Classifications

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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
  • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
  • C07D513/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
  • C07D277/62—Benzothiazoles
  • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
  • C07D277/82—Nitrogen atoms
• • 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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
• • 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
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • 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
  • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
  • C09B33/02—Disazo dyes
  • C09B33/12—Disazo dyes in which the coupling component is a heterocyclic compound
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  • 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
  • C09B43/00—Preparation of azo dyes from other azo compounds
  • C09B43/08—Preparation of azo dyes from other azo compounds by reduction
  • C09B43/10—Preparation of azo dyes from other azo compounds by reduction with formation of a new azo or an azoxy bridge
• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/006—Preparation of organic pigments
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
  • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
  • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
  • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
  • C09K19/2014—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n-
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
  • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
  • C09K19/3001—Cyclohexane rings
  • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
  • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/60—Pleochroic dyes
  • C09K19/601—Azoic
• • 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
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
  • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Definitions

• the present invention relates to compounds useful for polarizing films and the like provided in display elements such as light control elements, liquid crystal elements (LCDs), and organic electroluminescence elements (OLEDs).
• display elements such as light control elements, liquid crystal elements (LCDs), and organic electroluminescence elements (OLEDs).
• the present invention also relates to an anisotropic dye film-forming composition, an anisotropic dye film and an optical element containing this compound.
• LCDs use linear polarizing films and circular polarizing films to control optical rotation and birefringence in display.
• OLEDs also use a circularly polarizing film to prevent reflection of external light in a bright place.
• a polarizing film for example, one containing a polarizing film (iodine-PVA polarizing film) obtained by dyeing polyvinyl alcohol (PVA) with a low concentration of iodine is known (Patent Document 1).
• a polarizing film iodine-PVA polarizing film obtained by dyeing polyvinyl alcohol (PVA) with a low concentration of iodine
• Patent Document 1 a polarizing film obtained by dyeing polyvinyl alcohol (PVA) with a low concentration of iodine
• the iodine-PVA polarizing plate with a low PVA concentration has problems such as iodine sublimation or deterioration depending on the usage environment, resulting in a change in color tone, and a problem that stretching of PVA is eased. There is a problem that warpage occurs.
• Patent Document 2 an anisotropic dye film formed by applying a liquid crystal composition containing a dye functions as a polarizing film.
• Patent Document 2 there is no disclosure of a dichroic dye that has a maximum absorption in the wavelength range of 560 nm to 800 nm and has both a sufficient dichroic ratio and solubility.
• an anisotropic dye film combining a dye having a benzothiazole or thienothiazole skeleton and a polymerizable liquid crystal is known (Patent Document 3).
• a dye having a benzothiazole or thienothiazole skeleton may precipitate in an anisotropic dye film-forming composition that requires solubility.
• a polarizing film formed by applying a liquid crystal composition containing a dye is desired to have high light absorption selection performance even in a thin film and to have no light leakage in the wavelength range of 350 nm to 800 nm. Therefore, it is necessary to use a plurality of dyes with high dichroism so as to comprehensively absorb the wavelength region of 350 nm to 800 nm.
• the composition contains a plurality of dyes, the dye concentration in the composition increases, and when the coating is performed under thin film conditions, the dye concentration relative to the liquid crystal increases, making it easier for the dye to precipitate, resulting in poor coating performance. descend.
• the inventors have found that a compound having a specific structure can solve the above problems.
• the present invention has the following aspects.
• a compound represented by the following formula (1) A compound represented by the following formula (1).
• -A 1 - and -A 2 - each independently have a polycyclic aromatic heterocyclic bivalent group containing one or more optionally substituted S atoms, or a substituent; represents a divalent group of an aromatic hydrocarbon ring that may be -A 3 - represents a divalent group of an aromatic hydrocarbon ring which may have a substituent;
• -X represents a monovalent organic group,
• —R x represents an optionally substituted alkyl group having 3 to 15 carbon atoms.
• —R y represents a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbon atoms, and the optionally branched alkyl group having 1 to 15 carbon atoms is a substituent; may have.
• R z represents a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbon atoms.
• n represents 1, 2 or 3; When n is 2 or 3, multiple -A 2 - may be the same or different. However, both -A 1 - and -A 2 - are not divalent groups of an aromatic hydrocarbon ring which may have a substituent. )
• the polycyclic aromatic heterocyclic ring containing one or more S atoms is a benzothiophene ring, a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, and a thienothiazole ring.
• a benzoisothiazole ring, or a benzothiazole ring the compound according to [1].
• At least one of -A 2 - is a polycyclic aromatic heterocyclic divalent group containing one or more optionally substituted S atoms, The compound according to [1] or [2].
• —Y is —N(—R y )—R x
• —R x is an optionally substituted branched C 3-15 alkyl
• -R y is a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbon atoms, and the total number of carbon atoms in the alkyl groups of -R x and -R y is 15 or less
• —Y is —N(—R y )—R x
• —R x is an optionally substituted branched C 3-15 alkyl -R y is a hydrogen atom or an unbranched C 1-15 alkyl group, and the unbranched C 1-15 alkyl group may have a substituent , the compound according to any one of [1] to [4].
• -X is an unbranched alkyl group having 3 or more carbon atoms, an alkoxy group, an alkyl ester group, an alkoxycarbonyl group or an alkylsulfanyl group, [1] to [7 ] The compound according to any one of the above.
• a composition for forming an anisotropic dye film containing the compound according to any one of [1] to [8] and a polymerizable liquid crystal compound containing the compound according to any one of [1] to [8] and a polymerizable liquid crystal compound.
• a method for producing an anisotropic dye film comprising the step of applying the anisotropic dye film-forming composition according to any one of [9] to [13] to a substrate.
• the compounds of the present invention have moderately bulky substituents and are compatible with high dichroism and solubility. Since the anisotropic dye film-forming composition of the present invention contains such a compound of the present invention, precipitation of the compound can be suppressed, coating performance can be improved, and a high dichroic ratio can be realized. According to the anisotropic dye film and the optical element using the composition for forming an anisotropic dye film of the present invention, excellent optical performance, particularly a sufficient dichroic ratio can be achieved.
• the anisotropic dye film refers to the electromagnetic properties in any two directions selected from a total of three directions in the three-dimensional coordinate system of the thickness direction of the anisotropic dye film and any two orthogonal in-plane directions. It is an anisotropic dye film. Electromagnetic properties include, for example, optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance. Examples of films having optical anisotropy such as absorption and refraction include polarizing films such as linear polarizing films and circular polarizing films, retardation films, and conductive anisotropic dye films. The anisotropic dye film of the present invention is preferably used as a polarizing film or a conductive anisotropic dye film, more preferably as a polarizing film.
• —R y represents a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbon atoms, and the optionally branched alkyl group having 1 to 15 carbon atoms is a substituent; may have.
• R z represents a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbon atoms.
• n represents 1, 2 or 3; When n is 2 or 3, multiple -A 2 - may be the same or different. However, both -A 1 - and -A 2 - are not divalent groups of an aromatic hydrocarbon ring which may have a substituent. )
• (-X) -X represents a monovalent organic group.
• the monovalent organic group for -X includes a hydrogen atom, a hydroxy group, an amino group, a cyano group, a carbamoyl group, a nitro group, a halogen atom, -R a , -OR a , -NH-R a , and -C.
