヘテロ原子を含む、５又は６員の複素環基に、１つのベンゼン環が縮環した縮環型５又は６員環の複素環アミノ基が挙げられる。このような縮環型複素環アミノ基の具体例としては、例えば、
　フタラニルアミノ等の複素環部分が５員脂環式の縮環型複素脂環式アミノ基；
　ベンゾピラニルアミノ等の複素環部分が６員脂環式の縮環型複素脂環式アミノ基；
　ベンゾピロールアミノ、ベンゾピラゾールアミノ、ベンゾイミダゾールアミノ、ベンゾトリアゾールアミノ、ベンゾフラニルアミノ、ベンゾチオフェン－２－イルアミノ、ベンゾチオフェン－３－イルアミノ、ベンゾオキサゾールアミノ、ベンゾチアゾールアミノ等の複素環部分が芳香族５員環の縮環型芳香族複素環式アミノ基；又は、
　キノリニルアミノ、シンノリニルアミノ、フタラジニルアミノ、キナゾリニルアミノ、キノキサリニルアミノ等の複素環部分が芳香族６員環の縮環型芳香族複素環式アミノ基等が挙げられる。
　前記複素環基は、複素環部分が芳香族環であることが好ましい。また、複素環を構成するヘテロ原子としては窒素原子、及び硫黄原子から選択されることが好ましい。 The above condensed heterocyclic amino group includes one benzene ring in a 5- or 6-membered heterocyclic group containing 1 to 3 heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms. Examples include a condensed 5- or 6-membered ring heterocyclic amino group. Specific examples of such condensed heterocyclic amino groups include, for example,
A condensed heteroalicyclic amino group in which the heterocyclic moiety is a 5-membered alicyclic structure such as phthalanylamino;
A fused-ring type heteroalicyclic amino group in which the heterocyclic moiety is a 6-membered alicyclic structure such as benzopyranyl amino;
The heterocyclic moiety is aromatic, such as benzopyrrolamino, benzopyrazoleamino, benzimidazolamino, benzotriazoleamino, benzofuranylamino, benzothiophen-2-ylamino, benzothiophen-3-ylamino, benzoxazoleamino, benzothiazoleamino, etc. a 5-membered ring condensed aromatic heterocyclic amino group; or
Examples include condensed aromatic heterocyclic amino groups in which the heterocyclic moiety is a 6-membered aromatic ring, such as quinolinylamino, cinnolinylamino, phthalazinylamino, quinazolinylamino, and quinoxalinylamino.
In the heterocyclic group, the heterocyclic moiety is preferably an aromatic ring. Furthermore, the heteroatom constituting the heterocycle is preferably selected from nitrogen atoms and sulfur atoms.
　上記アルキル基としては、直鎖状、分岐鎖状又は環状のアルキル基、好ましくはＣ１－Ｃ１０アルキル基が挙げられる。Ｃ１－Ｃ１０アルキル基の具体例としては、例えば、
　メチル、エチル、ｎ－プロピル、ｎ－ブチル、ｎ－ペンチル、ｎ－ヘキシル、ｎ－ヘプチル、ｎ－オクチル、ｎ－ノニル、ｎ－デシルといった直鎖状のＣ１－Ｃ１０アルコキシ基；
　イソプロピル、イソブチル、ｓｅｃ－ブチル、ｔ－ブチル、イソアミル、ｔ－アミル、イソヘキシル、ｔ－ヘキシル、イソヘプチル、ｔ－ヘプチル、イソオクチル、ｔ－オクチル、２－エチルヘキシル、イソノニル、イソデシル等の分岐鎖状のＣ３－Ｃ１０アルキル基；又は、
　シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル等の環状のＣ３－Ｃ７アルコキシ基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のアルコキシ基が好ましく、直鎖状又は分岐鎖状のＣ１－Ｃ４アルキル基がより好ましい。 Examples of the alkyl group include linear, branched or cyclic alkyl groups, preferably C 1 -C 10 alkyl groups. Specific examples of C 1 -C 10 alkyl groups include, for example:
Straight chain C 1 -C 10 alkoxy groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl;
Branched C such as isopropyl, isobutyl, sec-butyl, t-butyl, isoamyl, t-amyl, isohexyl, t-hexyl, isoheptyl, t-heptyl, isooctyl, t-octyl, 2-ethylhexyl, isononyl, isodecyl, etc. 3 -C 10 alkyl group; or
Examples include cyclic C 3 -C 7 alkoxy groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Among these, linear or branched alkoxy groups are preferred, and linear or branched C 1 -C 4 alkyl groups are more preferred.
　上記アルコキシ基としては、直鎖状、分岐鎖状又は環状のアルコキシ基、好ましくはＣ１－Ｃ１０アルコキシ基が挙げられる。Ｃ１－Ｃ１０アルコキシ基の具体例としては、例えば、
　メトキシ、エトキシ、ｎ－プロポキシ、ｎ－ブトキシ、ｎ－ペントキシ、ｎ－ヘキシロキシ、ｎ－ヘプトキシ、ｎ－オクチロキシ、ｎ－ノニロキシ、ｎ－デシロキシといった直鎖状のＣ１－Ｃ１０アルコキシ基；
　イソプロポキシ、イソブトキシ、ｓｅｃ－ブトキシ、ｔ－ブトキシ、イソアミロキシ、ｔ－アミロキシ、イソヘキシロキシ、ｔ－ヘキシロキシ、イソヘプトキシ、ｔ－ヘプトキシ、イソオクチロキシ、ｔ－オクチロキシ、２－エチルヘキシロキシ、イソノニロキシ、イソデシロキシ等の分岐鎖状のＣ３－Ｃ１０アルコキシ基；又は、
　シクロプロポキシ、シクロブトキシ、シクロペントキシ、シクロヘキシロキシ、シクロヘプトキシ等の環状のＣ３－Ｃ７アルコキシ基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のアルコキシ基が好ましく、直鎖状又は分岐鎖状のＣ１－Ｃ４アルコキシ基がより好ましい。 Examples of the alkoxy group include linear, branched or cyclic alkoxy groups, preferably C 1 -C 10 alkoxy groups. Specific examples of C 1 -C 10 alkoxy groups include, for example:
Straight chain C 1 -C 10 alkoxy groups such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptoxy, n-octyloxy, n-nonyloxy, n-decyloxy;
Branched chains such as isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isoamyloxy, t-amyloxy, isohexyloxy, t-hexyloxy, isoheptoxy, t-heptoxy, isooctyloxy, t-octyloxy, 2-ethylhexyloxy, isononyloxy, isodesyloxy, etc. a C 3 -C 10 alkoxy group; or
Examples include cyclic C 3 -C 7 alkoxy groups such as cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, and cycloheptoxy. Among these, linear or branched alkoxy groups are preferred, and linear or branched C 1 -C 4 alkoxy groups are more preferred.
　上記アルコキシ基としては、置換基を有するアルコキシ基でもよく、例えば、スルホ基を有するＣ１－Ｃ４のアルコキシ基が挙げられる。「スルホ基を有するＣ１－Ｃ４のアルコキシ基」としては、直鎖アルコキシ基が好ましく、スルホ基の置換位置としてはアルコキシ基末端が好ましい。より好ましくは３－スルホプロポキシ基及び４－スルホブトキシ基であり、特に好ましくは３－スルホプロポキシ基である。 The alkoxy group may be an alkoxy group having a substituent, for example, a C 1 -C 4 alkoxy group having a sulfo group. The "C 1 -C 4 alkoxy group having a sulfo group" is preferably a straight chain alkoxy group, and the substitution position of the sulfo group is preferably at the terminal of the alkoxy group. More preferred are 3-sulfopropoxy group and 4-sulfobutoxy group, particularly preferred is 3-sulfopropoxy group.
　上記アリールオキシ基は、好ましくはＣ６－Ｃ１２アリールオキシ基であり、具体例としては、例えば、フェノキシ、ナフチロキシ、ビフェニロキシ等が挙げられる。 The above aryloxy group is preferably a C 6 -C 12 aryloxy group, and specific examples include phenoxy, naphthyloxy, biphenyloxy and the like.
　上記アルキルカルボニルアミノ基としては、直鎖状、分岐鎖状又は環状のアルキルカルボニルアミノ基、好ましくはＣ１－Ｃ１０アルキルカルボニルアミノ基が挙げられる。Ｃ１－Ｃ１０アルキルカルボニルアミノ基の具体例としては、例えば、
　メチルカルボニルアミノ（アセチルアミノ）、エチルカルボニルアミノ、ｎ－プロピルカルボニルアミノ、ｎ－ブチルカルボニルアミノ、ｎ－ペンチルカルボニルアミノ、ｎ－ヘキシルカルボニルアミノ、ｎ－ヘプチルカルボニルアミノ、ｎ－オクチルカルボニルアミノ、ｎ－ノニルカルボニルアミノ、ｎ－デシルカルボニルアミノといった直鎖状のＣ１－Ｃ１０アルキルカルボニルアミノ基；
　イソプロピルカルボニルアミノ、イソブチルカルボニルアミノ、ｓｅｃ－ブチルカルボニルアミノ、ｔ－ブチルカルボニルアミノ、イソアミルカルボニルアミノ、ｔ－アミルカルボニルアミノ、イソヘキシルカルボニルアミノ、ｔ－ヘキシルカルボニルアミノ、イソヘプチルカルボニルアミノ、ｔ－ヘプチルカルボニルアミノ、イソオクチルカルボニルアミノ、ｔ－オクチルカルボニルアミノ、２－エチルヘキシルカルボニルアミノ、イソノニルカルボニルアミノ、イソデシルカルボニルアミノ等の分岐鎖状のＣ３－Ｃ１０アルキルカルボニルアミノ基；又は
　シクロプロピルカルボニルアミノ、シクロブチルカルボニルアミノ、シクロペンチルカルボニルアミノ、シクロヘキシルカルボニルアミノ、シクロヘプチルカルボニルアミノ等の環状のＣ３－Ｃ７アルキルカルボニルアミノ基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のアルキルカルボニルアミノ基が好ましく、直鎖状のアルキルカルボニルアミノ基がより好ましい。 Examples of the alkylcarbonylamino group include linear, branched or cyclic alkylcarbonylamino groups, preferably C 1 -C 10 alkylcarbonylamino groups. Specific examples of the C 1 -C 10 alkylcarbonylamino group include, for example,
Methylcarbonylamino (acetylamino), ethylcarbonylamino, n-propylcarbonylamino, n-butylcarbonylamino, n-pentylcarbonylamino, n-hexylcarbonylamino, n-heptylcarbonylamino, n-octylcarbonylamino, n- Straight-chain C 1 -C 10 alkylcarbonylamino groups such as nonylcarbonylamino and n-decylcarbonylamino;
Isopropylcarbonylamino, isobutylcarbonylamino, sec-butylcarbonylamino, t-butylcarbonylamino, isoamylcarbonylamino, t-amylcarbonylamino, isohexylcarbonylamino, t-hexylcarbonylamino, isoheptylcarbonylamino, t-heptylcarbonyl A branched C 3 -C 10 alkylcarbonylamino group such as amino, isooctylcarbonylamino, t-octylcarbonylamino, 2-ethylhexylcarbonylamino, isononylcarbonylamino, isodecylcarbonylamino; or cyclopropylcarbonylamino, Examples include cyclic C 3 -C 7 alkylcarbonylamino groups such as cyclobutylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, and cycloheptylcarbonylamino. Among these, linear or branched alkylcarbonylamino groups are preferred, and linear alkylcarbonylamino groups are more preferred.
　上記アリールカルボニルアミノ基は、好ましくはＣ６－Ｃ１２アリールカルボニルアミノ基であり、具体例としては、例えば、フェニルカルボニルアミノ（ベンゾイルアミノ）、ナフチルカルボニルアミノ、ビフェニルカルボニルアミノ等が挙げられる。 The above arylcarbonylamino group is preferably a C 6 -C 12 arylcarbonylamino group, and specific examples include phenylcarbonylamino (benzoylamino), naphthylcarbonylamino, biphenylcarbonylamino, and the like.
　上記アルキルカルボニルオキシ基としては、直鎖状、分岐鎖状又は環状のアルキルカルボニルオキシ基、好ましくはＣ１－Ｃ１０アルキルカルボニルオキシ基が挙げられる。Ｃ１－Ｃ１０アルキルカルボニルオキシ基の具体例としては、例えば、
　メチルカルボニルオキシ、エチルカルボニルオキシ、ｎ－プロピルカルボニルオキシ、ｎ－ブチルカルボニルオキシ、ｎ－ペンチルカルボニルオキシ、ｎ－ヘキシルカルボニルオキシ、ｎ－ヘプチルカルボニルオキシ、ｎ－オクチルカルボニルオキシ、ｎ－ノニルカルボニルオキシ、ｎ－デシルカルボニルオキシといった直鎖状のＣ１－Ｃ１０アルキルカルボニルオキシ基；
　イソプロピルカルボニルオキシ、イソブチルカルボニルオキシ、ｓｅｃ－ブチルカルボニルオキシ、ｔ－ブチルカルボニルオキシ、イソアミルカルボニルオキシ、ｔ－アミルカルボニルオキシ、イソヘキシルカルボニルオキシ、ｔ－ヘキシルカルボニルオキシ、イソヘプチルカルボニルオキシ、ｔ－ヘプチルカルボニルオキシ、イソオクチルカルボニルオキシ、ｔ－オクチルカルボニルオキシ、２－エチルヘキシルカルボニルオキシ、イソノニルカルボニルオキシ、イソデシルカルボニルオキシ等の分岐鎖状のＣ３－Ｃ１０アルキルカルボニルオキシ基；又は、
　シクロプロピルカルボニルオキシ、シクロブチルカルボニルオキシ、シクロペンチルカルボニルオキシ、シクロヘキシルカルボニルオキシ、シクロヘプチルカルボニルオキシ等の環状のＣ３－Ｃ７アルキルカルボニルオキシ基が挙げられる。これらの中でも、直鎖状又は分岐鎖のアルキルカルボニルオキシ基が好ましく、直鎖状のアルキルカルボニルオキシ基がより好ましい。 The alkylcarbonyloxy group mentioned above includes a linear, branched or cyclic alkylcarbonyloxy group, preferably a C 1 -C 10 alkylcarbonyloxy group. Specific examples of the C 1 -C 10 alkylcarbonyloxy group include, for example,
Methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, n-butylcarbonyloxy, n-pentylcarbonyloxy, n-hexylcarbonyloxy, n-heptylcarbonyloxy, n-octylcarbonyloxy, n-nonylcarbonyloxy, a linear C 1 -C 10 alkylcarbonyloxy group such as n-decylcarbonyloxy;
Isopropylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, t-butylcarbonyloxy, isoamylcarbonyloxy, t-amylcarbonyloxy, isohexylcarbonyloxy, t-hexylcarbonyloxy, isoheptylcarbonyloxy, t-heptylcarbonyl a branched C 3 -C 10 alkylcarbonyloxy group such as oxy, isooctylcarbonyloxy, t-octylcarbonyloxy, 2-ethylhexylcarbonyloxy, isononylcarbonyloxy, isodecylcarbonyloxy; or,
Examples include cyclic C 3 -C 7 alkylcarbonyloxy groups such as cyclopropylcarbonyloxy, cyclobutylcarbonyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, and cycloheptylcarbonyloxy. Among these, linear or branched alkylcarbonyloxy groups are preferred, and linear alkylcarbonyloxy groups are more preferred.
　上記アリールカルボニルオキシ基は、好ましくはＣ６－Ｃ１２アリールカルボニルオキシ基であり、具体例としては、例えば、フェニルカルボニルオキシ、ナフチルカルボニルオキシ、ビフェニルカルボニルオキシ等が挙げられる。 The above arylcarbonyloxy group is preferably a C 6 -C 12 arylcarbonyloxy group, and specific examples include phenylcarbonyloxy, naphthylcarbonyloxy, biphenylcarbonyloxy and the like.
　上記アルキルカルボニル基としては、直鎖、分岐鎖又は環状のアルキルカルボニル基、好ましくはＣ１－Ｃ１０アルキルカルボニル基が挙げられる。Ｃ１－Ｃ１０アルキルカルボニル基の具体例としては、例えば、
　メチルカルボニル、エチルカルボニル、ｎ－プロピルカルボニル、ｎ－ブチルカルボニル、ｎ－ペンチルカルボニル、ｎ－ヘキシルカルボニル、ｎ－ヘプチルカルボニル、ｎ－オクチルカルボニル、ｎ－ノニルカルボニル、ｎ－デシルカルボニルといった直鎖のＣ１－Ｃ１０アルキルカルボニル基；
　イソプロピルカルボニル、イソブチルカルボニル、ｓｅｃ－ブチルカルボニル、ｔ－ブチルカルボニル、イソアミルカルボニル、ｔ－アミルカルボニル、イソヘキシルカルボニル、ｔ－ヘキシルカルボニル、イソヘプチルカルボニル、ｔ－ヘプチルカルボニル、イソオクチルカルボニル、ｔ－オクチルカルボニル、２－エチルヘキシルカルボニル、イソノニルカルボニル、イソデシルカルボニル等の分岐鎖状のＣ３－Ｃ１０アルキルカルボニル基；又は、
　シクロプロピルカルボニル、シクロブチルカルボニル、シクロペンチルカルボニル、シクロヘキシルカルボニル、シクロヘプチルカルボニル等の環状のＣ３－Ｃ７アルキルカルボニル基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のアルキルカルボニル基が好ましく、直鎖状のアルキルカルボニル基がより好ましい。 The alkylcarbonyl group mentioned above includes a straight chain, branched chain or cyclic alkylcarbonyl group, preferably a C 1 -C 10 alkylcarbonyl group. Specific examples of the C 1 -C 10 alkylcarbonyl group include, for example,
Straight chain C such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, n-pentylcarbonyl, n-hexylcarbonyl, n-heptylcarbonyl, n-octylcarbonyl, n-nonylcarbonyl, n-decylcarbonyl 1 -C 10 alkylcarbonyl group;
Isopropylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, t-butylcarbonyl, isoamylcarbonyl, t-amylcarbonyl, isohexylcarbonyl, t-hexylcarbonyl, isoheptylcarbonyl, t-heptylcarbonyl, isooctylcarbonyl, t-octylcarbonyl , a branched C 3 -C 10 alkylcarbonyl group such as 2-ethylhexylcarbonyl, isononylcarbonyl, isodecylcarbonyl; or
Examples include cyclic C 3 -C 7 alkylcarbonyl groups such as cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, and cycloheptylcarbonyl. Among these, linear or branched alkylcarbonyl groups are preferred, and linear alkylcarbonyl groups are more preferred.
　上記アリールカルボニル基としては、好ましくはＣ６－Ｃ１２アリールカルボニル基であり、具体例としては、例えば、フェニルカルボニル（ベンゾイル）、ナフチルカルボニル、ビフェニルカルボニル等が挙げられる。 The arylcarbonyl group is preferably a C 6 -C 12 arylcarbonyl group, and specific examples include phenylcarbonyl (benzoyl), naphthylcarbonyl, biphenylcarbonyl, and the like.
　上記アルキルカルバモイル基としては、直鎖状、分岐鎖状又は環状のモノアルキルカルバモイル基或いはジアルキルカルバモイル基が挙げられる。 Examples of the alkylcarbamoyl group include linear, branched, or cyclic monoalkylcarbamoyl groups or dialkylcarbamoyl groups.
　モノアルキルカルバモイル基としては、好ましくはモノＣ１－Ｃ１０アルキルカルバモイル基であり、具体例としては、例えば、
　メチルカルバモイル、エチルカルバモイル、ｎ－プロピルカルバモイル、ｎ－ブチルカルバモイル、ｎ－ペンチルカルバモイル、ｎ－ヘキシルカルバモイル、ｎ－ヘプチルカルバモイル、ｎ－オクチルカルバモイル、ｎ－ノニルカルバモイル、ｎ－デシルカルバモイルといった直鎖状のモノＣ１－Ｃ１０アルキルカルバモイル基；
　イソプロピルカルバモイル、イソブチルカルバモイル、ｓｅｃ－ブチルカルバモイル、ｔ－ブチルカルバモイル、イソアミルカルバモイル、ｔ－アミルカルバモイル、イソヘキシルカルバモイル、ｔ－ヘキシルカルバモイル、イソヘプチルカルバモイル、ｔ－ヘプチルカルバモイル、イソオクチルカルバモイル、ｔ－オクチルカルバモイル、２－エチルヘキシルカルバモイル、イソノニルカルバモイル、イソデシルカルバモイル等の分岐鎖状のモノＣ３－Ｃ１０アルキルカルバモイル基；又は、
　シクロプロピルカルバモイル、シクロブチルカルバモイル、シクロペンチルカルバモイル、シクロヘキシルカルバモイル、シクロヘプチルカルバモイル等の環状のモノＣ３－Ｃ７アルキルカルバモイル基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のモノアルキルカルバモイル基が好ましく、直鎖状のモノアルキルカルバモイル基がより好ましい。 The monoalkylcarbamoyl group is preferably a mono-C 1 -C 10 alkylcarbamoyl group, and specific examples include, for example,
Straight-chain carbamoyl, ethylcarbamoyl, n-propylcarbamoyl, n-butylcarbamoyl, n-pentylcarbamoyl, n-hexylcarbamoyl, n-heptylcarbamoyl, n-octylcarbamoyl, n-nonylcarbamoyl, n-decylcarbamoyl mono C 1 -C 10 alkylcarbamoyl group;
Isopropylcarbamoyl, isobutylcarbamoyl, sec-butylcarbamoyl, t-butylcarbamoyl, isoamylcarbamoyl, t-amylcarbamoyl, isohexylcarbamoyl, t-hexylcarbamoyl, isoheptylcarbamoyl, t-heptylcarbamoyl, isooctylcarbamoyl, t-octylcarbamoyl , a branched mono-C 3 -C 10 alkylcarbamoyl group such as 2-ethylhexylcarbamoyl, isononylcarbamoyl, isodecylcarbamoyl; or
Examples include cyclic monoC 3 -C 7 alkylcarbamoyl groups such as cyclopropylcarbamoyl, cyclobutylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, and cycloheptylcarbamoyl. Among these, linear or branched monoalkylcarbamoyl groups are preferred, and linear monoalkylcarbamoyl groups are more preferred.
　ジアルキルカルバモイル基としては、好ましくはジＣ１－Ｃ１０アルキルカルバモイル基であり、具体例としては、例えば、
　ジメチルカルバモイル、ジエチルカルバモイル、ジ－ｎ－プロピルカルバモイル、ジ－ｎ－ブチルカルバモイル、ジ－ｎ－ペンチルカルバモイル、ジ－ｎ－ヘキシルカルバモイル、ジ－ｎ－ヘプチルカルバモイル、ジ－ｎ－オクチルカルバモイル、ジ－ｎ－ノニルカルバモイル、ジ－ｎ－デシルカルバモイルといった直鎖状のジＣ１－Ｃ１０アルキルカルバモイル基；
　ジイソプロピルカルバモイル、ジイソブチルカルバモイル、ジ－ｓｅｃ－ブチルカルバモイル、ジ－ｔ－ブチルカルバモイル、ジイソアミルカルバモイル、ジ－ｔ－アミルカルバモイル、ジイソヘキシルカルバモイル、ジ－ｔ－ヘキシルカルバモイル、ジイソヘプチルカルバモイル、ジ－ｔ－ヘプチルカルバモイル、ジイソオクチルカルバモイル、ジ－ｔ－オクチルカルバモイル、ジ－（２－エチルヘキシル）カルバモイル、ジイソノニルカルバモイル、ジイソデシルカルバモイル等の分岐鎖を２つ有する分岐鎖状のジＣ３－Ｃ１０アルキルカルバモイル基；又は、
　ジシクロプロピルカルバモイル、ジシクロブチルカルバモイル、ジシクロペンチルカルバモイル、ジシクロヘキシルカルバモイル、ジシクロヘプチルカルバモイル等の環を２つ有する環状のジＣ３－Ｃ７アルキルカルバモイル基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のジアルキルカルバモイル基が好ましく、直鎖状のジアルキルカルバモイル基がより好ましい。 The dialkylcarbamoyl group is preferably a di-C 1 -C 10 alkylcarbamoyl group, and specific examples include, for example,
Dimethylcarbamoyl, diethylcarbamoyl, di-n-propylcarbamoyl, di-n-butylcarbamoyl, di-n-pentylcarbamoyl, di-n-hexylcarbamoyl, di-n-heptylcarbamoyl, di-n-octylcarbamoyl, di- Straight-chain di-C 1 -C 10 alkylcarbamoyl groups such as n-nonylcarbamoyl and di-n-decylcarbamoyl;
Diisopropylcarbamoyl, diisobutylcarbamoyl, di-sec-butylcarbamoyl, di-t-butylcarbamoyl, diisoamylcarbamoyl, di-t-amylcarbamoyl, diisohexylcarbamoyl, di-t-hexylcarbamoyl, diisoheptylcarbamoyl, di- Branched diC 3 -C 10 alkyl having two branches such as t-heptylcarbamoyl, diisooctylcarbamoyl, di-t-octylcarbamoyl, di-(2-ethylhexyl)carbamoyl, diisononylcarbamoyl, diisodecylcarbamoyl, etc. Carbamoyl group; or
Examples include cyclic diC 3 -C 7 alkylcarbamoyl groups having two rings such as dicyclopropylcarbamoyl, dicyclobutylcarbamoyl, dicyclopentylcarbamoyl, dicyclohexylcarbamoyl, and dicycloheptylcarbamoyl. Among these, linear or branched dialkylcarbamoyl groups are preferred, and linear dialkylcarbamoyl groups are more preferred.
　上記アリールカルバモイル基としては、モノアリールカルバモイル基又はジアリールカルバモイル基が挙げられる。 Examples of the arylcarbamoyl group include a monoarylcarbamoyl group and a diarylcarbamoyl group.
　モノアリールカルバモイル基は、好ましくはモノＣ６－Ｃ１２アリールカルバモイル基であり、具体例としては、例えば、フェニルカルバモイル、ナフチルカルバモイル、ビフェニルカルバモイル等が挙げられる。 The monoarylcarbamoyl group is preferably a monoC 6 -C 12 arylcarbamoyl group, and specific examples include phenylcarbamoyl, naphthylcarbamoyl, biphenylcarbamoyl, and the like.
　ジアリールカルバモイル基としては、好ましくはジＣ６－Ｃ１２アリールカルバモイル基であり、具体例としては、例えば、ジフェニルカルバモイル、ジナフチルカルバモイル、ジ（ビフェニル）カルバモイル等が挙げられる。 The diarylcarbamoyl group is preferably a diC 6 -C 12 arylcarbamoyl group, and specific examples include diphenylcarbamoyl, dinaphthylcarbamoyl, di(biphenyl)carbamoyl, and the like.
　上記アルコキシカルボニル基としては、直鎖状、分岐鎖状又は環状のアルコキシカルボニル基、好ましくはＣ１－Ｃ１０アルコキシカルボニル基が挙げられる。Ｃ１－Ｃ１０アルコキシカルボニル基の具体例としては、
　例えば、メトキシカルボニル、エトキシカルボニル、ｎ－プロポキシカルボニル、ｎ－ブトキシカルボニル、ｎ－ペントキシカルボニル、ｎ－ヘキシロキシカルボニル、ｎ－ヘプトキシカルボニル、ｎ－オクチロキシカルボニル、ｎ－ノニロキシカルボニル、ｎ－デシロキシカルボニルといった直鎖のＣ１－Ｃ１０アルコキシカルボニル基；
　イソプロポキシカルボニル、イソブトキシカルボニル、ｓｅｃ－ブトキシカルボニル、ｔ－ブトキシカルボニル、イソアミロキシカルボニル、ｔ－アミロキシカルボニル、イソヘキシロキシカルボニル、ｔ－ヘキシロキシカルボニル、イソヘプトキシカルボニル、ｔ－ヘプトキシカルボニル、イソオクチロキシカルボニル、ｔ－オクチロキシカルボニル、２－エチルヘキシロキシカルボニル、イソノニロキシカルボニル、イソデシロキシカルボニル等の分岐鎖状のＣ３－Ｃ１０アルコキシカルボニル基；又は、
　シクロプロポキシカルボニル、シクロブトキシカルボニル、シクロペントキシカルボニル、シクロヘキシロキシカルボニル、シクロヘプトキシカルボニル等の環状のＣ３－Ｃ７アルコキシカルボニル基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のアルコキシカルボニル基が好ましく、直鎖状のアルコキシカルボニル基がより好ましい。 The alkoxycarbonyl group mentioned above includes a linear, branched or cyclic alkoxycarbonyl group, preferably a C 1 -C 10 alkoxycarbonyl group. Specific examples of C 1 -C 10 alkoxycarbonyl groups include:
For example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentoxycarbonyl, n-hexyloxycarbonyl, n-heptoxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, n- Straight chain C 1 -C 10 alkoxycarbonyl groups such as decyloxycarbonyl;
Isopropoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl, isoamyloxycarbonyl, t-amyloxycarbonyl, isohexyloxycarbonyl, t-hexyloxycarbonyl, isoheptoxycarbonyl, t-heptoxycarbonyl , a branched C 3 -C 10 alkoxycarbonyl group such as isooctyloxycarbonyl, t-octyloxycarbonyl, 2-ethylhexyloxycarbonyl, isononyloxycarbonyl, isodecyloxycarbonyl; or,
Examples include cyclic C 3 -C 7 alkoxycarbonyl groups such as cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl, cyclohexyloxycarbonyl, and cycloheptoxycarbonyl. Among these, linear or branched alkoxycarbonyl groups are preferred, and linear alkoxycarbonyl groups are more preferred.
　上記アリールオキシカルボニル基は、好ましくはＣ６－Ｃ１２アリールオキシカルボニル基であり、具体例としては、例えば、フェノキシカルボニル、ナフチロキシカルボニル、ビフェニロキシカルボニル等が挙げられる。 The above aryloxycarbonyl group is preferably a C 6 -C 12 aryloxycarbonyl group, and specific examples include phenoxycarbonyl, naphthyloxycarbonyl, biphenyloxycarbonyl and the like.
　上記アルキルスルホニルアミノ基としては、直鎖状、分岐鎖状又は環状のアルキルスルホニルアミノ基、好ましくはＣ１－Ｃ１０アルキルスルホニルアミノ基が挙げられる。Ｃ１－Ｃ１０アルキルスルホニルアミノ基の具体例としては、例えば、
　メチルスルホニルアミノ、エチルスルホニルアミノ、ｎ－プロピルスルホニルアミノ、ｎ－ブチルスルホニルアミノ、ｎ－ペンチルスルホニルアミノ、ｎ－ヘキシルスルホニルアミノ、ｎ－ヘプチルスルホニルアミノ、ｎ－オクチルスルホニルアミノ、ｎ－ノニルスルホニルアミノ、ｎ－デシルスルホニルアミノといった直鎖状のＣ１－Ｃ１０アルキルスルホニルアミノ基；
　イソプロピルスルホニルアミノ、イソブチルスルホニルアミノ、ｓｅｃ－ブチルスルホニルアミノ、ｔ－ブチルスルホニルアミノ、イソアミルスルホニルアミノ、ｔ－アミルスルホニルアミノ、イソヘキシルスルホニルアミノ、ｔ－ヘキシルスルホニルアミノ、イソヘプチルスルホニルアミノ、ｔ－ヘプチルスルホニルアミノ、イソオクチルスルホニルアミノ、ｔ－オクチルスルホニルアミノ、２－エチルヘキシルスルホニルアミノ、イソノニルスルホニルアミノ、イソデシルスルホニルアミノ等の分岐鎖状のＣ３－Ｃ１０アルキルスルホニルアミノ基；又は、
　シクロプロピルスルホニルアミノ、シクロブチルスルホニルアミノ、シクロペンチルスルホニルアミノ、シクロヘキシルスルホニルアミノ、シクロヘプチルスルホニルアミノ等の環状のＣ３－Ｃ７アルキルスルホニルアミノ基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のアルキルスルホニルアミノ基が好ましく、直鎖状のアルキルスルホニルアミノ基がより好ましい。 Examples of the alkylsulfonylamino group include linear, branched or cyclic alkylsulfonylamino groups, preferably C 1 -C 10 alkylsulfonylamino groups. Specific examples of the C 1 -C 10 alkylsulfonylamino group include, for example,
Methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, n-butylsulfonylamino, n-pentylsulfonylamino, n-hexylsulfonylamino, n-heptylsulfonylamino, n-octylsulfonylamino, n-nonylsulfonylamino, A linear C 1 -C 10 alkylsulfonylamino group such as n-decylsulfonylamino;
Isopropylsulfonylamino, isobutylsulfonylamino, sec-butylsulfonylamino, t-butylsulfonylamino, isoamylsulfonylamino, t-amylsulfonylamino, isohexylsulfonylamino, t-hexylsulfonylamino, isoheptylsulfonylamino, t-heptylsulfonylamino A branched C 3 -C 10 alkylsulfonylamino group such as amino, isooctylsulfonylamino, t-octylsulfonylamino, 2-ethylhexylsulfonylamino, isononylsulfonylamino, isodecylsulfonylamino; or
Examples include cyclic C 3 -C 7 alkylsulfonylamino groups such as cyclopropylsulfonylamino, cyclobutylsulfonylamino, cyclopentylsulfonylamino, cyclohexylsulfonylamino, and cycloheptylsulfonylamino. Among these, linear or branched alkylsulfonylamino groups are preferred, and linear alkylsulfonylamino groups are more preferred.
　上記アリールスルホニルアミノ基は、好ましくはＣ６－Ｃ１２アリールスルホニルアミノ基であり、具体例としては、例えば、フェニルスルホニルアミノ、トルエンスルホニルアミノ、ナフチルスルホニルアミノ、ビフェニルスルホニルアミノ等が挙げられる。 The above arylsulfonylamino group is preferably a C 6 -C 12 arylsulfonylamino group, and specific examples include phenylsulfonylamino, toluenesulfonylamino, naphthylsulfonylamino, biphenylsulfonylamino and the like.
　上記アルキルスルファモイル基としては、直鎖状、分岐鎖状又は環状のモノアルキルスルファモイル基或いはジアルキルスルファモイル基が挙げられる。 Examples of the alkylsulfamoyl group include linear, branched, or cyclic monoalkylsulfamoyl groups or dialkylsulfamoyl groups.
　モノアルキルスルファモイル基は、好ましくはモノＣ１－Ｃ１０アルキルスルファモイル基であり、具体例としては、例えば、
　メチルスルファモイル、エチルスルファモイル、ｎ－プロピルスルファモイル、ｎ－ブチルスルファモイル、ｎ－ペンチルスルファモイル、ｎ－ヘキシルスルファモイル、ｎ－ヘプチルスルファモイル、ｎ－オクチルスルファモイル、ｎ－ノニルスルファモイル、ｎ－デシルスルファモイルといった直鎖のモノＣ１－Ｃ１０アルキルスルファモイル基；
　イソプロピルスルファモイル、イソブチルスルファモイル、ｓｅｃ－ブチルスルファモイル、ｔ－ブチルスルファモイル、イソアミルスルファモイル、ｔ－アミルスルファモイル、イソヘキシルスルファモイル、ｔ－ヘキシルスルファモイル、イソヘプチルスルファモイル、ｔ－ヘプチルスルファモイル、イソオクチルスルファモイル、ｔ－オクチルスルファモイル、２－エチルヘキシルスルファモイル、イソノニルスルファモイル、イソデシルスルファモイル等の分岐鎖状のモノＣ３－Ｃ１０アルキルスルファモイル基；又は、
　シクロプロピルスルファモイル、シクロブチルスルファモイル、シクロペンチルスルファモイル、シクロヘキシルスルファモイル、シクロヘプチルスルファモイル等の環状のモノＣ３－Ｃ７アルキルスルファモイル基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のモノアルキルスルファモイル基が好ましく、直鎖状のモノアルキルスルファモイル基がより好ましい。 The monoalkylsulfamoyl group is preferably a mono-C 1 -C 10 alkylsulfamoyl group, and specific examples include, for example,
Methylsulfamoyl, ethylsulfamoyl, n-propylsulfamoyl, n-butylsulfamoyl, n-pentylsulfamoyl, n-hexylsulfamoyl, n-heptylsulfamoyl, n-octylsulfamoyl Straight chain mono C 1 -C 10 alkylsulfamoyl groups such as moyl, n-nonylsulfamoyl, n-decylsulfamoyl;
Isopropylsulfamoyl, isobutylsulfamoyl, sec-butylsulfamoyl, t-butylsulfamoyl, isoamylsulfamoyl, t-amylsulfamoyl, isohexylsulfamoyl, t-hexylsulfamoyl, iso Branched mono-Cs such as heptylsulfamoyl, t-heptylsulfamoyl, isooctylsulfamoyl, t-octylsulfamoyl, 2-ethylhexylsulfamoyl, isononylsulfamoyl, isodecylsulfamoyl, etc. 3 -C 10 alkylsulfamoyl group; or
Examples include cyclic monoC 3 -C 7 alkylsulfamoyl groups such as cyclopropylsulfamoyl, cyclobutylsulfamoyl, cyclopentylsulfamoyl, cyclohexylsulfamoyl, and cycloheptylsulfamoyl. Among these, linear or branched monoalkylsulfamoyl groups are preferred, and linear monoalkylsulfamoyl groups are more preferred.
　ジアルキルスルファモイル基は、好ましくはジＣ１－Ｃ１０アルキルスルファモイル基であり、具体例としては、例えば、
　ジメチルスルファモイル、ジエチルスルファモイル、ジ－ｎ－プロピルスルファモイル、ジ－ｎ－ブチルスルファモイル、ジ－ｎ－ペンチルスルファモイル、ジ－ｎ－ヘキシルスルファモイル、ジ－ｎ－ヘプチルスルファモイル、ジ－ｎ－オクチルスルファモイル、ジ－ｎ－ノニルスルファモイル、ジ－ｎ－デシルスルファモイルといった直鎖のジＣ１－Ｃ１０アルキルスルファモイル基；
　ジイソプロピルスルファモイル、ジイソブチルスルファモイル、ジ－ｓｅｃ－ブチルスルファモイル、ジ－ｔ－ブチルスルファモイル、ジイソアミルスルファモイル、ジ－ｔ－アミルスルファモイル、ジイソヘキシルスルファモイル、ジ－ｔ－ヘキシルスルファモイル、ジイソヘプチルスルファモイル、ジ－ｔ－ヘプチルスルファモイル、ジイソオクチルスルファモイル、ジ－ｔ－オクチルスルファモイル、ジ－（２－エチルヘキシル）スルファモイル、ジイソノニルスルファモイル、ジイソデシルスルファモイル等の分岐鎖を２つ有する分岐鎖状のジＣ３－Ｃ１０アルキルスルファモイル基；又は、
　ジシクロプロピルスルファモイル、ジシクロブチルスルファモイル、ジシクロペンチルスルファモイル、ジシクロヘキシルスルファモイル、ジシクロヘプチルスルファモイル等の環を２つ有する環状のジＣ３－Ｃ７アルキルスルファモイル基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のジアルキルスルファモイル基が好ましく、直鎖状のジアルキルスルファモイル基がより好ましい。 The dialkylsulfamoyl group is preferably a di-C 1 -C 10 alkylsulfamoyl group, and specific examples include, for example,
Dimethylsulfamoyl, diethylsulfamoyl, di-n-propylsulfamoyl, di-n-butylsulfamoyl, di-n-pentylsulfamoyl, di-n-hexylsulfamoyl, di-n- Straight chain di-C 1 -C 10 alkylsulfamoyl groups such as heptylsulfamoyl, di-n-octylsulfamoyl, di-n-nonylsulfamoyl, di-n-decylsulfamoyl;
Diisopropylsulfamoyl, diisobutylsulfamoyl, di-sec-butylsulfamoyl, di-t-butylsulfamoyl, diisoamylsulfamoyl, di-t-amylsulfamoyl, diisohexylsulfamoyl, Di-t-hexylsulfamoyl, diisoheptylsulfamoyl, di-t-heptylsulfamoyl, diisooctylsulfamoyl, di-t-octylsulfamoyl, di-(2-ethylhexyl)sulfamoyl, A branched diC 3 -C 10 alkylsulfamoyl group having two branches such as diisononylsulfamoyl and diisodecylsulfamoyl; or
Cyclic diC 3 -C 7 alkylsulfamoyl having two rings such as dicyclopropylsulfamoyl, dicyclobutylsulfamoyl, dicyclopentylsulfamoyl, dicyclohexylsulfamoyl, dicycloheptylsulfamoyl, etc. Examples include groups. Among these, linear or branched dialkylsulfamoyl groups are preferred, and linear dialkylsulfamoyl groups are more preferred.
　上記アリールスルファモイル基としては、モノアリールスルファモイル基又はジアリールスルファモイル基が挙げられる。 Examples of the arylsulfamoyl group include a monoarylsulfamoyl group and a diarylsulfamoyl group.
　モノアリールスルファモイル基は、好ましくはモノＣ６－Ｃ１２アリールスルファモイル基であり、具体例としては、例えば、フェニルスルファモイル、ナフチルスルファモイル、ビフェニルスルファモイル等が挙げられる。 The monoarylsulfamoyl group is preferably a monoC 6 -C 12 arylsulfamoyl group, and specific examples thereof include phenylsulfamoyl, naphthylsulfamoyl, biphenylsulfamoyl and the like.
　ジアリールスルファモイル基は、好ましくはジＣ６－Ｃ１２アリールスルファモイル基であり、具体例としては、例えば、ジフェニルスルファモイル、ジナフチルスルファモイル、ジ（ビフェニル）スルファモイル等が挙げられる。 The diarylsulfamoyl group is preferably a diC 6 -C 12 arylsulfamoyl group, and specific examples include diphenylsulfamoyl, dinaphthylsulfamoyl, di(biphenyl)sulfamoyl, etc. .