• —R a and —R b are each independently an optionally branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and the number of atoms constituting the ring represents a cycloalkyl group having 5 to 14, preferably 5 to 10 atoms or an aryl group having 5 to 14, preferably 5 to 10 ring atoms.
• Each of the alkyl group, cycloalkyl group and aryl group may have a substituent.
• —R a and —R b may together form a ring having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, and the ring may have a substituent.
• R f and —R g each independently represent a straight or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.
• One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms are -O-, -S-, -NH-, -N(R h )-, ( _ displace) structure, or a structure replaced with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.
• R h represents a linear or branched alkyl group having 1 to 6 carbon atoms.
• the substituent acceptable for the optionally branched alkyl group having 1 to 15 carbon atoms in -R a and -R b is preferably -OR f , for example, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, acryloyloxy group, methacryloyloxy group, glycidyloxy group and the like.
• -R i and -R j each independently represent a linear
• -R i and -O-R i are preferred as the substituents permissible for the cycloalkyl group or aryl group having 5 to 14 ring-constituting atoms in -R a and -R b .
• the cycloalkane ring of the cycloalkyl group having 5 to 14 atoms constituting the rings of -R a and -R b includes, for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, Cyclooctane ring, cyclohexene ring, norbornane ring, bornane ring, adamantane ring, tetrahydronaphthalene ring, bicyclo[2.2.2]octane ring and the like.
• the aryl group having 5 to 14 atoms constituting the ring of -R a and -R b includes a monovalent aromatic heterocyclic ring and a ring exemplified later as an aromatic hydrocarbon ring in -A 3 - can be mentioned.
• —R a and —R b are optionally branched alkyl groups having 1 to 15 carbon atoms, or —R a and —R b together have a substituent It preferably forms a ring having 2 to 15 carbon atoms, which may be Furthermore, it is more preferably an optionally branched alkyl group having 1 to 6 carbon atoms, or —R a and —R b together form a ring; It is more preferably an alkyl group having 1 to 3 carbon atoms which may be substituted, or --R a and --R b together form a ring. Due to the above, the molecular orientation of the compound of the present invention tends to be good.
• the number of carbon atoms in -X is preferably 3 or more and 15 or less, more preferably 3 or more and 10 or less, from the viewpoint of good molecular alignment with the polymerizable liquid crystal compound used in the present invention.
• -R includes, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-nonyl group. From the viewpoint of good molecular alignment with the polymerizable liquid crystal compound used in the present invention, -R is preferably an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, or an n-octyl group. .
• the monovalent organic group in -X preferably does not have a polymerizable group from the viewpoint of improving the molecular alignment with the polymerizable liquid crystal compound.
• the monovalent organic group in -X preferably has a polymerizable group from the viewpoint of improving the mechanical strength of the anisotropic dye film.
• Y is preferably -N(-R y )-R x from the viewpoint of good molecular orientation of the compound of the present invention.
• —R x represents a branched alkyl group having 3 to 15 carbon atoms, which may have a substituent, and from the viewpoint of good molecular orientation with the polymerizable liquid crystal compound, The number of carbon atoms is preferably 3-10, more preferably 3-8, even more preferably 3-6.
• R x specifically includes, for example, 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,2-dimethylpropyl group, 2,2 -dimethylpropyl group, 1,2,2-trimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3- dimethylbutyl group, 1,3,3-trimethylbutyl group, 2,3,3-trimethylbutyl group, 2,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 4,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,2-dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-d
• R x is a 1-methylethyl group, a 1,1-dimethylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2,2-trimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 3,3-dimethylbutyl group, 2 ,3-dimethylbutyl group, 1,3-dimethylbutyl group, 1,3,3-trimethylbutyl group, 2,3,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 4-methylpentyl group , 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 4,4-dimethylpentyl group, 3,4,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 2,4,4-trimethylpentyl
• a structure having a branch on the root side of —R x is preferable, such as 1-methylethyl group, 1-methylpropyl group, 1-methylbutyl group, 1 , 2-dimethylbutyl group, 1-methylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,2,3-trimethylpentyl group, 1-methylhexyl group, 1,2-dimethyl hexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,2,3-trimethylhexyl group, 1,3,4-trimethylhexyl group, 1-methylheptyl group, 1,2-dimethyl A heptyl group, a 1,3-dimethylheptyl group, a 1,4-dimethylheptyl group and a 1,5-dimethylheptyl group
• —R z represents a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbon atoms.
• optionally branched alkyl group having 1 to 15 carbon atoms include alkyl groups having 1 to 15 carbon atoms which may be branched among the above-mentioned -X monovalent organic groups. Those exemplified as the group can be mentioned.
• R z1 and —R z2 each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.
• One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms are -O-, -S-, -NH-, -N(R z3 )-, ( _ displace) structure, or a structure replaced with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.
• R z3 represents a linear or branched alkyl group having 1 to 6 carbon atoms.
• the substituent acceptable for the branched alkyl group having 3 to 15 carbon atoms in -R x is preferably -OR z1 , and specific examples thereof include methoxy, ethoxy, n- Propoxy group, n-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, acryloyloxy group, methacryloyloxy group and glycidyloxy group.
• the branched alkyl group having 3 to 15 carbon atoms in —R x preferably does not have a cycloalkyl structure from the viewpoint of improving the molecular alignment with the polymerizable liquid crystal compound.
• the branched alkyl group having 3 to 15 carbon atoms in —R x preferably does not have a polymerizable group from the viewpoint of improving the molecular orientation with the polymerizable liquid crystal compound.
• the branched alkyl group having 3 to 15 carbon atoms preferably has a polymerizable group from the viewpoint of improving the mechanical strength of the anisotropic dye film.
• R y represents a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbon atoms, and the optionally branched alkyl group having 1 to 15 carbon atoms is a substituent; may have.
• Specific examples of the optionally branched alkyl group having 1 to 15 carbon atoms include alkyl groups having 1 to 15 carbon atoms which may be branched among the above-mentioned -X monovalent organic groups. Those exemplified as the group can be mentioned.
• —R z represents a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbon atoms.
• optionally branched alkyl group having 1 to 15 carbon atoms include alkyl groups having 1 to 15 carbon atoms which may be branched among the above-mentioned -X monovalent organic groups. Those exemplified as the group can be mentioned.
• R z1 and —R z2 each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.
• One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms are -O-, -S-, -NH-, -N(R z3 )-, ( _ displace) structure, or a structure substituted with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.
• R z3 represents a linear or branched alkyl group having 1 to 6 carbon atoms.
• the acceptable substituent for the optionally branched alkyl group having 1 to 15 carbon atoms in -R y is preferably -O-R z1 , specifically for example, a methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, acryloyloxy group, methacryloyloxy group and glycidyloxy group.
• the optionally branched alkyl group having 1 to 15 carbon atoms in —R y preferably does not have a cycloalkyl structure from the viewpoint of improving the molecular orientation with the polymerizable liquid crystal compound.
• -R y is preferably a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbon atoms, and a hydrogen atom or an optionally branched carbon number
• An alkyl group of 1 to 10 is more preferred, and a hydrogen atom or an optionally branched alkyl group of 1 to 4 carbon atoms is even more preferred.
• -R x and -R y are preferably different from the viewpoint that the molecular orientation can be further improved since the compound of the present invention has an asymmetric structure.
• -R y is preferably a hydrogen atom or an unbranched alkyl group having 1 to 15 carbon atoms, more preferably a hydrogen atom or an unbranched alkyl group having 1 to 10 carbon atoms.
• a hydrogen atom, or an unbranched alkyl group having 1 to 4 carbon atoms is more preferable.
• the number of branches possessed by -Y is not particularly defined, it is preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1, from the viewpoint of good molecular orientation.
• -Y is -N(-R y )-R x in the formula (1), and carbon atoms in -R x and -R y
• the total number is preferably 15 or less, more preferably 13 or less, even more preferably 11 or less, even more preferably 9 or less, and particularly preferably 7 or less.
• -Y is -N(-R y )-R x in the formula (1), and -R x has a substituent.
• —R y is a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbon atoms
• -Y is -N(-R y )-R x in the above formula (1), and -R x is a substituent.
• a branched alkyl group having 3 to 15 carbon atoms, and —R y is preferably a hydrogen atom or an unbranched alkyl group having 1 to 15 carbon atoms, and the branched Alkyl groups having 1 to 15 carbon atoms which do not have may have a substituent.
• -Y in the above formula (1) preferably has a plurality of branched structures near the Y terminal of -A 3 -. It is considered that the presence of a plurality of branched structures near the -A 3 - terminal tends to suppress the association and aggregation of the compound, thereby improving the solubility of the compound of the present invention.
• -Y it is preferable that two or more branched structures are present at positions where the number of covalent bonds from the Y-end of -A 3 - is 5 or less, and More preferably, two or more branched structures are present at positions where the number of covalent bonds is three or less.
• the number of covalent bonds mentioned above means the number of covalent bonds from the Y-side terminal atom of -A 3 - to the branch starting point atom.
• -Y is -N(-R y )-R x and -R y is an optionally branched C 1-15 alkyl group
• -R x and -R y are bonds A branched structure exists at the position where the number of covalent bonds from the Y-side end of -A 3 - is one.
• ( -A3- ) -A 3 - represents a divalent group of an aromatic hydrocarbon ring which may have a substituent.
• the aromatic hydrocarbon ring of -A 3 - includes benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring and fluorene. ring and the like.
• the divalent group of the aromatic hydrocarbon ring of -A 3 - the absorption transition moment of the compound of the present invention tends to coincide with the long axis direction of the dye, and the dichroic ratio can be increased.
• a 1,4-phenylene group, a 1,4-naphthylene group and a 2,6-naphthylene group are more preferred, a 1,4-phenylene group is even more preferred, and a 1,4-phenylene group having no substituent is particularly preferred. preferable. Due to the above, the absorption transition moment of the compound of the present invention tends to coincide with the long axis direction of the compound, and the dichroic ratio can be increased.
• -R A and -R B each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms.
• the number of carbon atoms in -R A and -R B is preferably 1 or more and 12 or less, more preferably 1 or more and 9 or less, from the viewpoint of good molecular alignment with the polymerizable liquid crystal compound used in the present invention.
• One or more methylene groups contained in the linear or branched alkyl group may be an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom (—NH—, —N(R z )— :
• R z represents a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
• carbonyl group, ester bond, amide bond, -CHF-, -CF 2- , -CHCl-, or -CCl 2 - may be substituted, or polymerizable groups such as acryloyloxy, methacryloyloxy, and glycidyloxy groups may be substituted.
• substituents for the divalent group of the aromatic hydrocarbon ring in -A 3 - are -R A , -OR A , trifluoromethyl group and fluoro group.
• -R A includes, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 5,5-dimethyl-3-methylhexyl group and the like. mentioned. Having the above substituent tends to improve the molecular orientation of the dye of the compound of the present invention.
• (-A 1 - and -A 2 -) -A 1 - and -A 2 - each independently have a polycyclic aromatic heterocyclic bivalent group containing one or more optionally substituted S atoms, or a substituent; is a divalent group of an aromatic hydrocarbon ring which may be However, both -A 1 - and -A 2 - are not divalent groups of an aromatic hydrocarbon ring which may have a substituent.
• the aromatic hydrocarbon ring optionally having substituents -A 1 - and -A 2 - the aromatic hydrocarbon ring optionally having substituents -A 3 - and the types and preferred substituents that may be possessed are also the same.
• a polycyclic aromatic heterocyclic bivalent group containing one or more S atoms which may have substituents -A 1 - and -A 2 - is a condensed aromatic heterocyclic group.
• the number of carbon atoms in the aromatic heterocycle is not particularly limited, it is preferably 4 or more and 20 or less.
• aromatic heterocyclic rings of -A 1 - and -A 2 - include benzothiophene ring, thienopyrrole ring, thienothiophene ring, furothiazole ring, thienofuran ring, thienothiazole ring, benzoisothiazole ring and benzothiazole ring. ring and the like.
• a benzothiophene ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, a benzoisothiazole ring, and a benzothiazole ring are preferable from the viewpoint of good molecular orientation of the compound of the present invention.
• the absorption transition moment of the compound (1) tends to coincide with the long axis direction of the dye, and the structure shown below is more preferable for the reason that the dichroic ratio can be increased. (*1 and *2 in the structure below represent the bond in formula (1))
• At least one of —A 2 — in formula (1) contains one or more S atoms which may have a substituent. It is preferably a divalent group of a polycyclic aromatic heterocycle.
• the divalent group, a polycyclic aromatic heterocycle containing one or more S atoms is a benzothiophene ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, a benzoisothiazole ring, and a benzothiazole ring.
• a ring is preferred.
• -A 1 - in formula (1) is a divalent group of an aromatic hydrocarbon ring which may have a substituent.
• the absorption transition moment of the compound of the present invention tends to coincide with the long axis direction of the dye, and the dichroic ratio can be increased.
• a naphthalene ring divalent group (naphthylene group) is preferred, and a benzene ring divalent group (phenylene group) is more preferred.
• a 1,4-phenylene group, a 1,4-naphthylene group and a 2,6-naphthylene group are more preferred, a 1,4-phenylene group is even more preferred, and a 1,4-phenylene group having no substituent is particularly preferred. preferable. Due to the above, the absorption transition moment of the compound of the present invention tends to coincide with the long axis direction of the compound, and the dichroic ratio can be increased.
• n represents 1, 2, or 3; n is preferably 1 or 2, more preferably 1. Due to the above, the molecular orientation of the compound of the present invention tends to be good. When n is 2 or 3, each -A 2 - may be the same or different.
• Specific examples of the compound of the present invention include, but are not limited to, the following compounds.
• the compound of the present invention may have a maximum absorption ( ⁇ max1) in the wavelength range of 350 to 800 nm, preferably in the wavelength range of 450 to 800 nm, in the anisotropic dye film prepared by the method described later. It has absorption, more preferably in the wavelength range of 510 to 750 nm, more preferably in the wavelength range of 510 to 700 nm.
• ⁇ max1 maximum absorption
• the compound of the present invention preferably has a maximum absorption ( ⁇ max1 described above) in the anisotropic dye film at a longer wavelength than the maximum absorption ( ⁇ max2) measured by dissolving in a solvent.