　上記アルキルスルホニル基としては、直鎖状、分岐鎖状又は環状のアルキルスルホニル基、好ましくはＣ１－Ｃ１２アルキルスルホニル基が挙げられる。Ｃ１－Ｃ１２アルキルスルホニル基の具体例としては、例えば、
　メチルスルホニル、エチルスルホニル、ｎ－プロピルスルホニル、ｎ－ブチルスルホニル、ｎ－ペンチルスルホニル、ｎ－ヘキシルスルホニル、ｎ－ヘプチルスルホニル、ｎ－オクチルスルホニル、ｎ－ノニルスルホニル、ｎ－デシルスルホニル、ｎ－ウンデシルスルホニル、ｎ－ドデシルスルホニルといった直鎖状のＣ１－Ｃ１２アルキルスルホニル基；
　イソプロピルスルホニル、イソブチルスルホニル、ｓｅｃ－ブチルスルホニル、ｔ－ブチルスルホニル、イソアミルスルホニル、ｔ－アミルスルホニル、イソヘキシルスルホニル、ｔ－ヘキシルスルホニル、イソヘプチルスルホニル、ｔ－ヘプチルスルホニル、イソオクチルスルホニル、ｔ－オクチルスルホニル、２－エチルヘキシルスルホニル、イソノニルスルホニル、イソデシルスルホニル、イソウンデシルスルホニル、ｔ－ウンデシルスルホニル、イソドデシルスルホニル、ｔ－ドデシルスルホニル等の分岐鎖状のＣ３－Ｃ１２アルキルスルホニル基；又は、
　シクロプロピルスルホニル、シクロブチルスルホニル、シクロペンチルスルホニル、シクロヘキシルスルホニル、シクロヘプチルスルホニル等の環状のＣ３－Ｃ７アルキルスルホニル基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のアルキルスルホニル基が好ましく、直鎖状のアルキルスルホニル基がより好ましい。 Examples of the alkylsulfonyl group include linear, branched or cyclic alkylsulfonyl groups, preferably C 1 -C 12 alkylsulfonyl groups. Specific examples of the C 1 -C 12 alkylsulfonyl group include, for example,
Methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl, n-pentylsulfonyl, n-hexylsulfonyl, n-heptylsulfonyl, n-octylsulfonyl, n-nonylsulfonyl, n-decylsulfonyl, n-undecyl Straight chain C 1 -C 12 alkylsulfonyl groups such as sulfonyl and n-dodecylsulfonyl;
Isopropylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, t-butylsulfonyl, isoamylsulfonyl, t-amylsulfonyl, isohexylsulfonyl, t-hexylsulfonyl, isoheptylsulfonyl, t-heptylsulfonyl, isooctylsulfonyl, t-octylsulfonyl , a branched C 3 -C 12 alkylsulfonyl group such as 2-ethylhexylsulfonyl, isononylsulfonyl, isodecylsulfonyl, isoundecylsulfonyl, t-undecylsulfonyl, isododecylsulfonyl, t-dodecylsulfonyl; or,
Examples include cyclic C 3 -C 7 alkylsulfonyl groups such as cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, and cycloheptylsulfonyl. Among these, linear or branched alkylsulfonyl groups are preferred, and linear alkylsulfonyl groups are more preferred.
　上記アリールスルホニル基は、好ましくはＣ６－Ｃ１２アリールスルホニル基であり、具体例としては、例えば、フェニルスルホニル、ナフチルスルホニル、ビフェニルスルホニル等が挙げられる。 The above arylsulfonyl group is preferably a C 6 -C 12 arylsulfonyl group, and specific examples include phenylsulfonyl, naphthylsulfonyl, biphenylsulfonyl and the like.
　上記アルキルチオ基としては、直鎖状、分岐鎖状又は環状のアルキルチオ基、好ましくはＣ１－Ｃ１０アルキルチオ基が挙げられる。Ｃ１－Ｃ１０アルキルチオ基の具体例としては、例えば、
　メチルチオ、エチルチオ、ｎ－プロピルチオ、ｎ－ブチルチオ、ｎ－ペンチルチオ、ｎ－ヘキシルチオ、ｎ－ヘプチルチオ、ｎ－オクチルチオ、ｎ－ノニルチオ、ｎ－デシルチオといった直鎖状のＣ１－Ｃ１０アルキルチオ基；
　イソプロピルチオ、イソブチルチオ、ｓｅｃ－ブチルチオ、ｔ－ブチルチオ、イソアミルチオ、ｔ－アミルチオ、イソヘキシルチオ、ｔ－ヘキシルチオ、イソヘプチルチオ、ｔ－ヘプチルチオ、イソオクチルチオ、ｔ－オクチルチオ、２－エチルヘキシルチオ、イソノニルチオ、イソデシルチオ等の分岐鎖状のＣ３－Ｃ１０アルキルチオ基；又は、
　シクロプロピルチオ、シクロブチルチオ、シクロペンチルチオ、シクロヘキシルチオ、シクロヘプチルチオ等の環状のＣ３－Ｃ７アルキルチオ基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のアルキルチオ基が好ましく、直鎖状のアルキルチオ基がより好ましい。 The alkylthio group mentioned above includes a linear, branched or cyclic alkylthio group, preferably a C 1 -C 10 alkylthio group. Specific examples of C 1 -C 10 alkylthio groups include, for example:
Straight chain C 1 - C 10 alkylthio groups such as methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio;
Isopropylthio, isobutylthio, sec-butylthio, t-butylthio, isoamylthio, t-amylthio, isohexylthio, t-hexylthio, isoheptylthio, t-heptylthio, isooctylthio, t-octylthio, 2-ethylhexylthio, isononylthio, a branched C 3 -C 10 alkylthio group such as isodecylthio; or
Examples include cyclic C 3 -C 7 alkylthio groups such as cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, and cycloheptylthio. Among these, linear or branched alkylthio groups are preferred, and linear alkylthio groups are more preferred.
　上記アリールチオ基は、好ましくはＣ６－Ｃ１２アリールチオ基であり、具体例としては、例えば、フェニルチオ、ナフチルチオ、ビフェニルチオ等が挙げられる。 The above arylthio group is preferably a C 6 -C 12 arylthio group, and specific examples include phenylthio, naphthylthio, biphenylthio and the like.
　上記アルキルウレイド基としては、直鎖状、分岐鎖状又は環状のモノアルキルウレイド基或いはジアルキルウレイド基が挙げられる。 Examples of the alkylureido group include linear, branched, or cyclic monoalkylureido groups or dialkylureido groups.
　モノアルキルウレイド基としては、好ましくはモノＣ１－Ｃ１０アルキルウレイド基であり、具体例としては、例えば、
　メチルウレイド、エチルウレイド、ｎ－プロピルウレイド、ｎ－ブチルウレイド、ｎ－ペンチルウレイド、ｎ－ヘキシルウレイド、ｎ－ヘプチルウレイド、ｎ－オクチルウレイド、ｎ－ノニルウレイド、ｎ－デシルウレイドといった直鎖状のモノＣ１－Ｃ１０アルキルウレイド基；
　イソプロピルウレイド、イソブチルウレイド、ｓｅｃ－ブチルウレイド、ｔ－ブチルウレイド、イソアミルウレイド、ｔ－アミルウレイド、イソヘキシルウレイド、ｔ－ヘキシルウレイド、イソヘプチルウレイド、ｔ－ヘプチルウレイド、イソオクチルウレイド、ｔ－オクチルウレイド、２－エチルヘキシルウレイド、イソノニルウレイド、イソデシルウレイド等の分岐鎖状のモノＣ３－Ｃ１０アルキルウレイド基；又は、
　シクロプロピルウレイド、シクロブチルウレイド、シクロペンチルウレイド、シクロヘキシルウレイド、シクロヘプチルウレイド等の環状のモノＣ３－Ｃ７アルキルウレイド基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のアルキルウレイド基が好ましく、直鎖状のアルキルウレイド基が挙げられる。 The monoalkylureido group is preferably a mono-C 1 -C 10 alkylureido group, and specific examples include, for example,
Linear mono-C such as methylureido, ethylureido, n-propylureido, n-butylureido, n-pentylureido, n-hexylureido, n-heptylureido, n-octylureido, n-nonylureido, n-decylureido 1 -C 10 alkylureido group;
Isopropylureido, isobutylureido, sec-butylureido, t-butylureido, isoamylureido, t-amylureido, isohexylureido, t-hexylureido, isoheptylureido, t-heptylureido, isooctylureido, t-octylureido, A branched mono C 3 -C 10 alkyl ureido group such as 2-ethylhexylureido, isononylureido, isodecylureido; or
Examples include cyclic mono C 3 -C 7 alkyl ureido groups such as cyclopropyl ureido, cyclobutyl ureido, cyclopentyl ureido, cyclohexyl ureido, and cycloheptyl ureido. Among these, linear or branched alkylureido groups are preferred, including linear alkylureido groups.
　ジアルキルウレイド基は、好ましくはジＣ１－Ｃ１０アルキルウレイド基であり、具体例としては、例えば、
　ジメチルウレイド、ジエチルウレイド、ジ－ｎ－プロピルウレイド、ジ－ｎ－ブチルウレイド、ジ－ｎ－ペンチルウレイド、ジ－ｎ－ヘキシルウレイド、ジ－ｎ－ヘプチルウレイド、ジ－ｎ－オクチルウレイド、ジ－ｎ－ノニルウレイド、ジ－ｎ－デシルウレイドといった直鎖状のジＣ１－Ｃ１０アルキルウレイド基；
　ジイソプロピルウレイド、ジイソブチルウレイド、ジ－ｓｅｃ－ブチルウレイド、ジ－ｔ－ブチルウレイド、ジイソアミルウレイド、ジ－ｔ－アミルウレイド、ジイソヘキシルウレイド、ジ－ｔ－ヘキシルウレイド、ジイソヘプチルウレイド、ジ－ｔ－ヘプチルウレイド、ジイソオクチルウレイド、ジ－ｔ－オクチルウレイド、ジ－（２－エチルヘキシル）ウレイド、ジイソノニルウレイド、ジイソデシルウレイド等の分岐鎖を２つ有する分岐鎖状のジＣ３－Ｃ１０アルキルウレイド基；又は、
　ジシクロプロピルウレイド、ジシクロブチルウレイド、ジシクロペンチルウレイド、ジシクロヘキシルウレイド、ジシクロヘプチルウレイド等の環を２つ有する環状のジＣ３－Ｃ７アルキルウレイド基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のジアルキルウレイド基が好ましく、直鎖状のジアルキルウレイド基がより好ましい。 The dialkylureido group is preferably a di-C 1 -C 10 alkylureido group, and specific examples include, for example:
Dimethylureido, diethylureido, di-n-propylureido, di-n-butylureido, di-n-pentylureido, di-n-hexylureido, di-n-heptylureido, di-n-octylureido, di- Straight-chain diC 1 -C 10 alkylureido groups such as n-nonylureido and di-n-decylureido;
Diisopropylureido, diisobutylureido, di-sec-butylureido, di-t-butylureido, diisoamylureido, di-t-amylureido, diisohexylureido, di-t-hexylureido, diisoheptylureido, di-t - Branched di-C 3 -C 10 alkyl ureido having two branches such as heptyl ureido, diisooctyl ureido, di-t-octyl ureido, di-(2-ethylhexyl) ureido, diisononyl ureido, diisodecyl ureido, etc. group; or
Examples include cyclic diC 3 -C 7 alkylureido groups having two rings such as dicyclopropylureido, dicyclobutylureido, dicyclopentylureido, dicyclohexylureido, and dicycloheptylureido. Among these, linear or branched dialkylureido groups are preferred, and linear dialkylureido groups are more preferred.
　上記アリールウレイド基としては、モノアリールウレイド基又はジアリールウレイド基が挙げられる。 The above aryl ureido group includes a monoarylureido group or a diarylureido group.
　モノアリールウレイド基としては、好ましくはモノＣ６－Ｃ１２アリールウレイド基であり、具体例としては、例えば、フェニルウレイド、ナフチルウレイド、ビフェニルウレイド等が挙げられる。 The monoarylureido group is preferably a monoC 6 -C 12 arylureido group, and specific examples include phenylureido, naphthylureido, biphenylureido, and the like.
　ジアリールウレイド基は、好ましくはジＣ６－Ｃ１２アリールウレイド基であり、具体例としては、例えば、ジフェニルウレイド、ジナフチルウレイド、ジ（ビフェニル）ウレイド等が挙げられる。 The diarylureido group is preferably a diC 6 -C 12 arylureido group, and specific examples include diphenylureido, dinaphthylureido, di(biphenyl)ureido, and the like.
　上記アルコキシカルボニルアミノ基としては、直鎖状、分岐鎖状又は環状のアルコキシカルボニルアミノ基、好ましくはＣ１－Ｃ１０アルコキシカルボニルアミノ基が挙げられる。Ｃ１－Ｃ１０アルコキシカルボニルアミノ基の具体例としては、例えば、
　メトキシカルボニルアミノ、エトキシカルボニルアミノ、ｎ－プロポキシカルボニルアミノ、ｎ－ブトキシカルボニルアミノ、ｎ－ペントキシカルボニルアミノ、ｎ－ヘキシロキシカルボニルアミノ、ｎ－ヘプトキシカルボニルアミノ、ｎ－オクチロキシカルボニルアミノ、ｎ－ノニロキシカルボニルアミノ、ｎ－デシロキシカルボニルアミノといった直鎖状のＣ１－Ｃ１０アルコキシカルボニルアミノ基；
　イソプロポキシカルボニルアミノ、イソブトキシカルボニルアミノ、ｓｅｃ－ブトキシカルボニルアミノ、ｔ－ブトキシカルボニルアミノ、イソアミロキシカルボニルアミノ、ｔ－アミロキシカルボニルアミノ、イソヘキシロキシカルボニルアミノ、ｔ－ヘキシロキシカルボニルアミノ、イソヘプトキシカルボニルアミノ、ｔ－ヘプトキシカルボニルアミノ、イソオクチロキシカルボニルアミノ、ｔ－オクチロキシカルボニルアミノ、２－エチルヘキシロキシカルボニルアミノ、イソノニロキシカルボニルアミノ、イソデシロキシカルボニルアミノ等の分岐鎖状のＣ３－Ｃ１０アルコキシカルボニルアミノ基；又は、
　シクロプロポキシカルボニルアミノ、シクロブトキシカルボニルアミノ、シクロペントキシカルボニルアミノ、シクロヘキシロキシカルボニルアミノ、シクロヘプトキシカルボニルアミノ等の環状のＣ３－Ｃ７アルコキシカルボニルアミノ基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のアルコキシカルボニルアミノ基が好ましく、直鎖状のアルコキシカルボニルアミノ基がより好ましい。 The alkoxycarbonylamino group mentioned above includes a linear, branched or cyclic alkoxycarbonylamino group, preferably a C 1 -C 10 alkoxycarbonylamino group. Specific examples of the C 1 -C 10 alkoxycarbonylamino group include, for example,
Methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, n-butoxycarbonylamino, n-pentoxycarbonylamino, n-hexyloxycarbonylamino, n-heptoxycarbonylamino, n-octyloxycarbonylamino, n- Straight-chain C 1 -C 10 alkoxycarbonylamino groups such as nonyloxycarbonylamino and n-decyloxycarbonylamino;
Isopropoxycarbonylamino, isobutoxycarbonylamino, sec-butoxycarbonylamino, t-butoxycarbonylamino, isoamyloxycarbonylamino, t-amyloxycarbonylamino, isohexyloxycarbonylamino, t-hexyloxycarbonylamino, isohep Branched C such as toxycarbonylamino, t-heptoxycarbonylamino, isooctyloxycarbonylamino, t-octyloxycarbonylamino, 2-ethylhexyloxycarbonylamino, isononyloxycarbonylamino, isodesyloxycarbonylamino, etc. 3 -C 10 alkoxycarbonylamino group; or
Examples include cyclic C 3 -C 7 alkoxycarbonylamino groups such as cyclopropoxycarbonylamino, cyclobutoxycarbonylamino, cyclopentoxycarbonylamino, cyclohexyloxycarbonylamino, and cycloheptoxycarbonylamino. Among these, linear or branched alkoxycarbonylamino groups are preferred, and linear alkoxycarbonylamino groups are more preferred.
　上記アリールオキシカルボニルアミノ基としては、好ましくはＣ６－Ｃ１２アリールオキシカルボニルアミノ基であり、具体例としては、例えば、フェニルカルボニルアミノ、ナフチルカルボニルアミノ、ビフェニルカルボニルアミノ等が挙げられる。 The aryloxycarbonylamino group is preferably a C 6 -C 12 aryloxycarbonylamino group, and specific examples include phenylcarbonylamino, naphthylcarbonylamino, biphenylcarbonylamino, and the like.
　上記アルキルアミノ基としては、直鎖状、分岐鎖状又は環状のモノアルキルアミノ基又はジアルキルアミノ基が挙げられる。 Examples of the alkylamino group include linear, branched, or cyclic monoalkylamino groups or dialkylamino groups.
　モノアルキルアミノ基は、好ましくはモノＣ１－Ｃ１０アルキルアミノ基であり、具体例としては、例えば、
　メチルアミノ、エチルアミノ、ｎ－プロピルアミノ、ｎ－ブチルアミノ、ｎ－ペンチルアミノ、ｎ－ヘキシルアミノ、ｎ－ヘプチルアミノ、ｎ－オクチルアミノ、ｎ－ノニルアミノ、ｎ－デシルアミノといった直鎖状のモノＣ１－Ｃ１０アルキルアミノ基；
　イソプロピルアミノ、イソブチルアミノ、ｓｅｃ－ブチルアミノ、ｔ－ブチルアミノ、イソアミルアミノ、ｔ－アミルアミノ、イソヘキシルアミノ、ｔ－ヘキシルアミノ、イソヘプチルアミノ、ｔ－ヘプチルアミノ、イソオクチルアミノ、ｔ－オクチルアミノ、２－エチルヘキシルアミノ、イソノニルアミノ、イソデシルアミノ等の分岐鎖状のモノＣ３－Ｃ１０アルキルアミノ基；又は、
　シクロプロピルアミノ、シクロブチルアミノ、シクロペンチルアミノ、シクロヘキシルアミノ、シクロヘプチルアミノ等の環状モノＣ３－Ｃ７アルキルアミノ基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のモノアルキルアミノ基が好ましく、直鎖状のモノアルキルアミノ基がより好ましい。 The monoalkylamino group is preferably a mono-C 1 -C 10 alkylamino group, and specific examples include, for example,
Linear mono-Cs such as methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, and n-decylamino 1 -C 10 alkylamino group;
Isopropylamino, isobutylamino, sec-butylamino, t-butylamino, isoamylamino, t-amylamino, isohexylamino, t-hexylamino, isoheptylamino, t-heptylamino, isooctylamino, t-octylamino, a branched mono C 3 -C 10 alkylamino group such as 2-ethylhexylamino, isononylamino, isodecylamino; or
Examples include cyclic mono C 3 -C 7 alkylamino groups such as cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, and cycloheptylamino. Among these, linear or branched monoalkylamino groups are preferred, and linear monoalkylamino groups are more preferred.
　ジアルキルアミノ基は、好ましくはジＣ１－Ｃ１０アルキルアミノ基であり、具体例としては、例えば、
　ジメチルアミノ、ジエチルアミノ、ジ－ｎ－プロピルアミノ、ジ－ｎ－ブチルアミノ、ジ－ｎ－ペンチルアミノ、ジ－ｎ－ヘキシルアミノ、ジ－ｎ－ヘプチルアミノ、ジ－ｎ－オクチルアミノ、ジ－ｎ－ノニルアミノ、ジ－ｎ－デシルアミノといった直鎖のジＣ１－Ｃ１０アルキルアミノ基；
　ジイソプロピルアミノ、ジイソブチルアミノ、ジ－ｓｅｃ－ブチルアミノ、ジ－ｔ－ブチルアミノ、ジイソアミルアミノ、ジ－ｔ－アミルアミノ、ジイソヘキシルアミノ、ジ－ｔ－ヘキシルアミノ、ジイソヘプチルアミノ、ジ－ｔ－ヘプチルアミノ、ジイソオクチルアミノ、ジ－ｔ－オクチルアミノ、ジ－（２－エチルヘキシル）アミノ、ジイソノニルアミノ、ジイソデシルアミノ等の分岐鎖を２つ有する分岐鎖状のジＣ３－Ｃ１０アルキルアミノ基；又は、
　ジシクロプロピルアミノ、ジシクロブチルアミノ、ジシクロペンチルアミノ、ジシクロヘキシルアミノ、ジシクロヘプチルアミノ等の環を２つ有する環状ジＣ３－Ｃ７アルキルアミノ基が挙げられる。これらの中でも、直鎖状又は分岐鎖状のジアルキルアミノ基が好ましく、直鎖状のジアルキルアミノ基がより好ましい。 The dialkylamino group is preferably a di-C 1 -C 10 alkylamino group, and specific examples include, for example,
Dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, di-n-pentylamino, di-n-hexylamino, di-n-heptylamino, di-n-octylamino, di-n - straight-chain di-C 1 -C 10 alkylamino groups such as nonylamino and di-n-decylamino;
Diisopropylamino, diisobutylamino, di-sec-butylamino, di-t-butylamino, diisoamylamino, di-t-amylamino, diisohexylamino, di-t-hexylamino, diisoheptylamino, di-t - Branched di-C 3 -C 10 alkylamino having two branches such as heptylamino, diisooctylamino, di-t-octylamino, di-(2-ethylhexyl)amino, diisononylamino, diisodecylamino, etc. group; or
Examples include cyclic diC 3 -C 7 alkylamino groups having two rings such as dicyclopropylamino, dicyclobutylamino, dicyclopentylamino, dicyclohexylamino, and dicycloheptylamino. Among these, linear or branched dialkylamino groups are preferred, and linear dialkylamino groups are more preferred.