• This long wavelength shift is a phenomenon that occurs when the compound represented by formula (1) is dispersed in a polymer having units based on a polymerizable liquid crystal compound and/or a polymerizable liquid crystal compound, and formula (1 ) and the polymerizable liquid crystal compound and/or the polymer having units based on the polymerizable liquid crystal compound are strongly intermolecularly interacting.
• the long wavelength shift means that the difference between the absorption maxima ( ⁇ max1 ⁇ max2) becomes a positive value, and the difference is preferably 10 nm or more, more preferably 20 nm or more, and 30 nm or more. It is even more preferable to have
• the solubility of the compound of the present invention is not particularly limited, but the solubility in cyclopentanone is preferably 0.4 mass % or more, more preferably 0.6 mass % or more, and 0.8 mass % or more. It is even more preferable to have When the solubility is at least the above lower limit, there is a tendency that good coating film performance is obtained.
• composition for forming anisotropic dye film contains a dye and a polymerizable liquid crystal compound, and contains at least the compound of the present invention represented by the formula (1) as the dye.
• the anisotropic dye film-forming composition of the present invention may contain only one of the compounds of the present invention, or may contain two or more thereof.
• the anisotropic dye film-forming composition of the present invention has the same A 1 , A 2 , A 3 and n in formula (1) from the viewpoint of suppressing precipitation in the composition. and more preferably contain only one compound of the present invention.
• the anisotropic dye film-forming composition of the present invention may be in a solution, a liquid crystal, or a dispersed state as long as it does not cause phase separation.
• the composition for forming an anisotropic dye film is preferably in the form of a solution from the viewpoint of easy application to a substrate. From the viewpoint of aligning the solid components of the anisotropic dye film-forming composition on the substrate as described later, the composition for forming an anisotropic dye film of the present invention can be liquid crystal at any temperature. It is preferably in phase.
• the state of the liquid crystal phase is specifically described in "Fundamentals and Applications of Liquid Crystals” (Shoichi Matsumoto, Ichiyoshi Tsunoda; 1991), pages 1 to 16. , is a liquid crystal state exhibiting properties between liquid and crystal, or intermediate, and refers to a nematic phase, smectic phase, cholesteric phase, or discotic phase.
• a dye is a substance or compound that absorbs at least part of the wavelengths in the visible light region (350 nm to 800 nm).
• Dyes that can be used in the present invention include dichroic dyes.
• a dichroic dye is a dye that has different absorbances in the long-axis direction and the short-axis direction of the molecule.
• the pigment may be a pigment having liquid crystallinity or may not have liquid crystallinity. Note that having liquid crystallinity means exhibiting a liquid crystal phase at an arbitrary temperature.
• the anisotropic dye film-forming composition of the present invention contains the compound of the present invention represented by the formula (1) as a dye, but may contain dyes other than the compound of the present invention.
• Dyes other than the compound of the present invention represented by the formula (1) contained in the anisotropic dye film-forming composition of the present invention include azo dyes, quinone dyes (naphthoquinone dyes, anthraquinone dyes, etc.). ), stilbene dyes, cyanine dyes, phthalocyanine dyes, indigo dyes, condensed polycyclic dyes (including perylene dyes, oxazine dyes, acridine dyes, etc.).
• the anisotropic dye film composition of the present invention may contain only one dye other than the compound of the present invention, or may contain two or more dyes in any combination and ratio. good.
• azo dyes are preferable because they can have a high molecular arrangement in an anisotropic dye film.
• Examples of azo dyes include compounds represented by the following formula (A).
• -E 1 -, -E 2 - and -E 3 - each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group, or a substituted represents a divalent heterocyclic group that may be p represents an integer from 0 to 4; when p is an integer of 2 or more, multiple -E 2 - may be the same or different;
• R 11 and R 12 each independently represent a monovalent organic group.
• -E 1 -, -E 2 - and -E 3 - each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group, or a substituted represents a divalent heterocyclic group which may be
• a 1,4-phenylene group is preferable because the linearity of the molecule is high.
• a 1,4-naphthylene group or a 2,6-naphthylene group is preferable because the linearity of the molecule is high.
• the divalent heterocyclic group preferably has 3 or more and 14 or less, more preferably 10 or less carbon atoms forming a ring.
• a monocyclic or bicyclic heterocyclic group is particularly preferred.
• Atoms other than carbon constituting the divalent heterocyclic group include at least one selected from a nitrogen atom, a sulfur atom and an oxygen atom.
• the heterocyclic group has a plurality of non-carbon ring-constituting atoms, these may be the same or different.
• divalent heterocyclic groups include a pyridinediyl group, a quinolinediyl group, an isoquinolinediyl group, a thiazoldiyl group, a benzothiazoldiyl group, a thienothiazoldiyl group, a thienothiophenediyl group, and a benzimidazolidinonediyl group.
• a benzofurandiyl group a phthalimidodiyl group, an oxazoldiyl group, a benzoxazoldiyl group, and the like.
• the substituents optionally possessed by the phenylene group, naphthylene group and divalent heterocyclic group in -E 1 -, -E 2 - and -E 3 - include alkyl groups having 1 to 4 carbon atoms; methoxy group, ethoxy group; alkoxy group having 1 to 4 carbon atoms such as group and butoxy group; fluorinated alkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; cyano group; nitro group; hydroxyl group; halogen atom; amino group, diethylamino group, and A substituted or unsubstituted amino group such as a pyrrolidino group (substituted amino group is an amino group having one or two alkyl groups having 1 to 4 carbon atoms, or an amino group having two substituted alkyl groups bonded to each other and having 2 to 2 carbon atoms) means an amino group forming an alkanediyl group of 8.
• An unsubstituted amino group is -NH2 .
• alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group and butyl group.
• alkanediyl groups having 2 to 8 carbon atoms include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. , hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like. ).
• the phenylene group, naphthylene group and divalent heterocyclic group in -E 1 -, -E 2 - and -E 3 - are unsubstituted or substituted in view of high molecular linearity. In some cases, it is preferably substituted with a methyl group, methoxy group, hydroxyl group, fluorine atom, chlorine atom, dimethylamino group, pyrrolidinyl group or piperidinyl group.
• p represents an integer from 0 to 4. From the viewpoints of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of production, p is preferably 1 or more, preferably 4 or less, and more preferably 3 or less.
• R 11 and R 12 represent the same or different monovalent organic groups.
• the monovalent organic groups for R 11 and R 12 include a hydrogen atom, an optionally branched alkyl group having 1 to 15 carbon atoms; an alicyclic alkyl group having 1 to 15 carbon atoms; a methoxy group; An alkoxy group having 1 to 15 carbon atoms which may have a branch such as an ethoxy group and a butoxy group; A fluorinated alkyl group having 1 to 15 carbon atoms which may have a branch such as a trifluoromethyl group; Cyano nitro group; hydroxyl group; halogen atom; substituted or unsubstituted amino group such as amino group, diethylamino group and pyrrolidino group; carboxy group; alkyloxycarbonyl group; alkylphenylalkenyl group such as 2-(4-butylphenyl)ethenyl group; carbamoyl group; alkylcarbam
• the substituted amino group means an amino group having one or two alkyl groups having 1 to 4 carbon atoms, or two substituted alkyl groups bonded together to form an alkanediyl group having 2 to 8 carbon atoms. means an amino group.
• An unsubstituted amino group is -NH2 .
• alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group and butyl group.