　上記アリールアミノ基としては、モノアリールアミノ基又はジアリールアミノ基が挙げられる。 Examples of the above arylamino group include a monoarylamino group and a diarylamino group.
　モノアリールアミノ基としては、好ましくはモノＣ６－Ｃ１２アリールアミノ基であり、具体例としては、例えば、フェニルアミノ（アニリノ）、ナフチルアミノ、ビフェニルアミノ等が挙げられる。 The monoarylamino group is preferably a mono-C 6 -C 12 arylamino group, and specific examples include phenylamino (anilino), naphthylamino, biphenylamino, and the like.
　ジアリールアミノ基は、好ましくはジＣ６－Ｃ１２アリールアミノ基であり、具体例としては、例えば、ジフェニルアミノ、ジナフチルアミノ、ジ（ビフェニル）アミノ等が挙げられる。 The diarylamino group is preferably a di-C 6 -C 12 arylamino group, and specific examples include diphenylamino, dinaphthylamino, di(biphenyl)amino, and the like.
　上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、フッ素原子、塩素原子、又は臭素原子が好ましい。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom, a chlorine atom, or a bromine atom being preferred.
　より好ましいＡとしては、例えば、水素原子、Ｃ１－Ｃ４アルキル基、Ｃ１－Ｃ４アルコキシ基、スルホ基を有するＣ１－Ｃ４アルコキシ基、ニトロ基、スルホ基が挙げられる。 More preferable examples of A include, for example, a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkoxy group having a sulfo group, a nitro group, and a sulfo group.
　上記式（１）中、Ａｒは置換基を有してもよいベンゼン環、置換基を有してもよいナフタレン環、又は置換基を有してもよい複素環を示し、Ａｒが複素環の場合は例えば、窒素原子、酸素原子及び硫黄原子からなる群から選択される１～３つのヘテロ原子を含む、５又は６員環の複素環が挙げられる。このような複素環の具体例としては、例えば、
　ピロリジン、テトラヒドロフラン、テトラヒドロチオフェン等の脂環式の複素５員環；
　ピペリジン、ピペラジン、ジオキサン、モルホリン、チオモルホリン等の脂環式の複素６員環；
　ピロール、ピラゾール、イミダゾール、トリアゾール、フラン、チオフェン、オキサゾール、チアゾール等の芳香族複素５員環；
ピリジン、ピラジン、ピリダジン、トリアジン等の芳香族複素６員環；
　フタラン、インドリン、イソインドリン等の複素環部分が５員脂環式の縮環型脂肪族複素環；
　ベンゾピロール、ベンゾピラゾール、ベンゾイミダゾール、ベンゾトリアゾール、ベンゾフラニル、ベンゾチオフェン、ベンゾキサゾール、ベンゾチアゾール、ナフトチアゾール等の複素環部分が芳香族５員環の縮環型芳香族複素環；又は、
　キノリン、シンノリン、フタラジン、キナゾリン、キノキサリン等の複素環部分が芳香族６員環の縮環型芳香族複素環、等が挙げられる。
　前記複素環基は、複素環部分が芳香族環であることが好ましい。また、複素環を構成するヘテロ原子としては窒素原子、及び硫黄原子から選択されることが好ましい。 In the above formula (1), Ar represents a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a heterocycle which may have a substituent; Examples include a 5- or 6-membered heterocycle containing 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms. Specific examples of such heterocycles include, for example,
Five-membered alicyclic heterocycles such as pyrrolidine, tetrahydrofuran, and tetrahydrothiophene;
6-membered alicyclic heterocycles such as piperidine, piperazine, dioxane, morpholine, thiomorpholine;
Aromatic hetero5-membered rings such as pyrrole, pyrazole, imidazole, triazole, furan, thiophene, oxazole, thiazole;
Aromatic 6-membered heterocycles such as pyridine, pyrazine, pyridazine, triazine;
A condensed aliphatic heterocycle in which the heterocyclic moiety is a 5-membered alicyclic structure such as phthalane, indoline, isoindoline;
A condensed aromatic heterocycle in which the heterocyclic moiety is a 5-membered aromatic ring such as benzopyrrole, benzopyrazole, benzimidazole, benzotriazole, benzofuranyl, benzothiophene, benzoxazole, benzothiazole, naphthothiazole; or
Examples include condensed aromatic heterocycles in which the heterocyclic moiety is a 6-membered aromatic ring, such as quinoline, cinnoline, phthalazine, quinazoline, and quinoxaline.
In the heterocyclic group, the heterocyclic moiety is preferably an aromatic ring. Furthermore, the heteroatom constituting the heterocycle is preferably selected from nitrogen atoms and sulfur atoms.
　式（１）で表されるアゾ化合物が下記式（２）で表されるとき、より透過率、高偏光度な偏光膜を提供できるため好ましい。
Figure JPOXMLDOC01-appb-C000008
　式（２）中、Ｒ１～Ｒ８は各々独立に任意の置換基を表し、ｍは０又は１を、またｎは０又は１を示す。 When the azo compound represented by formula (1) is represented by formula (2) below, it is preferable because a polarizing film with higher transmittance and higher degree of polarization can be provided.
Figure JPOXMLDOC01-appb-C000008
In formula (2), R 1 to R 8 each independently represent an arbitrary substituent, m represents 0 or 1, and n represents 0 or 1.
　式（２）中、実線及び破線で描かれる環構造は、フェニル（フェニレン）基又はナフチル（ナフチレン）基を表す。 In formula (2), the ring structure drawn by a solid line and a broken line represents a phenyl (phenylene) group or a naphthyl (naphthylene) group.
　上記式（２）中、Ｒ１～Ｒ８は各々独立に任意の置換基を表し、任意の置換基としては、例えば、式（１）中の有してもよい置換基と同じ置換基が挙げられ、ただし式（１）中の有してもよい置換基とは独立して選択される。また、ｍは０又は１を、ｎは０又は１を示し、好ましくはｎが０である。好ましいＲ１～Ｒ８は、各々独立に水素原子、Ｃ１－Ｃ４のアルキル基、Ｃ１－Ｃ４のアルコキシ基、ハロゲン原子、カルボキシ基、スルホ基、スルホ基を有するＣ１－Ｃ４のアルコキシ基、アミノ基、アセチルアミノ基、又は置換基を有してもよいベンゾイルアミノ基である。 In the above formula (2), R 1 to R 8 each independently represent an arbitrary substituent, and examples of the arbitrary substituent include the same substituent as the optional substituent in the formula (1). However, it is selected independently of the optional substituents in formula (1). Further, m represents 0 or 1, n represents 0 or 1, and preferably n is 0. Preferred R 1 to R 8 are each independently a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a halogen atom, a carboxy group, a sulfo group, or a C 1 -C 4 group having a sulfo group. is an alkoxy group, an amino group, an acetylamino group, or a benzoylamino group which may have a substituent.
　式（２）で表されるアゾ化合物は、より好ましくは、下記式（３）で表される。
Figure JPOXMLDOC01-appb-C000009
　上記式（３）中、Ｒ１～Ｒ６は各々独立に任意の置換基を表し、ｍは０又は１を示す。 The azo compound represented by the formula (2) is more preferably represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000009
In the above formula (3), R 1 to R 6 each independently represent an arbitrary substituent, and m represents 0 or 1.
　上記式（３）中、Ｒ１～Ｒ６はそれぞれ式（２）におけるものと同じ意味を表す。また、ｍは０又は１を示す。より好ましくは、ｍが０であり、Ｒ１～Ｒ６（Ｒ１～Ｒ４）が各々独立に水素原子、Ｃ１－Ｃ４のアルキル基、Ｃ１－Ｃ４のアルコキシ基、ハロゲン原子、カルボキシ基、スルホ基、スルホ基を有するＣ１－Ｃ４のアルコキシ基、アミノ基、アセチルアミノ基、置換基を有してもよいベンゾイルアミノ基である。 In the above formula (3), R 1 to R 6 each represent the same meaning as in formula (2). Moreover, m represents 0 or 1. More preferably, m is 0, and R 1 to R 6 (R 1 to R 4 ) are each independently a hydrogen atom, a C 1 to C 4 alkyl group, a C 1 to C 4 alkoxy group, a halogen atom, These include a carboxyl group, a sulfo group, a C 1 -C 4 alkoxy group having a sulfo group, an amino group, an acetylamino group, and a benzoylamino group which may have a substituent.
　式（２）及び式（３）中、「Ｃ１－Ｃ４のアルキル基」としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基等の直鎖アルキル基、ｓｅｃ－ブチル基、ｔｅｒｔ―ブチル基等の分鎖アルキル基、ビニル基等の不飽和炭化水素基等が挙げられる。 In formulas (2) and (3), the "C 1 -C 4 alkyl group" includes, for example, straight chain alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, sec- Examples include branched alkyl groups such as a butyl group and tert-butyl group, and unsaturated hydrocarbon groups such as a vinyl group.
　式（２）及び式（３）中「Ｃ１－Ｃ４のアルコキシ基」としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ｎ－ブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基等が挙げられる。 Examples of the "C 1 -C 4 alkoxy group" in formulas (2) and (3) include methoxy group, ethoxy group, propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, etc. Can be mentioned.
　式（２）及び式（３）中「スルホ基を有するＣ１－Ｃ４のアルコキシ基」としては、直鎖アルコキシ基が好ましく、スルホ基の置換位置としてはアルコキシ基末端が好ましい。より好ましくは３－スルホプロポキシ基及び４－スルホブトキシ基であり、特に好ましくは３－スルホプロポキシ基である。 In formulas (2) and (3), the "C 1 -C 4 alkoxy group having a sulfo group" is preferably a straight chain alkoxy group, and the substitution position of the sulfo group is preferably at the terminal of the alkoxy group. More preferred are 3-sulfopropoxy group and 4-sulfobutoxy group, particularly preferred is 3-sulfopropoxy group.
　式（２）及び式（３）中「置換基を有してもよいベンゾイルアミノ基」としては、置換基としては特に限定されるものではないが、水溶性基である場合が好ましく、カルボキシ基、スルホ基である場合がより好ましい。 In formulas (2) and (3), the "benzoylamino group which may have a substituent" is not particularly limited as a substituent, but is preferably a water-soluble group, such as a carboxy group. , a sulfo group is more preferable.
　上記式（１）で表されるアゾ化合物又はその塩は、非特許文献１に記載されるような通常のアゾ染料の製法に従い、公知のジアゾ化、カップリングを行うことにより容易に製造できる。式（２）アゾ化合物であってｍ＝１、ｎ＝０の場合を例に合成方法を例示する。 The azo compound represented by the above formula (1) or its salt can be easily produced by performing known diazotization and coupling according to the usual method for producing azo dyes as described in Non-Patent Document 1. The synthesis method will be exemplified using the azo compound of formula (2) where m=1 and n=0.
　まず、下記式（Ａ）で示される芳香族アミン類を非特許文献１に記載されるような公知の方法でジアゾ化し、下記式（Ｂ）の芳香族アミン類と一次カップリングさせ、下記式（Ｃ）で示されるモノアゾアミノ化合物を得る。
Figure JPOXMLDOC01-appb-C000010
（式（Ａ）～式（Ｃ）中、Ｒ１～Ｒ４はそれぞれ式（１）におけるものと同じ意味を表す。） First, aromatic amines represented by the following formula (A) are diazotized by a known method as described in Non-Patent Document 1, and primary coupled with aromatic amines represented by the following formula (B), and the aromatic amines represented by the following formula A monoazoamino compound represented by (C) is obtained.
Figure JPOXMLDOC01-appb-C000010
(In formulas (A) to (C), R 1 to R 4 each have the same meaning as in formula (1).)
　次いで、このモノアゾアミノ化合物（Ｃ）を非特許文献１に記載されるような公知の方法でジアゾ化し、下記式（Ｄ）の芳香族アミン類と二次カップリングさせ、下記式（Ｅ）で示されるジスアゾアミノ化合物を得る。
Figure JPOXMLDOC01-appb-C000011
（式（Ｄ）及び式（Ｅ）中、Ｒ１～Ｒ６はそれぞれ式（１）におけるものと同じ意味を表す。） Next, this monoazoamino compound (C) is diazotized by a known method as described in Non-Patent Document 1, and is subjected to secondary coupling with an aromatic amine of the following formula (D) to form the monoazoamino compound (C) with the following formula (E). The disazoamino compound shown is obtained.
Figure JPOXMLDOC01-appb-C000011
(In formula (D) and formula (E), R 1 to R 6 each represent the same meaning as in formula (1).)
　次いで、式（Ｅ）を非特許文献１に記載されるような公知の方法でジアゾ化し、下記式（Ｆ）で表されるイソインドリル基が置換した１－ナフトール－３－スルホン酸誘導体とカップリングさせることにより式（２）のアゾ化合物が得られる。
Figure JPOXMLDOC01-appb-C000012
 Next, formula (E) is diazotized by a known method as described in Non-Patent Document 1, and coupled with a 1-naphthol-3-sulfonic acid derivative substituted with an isoindolyl group represented by the following formula (F). By doing so, an azo compound of formula (2) is obtained.
Figure JPOXMLDOC01-appb-C000012
　上記反応において、ジアゾ化工程はジアゾ成分の塩酸、硫酸などの鉱酸水溶液又はけん濁液に亜硝酸ナトリウムなどの亜硝酸塩を混合するという順法によるか、又はジアゾ成分の中性若しくは弱アルカリ性の水溶液に亜硝酸塩を加えておき、これと鉱酸を混合するという逆法によって行われる。ジアゾ化の温度は、－１０～４０℃が適当である。また、芳香族アミン類とのカップリング工程は塩酸、酢酸などの酸性水溶液と上記各ジアゾ液を混合し、温度が－１０～４０℃でｐＨ２～７の酸性条件で行われる。 In the above reaction, the diazotization step is carried out by a conventional method of mixing a nitrite such as sodium nitrite with an aqueous solution or suspension of a mineral acid such as hydrochloric acid or sulfuric acid of the diazo component, or a neutral or weakly alkaline solution of the diazo component. This is done by adding nitrite to an aqueous solution and mixing it with mineral acid. The appropriate temperature for diazotization is -10 to 40°C. In addition, the coupling step with aromatic amines is carried out by mixing an acidic aqueous solution such as hydrochloric acid or acetic acid with each of the above diazo liquids under acidic conditions at a temperature of -10 to 40°C and a pH of 2 to 7.
　カップリングして得られたモノアゾ化合物、ジスアゾ化合物はそのままあるいは酸析や塩析により析出させ濾過して取り出すか、溶液又はけん濁液のまま次の工程へ進むこともできる。カップリングして得られたモノアゾ化合物、ジスアゾ化合物が難溶性でけん濁液となっている場合は濾過し、プレスケーキとして次のカップリング工程で使うこともできる。 The monoazo compound and disazo compound obtained by coupling can be used as they are, or they can be precipitated by acid precipitation or salting out and then filtered out, or they can proceed to the next step as a solution or suspension. If the monoazo compound or disazo compound obtained by coupling is poorly soluble and forms a suspension, it can be filtered and used as a press cake in the next coupling step.
　ジスアゾ化合物のジアゾ化物と、式（Ｆ）で表されるナフトール類とのカップリング反応は、温度が－１０～４０℃でｐＨ７～１０の中性からアルカリ性条件で行われる。反応終了後、塩析により析出させ濾過して取り出す。また精製が必要な場合には、塩析を繰り返すか又は有機溶媒を使用して水中から析出させればよい。精製に使用する有機溶媒としては、例えばメタノール、エタノール等のアルコール類、アセトン等のケトン類等の水溶性有機溶媒があげられる。 The coupling reaction between the diazotized product of the disazo compound and the naphthol represented by formula (F) is carried out at a temperature of -10 to 40°C and a pH of 7 to 10 under neutral to alkaline conditions. After the reaction is completed, the precipitate is precipitated by salting out and taken out by filtration. If purification is required, salting out may be repeated or precipitation may be performed from water using an organic solvent. Examples of organic solvents used for purification include water-soluble organic solvents such as alcohols such as methanol and ethanol, and ketones such as acetone.
　前記式（２）で表されるアゾ化合物又はその塩を合成するための出発原料となる式（Ａ）で表される芳香族アミン類が置換ナフチルアミン化合物である場合、例えば、２－アミノナフタレン－６－スルホン酸、２－アミノナフタレン－６，８－ジスルホン酸、２－アミノナフタレン－５，７－ジスルホン酸、２－アミノナフタレン－４，８－ジスルホン酸、２－アミノナフタレン－４，６，８－トリスルホン酸、２－アミノナフタレン－３，６，８－トリスルホン酸、２－アミノ－１－ヒドロキシ－ナフタレン－６－スルホン酸、３－アミノ－１－ヒドロキシ－ナフタレン－６－スルホン酸、２－アミノ－８－ヒドロキシ－ナフタレン－６－スルホン酸、３－アミノ－８－ヒドロキシ－ナフタレン－６－スルホン酸、２－アミノ－１，８－ジヒドロキシ－ナフタレン－６－スルホン酸、３－アミノ－１，８－ジヒドロキシ－ナフタレン－６－スルホン酸、２－アミノ－１，８－ジヒドロキシ－ナフタレン－３－スルホン酸、２－アミノ－１，８－ジヒドロキシ－ナフタレン－３，６－ジスルホン酸、２－アミノ－１－メトキシ－８－ヒドロキシ－ナフタレン－６－スルホン酸、３－アミノ－１－メトキシ－８－ヒドロキシ－ナフタレン－６－スルホン酸、２－アミノ－１－ヒドロキシ－８－メトキシ－ナフタレン－６－スルホン酸、３－アミノ－１－ヒドロキシ－８－メトキシ－ナフタレン－６－スルホン酸、２－アミノ－１－ヒドロキシ－８－（３－スルホプロポキシ）－ナフタレン－３－スルホン酸、２－アミノ－１－ヒドロキシ－８－（４－スルホブトキシ）－ナフタレン－３－スルホン酸、２－アミノ－１－（３－スルホプロポキシ）－８－ヒドロキシ－ナフタレン－３－スルホン酸、２－アミノ－１－（４－スルホブトキシ）－８－ヒドロキシ－ナフタレン－３－スルホン酸、２－アミノ－１，８－ジヒドロキシ－ナフタレン－６－アミノメチル－３－ジスルホン酸等が挙げられるが、これらに限定されるものではない。好ましくは２－アミノナフタレン－６，８－ジスルホン酸、２－アミノナフタレン－５，７－ジスルホン酸、２－アミノナフタレン－４，８－ジスルホン酸、２－アミノナフタレン－３，６，８－トリスルホン酸、である。 When the aromatic amine represented by formula (A) which is the starting material for synthesizing the azo compound represented by formula (2) or its salt is a substituted naphthylamine compound, for example, 2-aminonaphthalene- 6-sulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-4,6, 8-trisulfonic acid, 2-aminonaphthalene-3,6,8-trisulfonic acid, 2-amino-1-hydroxy-naphthalene-6-sulfonic acid, 3-amino-1-hydroxy-naphthalene-6-sulfonic acid , 2-amino-8-hydroxy-naphthalene-6-sulfonic acid, 3-amino-8-hydroxy-naphthalene-6-sulfonic acid, 2-amino-1,8-dihydroxy-naphthalene-6-sulfonic acid, 3- Amino-1,8-dihydroxy-naphthalene-6-sulfonic acid, 2-amino-1,8-dihydroxy-naphthalene-3-sulfonic acid, 2-amino-1,8-dihydroxy-naphthalene-3,6-disulfonic acid , 2-amino-1-methoxy-8-hydroxy-naphthalene-6-sulfonic acid, 3-amino-1-methoxy-8-hydroxy-naphthalene-6-sulfonic acid, 2-amino-1-hydroxy-8-methoxy -Naphthalene-6-sulfonic acid, 3-amino-1-hydroxy-8-methoxy-naphthalene-6-sulfonic acid, 2-amino-1-hydroxy-8-(3-sulfopropoxy)-naphthalene-3-sulfonic acid , 2-amino-1-hydroxy-8-(4-sulfobutoxy)-naphthalene-3-sulfonic acid, 2-amino-1-(3-sulfopropoxy)-8-hydroxy-naphthalene-3-sulfonic acid, 2 -amino-1-(4-sulfobutoxy)-8-hydroxy-naphthalene-3-sulfonic acid, 2-amino-1,8-dihydroxy-naphthalene-6-aminomethyl-3-disulfonic acid, etc. It is not limited to these. Preferably 2-aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, and 2-aminonaphthalene-3,6,8-trisulfonic acid. It is sulfonic acid.
　前記式（２）で表されるアゾ化合物又はその塩を合成するための出発原料となる式（Ａ）で表される芳香族アミン類が置換フェニルアミン化合物である場合、例えば、４－スルホアニリン、３－スルホアニリン、２－スルホアニリン、２，４－ジスルホアニリン、２，５－ジスルホアニリン、２－アミノ安息香酸、３－アミノ安息香酸、４－アミノ安息香酸、５－アミノイソフタル酸、２－アミノテレフタル酸、４－アミノフタル酸、４－ニトロ－２－スルホアニリン、２－ニトロ－４－スルホアニリン、４－メトキシ－２－スルホアニリン、２－メトキシ－４－スルホアニリン、４－クロロ－３－スルホアニリン、４－クロロ－３－カルボキシアニリン、４－（３－スルホプロポキシ）アニリン、４－（４－アミノベンゾイルアミド）ベンゼン－１，３－ジスルホン酸、５－（４－アミノベンゾイルアミド）ベンゼン－１，３－ジカルボン酸、が挙げられるがこれらに限定されるものではない。好ましくは４－スルホアニリン、４－アミノ安息香酸、２，４－ジスルホアニリン、４－（４－アミノベンゾイルアミド）ベンゼン－１，３－ジスルホン酸、５－（４－アミノベンゾイルアミド）ベンゼン－１，３－ジカルボン酸である。 When the aromatic amine represented by formula (A) which is the starting material for synthesizing the azo compound represented by formula (2) or its salt is a substituted phenylamine compound, for example, 4-sulfoaniline , 3-sulfoaniline, 2-sulfoaniline, 2,4-disulfoaniline, 2,5-disulfoaniline, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 5-aminoisophthalic acid , 2-aminoterephthalic acid, 4-aminophthalic acid, 4-nitro-2-sulfoaniline, 2-nitro-4-sulfoaniline, 4-methoxy-2-sulfoaniline, 2-methoxy-4-sulfoaniline, 4- Chloro-3-sulfoaniline, 4-chloro-3-carboxyaniline, 4-(3-sulfopropoxy)aniline, 4-(4-aminobenzoylamido)benzene-1,3-disulfonic acid, 5-(4-amino Examples include, but are not limited to, benzoylamido)benzene-1,3-dicarboxylic acid. Preferably 4-sulfoaniline, 4-aminobenzoic acid, 2,4-disulfoaniline, 4-(4-aminobenzoylamide)benzene-1,3-disulfonic acid, 5-(4-aminobenzoylamide)benzene- It is a 1,3-dicarboxylic acid.
　前記式（２）で表されるアゾ化合物又はその塩を合成するための出発原料となる式（Ｂ）、及び式（Ｄ）で表される芳香族アミン類が置換フェニルアミン化合物である場合、例えば、アニリン、２－メチルアニリン、２－エチルアニリン、２－プロピルアニリン、２－ブチルアニリン、３－メチルアニリン、３－エチルアニリン、３－プロピルアニリン、３－ブチルアニリン、２，５－ジメチルアニリン、２，５－ジエチルアニリン、２－メトキシアニリン、２－エトキシアニリン、２－プロポキシアニリン、２－ブトキシアニリン、３－メトキシアニリン、３－エトキシアニリン、３－プロポキシアニリン、３－ブトキシアニリン、２－メトキシ－５－メチルアニリン、２，５－ジメトキシアニリン、３，５－ジメチルアニリン、２，６－ジメチルアニリン、３，５－ジメトキシアニリン、２－クロロアニリン、３－クロロアニリン、３－（２－アミノ－４－メチルフェノキシ）プロパン－１－スルホン酸、３－（２－アミノフェノキシ）プロパン－１－スルホン酸、４－（２－アミノ－４－メチルフェノキシ）ブタン－１－スルホン酸、４－（２－アミノフェノキシ）ブタン－１－スルホン酸、２－（２－アミノ－４－メチルフェノキシ）エタン―１－スルホン酸、２－（２－アミノフェノキシ）エタン－１－スルホン酸、３－（３－アミノ－４－メチルフェノキシ）プロパン－１－スルホン酸、３－（３－アミノフェノキシ）プロパン－１－スルホン酸、４－（３－アミノ－４－メチルフェノキシ）ブタン－１－スルホン酸、４－（３－アミノフェノキシ）ブタン－１－スルホン酸、２－（３－アミノ－４－メチルフェノキシ）エタン－１－スルホン酸、２－（３－アミノフェノキシ）エタン－１－スルホン酸、３－（２－アミノ－４－メトキシフェノキシ）プロパン－１－スルホン酸、４－（２－アミノ－４－メトキシフェノキシ）ブタン－１－スルホン酸、２－（２－アミノ－４－メトキシフェノキシ）エタン―１－スルホン酸、３－（３－アミノ－４－メトキシフェノキシ）プロパン－１－スルホン酸、４－（３－アミノ－４－メトキシフェノキシ）ブタン－１－スルホン酸、２－（３－アミノ－４－メトキシフェノキシ）エタン－１－スルホン酸、３－（２－アミノ－４－エトキシフェノキシ）プロパン－１－スルホン酸、４－（２－アミノ－４－エトキシフェノキシ）ブタン－１－スルホン酸、２－（２－アミノ－４－エトキシフェノキシ）エタン―１－スルホン酸、３－（３－アミノ－４－エトキシフェノキシ）プロパン－１－スルホン酸、４－（３－アミノ－４－エトキシフェノキシ）ブタン－１－スルホン酸、２－（３－アミノ－４－エトキシフェノキシ）エタン－１－スルホン酸等が挙げられるがこれらに限定されるものではない。またこれらの芳香族アミン類はアミノ基が保護されていてもよい。保護基としては、例えばω－メタンスルホン基が挙げられる。 When the aromatic amines represented by formula (B) and formula (D), which are the starting materials for synthesizing the azo compound represented by formula (2) or its salt, are substituted phenylamine compounds, For example, aniline, 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 3-methylaniline, 3-ethylaniline, 3-propylaniline, 3-butylaniline, 2,5-dimethylaniline , 2,5-diethylaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-propoxyaniline, 2-butoxyaniline, 3-methoxyaniline, 3-ethoxyaniline, 3-propoxyaniline, 3-butoxyaniline, 2- Methoxy-5-methylaniline, 2,5-dimethoxyaniline, 3,5-dimethylaniline, 2,6-dimethylaniline, 3,5-dimethoxyaniline, 2-chloroaniline, 3-chloroaniline, 3-(2- Amino-4-methylphenoxy)propane-1-sulfonic acid, 3-(2-aminophenoxy)propane-1-sulfonic acid, 4-(2-amino-4-methylphenoxy)butane-1-sulfonic acid, 4- (2-aminophenoxy)butane-1-sulfonic acid, 2-(2-amino-4-methylphenoxy)ethane-1-sulfonic acid, 2-(2-aminophenoxy)ethane-1-sulfonic acid, 3-( 3-amino-4-methylphenoxy)propane-1-sulfonic acid, 3-(3-aminophenoxy)propane-1-sulfonic acid, 4-(3-amino-4-methylphenoxy)butane-1-sulfonic acid, 4-(3-aminophenoxy)butane-1-sulfonic acid, 2-(3-amino-4-methylphenoxy)ethane-1-sulfonic acid, 2-(3-aminophenoxy)ethane-1-sulfonic acid, 3 -(2-amino-4-methoxyphenoxy)propane-1-sulfonic acid, 4-(2-amino-4-methoxyphenoxy)butane-1-sulfonic acid, 2-(2-amino-4-methoxyphenoxy)ethane -1-sulfonic acid, 3-(3-amino-4-methoxyphenoxy)propane-1-sulfonic acid, 4-(3-amino-4-methoxyphenoxy)butane-1-sulfonic acid, 2-(3-amino -4-methoxyphenoxy)ethane-1-sulfonic acid, 3-(2-amino-4-ethoxyphenoxy)propane-1-sulfonic acid, 4-(2-amino-4-ethoxyphenoxy)butane-1-sulfonic acid , 2-(2-amino-4-ethoxyphenoxy)ethane-1-sulfonic acid, 3-(3-amino-4-ethoxyphenoxy)propane-1-sulfonic acid, 4-(3-amino-4-ethoxyphenoxy) ) butane-1-sulfonic acid, 2-(3-amino-4-ethoxyphenoxy)ethane-1-sulfonic acid, etc., but are not limited to these. Moreover, the amino group of these aromatic amines may be protected. Examples of the protecting group include ω-methanesulfone group.
　前記式（２）で表されるアゾ化合物又はその塩を合成するための出発原料となる式（Ｂ）、及び式（Ｄ）で表される芳香族アミン類が置換ナフチルアミン化合物である場合、例えば、１－アミノ－６－ナフタレンスルホン酸、１－アミノ－７－ナフタレンスルホン酸、１－アミノ－２－メトキシ－６－ナフタレンスルホン酸、１－アミノ－２－メトキシ－７－ナフタレンスルホン酸、１－アミノ－２－エトキシ－６－ナフタレンスルホン酸、１－アミノ－２－エトキシ－７－ナフタレンスルホン酸、１－アミノ－５－ヒドロキシ－７－ナフタレンスルホン酸などが挙げられるがこれらに限定されるものではない。 When the aromatic amines represented by formula (B) and formula (D), which are the starting materials for synthesizing the azo compound represented by formula (2) or its salt, are substituted naphthylamine compounds, for example, , 1-amino-6-naphthalenesulfonic acid, 1-amino-7-naphthalenesulfonic acid, 1-amino-2-methoxy-6-naphthalenesulfonic acid, 1-amino-2-methoxy-7-naphthalenesulfonic acid, 1 -Amino-2-ethoxy-6-naphthalenesulfonic acid, 1-amino-2-ethoxy-7-naphthalenesulfonic acid, 1-amino-5-hydroxy-7-naphthalenesulfonic acid, etc., but are limited to these. It's not a thing.
　前記式（１）で表されるアゾ化合物又はその塩の具体例を以下に挙げる。なお、アゾ化合物は遊離酸の形式で表す。
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
 Specific examples of the azo compound represented by the formula (1) or its salt are listed below. Note that the azo compound is expressed in the form of a free acid.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
　上記式（１）で表されるアゾ化合物は、それぞれ遊離酸形態であっても、塩の形態であってもよいが、金属イオン、アンモニウムイオンの塩であってもよい。金属イオンとしては、例えば、リチウムイオン、ナトリウム、カリウムイオン等のアルカリ金属イオン、カルシウムイオン、マグネシウムイオン等のアルカリ土類金属イオン等が挙げられる。アンモニウムイオンとしては、例えば、アンモニウムイオン、メチルアンモニウムイオン、ジメチルアンモニウムイオン、トリエチルアンモニウムイオン、テトラエチルアンモニウムイオン、テトラ－ｎ－プロピルアンモニウムイオン、テトラ－ｎ－ブチルアンモニウムイオン、トリエタノールアンモニウムイオン等が挙げられる。より具体的には、例えば、遊離酸の場合はスルホン酸（－ＳＯ３Ｈ）を、ナトリウムイオンの場合はスルホン酸ナトリウム（－ＳＯ３Ｎａ）を、アンモニウムイオンの場合はスルホン酸アンモニウム（－ＳＯ３ＮＨ４）を表す。 The azo compound represented by the above formula (1) may be in the form of a free acid or a salt, or may be a salt of a metal ion or an ammonium ion. Examples of metal ions include alkali metal ions such as lithium ions, sodium and potassium ions, alkaline earth metal ions such as calcium ions and magnesium ions. Examples of ammonium ions include ammonium ion, methylammonium ion, dimethylammonium ion, triethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, triethanolammonium ion, etc. . More specifically, for example, in the case of a free acid, use sulfonic acid (-SO 3 H), in the case of sodium ion, use sodium sulfonate (-SO 3 Na), and in the case of ammonium ion, use ammonium sulfonate (-SO 3 H). 3NH 4 ).
＜偏光膜＞
　本発明の偏光膜は、二色性染料として上記式（１）で表されるアゾ化合物又はその塩を含有する。偏光膜は、ニュートラルグレー偏光膜及びカラー偏光膜の態様があり、好ましくはニュートラルグレー偏光膜である。ここで、「ニュートラルグレー」とは、２枚の偏光膜をその配向方向が互いに直交するように重ね合せた状態（以下、「直交位」とも称する。）で、可視光領域の波長領域における特定波長の光漏れ（色漏れ）が少ないことを意味する。 <Polarizing film>
The polarizing film of the present invention contains an azo compound represented by the above formula (1) or a salt thereof as a dichroic dye. The polarizing film may be a neutral gray polarizing film or a color polarizing film, and preferably a neutral gray polarizing film. Here, "neutral gray" refers to a state in which two polarizing films are stacked so that their orientation directions are perpendicular to each other (hereinafter also referred to as "orthogonal position"). This means that there is less wavelength light leakage (color leakage).
　本発明の偏光膜は、二色性染料として上記式（１）で表されるアゾ化合物又はその塩を１種単独又は複数種類の組合せを含み、必要に応じて、上記式（１）で表されるアゾ化合物以外の他の有機染料を１種以上さらに含有することができる。他の有機染料としては、特に制限されないが、上記式（１）で表されるアゾ化合物又はその塩の吸収波長領域と異なる波長領域に吸収特性を有する染料であって、二色性の高いものが好ましい。その他の有機染料としては、例えばシー．アイ．ダイレクト．イエロー１２、シー．アイ．ダイレクト．イエロー２８、シー．アイ．ダイレクト．イエロー４４、シー．アイ．ダイレクト．オレンジ２６、シー．アイ．ダイレクト．オレンジ３９、シー．アイ．ダイレクト．オレンジ７１、シー．アイ．ダイレクト．オレンジ１０７、シー．アイ．ダイレクト．レッド２、シー．アイ．ダイレクト．レッド３１、シー．アイ．ダイレクト．レッド７９、シー．アイ．ダイレクト．レッド８１、シー．アイ．ダイレクト．レッド２４７、シー．アイ．ダイレクト．ブルー６９、シー．アイ．ダイレクト．グリーン８０、及びシー．アイ．ダイレクト．グリーン５９、並びに非特許文献２に記載された染料が代表例として挙げられるが、目的に応じて特許文献１～４に記載されているような偏光板用に開発された染料を用いることが好ましい。これらの有機染料は、遊離酸、アルカリ金属塩（例えばＮａ塩、Ｋ塩、Ｌｉ塩）、アンモニウム塩、又はアミン類の塩として用いられる。 The polarizing film of the present invention contains an azo compound represented by the above formula (1) or a salt thereof as a dichroic dye, or a combination of two or more kinds, and if necessary, the azo compound represented by the above formula (1) or a salt thereof. The composition may further contain one or more organic dyes other than the azo compound. Other organic dyes are not particularly limited, but are dyes with high dichroism that have absorption characteristics in a wavelength range different from the absorption wavelength range of the azo compound represented by the above formula (1) or its salt. is preferred. Other organic dyes include, for example, C. Ai. direct. Yellow 12, C. Ai. direct. Yellow 28, C. Ai. direct. Yellow 44, C. Ai. direct. Orange 26, C. Ai. direct. Orange 39, C. Ai. direct. Orange 71, C. Ai. direct. Orange 107, C. Ai. direct. Red 2, C. Ai. direct. Red 31, C. Ai. direct. Red 79, C. Ai. direct. Red 81, C. Ai. direct. Red 247, C. Ai. direct. Blue 69, C. Ai. direct. Green 80, and Sea. Ai. direct. Typical examples include Green 59 and the dyes described in Non-Patent Document 2, but depending on the purpose, it is preferable to use dyes developed for polarizing plates such as those described in Patent Documents 1 to 4. . These organic dyes are used as free acids, alkali metal salts (for example, Na salts, K salts, Li salts), ammonium salts, or salts of amines.
　他の有機染料を併用する場合、目的とする偏光膜が、ニュートラルグレーの偏光膜、液晶プロジェクター用カラー偏光膜、その他のカラー偏光膜に応じて、それぞれ配合する有機染料の種類は異なる。その配合割合は特に限定されるものではないが、一般的には、式（１）のアゾ化合物又はその塩１質量部に対して、他の有機染料の少なくとも１種以上の合計を０．０１～１００質量部の範囲で用いるのが好ましく、０．１～１０質量部の範囲がさらに好ましい。 When using other organic dyes in combination, the types of organic dyes to be blended will differ depending on whether the intended polarizing film is a neutral gray polarizing film, a color polarizing film for liquid crystal projectors, or another color polarizing film. The blending ratio is not particularly limited, but in general, the total amount of at least one or more other organic dyes is 0.01 parts by mass of the azo compound of formula (1) or its salt. It is preferably used in a range of 100 parts by mass, more preferably 0.1 to 10 parts by mass.
　目的とする偏光膜がニュートラルグレー偏光膜である場合、得られる偏光膜の可視光領域の波長領域における色漏れが少なくなるように、併用されるその他の有機染料の種類及び配合割合が調整される。 When the intended polarizing film is a neutral gray polarizing film, the type and blending ratio of other organic dyes used in combination are adjusted so that the resulting polarizing film has less color leakage in the visible light wavelength range. .
　目的とする偏光膜がカラー偏光膜である場合、得られる偏光膜の特定波長域において高い単板平均光透過率を有し、直交位の平均光透過率が低くなるように、例えば、特定の波長域において３９％以上の単板平均光透過率と、０．４％以下の直交位の平均光透過率を有するように、併用されるその他の有機染料の種類及び配合割合の調整が行われる。 When the intended polarizing film is a color polarizing film, for example, a specific polarizing film is used so that the resulting polarizing film has a high single-plate average light transmittance in a specific wavelength range and a low average light transmittance in the orthogonal position. The type and blending ratio of other organic dyes used in combination are adjusted so that the single plate has an average light transmittance of 39% or more in the wavelength range and an orthogonal average light transmittance of 0.4% or less. .
　本発明の偏光膜は、上記式（１）で表されるアゾ化合物又はその塩と、必要に応じて他の染料とを含む二色性染料を、偏光膜基材（単に、「基材」ともいう。）に公知の方法で含有させ配向させることにより製造することができる。 In the polarizing film of the present invention, a dichroic dye containing an azo compound represented by the above formula (1) or a salt thereof and, if necessary, other dyes is applied to a polarizing film base material (simply referred to as a "base material"). ) can be produced by incorporating and orienting it by a known method.
　偏光膜基材は、好ましく高分子フィルムであり、ポリビニルアルコール樹脂又はその誘導体からなるフィルムであることがより好ましい。偏光膜基材の具体例としてはポリビニルアルコール樹脂又はこれをエチレン、プロピレンのようなオレフィンや、クロトン酸、アクリル酸、メタクリル酸、及びマレイン酸のような不飽和カルボン酸などで変性したもの等が挙げられる。偏光膜基材としては、ポリビニルアルコール樹脂又はその誘導体からなるフィルムが、染料の吸着性及び配向性の点から、好適に用いられる。偏光膜基材の厚さは通常１０～１００μｍであり、好ましくは２０～８０μｍ程度である。 The polarizing film base material is preferably a polymer film, and more preferably a film made of polyvinyl alcohol resin or a derivative thereof. Specific examples of polarizing film base materials include polyvinyl alcohol resins or those modified with olefins such as ethylene and propylene, and unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, and maleic acid. Can be mentioned. As the polarizing film base material, a film made of polyvinyl alcohol resin or a derivative thereof is preferably used from the viewpoint of dye adsorption and orientation. The thickness of the polarizing film base material is usually 10 to 100 μm, preferably about 20 to 80 μm.
　偏光膜基材が高分子フィルムである場合、上記式（１）のアゾ化合物又はその塩を含有させるには、通常、高分子フィルムを染色する方法が採用される。染色は、例えば次のように行われる。まず、上記式（１）で表されるアゾ化合物又はその塩、及び必要によりその他の有機染料を水に溶解して染浴を調製する。染浴中の染料濃度は特に制限されないが、通常は０．００１～１０質量％程度の範囲から選択される。また、必要により染色助剤を用いてもよく、例えば、芒硝を例えば０．１～１０質量％程度の濃度で用いるのが好適である。このようにして調製した染浴に高分子フィルムを例えば１～１０分間浸漬し、染色を行うことができる。染色温度は、好ましくは３０～８０℃程度である。 When the polarizing film base material is a polymer film, a method of dyeing the polymer film is usually adopted to incorporate the azo compound of formula (1) or its salt. Staining is performed, for example, as follows. First, a dye bath is prepared by dissolving the azo compound represented by the above formula (1) or a salt thereof and, if necessary, other organic dyes in water. The dye concentration in the dye bath is not particularly limited, but is usually selected from a range of about 0.001 to 10% by mass. Further, a dyeing aid may be used if necessary, and for example, it is preferable to use Glauber's salt at a concentration of about 0.1 to 10% by mass. Dyeing can be carried out by immersing the polymer film in the dye bath thus prepared for, for example, 1 to 10 minutes. The dyeing temperature is preferably about 30 to 80°C.