• alkanediyl groups having 2 to 8 carbon atoms include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. , hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like.
• hydrogen atoms and aliphatic organic groups are preferred, and in another embodiment, hydrogen atoms and aliphatic organic groups are preferred. In still another embodiment, hydrogen atoms and aliphatic organic groups in which part of the carbon atoms are replaced with nitrogen atoms and/or oxygen atoms groups are preferred.
• the chain group As the chain group, the above alkyl group having 1 to 15 carbon atoms which may be branched; alkoxy group having 1 to 15 carbon atoms which may be branched; A fluorinated alkyl group having 1 to 15 carbon atoms; a substituted or unsubstituted amino group (a substituted amino group is an amino group having one or two optionally branched alkyl groups having 1 to 15 carbon atoms An unsubstituted amino group is —NH 2.
• a carboxy group ; an optionally branched C1-15 alkyloxycarbonyl group; a carbamoyl group; Alkylcarbamoyl group having 1 to 15 carbon atoms which may have; sulfamoyl group; Alkylsulfamoyl group having 1 to 15 carbon atoms which may have branch; an acyloxy group having 1 to 15 carbon atoms which may have a branch; a sulfanyl group; an alkylsulfanyl group having 1 to 15 carbon atoms; The chain group and the aliphatic organic group partially overlap.
• aliphatic organic group examples include the above-described optionally branched alkyl group having 1 to 15 carbon atoms, alicyclic alkyl group having 1 to 15 carbon atoms, and the like.
• Aliphatic organic groups in which a portion of the carbon atoms are replaced with nitrogen atoms and/or oxygen atoms include the above optionally branched alkoxy groups having 1 to 15 carbon atoms; substituted or unsubstituted amino groups.
• the substituted amino group means an amino group having one or two optionally branched alkyl groups having 1 to 15 carbon atoms, or an amino group having two substituted alkyl groups bonded to each other and having 2 to 15 carbon atoms. It means an amino group forming an alkanediyl group.
• An unsubstituted amino group is -NH2 .
• alkyl groups having 1 to 15 carbon atoms include methyl group, ethyl group and butyl group.
• alkanediyl groups having 2 to 15 carbon atoms include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. , hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like.
• R 11 and R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms such as a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group; It is preferably substituted with an alkoxy group having 1 to 10 carbon atoms such as butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, diethylamino group, pyrrolidino group and piperidinyl group.
• R 11 and R 12 -R 1 and -R 2 in the liquid crystal compound described below are also preferable.
• the azo dye other than the compound of the present invention contained in the anisotropic dye film-forming composition of the present invention is not particularly limited, and known azo dyes can also be used.
• known azo dyes include, for example, the above-mentioned Patent Document 1, Patent No. 5982762, JP 2017-025317, JP 2014-095899 described in the dyes (dichroic dyes, dichroic dyes).
• the wavelength showing the maximum value in the absorption curve in the wavelength range of 350 nm to 800 nm is , which is contained in the anisotropic dye film-forming composition and which is shorter than the wavelength showing the maximum value in the absorption curve of the compound of the present invention represented by formula (1) in the wavelength range of 350 nm to 800 nm.
• Preferred are azo dyes.
• the difference in wavelength is preferably 5 nm or more, more preferably 10 nm or more.
• the anisotropic dye film formed using the composition for forming an anisotropic dye film of the present invention is applied to a polarizing element such as a display, the polarization characteristics are exhibited in a wide range of the visible region. can do.
• the molecular weight of the dye contained in the composition for forming an anisotropic dye film of the present invention is preferably 300 or more, more preferably 350 or more, and 380 or more. is more preferably 1500 or less, more preferably 1200 or less, and even more preferably 1000 or less.
• the molecular weight of the dye contained in the anisotropic dye film-forming composition of the present invention is preferably 300 to 1,500, more preferably 350 to 1,200, and even more preferably 380 to 1,000. Within the above range, the molecular length and bulkiness of the dye are appropriate, so that the molecular orientation of the dye tends to be favorable.
• the molecular weight of a dye is the sum of the atomic weights contained in the dye.
• the content of dyes such as dichroic dyes in the anisotropic dye film-forming composition of the present invention is, for example, anisotropic Based on the solid content (100 parts by mass) of the dye film-forming composition, the amount is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, preferably 30 parts by mass or less, and 25 parts by mass or less. It is more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less.
• the content of the dye (dichroic dye) in the anisotropic dye film-forming composition is, for example, 0.01 to 30 parts by mass, preferably 0.05 to 20 parts by mass, more preferably 0.05 to 10 parts by mass.
• the composition for forming an anisotropic dye film of the present invention does not disturb the orientation of the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention. It tends to be able to polymerize the polymerizable liquid crystal compound contained.
• the content of the dye is at least the above lower limit, sufficient light absorption tends to be obtained and sufficient polarizing performance can be obtained. If the content of the dye is equal to or less than the upper limit, the inhibition of alignment of liquid crystal molecules tends to be suppressed.
• the solid content of the composition for the anisotropic dye film corresponds to the sum of all components other than the solvent in the composition for the anisotropic dye film.
• the anisotropic dye film composition of the present invention may contain the compound of the present invention as a dye as an essential component, and may contain the other dyes described above together with the compound of the present invention.
• the composition for an anisotropic dye film of the present invention contains other dyes, from the viewpoint of more effectively obtaining the effects of the present invention by using the compound of the present invention, the composition for an anisotropic dye film of the present invention
• the proportion of the compound of the present invention in 100% by mass of the total amount of dyes in the product is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. , 20% by mass or more.
• the ratio is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. , 40% by mass or less.
• the dye such as the compound of the present invention contained in the composition for forming an anisotropic dye film of the present invention undergoes alkylation reaction, esterification reaction, amidation reaction, etherification reaction, ipso substitution reaction, diazo coupling reaction, It can be produced by combining known chemical reactions such as a coupling reaction using a metal catalyst.
• the compounds of the present invention can be prepared by the methods described in Examples below, “New Dyestuff Chemistry” (Yutaka Hosoda, December 21, 1973, Gihodo), “Review Synthetic Dyes” (Hiroshi Horiguchi, Sankyo Publishing, 1968) and “Theory Manufacturing Dye Chemistry” (Yutaka Hosoda, 1957, Gihodo).
• a liquid crystal compound refers to a substance exhibiting a liquid crystal state, and is specifically described on pages 1 to 28 of "Liquid Crystal Handbook" (published by Maruzen Co., Ltd., October 30, 2000). A compound that does not transition directly from a crystal to a liquid, but goes through an intermediate state that exhibits the properties of both crystals and liquids.
• the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention is a liquid crystal compound having a polymerizable group, which will be described later.
• the polymerizable group can be arranged at any position in the liquid crystal compound molecule, but it is preferable that the polymerizable group is substituted at the end of the liquid crystal compound molecule from the viewpoint of ease of polymerization. .
• one or more polymerizable groups can be present in the liquid crystal compound molecule. When two or more polymerizable groups are present, the polymerizable groups should be present at both ends of the liquid crystal compound molecule to facilitate polymerization. It is preferable from the viewpoint of flexibility.
• the polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond in the liquid crystal compound molecule.