　上記式（１）で表されるアゾ化合物又はその塩の配向は、二色性染料で染色された高分子フィルムを延伸することによって行われる。延伸倍率は、一般的に２～９倍であり、好ましくは３～８倍であり、より好ましくは４～７倍が適用される。延伸する方法としては、例えば、湿式法、乾式法など、公知のいずれの方法を用いてもよい。高分子フィルムの延伸は、場合により、染色の前に行ってもよい。この場合には、染色の時点で水溶性染料の配向が行われる。水溶性染料を含有し、配向させた高分子フィルムは、必要に応じて公知の方法によりホウ酸処理などの後処理が施される。このような後処理は、偏光膜の光線透過率及び偏光度を向上させる目的で行われる。ホウ酸処理の条件は、用いる高分子フィルムの種類や用いる染料の種類によって異なるが、一般的にはホウ酸水溶液のホウ酸濃度を例えば０．１～１５質量％であり、好ましくは１～１０質量％の範囲とし、処理温度は３０～８０℃であり、好ましくは４０～７５℃であり、０．５～１０分間浸漬して行われる。さらに必要に応じて、カチオン系高分子化合物を含む水溶液で、フィックス処理を併せて行ってもよい。 The orientation of the azo compound represented by the above formula (1) or its salt is performed by stretching a polymer film dyed with a dichroic dye. The stretching ratio is generally 2 to 9 times, preferably 3 to 8 times, and more preferably 4 to 7 times. As the stretching method, any known method such as a wet method or a dry method may be used. Stretching of the polymer film may optionally be carried out before dyeing. In this case, the water-soluble dye is oriented at the time of dyeing. The oriented polymer film containing a water-soluble dye is subjected to post-treatment such as boric acid treatment by a known method, if necessary. Such post-treatment is performed for the purpose of improving the light transmittance and polarization degree of the polarizing film. The conditions for the boric acid treatment vary depending on the type of polymer film used and the type of dye used, but generally the boric acid concentration of the boric acid aqueous solution is, for example, 0.1 to 15% by mass, preferably 1 to 10% by mass. The treatment temperature is 30 to 80°C, preferably 40 to 75°C, and the treatment is carried out by immersion for 0.5 to 10 minutes. Furthermore, if necessary, a fixing treatment may also be performed using an aqueous solution containing a cationic polymer compound.
　本発明の偏光膜の用途としては、例えば、液晶プロジェクター、電卓、時計、ノートパソコン、ワープロ、液晶テレビ、カーナビゲーション、屋内外の計測器や表示器等、及びレンズやメガネ等が挙げられる。本発明の染料を用いて作製された偏光膜（以下、「染料系偏光膜」ともいう。）は、ヨウ素を用いて作製された偏光膜（以下、「ヨウ素系偏光膜」ともいう。）に匹敵する高い偏光性能を有し、かつ、耐久性にも優れる。このため、高い偏光性能と耐久性を必要とする用途、例えば、車載用及び屋外表示用（例えば、工業計器類の表示用途やウェアラブル用途）等の各種液晶表示体、及び液晶プロジェクターに特に好適である。 Applications of the polarizing film of the present invention include, for example, liquid crystal projectors, calculators, watches, notebook computers, word processors, liquid crystal televisions, car navigation systems, indoor and outdoor measuring instruments and displays, and lenses and glasses. The polarizing film made using the dye of the present invention (hereinafter also referred to as "dye-based polarizing film") is different from the polarizing film made using iodine (hereinafter also referred to as "iodine-based polarizing film"). It has comparable high polarization performance and excellent durability. Therefore, it is particularly suitable for applications that require high polarization performance and durability, such as various liquid crystal displays for in-vehicle and outdoor displays (e.g., industrial instrument displays and wearable applications), and liquid crystal projectors. be.
＜偏光板＞
　本発明の偏光板（以下、「染料系偏光板」ともいう。）は、本発明の偏光膜の片面又は両面に、透明保護膜を貼合して得ることができる。本発明の偏光板は、優れた偏光性能及び耐久性（耐湿性、耐熱性、耐光性）を有する。透明保護膜を形成する材料としては、光学的透明性及び機械的強度に優れる材料が好ましく、例えば、セルロースアセテート系フィルム、アクリル系フィルム、四フッ化エチレン／六フッ化プロピレン系共重合体等のフッ素系フィルム、ポリエステル樹脂、ポリオレフィン樹脂又はポリアミド系樹脂からなるフィルム等が挙げられる。透明保護膜は、好ましくはトリアセチルセルロース（ＴＡＣ）フィルム又はシクロオレフィン系フィルムである。保護膜の厚さは通常４０～２００μｍであることが好ましい。 <Polarizing plate>
The polarizing plate of the present invention (hereinafter also referred to as "dye-based polarizing plate") can be obtained by laminating a transparent protective film on one or both sides of the polarizing film of the present invention. The polarizing plate of the present invention has excellent polarizing performance and durability (moisture resistance, heat resistance, light resistance). The material for forming the transparent protective film is preferably a material with excellent optical transparency and mechanical strength, such as cellulose acetate film, acrylic film, tetrafluoroethylene/hexafluoropropylene copolymer, etc. Examples include fluorine-based films, films made of polyester resins, polyolefin resins, or polyamide-based resins. The transparent protective film is preferably a triacetyl cellulose (TAC) film or a cycloolefin film. The thickness of the protective film is usually preferably 40 to 200 μm.
　本発明の偏光膜と保護膜を貼り合わせるために、接着剤を用いることができる。用いることができる接着剤としては、例えば、ポリビニルアルコール系接着剤、ウレタンエマルジョン系接着剤、アクリル系接着剤、及びポリエステルーイソシアネート系接着剤などが挙げられ、ポリビニルアルコール系接着剤が好適である。 An adhesive can be used to bond the polarizing film and protective film of the present invention together. Examples of adhesives that can be used include polyvinyl alcohol adhesives, urethane emulsion adhesives, acrylic adhesives, and polyester-isocyanate adhesives, with polyvinyl alcohol adhesives being preferred.
　本発明の偏光板の表面には、透明な保護層をさらに設けてもよい。透明な保護層としては、例えば、アクリル系やポリシロキサン系のハードコート層やウレタン系の保護層等が挙げられる。また、単板光透過率をより向上させるために、この透明保護層の上に反射防止層（ＡＲ層）を設けることが好ましい。ＡＲ層は、例えば二酸化珪素、酸化チタン等の物質を蒸着又はスパッタリング処理によって形成することができ、またフッ素系物質を薄く塗布することにより形成することができる。染料系偏光板は、支持体をさらに備えることが好ましい。染料系偏光板は、表面に位相差板を貼付し、楕円偏光板として使用することもできる。 A transparent protective layer may be further provided on the surface of the polarizing plate of the present invention. Examples of the transparent protective layer include an acrylic-based or polysiloxane-based hard coat layer, a urethane-based protective layer, and the like. Further, in order to further improve the light transmittance of the veneer, it is preferable to provide an antireflection layer (AR layer) on the transparent protective layer. The AR layer can be formed by vapor deposition or sputtering of a substance such as silicon dioxide or titanium oxide, or by thinly applying a fluorine-based substance. It is preferable that the dye-based polarizing plate further includes a support. The dye-based polarizing plate can also be used as an elliptically polarizing plate by pasting a retardation plate on the surface.
　本発明の偏光板は、用途に応じてニュートラルグレー偏光板及びカラー偏光板のいずれであってもよい。 The polarizing plate of the present invention may be either a neutral gray polarizing plate or a color polarizing plate depending on the purpose.
　本発明のニュートラルグレー偏光板は、中性色を有し、可視光領域の偏光領域において直交位の色漏れが少なく、偏光性能に優れ、さらに高温高湿状態でも変色や偏光性能の低下が抑制され、耐久性が高いため、車載用又は屋外表示用に好適である。 The neutral gray polarizing plate of the present invention has a neutral color, has little orthogonal color leakage in the polarization region of the visible light region, has excellent polarization performance, and also suppresses discoloration and deterioration of polarization performance even under high temperature and high humidity conditions. It has high durability and is suitable for use in vehicles or outdoor displays.
　車載用又は屋外表示用のニュートラルグレー偏光板は、本発明の偏光膜と透明保護膜から構成される偏光板に、単体光透過率をより向上させるために、ＡＲ層を設け、ＡＲ層付き偏光板としたものであることが好ましく、ＡＲ層と透明樹脂などの支持体との両方を貼付したＡＲ層及び支持体付き偏光板がより好ましい。ＡＲ層は、偏光板の片面又は両面に設けることができる。支持体は、偏光板の片面に設けることが好ましく、偏光板に直接設けられていてもよく、支持体にＡＲ層付き偏光板（ＡＲ層／偏光板／ＡＲ層）が設けられていてもよい。ＡＲ層及び支持体付き偏光板は、ＡＲ層／偏光板／ＡＲ層／支持体をこの順に備えることが好ましい。支持体は偏光板を貼付するための平面部を有しているものが好ましく、また光学用途であるため、透明基板であることが好ましい。透明基板としては、大きく分けて無機基板と有機基板があり、ソーダガラス、ホウ珪酸ガラス、水晶基板、サファイア基板、及びスピネル基板等の無機基板、並びにアクリル、ポリカーボネート、ポリエチレンテレフタレート、ポリエチレンナフタレート、及びシクロオレフィンポリマー等の有機基板が挙げられるが、有機基板が好ましい。透明基板の厚さや大きさは所望のサイズでよい。 A neutral gray polarizing plate for automotive use or outdoor display is a polarizing plate composed of the polarizing film of the present invention and a transparent protective film, and an AR layer is provided in order to further improve the single light transmittance. A plate is preferable, and a polarizing plate with an AR layer and a support, in which both an AR layer and a support such as a transparent resin are attached, is more preferable. The AR layer can be provided on one or both sides of the polarizing plate. The support is preferably provided on one side of the polarizing plate, and may be provided directly on the polarizing plate, or a polarizing plate with an AR layer (AR layer/polarizing plate/AR layer) may be provided on the support. . The polarizing plate with an AR layer and a support preferably includes an AR layer/polarizing plate/AR layer/support in this order. The support preferably has a flat surface for attaching a polarizing plate, and since it is used for optical purposes, it is preferably a transparent substrate. Transparent substrates can be broadly divided into inorganic substrates and organic substrates, including inorganic substrates such as soda glass, borosilicate glass, crystal substrates, sapphire substrates, and spinel substrates, as well as acrylic, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, and Examples include organic substrates such as cycloolefin polymers, and organic substrates are preferred. The thickness and size of the transparent substrate may be any desired size.
　カラー偏光板は、偏光性能に優れ、高温高湿状態でも変色や偏光性能の低下を起こさないため、液晶プロジェクター用、及び車載用や屋外表示用等の表示装置用に好適である。 Color polarizing plates have excellent polarization performance and do not cause discoloration or deterioration of polarization performance even under high temperature and high humidity conditions, so they are suitable for use in liquid crystal projectors and display devices such as in-vehicle and outdoor displays.
　液晶プロジェクター用カラー偏光板は、明るさと優れた偏光性能を有しており、該偏光板の必要波長域（Ａ．超高圧水銀ランプを用いた場合；青色チャンネル用４２０～５００ｎｍ、緑色チャンネル５００～５８０ｎｍ、赤色チャンネル６００～６８０ｎｍ、Ｂ．３原色ＬＥＤランプを用いた場合のピーク波長；青色チャンネル用４３０～４５０ｎｍ、緑色チャンネル５２０～５３５ｎｍ、赤色チャンネル６２０～６３５ｎｍ）における、単板平均光透過率が３９％以上、直交位の平均光透過率が０．４％以下で、より好ましくは該偏光板の必要波長域における単板平均光透過率が４１％以上、直交位の平均光透過率が０．３％以下、より好ましくは０．２％以下である。さらに好ましくは、該偏光板の必要波長域における単板平均光透過率が４２％以上、直交位の平均光透過率が０．１％以下である。 The color polarizing plate for liquid crystal projectors has brightness and excellent polarization performance, and the required wavelength range of the polarizing plate (A. When using an ultra-high pressure mercury lamp; 420 to 500 nm for the blue channel, 500 to 500 nm for the green channel) The average light transmittance of a single plate is 39% or more, the average light transmittance in the orthogonal position is 0.4% or less, more preferably the single plate average light transmittance in the required wavelength range of the polarizing plate is 41% or more, and the average light transmittance in the orthogonal position is 0. .3% or less, more preferably 0.2% or less. More preferably, the single-plate average light transmittance in the required wavelength range of the polarizing plate is 42% or more, and the average light transmittance in the orthogonal position is 0.1% or less.
　なお、単板平均光透過率は、ＡＲ層及び透明ガラス板等の支持体を設けていない１枚の偏光板（以下、単に「偏光板」とも称する）に自然光を入射したときの特定波長領域における光線透過率の平均値である。直交位の平均光透過率は、２枚の偏光板をその配向方向が互いに直交するように重ね合せた状態で自然光を入射したときの特定波長領域における光線透過率の平均値である。 Note that the average light transmittance of a single plate is a specific wavelength range when natural light is incident on a single polarizing plate (hereinafter also simply referred to as a "polarizing plate") that is not provided with an AR layer or a support such as a transparent glass plate. This is the average value of light transmittance at . The orthogonal average light transmittance is the average value of the light transmittance in a specific wavelength region when natural light is incident on two polarizing plates stacked so that their orientation directions are orthogonal to each other.
　車載用又は屋外表示用のカラー偏光板に使用される偏光膜は、ニュートラルグレー偏光板と同様に、染料系偏光板に必要に応じて保護層又はＡＲ層及び支持体等が設けられていてもよい。支持体付カラー偏光板は、例えば、支持体平面部に透明な接着（粘着）剤を塗布し、ついでこの塗布面に染料系偏光板を貼付することにより得られる。又は、染料系偏光板に透明な接着（粘着）剤を塗布し、ついでこの塗布面に支持体を貼付してもよい。接着（粘着）剤は、例えばアクリル酸エステル系のものが好ましい。なお、この染料系偏光板を楕円偏光板として使用する場合、位相差板側を支持体に貼付して染料系偏光板／位相差板／支持体の積層順とするのが通常であるが、偏光板側を支持体に貼付して位相差板／偏光板／支持体の積層順としてもよい。 Polarizing films used for color polarizing plates for automobiles or outdoor displays are similar to neutral gray polarizing plates, even if dye-based polarizing plates are provided with a protective layer or an AR layer and a support as necessary. good. A color polarizing plate with a support can be obtained, for example, by applying a transparent adhesive (adhesive) to the flat surface of the support, and then attaching a dye-based polarizing plate to the coated surface. Alternatively, a dye-based polarizing plate may be coated with a transparent adhesive (adhesive), and then a support may be attached to the coated surface. The adhesive (pressure-sensitive adhesive) is preferably one based on acrylic ester, for example. Note that when this dye-based polarizing plate is used as an elliptically polarizing plate, the retardation plate side is usually attached to a support to form a stacking order of dye-based polarizing plate/retardation plate/support. The polarizing plate side may be attached to the support and the stacking order may be retardation plate/polarizing plate/support.
＜表示装置＞
　本発明の表示装置は、本発明の偏光膜又は偏光板を備える。表示装置としては、液晶表示装置又は有機エレクトロニクス表示装置が挙げられ、例えば、電卓、時計、ノートパソコン、ワープロ、液晶テレビ、カーナビゲーション、及び屋内外の計測器や表示器等のディスプレイ用であり、特に、高い偏光性能と耐久性を必要とする各種表示体、例えば車載用又は屋外表示用（例えば、工業計器類の表示用途やウェアラブル用途）に好適に用いられる。表示装置に備えられる染料系偏光膜又は染料系偏光板は、ニュートラルグレーであることが好適である。 <Display device>
The display device of the present invention includes the polarizing film or polarizing plate of the present invention. Examples of the display device include a liquid crystal display device or an organic electronics display device, for example, for displays such as calculators, watches, notebook computers, word processors, liquid crystal televisions, car navigation systems, and indoor and outdoor measuring instruments and indicators, In particular, it is suitably used for various displays that require high polarization performance and durability, such as in-vehicle or outdoor displays (for example, display applications for industrial instruments and wearable applications). The dye-based polarizing film or dye-based polarizing plate provided in the display device is preferably neutral gray.
　液晶表示装置においては、液晶セルの入射側又は出射側のいずれか一方又は両方に染料系偏光板が配置される。染料系偏光板は液晶セルに接触していても、接触していなくてもよいが、耐久性の観点から、接触していない方が好ましい。液晶セルの出射側において、染料系偏光板が液晶セルに接触している場合、液晶セルを染料系偏光板の支持体とすることができる。染料系偏光板が液晶セルに接触していない場合、液晶セル以外の支持体が設けられた染料系偏光板を使用することが好ましい。また、耐久性の観点からすると、液晶セルの入射側及び出射側の両方に染料系偏光板が配置されることが好ましく、さらに染料系偏光板の偏光板面を液晶セル側に、支持体面を光源側に配置することが好ましい。なお、液晶セルの入射側とは、光源側のことであり、反対側を出射側という。 In a liquid crystal display device, a dye-based polarizing plate is arranged on either or both of the incident side and the output side of the liquid crystal cell. The dye-based polarizing plate may or may not be in contact with the liquid crystal cell, but from the viewpoint of durability, it is preferably not in contact with the liquid crystal cell. When the dye-based polarizing plate is in contact with the liquid crystal cell on the output side of the liquid crystal cell, the liquid crystal cell can be used as a support for the dye-based polarizing plate. When the dye-based polarizing plate is not in contact with the liquid crystal cell, it is preferable to use a dye-based polarizing plate provided with a support other than the liquid crystal cell. In addition, from the viewpoint of durability, it is preferable to arrange dye-based polarizing plates on both the incident side and the output side of the liquid crystal cell, and furthermore, the polarizing plate side of the dye-based polarizing plate is placed on the liquid crystal cell side, and the support side is placed on the liquid crystal cell side. It is preferable to arrange it on the light source side. Note that the incident side of the liquid crystal cell refers to the light source side, and the opposite side is referred to as the output side.
　液晶表示装置に備えられる液晶セルは、例えばアクティブマトリクス型であり、電極及びＴＦＴが形成された透明基板と対向電極が形成された透明基板との間に液晶を封入して形成されるものであることが好ましい。冷陰極管ランプ又は白色ＬＥＤ等の光源から放射された光は、染料系偏光板を通過し、ついで液晶セル、カラーフィルター、さらに染料系偏光板を通過し表示画面上に投影される。 A liquid crystal cell included in a liquid crystal display device is, for example, an active matrix type, and is formed by sealing liquid crystal between a transparent substrate on which electrodes and TFTs are formed and a transparent substrate on which a counter electrode is formed. It is preferable. Light emitted from a light source such as a cold cathode tube lamp or a white LED passes through a dye-based polarizing plate, then passes through a liquid crystal cell, a color filter, and then a dye-based polarizing plate and is projected onto a display screen.
　液晶表示装置は、染料系偏光板が明るさと優れた偏光性能並びに偏光性及び耐光性を有するため、車内や屋外等の高温、高湿状態でも変色や偏光性能の低下を起こし難く、信頼性が高い。 Since dye-based polarizing plates have brightness, excellent polarization performance, polarization properties, and light resistance, liquid crystal display devices are less likely to discolor or deteriorate in polarization performance even in high-temperature, high-humidity conditions such as inside a car or outdoors, making them highly reliable. expensive.
　以下、実施例により本発明をさらに詳細に説明するが、これらは例示的なものであって、本発明を何ら限定するものではない。例中にある％及び部は、特にことわらないかぎり質量基準である。 Hereinafter, the present invention will be explained in more detail with reference to Examples, but these are merely illustrative and do not limit the present invention in any way. The percentages and parts in the examples are by weight unless otherwise specified.
［実施例１］
（工程１）
　市販品として入手可能な６－アミノ－１－ナフトール－３－スルホン酸７１．７部とα，α’－ジクロロ－ｏ－キシレン５２．５部を水９００部とＮ－メチル－２－ピロリドン１５０部の混合溶液に加え、２５％水酸化ナトリウム水溶液を用いてｐＨを３．０～７．５を維持しながら５０℃で８時間反応させた。得られた反応液に塩化ナトリウム１８０部を加え、析出した固体を濾別・乾燥することによって下記式（１０）で示される６－（イソインドリン－２－イル）－１－ナフトール－３－スルホン酸を３４．１部得た。
Figure JPOXMLDOC01-appb-C000022
 [Example 1]
(Step 1)
71.7 parts of commercially available 6-amino-1-naphthol-3-sulfonic acid and 52.5 parts of α,α'-dichloro-o-xylene were mixed with 900 parts of water and 150 parts of N-methyl-2-pyrrolidone. The mixture was added to the mixed solution of 50% and reacted at 50° C. for 8 hours while maintaining the pH at 3.0 to 7.5 using a 25% aqueous sodium hydroxide solution. 180 parts of sodium chloride was added to the resulting reaction solution, and the precipitated solid was filtered and dried to obtain 6-(isoindolin-2-yl)-1-naphthol-3-sulfone represented by the following formula (10). 34.1 parts of acid were obtained.