• the carbon-carbon triple bond is capable of rotational motion and can be the core of a liquid crystal molecule, the mobility of the molecule is high, and the liquid crystal molecules are highly mobile. It has a strong intermolecular interaction with compounds having a ⁇ -conjugated system such as dye molecules, and tends to have a high molecular orientation.
• the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention is not particularly limited, and a liquid crystal compound having a polymerizable group can be used.
• polymerizable liquid crystal compound (2) a compound represented by the following formula (2) (hereinafter sometimes referred to as "polymerizable liquid crystal compound (2)" Yes.) can be mentioned.
• -Q 1 represents a hydrogen atom or a polymerizable group
• -Q 2 represents a polymerizable group
• -R 1 - and -R 2 - each independently represent a chain organic group
• -A 11 - and -A 13 - each independently represent a partial structure represented by the following formula (3), a divalent organic group, or a single bond
• -A 12 - represents a partial structure or a divalent organic group represented by the following formula (3)
• formula (2) may be the following formula (2A) or the following formula (2B).
• Q 1 -R 1 -X 1 -C ⁇ CX 2 -C y -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 (2B)
• formula (2) may be the following formula (2C) or the following formula (2D).
• Q 1 -R 1 -A 11 -Y 1 -X 1 -C ⁇ CX 2 -C y -(Y 2 -A 13 ) k -R 2 -Q 2 (2D)
• formula (2) may be the following formula (2E) or the following formula (2F).
• Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -X 1 -C ⁇ CX 2 -C y ) k -R 2 -Q 2 (2F)
• -A 11 -, -A 12 -, and -A 13 - are each independently a partial structure or a divalent organic group represented by formula (3), and -A 11 - and -A 13 - may be single bonds, but both -A 11 - and -A 13 - are not single bonds.
• the hydrocarbon ring group for -C y - includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.
• Aromatic hydrocarbon ring groups include unlinked aromatic hydrocarbon ring groups and linked aromatic hydrocarbon ring groups.
• the non-connected aromatic hydrocarbon ring group is a monocyclic or condensed aromatic hydrocarbon ring divalent group, and has 6 to 20 carbon atoms. It is preferable because it is good.
• the number of carbon atoms in the non-connected aromatic hydrocarbon ring group is more preferably 6-15.
• aromatic hydrocarbon rings include benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzpyrene, chrysene, triphenylene, acenaphthene, fluoranthene, and fluorene rings. mentioned.
• a linked aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are linked by single bonds and have bonds on the atoms constituting the ring.
• a single ring or a condensed ring having 6 to 20 carbon atoms is preferable because an appropriate core size provides good molecular orientation.
• the monocyclic or condensed ring preferably has 6 to 15 carbon atoms.
• the linked aromatic hydrocarbon ring group includes, for example, a first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms.
• the ring are bonded with a single bond, and have the first bond on the atom constituting the ring of the first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms, and the second carbon number Divalent groups having a second bond on a ring-constituting atom of 6 to 20 monocyclic or condensed aromatic hydrocarbon rings are included.
• a specific example of the linked aromatic hydrocarbon ring group is a biphenyl-4,4'-diyl group.
• the aromatic hydrocarbon ring group a non-connected aromatic hydrocarbon ring group is preferable because it optimizes the intermolecular interaction acting between the liquid crystal compounds and thereby improves the molecular orientation.
• the aromatic hydrocarbon ring group is preferably a benzene ring divalent group or a naphthalene ring divalent group, more preferably a benzene ring divalent group (phenylene group).
• phenylene group a 1,4-phenylene group is preferred.
• —C y — is one of these groups, the linearity of liquid crystal molecules tends to be enhanced, and the effect of improving molecular orientation tends to be obtained.
• the non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.
• the non-linked non-aromatic hydrocarbon ring group is a divalent group of monocyclic or condensed non-aromatic hydrocarbon rings, and has 3 to 20 carbon atoms. It is preferable for the reason that the properties are good.
• the number of carbon atoms in the non-connected non-aromatic hydrocarbon ring group is more preferably 3-15.
• Non-aromatic hydrocarbon rings include, for example, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, bornane ring, adamantane ring, tetrahydronaphthalene ring, bicyclo [2.2.2] octane ring and the like.
• a non-linked non-aromatic hydrocarbon ring group is an alicyclic hydrocarbon ring group that does not have an unsaturated bond as an interatomic bond that constitutes the ring of the non-aromatic hydrocarbon ring, and a ring of the non-aromatic hydrocarbon ring. and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting As the non-connected non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferable from the viewpoint of productivity.
• a linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed non-aromatic hydrocarbon rings are bonded with single bonds and have bonds on the atoms constituting the ring; one or more rings selected from the group consisting of an aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring; It is a divalent group that is bonded to a condensed non-aromatic hydrocarbon ring via a single bond and has a bond on an atom that constitutes the ring.
• the number of carbon atoms in the single ring or condensed ring is preferably 3 to 20 for the reason that an appropriate core size provides good molecular orientation.
• Examples of linked non-aromatic hydrocarbon ring groups include a first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.
• a hydrocarbon ring is bonded with a single bond, and has a first bond on an atom constituting a ring of a first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and a second and a divalent group having a second bond on a ring-constituting atom of a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.
• a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, 20 monocyclic or condensed aromatic hydrocarbon ring having the first bond on the ring-constituting atom and constituting a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms
• linked non-aromatic hydrocarbon ring groups include bis(cyclohexane)-4,4'-diyl group and 1-cyclohexylbenzene-4,4'-diyl group.
• non-aromatic hydrocarbon ring group a non-connected non-aromatic hydrocarbon ring group is preferable because it optimizes the intermolecular interaction that works between liquid crystal compounds and thereby improves the molecular orientation.
• the non-linked non-aromatic hydrocarbon ring group is preferably a cyclohexane divalent group (cyclohexanediyl group), and the cyclohexanediyl group is preferably a cyclohexane-1,4-diyl group.
• cyclohexanediyl group cyclohexane divalent group
• cyclohexanediyl group is preferably a cyclohexane-1,4-diyl group.
• the heterocyclic group in -C y - includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.
• the aromatic heterocyclic group includes a non-linked aromatic heterocyclic group and a linked aromatic heterocyclic group.
• the non-linked aromatic heterocyclic group is a monocyclic or condensed aromatic heterocyclic divalent group and has 4 to 20 carbon atoms. preferred for a number of reasons.
• the number of carbon atoms in the unlinked aromatic heterocyclic group is more preferably 4-15.
• aromatic heterocyclic rings examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, oxadiazole ring, thiadiazole ring.
• a linked aromatic heterocyclic group is a divalent group in which a single ring or a plurality of condensed aromatic heterocyclic rings are linked by single bonds and have bonds on the atoms constituting the ring.
• a monocyclic ring or a condensed ring having 4 to 20 carbon atoms is preferable because an appropriate core size provides good molecular orientation.
• the number of carbon atoms in the linking aromatic heterocyclic group is more preferably 4-15.
• the linked aromatic heterocyclic group includes, for example, a first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms. bonded by a single bond, having a first bond on an atom constituting a first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms, and a second having 4 to 20 carbon atoms A divalent group having a second bond on an atom constituting a monocyclic or condensed aromatic heterocyclic ring is exemplified.
• the non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.
• the non-linked non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group, and has 4 to 20 carbon atoms. It is preferable because it is good.