Figure JPOXMLDOC01-appb-C000022
（工程２）
　市販品として入手可能な４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部を水３００部に加え攪拌し懸濁させ、２５％水酸化ナトリウムを用いてｐＨ９．０とし、そこに４０％亜硝酸ナトリウム水溶液１７．３部を加えた。得られた溶液を水１００部と３５％塩酸４２部の混合液に滴下し、ジアゾ液を調製した。次に、工程１で得られた式（１０）で表される６－（イソインドリン－２－イル）－１－ナフトール－３－スルホン酸３４．１部を水３００部に加え、２５％水酸化ナトリウム水溶液で弱アルカリ性として溶解した。この液に、先に得られたジアゾ液をｐＨ６．５～９．０に保って滴下し、攪拌してカップリング反応を完結させた。その後、塩化ナトリウムで塩析させた後、濾過して乾燥することにより式（１１）で示されるアゾ化合物（化合物例１－１）２５．０部を得た。
Figure JPOXMLDOC01-appb-C000023
 (Step 2)
Add 27.7 parts of commercially available 4-(4-aminophenylazo)benzenesulfonic acid to 300 parts of water, stir and suspend, adjust the pH to 9.0 using 25% sodium hydroxide, and add 40 17.3 parts of aqueous sodium nitrite solution was added. The obtained solution was added dropwise to a mixed solution of 100 parts of water and 42 parts of 35% hydrochloric acid to prepare a diazo liquid. Next, 34.1 parts of 6-(isoindolin-2-yl)-1-naphthol-3-sulfonic acid represented by formula (10) obtained in step 1 was added to 300 parts of water, and 25% water was added. It was dissolved in an aqueous sodium oxide solution to make it slightly alkaline. The previously obtained diazo liquid was added dropwise to this liquid while keeping the pH at 6.5 to 9.0, and the mixture was stirred to complete the coupling reaction. Thereafter, the mixture was salted out with sodium chloride, filtered and dried to obtain 25.0 parts of an azo compound represented by formula (11) (Compound Example 1-1).
Figure JPOXMLDOC01-appb-C000023
［実施例２］
　実施例１の工程２で用いた４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部に代えて、国際公開第２０２１／０１５１８８号公報の実施例（ｎ２）を参考にして合成することが出来るアゾ化合物である５－｛４－［（４－アミノ－２－メチルフェニル）ジアゼニル］ベンゾイルアミノ｝ベンゼン－１，３－ジカルボン酸４１．８部を用いる以外は実施例１と同様にして、式（１２）で示されるアゾ化合物（化合物例１－３８）２６．０部を得た。
Figure JPOXMLDOC01-appb-C000024
 [Example 2]
Instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, synthesize with reference to Example (n2) of International Publication No. 2021/015188. The procedure was repeated in the same manner as in Example 1, except that 41.8 parts of 5-{4-[(4-amino-2-methylphenyl)diazenyl]benzoylamino}benzene-1,3-dicarboxylic acid, which is an azo compound capable of , 26.0 parts of an azo compound represented by formula (12) (Compound Example 1-38) was obtained.
Figure JPOXMLDOC01-appb-C000024
［実施例３］
　実施例１の工程２で用いた４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部に代えて、国際公開第２０１７／１４６２１２号公報の実施例６を参考にして合成することが出来るアゾ化合物である５－（｛４－［（４－アミノ－６－スルホナフタレン－１－イル）ジアゼニル］－６－スルホナフタレン－１－イル｝ジアゼニル）ベンゼン－１，３－ジカルボン酸６５．０部を用いる以外は実施例１と同様にして、式（１３）で示されるアゾ化合物（化合物例１－４７）３２．５部を得た。
Figure JPOXMLDOC01-appb-C000025
 [Example 3]
Instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, it can be synthesized with reference to Example 6 of International Publication No. 2017/146212. 5-({4-[(4-amino-6-sulfonaphthalen-1-yl)diazenyl]-6-sulfonaphthalen-1-yl}diazenyl)benzene-1,3-dicarboxylic acid, an azo compound 65.0 32.5 parts of an azo compound represented by formula (13) (Compound Example 1-47) was obtained in the same manner as in Example 1 except that 1 part was used.
Figure JPOXMLDOC01-appb-C000025
［実施例４］
　実施例１の工程２で用いた４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部に代えて、国際公開第２０２１／０１５１８８号公報の実施例１を参考にして合成することが出来るアゾ化合物である４－（｛４－［（４－アミノ－６－スルホナフタレン－１－イル）ジアゼニル］－６－スルホナフタレン－１－イル｝ジアゼニル）安息香酸６０．６部を用いる以外は実施例１と同様にして、式（１４）で示されるアゾ化合物（化合物例１－４９）３１．０部を得た。
Figure JPOXMLDOC01-appb-C000026
 [Example 4]
Instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, it can be synthesized with reference to Example 1 of International Publication No. 2021/015188. The procedure was carried out except that 60.6 parts of 4-({4-[(4-amino-6-sulfonaphthalen-1-yl)diazenyl]-6-sulfonaphthalen-1-yl}diazenyl)benzoic acid, which is an azo compound, was used. In the same manner as in Example 1, 31.0 parts of an azo compound represented by formula (14) (Compound Example 1-49) was obtained.
Figure JPOXMLDOC01-appb-C000026
［実施例５］
　実施例１の工程２で用いた４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部に代えて、米国公開第２００４／０２２８０５号公報を参考にして合成することが出来るアゾ化合物である７－（４－アミノ－３－メトキシフェニルアゾ）ナフタレン－１，３－ジスルホン酸３７．５部を用いる以外は実施例１と同様にして、式（１５）で示されるアゾ化合物（化合物例１－２４）２７．０部を得た。
Figure JPOXMLDOC01-appb-C000027
 [Example 5]
It is an azo compound that can be synthesized with reference to US Publication No. 2004/022805 in place of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1. The azo compound represented by formula (15) (Compound Example 1 -24) 27.0 parts were obtained.
Figure JPOXMLDOC01-appb-C000027
［実施例６］
　実施例１の工程２で用いた４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部に代えて、国際公開第２０２１／０１５１８８号公報の実施例（ｎ２）と（ｎ４）を参考にして合成することが出来るアゾ化合物である４－｛（４－｛［４－（４－アミノ－２，５－ジメチルフェニル）ジアゼニル］－２－メチルフェニル｝ジアゼニル）ベンゾイルアミノ｝ベンゼン－１，３－ジスルホン酸６２．１部を用いる以外は実施例１と同様にして、式（１６）で示されるアゾ化合物（化合物例１－４２）２９．０部を得た。
Figure JPOXMLDOC01-appb-C000028
 [Example 6]
Instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, refer to Examples (n2) and (n4) of International Publication No. 2021/015188. 4-{(4-{[4-(4-amino-2,5-dimethylphenyl)diazenyl]-2-methylphenyl}diazenyl)benzoylamino}benzene-1,3, which is an azo compound that can be synthesized by -29.0 parts of an azo compound represented by formula (16) (Compound Example 1-42) was obtained in the same manner as in Example 1 except that 62.1 parts of -disulfonic acid was used.
Figure JPOXMLDOC01-appb-C000028
［実施例７］
　実施例１の工程２で用いた４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部に代えて、国際公開第２０１０／０３８３７９号公報の実施例１の式（８）を参考にして合成することが出来るアゾ化合物である７－（｛４－［（４－アミノ－２，５－ジメチルフェニル）ジアゼニル］－２－クロロ－５－（３－スルホプロポキシ）フェニル｝ジアゼニル）ナフタレン－１，３－ジスルホン酸７１．２部を用いる以外は実施例１と同様にして、式（１７）で示されるアゾ化合物（化合物例１－５３）２８．０部を得た。
Figure JPOXMLDOC01-appb-C000029
 [Example 7]
In place of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, formula (8) of Example 1 of International Publication No. 2010/038379 was used as a reference. 7-({4-[(4-amino-2,5-dimethylphenyl)diazenyl]-2-chloro-5-(3-sulfopropoxy)phenyl}diazenyl)naphthalene-1, which is an azo compound that can be synthesized. , 3-disulfonic acid 71.2 parts were used in the same manner as in Example 1 to obtain 28.0 parts of an azo compound represented by formula (17) (Compound Example 1-53).
Figure JPOXMLDOC01-appb-C000029
［実施例８］
　実施例１の工程２で用いた４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部に代えて、国際公開第２０１２／１０８１６９号公報の実施例１を参考にして合成することが出来るアゾ化合物である４－｛［４－（｛４－［（４－アミノ－２，５－ジメチルフェニル）ジアゼニル］－２－メチルフェニル｝ジアゼニル）－２－メチルフェニル］ジアゼニル｝ベンゼン－１，３－ジスルホン酸６２．２部を用いる以外は実施例１と同様にして、式（１８）で示されるアゾ化合物（化合物例１－４５）２２．５部を得た。
Figure JPOXMLDOC01-appb-C000030
 [Example 8]
Instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, it can be synthesized with reference to Example 1 of International Publication No. 2012/108169. The azo compound 4-{[4-({4-[(4-amino-2,5-dimethylphenyl)diazenyl]-2-methylphenyl}diazenyl)-2-methylphenyl]diazenyl}benzene-1,3 -22.5 parts of an azo compound represented by formula (18) (Compound Example 1-45) was obtained in the same manner as in Example 1 except that 62.2 parts of -disulfonic acid was used.
Figure JPOXMLDOC01-appb-C000030
［実施例９］
　実施例１の工程２で用いた４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部に代えて、国際公開第２０２１／０１５１８８号公報の実施例（ｎ２）を参考にして合成することが出来る中間体である５－［（４－アミノベンゾイル）アミノ］ベンゼン－１，３－ジカルボン酸３０．０部を用いる以外は実施例１と同様にして、式（１９）で示されるアゾ化合物（化合物例１－５２）２６．０部を得た。
Figure JPOXMLDOC01-appb-C000031
 [Example 9]
Instead of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid used in Step 2 of Example 1, synthesize with reference to Example (n2) of International Publication No. 2021/015188. An azo compound represented by formula (19) was prepared in the same manner as in Example 1 except for using 30.0 parts of 5-[(4-aminobenzoyl)amino]benzene-1,3-dicarboxylic acid, which is an intermediate capable of producing (Compound Example 1-52) 26.0 parts were obtained.
Figure JPOXMLDOC01-appb-C000031
［比較例１］
　市販品として入手可能な４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部を水３００部に加え攪拌し懸濁させ、２５％水酸化ナトリウムを用いてｐＨ９．０とし、そこに４０％亜硝酸ナトリウム水溶液１７．３部を加えた。得られた溶液を水１００部と３５％塩酸４２部の混合液に滴下し、ジアゾ液を調製した。次に、６－アニリノ－１－ナフトール－３－スルホン酸３１．５部を水３００部に加え、２５％水酸化ナトリウム水溶液で弱アルカリ性として溶解した。この液に、先に得られたジアゾ液をｐＨ６．５～９．０に保って滴下し、攪拌してカップリング反応を完結させた。その後、塩化ナトリウムで塩析させた後、濾過して乾燥することにより下記式（１０１）で示されるアゾ化合物３０．０部を得た。
Figure JPOXMLDOC01-appb-C000032
 [Comparative example 1]
Add 27.7 parts of commercially available 4-(4-aminophenylazo)benzenesulfonic acid to 300 parts of water, stir and suspend, adjust the pH to 9.0 using 25% sodium hydroxide, and add 40 17.3 parts of aqueous sodium nitrite solution was added. The obtained solution was added dropwise to a mixed solution of 100 parts of water and 42 parts of 35% hydrochloric acid to prepare a diazo liquid. Next, 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid was added to 300 parts of water, and the mixture was made weakly alkaline with a 25% aqueous sodium hydroxide solution and dissolved. The previously obtained diazo liquid was added dropwise to this liquid while keeping the pH at 6.5 to 9.0, and the mixture was stirred to complete the coupling reaction. Thereafter, the mixture was salted out with sodium chloride, filtered and dried to obtain 30.0 parts of an azo compound represented by the following formula (101).
Figure JPOXMLDOC01-appb-C000032
［比較例２］
　比較例１の６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－ベンゾイルアミノ－１－ナフトール－３－スルホン酸３４．３部を用いる以外は比較例１と同様にして、式（１０２）で示されるアゾ化合物（シー．アイ．ダイレクト．レッド８１）　２９．０部を得た。
Figure JPOXMLDOC01-appb-C000033
 [Comparative example 2]
Same as Comparative Example 1 except that 34.3 parts of 6-benzoylamino-1-naphthol-3-sulfonic acid was used instead of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid in Comparative Example 1. 29.0 parts of an azo compound (C.I. Direct. Red 81) represented by formula (102) was obtained.
Figure JPOXMLDOC01-appb-C000033
［比較例３］
　比較例１の６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－（４－アミノベンゾイル）アミノ－１－ナフトール－３－スルホン酸３５．８部を用いる以外は比較例１と同様にして、式（１０３）で示されるアゾ化合物２９．５部を得た。
Figure JPOXMLDOC01-appb-C000034
 [Comparative example 3]
Except that 35.8 parts of 6-(4-aminobenzoyl)amino-1-naphthol-3-sulfonic acid was used instead of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid in Comparative Example 1. In the same manner as in Comparative Example 1, 29.5 parts of an azo compound represented by formula (103) was obtained.
Figure JPOXMLDOC01-appb-C000034
［比較例４］
　比較例１の６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、７－ベンジルアミノ－１－ナフトール－３－スルホン酸３２．９部を用いる以外は比較例１と同様にして、式（１０４）で表されるアゾ化合物２８．５部得た。
Figure JPOXMLDOC01-appb-C000035
 [Comparative example 4]
Same as Comparative Example 1 except that 32.9 parts of 7-benzylamino-1-naphthol-3-sulfonic acid was used instead of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid in Comparative Example 1. 28.5 parts of an azo compound represented by formula (104) were obtained.
Figure JPOXMLDOC01-appb-C000035
［比較例５］
　比較例１の６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－アミノ－１－ナフトール－３－スルホン酸２３．９部を用いる以外は比較例１と同様にして、式（１０５）で示されるアゾ化合物１９．５部を得た。
Figure JPOXMLDOC01-appb-C000036
 [Comparative example 5]
Same procedure as Comparative Example 1 except that 23.9 parts of 6-amino-1-naphthol-3-sulfonic acid was used instead of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid in Comparative Example 1. Thus, 19.5 parts of an azo compound represented by formula (105) was obtained.
Figure JPOXMLDOC01-appb-C000036
［比較例６］
　比較例１の６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－メチルアミノ－１－ナフトール－３－スルホン酸２５．３部を用いる以外は比較例１と同様にして、式（１０６）で示されるアゾ化合物２０．０部を得た。
Figure JPOXMLDOC01-appb-C000037
 [Comparative example 6]
Same as Comparative Example 1 except that 25.3 parts of 6-methylamino-1-naphthol-3-sulfonic acid was used instead of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid in Comparative Example 1. 20.0 parts of an azo compound represented by formula (106) was obtained.
Figure JPOXMLDOC01-appb-C000037
［比較例７］
　比較例１の６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－ジメチルアミノ－１－ナフトール－３－スルホン酸２６．７部を用いる以外は比較例１と同様にして、式（１０７）で示されるアゾ化合物２０．３部を得た。
Figure JPOXMLDOC01-appb-C000038
 [Comparative Example 7]
Same as Comparative Example 1 except that 26.7 parts of 6-dimethylamino-1-naphthol-3-sulfonic acid was used instead of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid in Comparative Example 1. 20.3 parts of an azo compound represented by formula (107) were obtained.
Figure JPOXMLDOC01-appb-C000038
［比較例８］
　比較例１の６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－（ピロリジン－１－イル）－１－ナフトール－３－スルホン酸２８．３部を用いる以外は比較例１と同様にして、式（１０８）で示されるアゾ化合物２０．５部を得た。
Figure JPOXMLDOC01-appb-C000039
 [Comparative example 8]
Except that 28.3 parts of 6-(pyrrolidin-1-yl)-1-naphthol-3-sulfonic acid was used instead of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid in Comparative Example 1. In the same manner as in Comparative Example 1, 20.5 parts of an azo compound represented by formula (108) was obtained.
Figure JPOXMLDOC01-appb-C000039
［比較例９］
　比較例１の６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－（６，８－ジスルホ－２Ｈ－ナフト［１，２－ｄ］［１，２，３］トリアゾール－２－イル）－１－ナフトール－３－スルホン酸５５．１部を用いる以外は比較例１と同様にして、式（１０９）で示されるアゾ化合物３３．０部を得た。
Figure JPOXMLDOC01-appb-C000040
 [Comparative Example 9]
Instead of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid in Comparative Example 1, 6-(6,8-disulfo-2H-naphtho[1,2-d][1,2,3] 33.0 parts of an azo compound represented by formula (109) was obtained in the same manner as in Comparative Example 1 except that 55.1 parts of triazol-2-yl)-1-naphthol-3-sulfonic acid was used.
Figure JPOXMLDOC01-appb-C000040
［比較例１０］
　比較例１の６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－［４-ヒドロキシフェニル）ジアゼニル］－１－ナフトール－３－スルホン酸３４．４部を用いる以外は比較例１と同様にして、式（１１０）で示されるアゾ化合物３１．２部を得た。
Figure JPOXMLDOC01-appb-C000041
 [Comparative Example 10]
Except for using 34.4 parts of 6-[4-hydroxyphenyl)diazenyl]-1-naphthol-3-sulfonic acid in place of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid in Comparative Example 1. In the same manner as in Comparative Example 1, 31.2 parts of an azo compound represented by formula (110) was obtained.
Figure JPOXMLDOC01-appb-C000041
［比較例１１］
　比較例１の４－（４－アミノフェニルアゾ）ベンゼンスルホン酸２７．７部に代えて、国際公開第２０２１／０１５１８８号公報の実施例（ｎ２）を参考にして合成することが出来るアゾ化合物である５－｛４－［（４－アミノ－２－メチルフェニル）ジアゼニル］ベンゾイルアミノ｝ベンゼン－１，３－ジカルボン酸４１．８部を用いる以外は比較例１と同様にして、下記式（１１１）で表されるアゾ化合物２５．０部を得た。
Figure JPOXMLDOC01-appb-C000042
 [Comparative Example 11]
In place of 27.7 parts of 4-(4-aminophenylazo)benzenesulfonic acid in Comparative Example 1, an azo compound that can be synthesized with reference to Example (n2) of International Publication No. 2021/015188. The following formula (111 25.0 parts of an azo compound represented by ) was obtained.
Figure JPOXMLDOC01-appb-C000042
［比較例１２］
　比較例１１において使用する６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－ベンジルアミノ－１－ナフトール－３－スルホン酸３２．９部を用いる以外は比較例１１と同様にして、下記式（１１２）で表されるアゾ化合物２２．５部を得た。
Figure JPOXMLDOC01-appb-C000043
 [Comparative example 12]
Comparative Example 11 except that 32.9 parts of 6-benzylamino-1-naphthol-3-sulfonic acid was used in place of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid used in Comparative Example 11. In the same manner as above, 22.5 parts of an azo compound represented by the following formula (112) was obtained.
Figure JPOXMLDOC01-appb-C000043
［比較例１３］
　比較例１１において使用する６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－（４－アミノベンゾイル）アミノ－１－ナフトール－３－スルホン酸３５．８部を用いる以外は比較例１１と同様にして、式（１１３）で示されるアゾ化合物２８．０部を得た。
Figure JPOXMLDOC01-appb-C000044
 [Comparative Example 13]
Instead of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid used in Comparative Example 11, 35.8 parts of 6-(4-aminobenzoyl)amino-1-naphthol-3-sulfonic acid is used. In the same manner as in Comparative Example 11 except for this, 28.0 parts of an azo compound represented by formula (113) was obtained.
Figure JPOXMLDOC01-appb-C000044
［比較例１４］
　比較例１１において使用する６－アニリノ－１－ナフトール－３－スルホン酸３１．５部に代えて、６－［４-ヒドロキシフェニル）ジアゼニル］－１－ナフトール－３－スルホン酸３４．４部を用いる以外は比較例１１と同様にして、式（１１４）で示されるアゾ化合物３４．５部を得た。
Figure JPOXMLDOC01-appb-C000045
 [Comparative example 14]
Instead of 31.5 parts of 6-anilino-1-naphthol-3-sulfonic acid used in Comparative Example 11, 34.4 parts of 6-[4-hydroxyphenyl)diazenyl]-1-naphthol-3-sulfonic acid was used. 34.5 parts of an azo compound represented by formula (114) was obtained in the same manner as in Comparative Example 11 except for using the following.
Figure JPOXMLDOC01-appb-C000045
［比較例１５］
　国際公開第２０１７／１４６２１２号公報の実施例６に従い、当該例に記載の式（１－Ａ１４）の化合物を合成した。構造を式（１１５）で示す。
Figure JPOXMLDOC01-appb-C000046
 [Comparative Example 15]
According to Example 6 of International Publication No. 2017/146212, a compound of formula (1-A14) described in the example was synthesized. The structure is shown by formula (115).
Figure JPOXMLDOC01-appb-C000046
［比較例１６］
　国際公開第２０１７／１４６２１２号公報の実施例６を参考にして国際公開第２０１９／１１７１３１号公報の式（２－９）に記載の化合物を合成した。構造を式（１１６）で示す。
Figure JPOXMLDOC01-appb-C000047
 [Comparative Example 16]
The compound described in Formula (2-9) of International Publication No. 2019/117131 was synthesized with reference to Example 6 of International Publication No. 2017/146212. The structure is shown by formula (116).
Figure JPOXMLDOC01-appb-C000047
（実施例１～９及び比較例１～１６：偏光膜の作製）
　実施例１～９、比較例１～１６で得られた各々のアゾ化合物０．０３％及び芒硝０．１％の濃度とした４５℃の水溶液（染浴）に厚さ７５μｍのポリビニルアルコールフィルムを４分間浸漬した。このフィルムを３％ホウ酸水溶液中で、５０℃で５倍に延伸し、緊張状態を保ったまま、水洗、乾燥して偏光膜を得た。 (Examples 1 to 9 and Comparative Examples 1 to 16: Preparation of polarizing film)
A polyvinyl alcohol film with a thickness of 75 μm was placed in an aqueous solution (dye bath) at 45°C with a concentration of 0.03% of each azo compound obtained in Examples 1 to 9 and Comparative Examples 1 to 16 and 0.1% of Glauber's salt. Soaked for 4 minutes. This film was stretched 5 times in a 3% boric acid aqueous solution at 50° C., washed with water and dried while maintaining tension to obtain a polarizing film.
　実施例１～９及び比較例１～１６で得られた偏光膜の評価を次のようにして行った。
（ａ）偏光平行透過率（Ｋｙ）、及び偏光直交透過率（Ｋｚ）
　偏光膜の極大吸収波長、偏光平行透過率（Ｋｙ）及び偏光直交透過率（Ｋｚ）を、分光光度計（日立製作所社製　ＵＨ－４１５０）を用いて測定した。ここでＫｙとは、絶対偏光子の吸収軸と偏光膜の吸収軸を平行に重ね合わせて設置した際の透過率であり、Ｋｚとは、絶対偏光子の吸収軸と偏光膜の吸収軸を直交に重ね合わせて設置した際の透過率を示す。各波長の偏光平行透過率Ｋｙ及びＫｚは３８０ｎｍ～７８０ｎｍにおいて、１～１０ｎｍの波長間隔で測定した。
（ｂ）単体透過率（Ｔｓ）、平行透過率（Ｔｐ）、直交透過率（Ｔｃ）
　単体透過率（Ｔｓ）とは偏光膜１枚時の分光透過率を示し、平行透過率（Ｔｐ）とは偏光膜２枚の吸収軸を平行に重ね合わせて設置した際の分光透過率を示し、直交透過率（Ｔｃ）とは偏光膜２枚の吸収軸を直交に重ね合わせて設置した際の分光透過率を表す。測定により得られた極大吸収波長時のＫｙ、及び、Ｋｚより、下記計算式（Ｉ）～（ＩＩＩ）にて算出した。 The polarizing films obtained in Examples 1 to 9 and Comparative Examples 1 to 16 were evaluated as follows.
(a) Polarized parallel transmittance (Ky) and polarized cross transmittance (Kz)
The maximum absorption wavelength, parallel polarization transmittance (Ky), and cross polarization transmittance (Kz) of the polarizing film were measured using a spectrophotometer (UH-4150, manufactured by Hitachi, Ltd.). Here, Ky is the transmittance when the absorption axis of the absolute polarizer and the absorption axis of the polarizing film are placed parallel to each other, and Kz is the transmittance when the absorption axis of the absolute polarizer and the absorption axis of the polarizing film are superimposed in parallel. This shows the transmittance when installed orthogonally stacked. The polarized parallel transmittances Ky and Kz of each wavelength were measured at wavelength intervals of 1 to 10 nm at 380 nm to 780 nm.
(b) Single transmittance (Ts), parallel transmittance (Tp), orthogonal transmittance (Tc)
Single transmittance (Ts) indicates the spectral transmittance when one polarizing film is used, and parallel transmittance (Tp) indicates the spectral transmittance when two polarizing films are installed with their absorption axes superimposed in parallel. The orthogonal transmittance (Tc) represents the spectral transmittance when two polarizing films are installed with their absorption axes superimposed orthogonally. It was calculated using the following calculation formulas (I) to (III) from Ky and Kz at the maximum absorption wavelength obtained by measurement.
　Ｔｓ（％）＝(Ｋｙ＋Ｋｚ)／２　　　　　　　　　　　計算式（Ｉ）
　Ｔｐ（％）＝(Ｋｙ２＋Ｋｚ２）／２００　　　　　　　計算式（ＩＩ）
　Ｔｃ（％）＝(Ｋｙ×Ｋｚ）／１００　　　　　　　　計算式（ＩＩＩ） Ts(%)=(Ky+Kz)/2 Calculation formula (I)
Tp (%) = (Ky 2 + Kz 2 )/200 Calculation formula (II)
Tc (%) = (Ky×Kz)/100 Calculation formula (III)
（ｃ）偏光率（ρ）、二色比
　各測定試料の極大吸収波長時の偏光率（ρ）、及び二色比を、下記計算式（ＩＶ）、（Ｖ）より算出した。 (c) Polarization ratio (ρ), dichroic ratio The polarization ratio (ρ) and dichroic ratio at the maximum absorption wavelength of each measurement sample were calculated using the following formulas (IV) and (V).
　ρ（％）＝［（Ｋｙ－Ｋｚ）／（Ｋｙ＋Ｋｚ）］×１００　　　　　計算式（ＩＶ）
　二色比　＝ｌｏｇ（Ｋｚ／１００）／ｌｏｇ（Ｋｙ／１００）　　計算式（Ｖ） ρ (%) = [(Ky-Kz)/(Ky+Kz)]×100 Calculation formula (IV)
Dichroic ratio = log (Kz/100)/log (Ky/100) Calculation formula (V)
　表１に実施例１及び比較例１～１０の偏光膜の測定と計算によって得られた値を示す。
Figure JPOXMLDOC01-appb-T000048
 Table 1 shows the values obtained by measurement and calculation of the polarizing films of Example 1 and Comparative Examples 1 to 10.
Figure JPOXMLDOC01-appb-T000048
　表１の通り、実施例１のアゾ化合物を用いて作製した偏光膜は高い二色比を有していた。具体的には、実施例１の偏光膜は比較例１～１０のいずれの偏光膜よりも高い二色比を有していた。また比較例６や比較例４との比較においても十分な優位性を示していた。
　更に比較例８や９のアゾ化合物と比べても優位性を示していたことから、本願発明であるイソインドリル基を有することが性能向上に寄与していることが示された。 As shown in Table 1, the polarizing film produced using the azo compound of Example 1 had a high dichroic ratio. Specifically, the polarizing film of Example 1 had a higher dichroic ratio than any of the polarizing films of Comparative Examples 1 to 10. Further, in comparison with Comparative Example 6 and Comparative Example 4, sufficient superiority was shown.
Furthermore, since it showed superiority compared to the azo compounds of Comparative Examples 8 and 9, it was shown that having the isoindolyl group according to the present invention contributed to improved performance.
　表２に実施例２及び比較例１１～１４の偏光膜の測定と計算によって得られた値を示す。
Figure JPOXMLDOC01-appb-T000049
 Table 2 shows the values obtained by measurement and calculation of the polarizing films of Example 2 and Comparative Examples 11 to 14.
Figure JPOXMLDOC01-appb-T000049
　表１と同様に表２に関しても実施例２の本発明のアゾ化合物を用いて作製した偏光膜は高い二色比を有していた。具体的には、実施例２の偏光膜は単体透過率約４４％において二色比４５以上を示すのに対し、比較例１１、比較例１２、比較例１３、比較例１４ではいずれも二色比４５以下であり、本願化合物の性能に達するものは得られなかった。 Similar to Table 1, Table 2 also shows that the polarizing film produced using the azo compound of the present invention in Example 2 had a high dichroic ratio. Specifically, the polarizing film of Example 2 exhibits a dichroic ratio of 45 or more at a single transmittance of approximately 44%, whereas Comparative Examples 11, 12, 13, and 14 all have a dichroic ratio of 45 or more. The ratio was 45 or less, and no compound reaching the performance of the present compound was obtained.
　表３に、実施例３及び比較例１５の偏光膜の測定と計算によって得られた値を示す。また表４に、実施例４及び比較例１６の偏光膜の測定と計算によって得られた値を示す。
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000051
 Table 3 shows the values obtained by measurement and calculation of the polarizing films of Example 3 and Comparative Example 15. Table 4 also shows values obtained by measurement and calculation of the polarizing films of Example 4 and Comparative Example 16.
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000051
　表３と表４では極大吸収波長が６００ｎｍを超える青色染料として出願されている化合物との本願化合物との比較を示す。いずれの場合でも本願実施例の方が、比較例に比べて二色比が高く、本願化合物であるイソインドリル基が置換した１－ナフトール－３－スルホン酸誘導体を有することで性能の良い青色二色性染料が得られることが示された。 Tables 3 and 4 show a comparison between the present compound and a compound that has been applied as a blue dye with a maximum absorption wavelength exceeding 600 nm. In any case, the present example has a higher dichroic ratio than the comparative example, and has good blue dichroic performance because it has a 1-naphthol-3-sulfonic acid derivative substituted with the isoindolyl group, which is the present compound. It was shown that a color dye can be obtained.
　表５に実施例５～９及び比較例１～２の偏光膜の測定と計算によって得られた値を示す。
Figure JPOXMLDOC01-appb-T000052
 Table 5 shows the values obtained by measurement and calculation of the polarizing films of Examples 5 to 9 and Comparative Examples 1 and 2.
Figure JPOXMLDOC01-appb-T000052
　表５の通り、実施例５～９のアゾ化合物を用いて作製した偏光膜は、いずれも高い偏光率と二色比を有していた。具体的には、実施例５～９の偏光膜は単体透過率約４４％において偏光度９８％以上かつ高い二色比を示すのに対し、極大吸収波長が５００ｎｍ～５８０ｎｍである一般的なレッド系の水溶性二色性染料として知られている比較例１～２の偏光膜では偏光度９８％に達するものは得られなかった。つまり、表５より、アゾ基の数や置換基が変わっても本願化合物であるイソインドリル基が置換した１－ナフトール－３－スルホン酸誘導体を有するアゾ化合物であれば、高い性能を持つ二色性染料が得られることが分かる。 As shown in Table 5, the polarizing films produced using the azo compounds of Examples 5 to 9 all had high polarization index and dichroic ratio. Specifically, the polarizing films of Examples 5 to 9 exhibit a degree of polarization of 98% or more and a high dichroic ratio at a single transmittance of about 44%, whereas the polarizing films of Examples 5 to 9 exhibit a high dichroic ratio with a polarization degree of 98% or more at a single transmittance of about 44%. The polarizing films of Comparative Examples 1 and 2, which are known as water-soluble dichroic dyes, could not achieve a degree of polarization of 98%. In other words, from Table 5, even if the number of azo groups and substituents are changed, as long as the azo compound having a 1-naphthol-3-sulfonic acid derivative substituted with an isoindolyl group, which is the compound of the present invention, has high performance dichroism. It can be seen that a dye is obtained.
（実施例１０：ニュートラルグレー偏光板の作製）
　レッド染料として実施例３の式（１３）で表される化合物を０．２％、ブルー染料として国際公開第２０１７／１４６２１２号公報の実施例６に記載の式（１－Ａ１４）の化合物を０．３％、オレンジ染料としてシー．アイ．ダイレクト．オレンジ３９を０．２％、及び芒硝０．１％の濃度とした４５℃の水溶液（染浴）に厚さ７５μｍのポリビニルアルコールフィルムを４分間浸漬した。このフィルムを３％ホウ酸水溶液中で、５０℃で５倍に延伸し、緊張状態を保ったまま、水洗、乾燥して偏光膜を得た。得られた偏光膜の３８０ｎｍ～７８０ｎｍにおける単体平均透過率は４２％であり、直交位の平均透過率は０．１％であり、高い偏光度を有していた。この偏光膜の両面にポリビニルアルコール水溶液の接着剤を介してトリアセチルセルロースフィルム（ＴＡＣフィルム：富士フイルム社製：商品名ＴＤ－８０Ｕ）でラミネートし、ＴＡＣ／偏光膜／ＴＡＣの順に積層された染料系偏光板（ニュートラルグレー偏光板）を得た。得られたニュートラルグレー偏光板の片面に粘着剤を用いてガラスへ貼付し、ＴＡＣ／偏光膜／ＴＡＣ／ガラスがこの順に積層されたニュートラルグレー偏光板測定試料を作製した。 (Example 10: Production of neutral gray polarizing plate)
0.2% of the compound represented by the formula (13) of Example 3 as the red dye, and 0.0% of the compound of the formula (1-A14) described in Example 6 of International Publication No. 2017/146212 as the blue dye. .3%, C. as an orange dye. Ai. direct. A polyvinyl alcohol film with a thickness of 75 μm was immersed for 4 minutes in a 45° C. aqueous solution (dye bath) containing 0.2% Orange 39 and 0.1% Glauber's Salt. This film was stretched 5 times in a 3% boric acid aqueous solution at 50° C., washed with water and dried while maintaining tension to obtain a polarizing film. The obtained polarizing film had a single average transmittance of 42% in the wavelength range of 380 nm to 780 nm, and an average transmittance of 0.1% in the orthogonal position, indicating a high degree of polarization. Both sides of this polarizing film are laminated with triacetyl cellulose film (TAC film: manufactured by Fuji Film Co., Ltd., product name TD-80U) via an adhesive of polyvinyl alcohol aqueous solution, and the dye layer is laminated in the order of TAC/polarizing film/TAC. A system polarizing plate (neutral gray polarizing plate) was obtained. One side of the obtained neutral gray polarizing plate was attached to glass using an adhesive to prepare a neutral gray polarizing plate measurement sample in which TAC/polarizing film/TAC/glass were laminated in this order.
　実施例１０で得られたニュートラルグレー偏光板は、環境温度１０５℃の条件下で５００時間経過後、また環境温度８０℃・相対湿度９０％での条件下で５００時間経過後も単体平均透過率に変化がなく、高温且つ高湿の状態でも長時間にわたる耐久性を示した。さらに、実施例１０のニュートラルグレー偏光板は、キセノン耐光試験（スガ試験機社製　ＳＸ－７５）にて６０Ｗ、環境温度５０℃の条件で２００時間経過後でも単体平均透過率に変化がなく、光への長時間暴露に対する耐光性も優れていた。
　これらの結果から、本願化合物を用いて作製した実施例１０のニュートラルグレー偏光板は優れた偏光性能を有し、かつ、耐久性（耐湿性、耐熱性、耐光性）を有する高性能な染料系偏光板であることが示された。 The neutral gray polarizing plate obtained in Example 10 had a single average transmittance even after 500 hours at an environmental temperature of 105°C and after 500 hours at an environmental temperature of 80°C and a relative humidity of 90%. There was no change in , and it showed long-term durability even under high temperature and high humidity conditions. Furthermore, the neutral gray polarizing plate of Example 10 showed no change in average transmittance even after 200 hours in a xenon light resistance test (SX-75 manufactured by Suga Test Instruments Co., Ltd.) at 60 W and an environmental temperature of 50°C. The light resistance against long-term exposure to light was also excellent.
From these results, the neutral gray polarizing plate of Example 10 prepared using the compound of the present invention has excellent polarizing performance and is a high-performance dye-based plate with durability (moisture resistance, heat resistance, light resistance). It was shown to be a polarizing plate.
　本発明のアゾ化合物を用いて作製した偏光膜又はその偏光板は、必要に応じて保護層又は機能層及びガラス、水晶、サファイア等の透明な支持体等を設け、液晶プロジェクター、電卓、時計、ノートパソコン、ワープロ、液晶テレビ、偏光レンズ、偏光メガネ、カーナビゲーション、及び屋内外の計測器や表示器等に適用される。特に、本発明の偏光膜又は偏光板は、液晶表示装置、例えば、反射型液晶表示装置、半透過液晶表示装置、及び液晶表示装置以外でも有機エレクトロルミネッセンス等に好適に用いることができる。 The polarizing film or its polarizing plate produced using the azo compound of the present invention can be provided with a protective layer or a functional layer and a transparent support such as glass, crystal, sapphire, etc. as necessary, and can be used in liquid crystal projectors, calculators, watches, etc. Applicable to notebook computers, word processors, LCD televisions, polarized lenses, polarized glasses, car navigation systems, and indoor and outdoor measuring instruments and displays. In particular, the polarizing film or polarizing plate of the present invention can be suitably used for liquid crystal display devices, such as reflective liquid crystal display devices, transflective liquid crystal display devices, and organic electroluminescence devices other than liquid crystal display devices.

Claims (9)

  1. 　下記式（１）で表されるアゾ化合物又はその塩：
    Figure JPOXMLDOC01-appb-C000001
    （式（１）中、Ａｒは置換基を有してもよいベンゼン環、置換基を有してもよいナフタレン環、又は置換基を有してもよい複素環を示し、Ａは任意の置換基を示す）。     Azo compound or its salt represented by the following formula (1):
    Figure JPOXMLDOC01-appb-C000001
    (In formula (1), Ar represents a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a heterocycle which may have a substituent, and A is any substituent. ).
  2. 　前記式（１）で表されるアゾ化合物が下記式（２）で表される、請求項１に記載のアゾ化合物又はその塩：
    Figure JPOXMLDOC01-appb-C000002
    （式（２）中、Ｒ１～Ｒ８は各々独立に任意の置換基を表し、ｍは０又は１の整数を、またｎは０又は１を示す）。     The azo compound or its salt according to claim 1, wherein the azo compound represented by the formula (1) is represented by the following formula (2):
    Figure JPOXMLDOC01-appb-C000002
    (In formula (2), R 1 to R 8 each independently represent an arbitrary substituent, m represents an integer of 0 or 1, and n represents 0 or 1).
  3. 　前記式（１）で表されるアゾ化合物が下記式（３）で表される、請求項１に記載のアゾ化合物又はその塩：
    Figure JPOXMLDOC01-appb-C000003
    （上記式（３）中、Ｒ１～Ｒ６は各々独立に任意の置換基を表し、ｍは０又は１を示す）。     The azo compound or its salt according to claim 1, wherein the azo compound represented by the formula (1) is represented by the following formula (3):
    Figure JPOXMLDOC01-appb-C000003
    (In the above formula (3), R 1 to R 6 each independently represent an arbitrary substituent, and m represents 0 or 1).
  4. 　請求項１～３のいずれかに記載のアゾ化合物又はその塩を含有する偏光膜。 A polarizing film containing the azo compound or salt thereof according to any one of claims 1 to 3.
  5. 　基材を含む、請求項４に記載の偏光膜。 The polarizing film according to claim 4, comprising a base material.
  6. 　請求項１～３のいずれかに記載のアゾ化合物又はその塩以外の有機染料を１種類以上含有する請求項４に記載の偏光膜。 The polarizing film according to claim 4, which contains one or more organic dyes other than the azo compound or its salt according to any one of claims 1 to 3.
  7. 　ニュートラルグレー色を有する請求項４に記載の偏光膜。 The polarizing film according to claim 4, which has a neutral gray color.
  8. 　請求項４に記載の偏光膜及びその片面又は両面に設けられた透明保護膜を備える偏光板。 A polarizing plate comprising the polarizing film according to claim 4 and a transparent protective film provided on one or both surfaces thereof.
  9. 　請求項４に記載の偏光膜又は請求項８に記載の偏光板を備える表示装置。 A display device comprising the polarizing film according to claim 4 or the polarizing plate according to claim 8.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60262858A (en) * 1984-06-11 1985-12-26 Mitsui Toatsu Chem Inc Dichroic azo dye for use in liquid crystal, liquid crystal composition containing said dye and display device
JPH11172252A (en) * 1997-12-15 1999-06-29 Mitsubishi Chemical Corp Dichroic colorant, liquid composition containing same, and liquid crystal element
WO2009057676A1 (en) * 2007-11-02 2009-05-07 Nippon Kayaku Kabushiki Kaisha Azo compound, and dye-containing polarizing film comprising the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60262858A (en) * 1984-06-11 1985-12-26 Mitsui Toatsu Chem Inc Dichroic azo dye for use in liquid crystal, liquid crystal composition containing said dye and display device
JPH11172252A (en) * 1997-12-15 1999-06-29 Mitsubishi Chemical Corp Dichroic colorant, liquid composition containing same, and liquid crystal element
WO2009057676A1 (en) * 2007-11-02 2009-05-07 Nippon Kayaku Kabushiki Kaisha Azo compound, and dye-containing polarizing film comprising the same

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* Cited by examiner, † Cited by third party
Title
HALLAS, G. JALIL, M.A.: "The Effects of Cyclic Terminal Groups in 4-Aminoazobenzene and Related Azo Dyes. Part 6. Electronic Absorption Spectra of some Monoazo Dyes Derived from N-Phenylisoindoline", DYES AND PIGMENTS, ELSEVIER APPLIED SCIENCE PUBLISHERS BARKING, GB, vol. 32, no. 3, 1 November 1996 (1996-11-01), GB , pages 129 - 133, XP004069621, ISSN: 0143-7208, DOI: 10.1016/0143-7208(96)00030-7 *

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