• the number of carbon atoms in the unlinked non-aromatic heterocyclic group is more preferably 4-15.
• Non-aromatic heterocyclic ring of divalent group of monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms includes tetrahydrofuran ring, tetrahydropyran ring, dioxane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, pyrrolidine ring , piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring, quinuclidine ring, etc. be done.
• a linked non-aromatic heterocyclic group is a divalent group in which a single ring or a plurality of condensed non-aromatic heterocyclic rings are linked by single bonds and have bonds on atoms constituting the ring.
• a monocyclic ring or a condensed ring having 4 to 20 carbon atoms is preferable because an appropriate core size provides good molecular orientation.
• the number of carbon atoms in the linking non-aromatic heterocyclic group is more preferably 4-15.
• the linked aromatic heterocyclic group includes, for example, a first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms. is bonded with a single bond, has a first bond on an atom constituting the first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and has a second carbon number of 4 Bivalent groups having a second bond on a ring-constituting atom of up to 20 monocyclic or condensed non-aromatic heterocyclic rings can be mentioned.
• the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -C y - have a highly linear molecular structure, and the polymerizable liquid crystal compound (2) are each independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, preferably unsubstituted. is more preferable.
• the substituents of the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -C y - may be the same or different, and may be aromatic
• the hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may all be substituted, all may be unsubstituted, or some may be substituted. and a portion may be unsubstituted.
• -C y - is preferably a hydrocarbon ring group, and more preferably a phenylene group or a cyclohexanediyl group, because the polymerizable liquid crystal compound (2) has good molecular orientation.
• —C y — is more preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group, since the linearity of the molecular structure of the polymerizable liquid crystal compound (2) can be increased.
• -phenylene groups are particularly preferred.
• -X 1 - is preferably -CH 2 CH 2 -, -CH 2 O-, or -OCH 2 -.
• -C y - is a group having high linearity. and -C ⁇ C- are preferably linked.
• the polymerizable group in -Q 1 and -Q 2 is a group having a partial structure that can be polymerized by light, heat, and/or radiation, and is a functional group or atom necessary to ensure the function of polymerization. is a repertoire.
• the polymerizable group is preferably a photopolymerizable group from the viewpoint of producing an anisotropic dye film.
• polymerizable group examples include acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, vinyl group, vinyloxy group, ethynyl group, ethynyloxy group, 1,3 -butadienyl group, 1,3-butadienyloxy group, oxiranyl group, oxetanyl group, glycidyl group, glycidyloxy group, styryl group, styryloxy group and the like, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy acryloylamino group, methacryloylamino group, oxiranyl group, glycidyl group and glycidyloxy group are preferred, acryloyl group, methacryloyl group, acrylo
• the chain organic group in -R 1 - and -R 2 - is a divalent group that does not contain a cyclic structure such as the aforementioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocyclic ring, or non-aromatic heterocyclic ring.
• the alkylene group in these chain organic groups includes linear or branched alkylene groups having 1 to 25 carbon atoms. A part of the carbon-carbon bond of the alkylene group may be an unsaturated bond.
• R m represents a linear or branched alkyl group having 1 to 6 carbon atoms.
• alkylene group in these chain organic groups has high molecular linearity, some of the carbon atoms in the alkylene group may be unsaturated bonds, and one or more is preferably a linear alkylene group having 1 to 25 carbon atoms, which may have a structure in which the methylene group of is replaced by the above group.
• the number of atoms in the main chain (meaning the longest chain portion in the chain organic group) of the chain organic group is preferably 3-25, more preferably 5-20, and even more preferably 6-20.
• chain organic groups include -(CH 2 ) r -CH 2 -, -O-(CH 2 ) r -CH 2 -, -(O) r1 -(CH 2 CH 2 O) r2 -(CH 2 ) r3 -, -(O) r1 -(CH 2 ) r2 -(CH 2 CH 2 O) r3 - are preferred.
• r is an integer of 1 to 24, preferably an integer of 2 to 24, more preferably an integer of 4 to 19, and even more preferably an integer of 5 to 19.
• r1, r2, and r3 in these formulas each independently represent an integer, and the number of atoms in the main chain (meaning the longest chain portion in the chain organic group) in the chain organic group is preferably is appropriately adjusted to 3-25, more preferably 5-20, still more preferably 6-20.
• -R 1 - and -R 2 - are each independently preferably -(alkylene group)-, -O-(alkylene group)-, -(alkylene group)-, -O-(alkylene group) - is more preferred.
• the chain organic group in -R 1 - and -R 2 - is -(alkylene group)-, and in another embodiment, it is -O-(alkylene group)-.
• -X 1 - and -R 1 - or -X 1 - and -R 2 - are bonded as in formula (2B) and formula (2E); and -A 13 in formula (2B) - is a single bond, or -A 11 - is a single bond in the above formula (2E), and -R 1 - or -R 2 - is bonded to -Y 1 - or -Y 2 - is preferably -( alkylene group ) - .
• -R 1 - or -R 2 - not directly bonded to -X 1 -, -Y 1 - or -Y 2 - is preferably -O-( alkylene group)-.
• the divalent organic group in -A 11 -, -A 12 -, and -A 13 - is preferably a group represented by the following formula (4).
• Q3 represents a hydrocarbon ring group or a heterocyclic group.
• the hydrocarbon ring group for -Q 3 - includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.
• Aromatic hydrocarbon ring groups include unlinked aromatic hydrocarbon ring groups and linked aromatic hydrocarbon ring groups.
• the non-connected aromatic hydrocarbon ring group is a monocyclic or condensed aromatic hydrocarbon ring divalent group, and preferably has 6 to 20 carbon atoms. Due to the appropriate core size, molecular orientation is good. It is preferable for the following reason.
• the number of carbon atoms in the non-connected aromatic hydrocarbon ring group is more preferably 6-15.
• Aromatic hydrocarbon rings include benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzpyrene, chrysene, triphenylene, acenaphthene, fluoranthene, and fluorene rings. .
• a linked aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are linked by single bonds and have bonds on the atoms constituting the ring.
• a single ring or a condensed ring having 6 to 20 carbon atoms is preferred because an appropriate core size will result in good orientation.
• the number of carbon atoms in the linked aromatic hydrocarbon ring group is more preferably 6-15.
• the linked aromatic hydrocarbon ring group includes, for example, a first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms.
• the ring are bonded with a single bond, and have the first bond on the atom constituting the ring of the first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms, and the second carbon number Divalent groups having a second bond on a ring-constituting atom of 6 to 20 monocyclic or condensed aromatic hydrocarbon rings are included.
• a specific example of the linked aromatic hydrocarbon ring group is a biphenyl-4,4'-diyl group.
• the aromatic hydrocarbon ring group a non-connected aromatic hydrocarbon ring group is preferable because it optimizes the intermolecular interaction acting between the liquid crystal compounds and thereby improves the molecular orientation.
• the aromatic hydrocarbon ring group is preferably a benzene ring divalent group or a naphthalene ring divalent group, more preferably a benzene ring divalent group (phenylene group).
• phenylene group a 1,4-phenylene group is preferred.
• —Q 3 — is one of these groups, the linearity of liquid crystal molecules tends to be enhanced, and the effect of improving molecular orientation tends to be obtained.
• the non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.
• the non-linked non-aromatic hydrocarbon ring group is a divalent group of monocyclic or condensed non-aromatic hydrocarbon rings, and has 3 to 20 carbon atoms. It is preferable for the reason that the properties are good.
• the number of carbon atoms in the non-connected non-aromatic hydrocarbon ring group is more preferably 3-15.
• Non-aromatic hydrocarbon rings include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, bornane ring, adamantane ring, tetrahydronaphthalene ring, bicyclo[2] .2.2] octane ring and the like.
• a non-linked non-aromatic hydrocarbon ring group is an alicyclic hydrocarbon ring group that does not have an unsaturated bond as an interatomic bond that constitutes the ring of the non-aromatic hydrocarbon ring, and a ring of the non-aromatic hydrocarbon ring. and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting As the non-connected non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferable from the viewpoint of productivity.
• a linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed non-aromatic hydrocarbon rings are bonded with single bonds and have bonds on the atoms constituting the ring; one or more rings selected from the group consisting of an aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring; It is a divalent group that is bonded to a condensed non-aromatic hydrocarbon ring through a single bond and has a bond on an atom that constitutes the ring.
• the number of carbon atoms in the single ring or condensed ring is preferably 3 to 20 for the reason that an appropriate core size provides good molecular orientation.
• Examples of linked non-aromatic hydrocarbon ring groups include a first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.
• a hydrocarbon ring is bonded with a single bond, and has a first bond on an atom constituting a ring of a first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and a second and a divalent group having a second bond on a ring-constituting atom of a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.
• a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, 20 monocyclic or condensed aromatic hydrocarbon ring having the first bond on the ring-constituting atom and constituting a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms
• linked non-aromatic hydrocarbon ring group examples include bis(cyclohexane)-4,4'-diyl group and 1-cyclohexylbenzene-4,4'-diyl group.
• non-aromatic hydrocarbon ring group a non-connected non-aromatic hydrocarbon ring group is preferable because it optimizes the intermolecular interaction that works between liquid crystal compounds and thereby improves the molecular orientation.
• the non-linked non-aromatic hydrocarbon ring group is preferably a cyclohexane divalent group (cyclohexanediyl group), and the cyclohexanediyl group is preferably a cyclohexane-1,4-diyl group.
• the heterocyclic group in -Q 3 - includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.
• the aromatic heterocyclic group includes a non-linked aromatic heterocyclic group and a linked aromatic heterocyclic group.
• the non-linked aromatic heterocyclic group is a monocyclic or condensed aromatic heterocyclic divalent group and has 4 to 20 carbon atoms. preferred for a number of reasons.
• the number of carbon atoms in the unlinked aromatic heterocyclic group is more preferably 4-15.
• Aromatic heterocycles include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, thiazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, and pyrrolopyrazole ring.
• pyrrolopyrrole ring thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring , triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.
• a linked aromatic heterocyclic group is a divalent group in which a single ring or a plurality of condensed aromatic heterocyclic rings are linked by single bonds and have bonds on the atoms constituting the ring.
• a monocyclic ring or a condensed ring having 4 to 20 carbon atoms is preferable because an appropriate core size provides good molecular orientation.
• the number of carbon atoms in the linking aromatic heterocyclic group is more preferably 4-15.
• the linked aromatic heterocyclic group includes, for example, a first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms. bonded by a single bond, having a first bond on an atom constituting a first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms, and a second having 4 to 20 carbon atoms A divalent group having a second bond on an atom constituting a monocyclic or condensed aromatic heterocyclic ring is exemplified.
• the non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.
• the non-linked non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group, and has 4 to 20 carbon atoms. It is preferable because it is good.
• the number of carbon atoms in the unlinked non-aromatic heterocyclic group is more preferably 4-15.
• Non-aromatic heterocyclic ring of divalent group of monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms includes tetrahydrofuran ring, tetrahydropyran ring, dioxane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, pyrrolidine ring , piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring, quinuclidine ring, etc. be done.
• a linked non-aromatic heterocyclic group is a divalent group in which a single ring or a plurality of condensed non-aromatic heterocyclic rings are linked by single bonds and have bonds on atoms constituting the ring.
• a monocyclic ring or a condensed ring having 4 to 20 carbon atoms is preferable because an appropriate core size provides good molecular orientation.
• the number of carbon atoms in the linking non-aromatic heterocyclic group is more preferably 4-15.
• the linked aromatic heterocyclic group includes, for example, a first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms. is bonded with a single bond, has a first bond on an atom constituting the first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and has a second carbon number of 4 Bivalent groups having a second bond on a ring-constituting atom of up to 20 monocyclic or condensed non-aromatic heterocyclic rings can be mentioned.
• the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Q 3 - have a highly linear molecular structure, and the polymerizable liquid crystal compound (2) are each independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, preferably unsubstituted. is more preferable.
• the substituents of the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Q 3 - may be the same or different, and may be aromatic
• the hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may all be substituted, all may be unsubstituted, or some may be substituted. and a portion may be unsubstituted.
• the substituents possessed by the divalent organic groups in -A 11 -, -A 12 - and -A 13 - may be the same or different, and the divalent All of the organic groups may be substituted, all may be unsubstituted, or some may be substituted and some may be unsubstituted.
• -Q 3 - is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group.
• Q 3 — is more preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group, since it can increase the linearity of the molecular structure of the polymerizable liquid crystal compound (2).
• divalent organic groups of -A 11 -, -A 12 - and -A 13 -, -Q 3 - is a hydrocarbon ring group, that is, the divalent organic group is a hydrocarbon ring group.
• a phenylene group and a cyclohexanediyl group are more preferable, and a 1,4-phenylene group and a cyclohexane-1,4-phenylene group are preferred because they can increase the linearity of the molecular structure of the polymerizable liquid crystal compound (2).
• -diyl group is more preferred.
• one of -A 11 -, -A 12 - and -A 13 - is a partial structure represented by formula (3), and the other two are each It is independently preferably a divalent organic group, and among -A 11 -, -A 12 - and -A 13 -, -C y - of the partial structure represented by formula (3) is a hydrocarbon ring group.
• the divalent organic group is a hydrocarbon ring group.
• the hydrocarbon ring group is preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group.
• one of -A 11 - and -A 13 - is preferably a cyclohexane-1,4-diyl group.
• one of -A 11 - and -A 13 - is a partial structure represented by formula (3), and the other one and -A 12 - are more preferably divalent organic groups.
• one of -A 11 - and -A 13 - which is a divalent organic group is preferably a cyclohexane-1,4-diyl group, and -A 12 - is a 1,4-phenylene group. It is particularly preferred to have
• (k) k is 1 or 2; In one aspect, k is preferably 1. Alternatively, k is preferably two. When k is 2, each -Y 2 - may be the same or different, and each -A 13 - may be the same or different.
• a compound represented by the formula (2A), (2B), (2E) or (2F) is optimal for the intermolecular interaction acting between the liquid crystal compounds,
• the polymerizable liquid crystal compound used in the present invention is preferably a low-molecular-weight polymerizable liquid crystal compound, particularly a low-molecular-weight polymerizable liquid crystal compound that does not have a copolymer structure, from the viewpoint of the tendency to obtain good molecular orientation.
• Liquid crystal compounds are preferred.
• the molecular weight of the low molecular weight polymerizable liquid crystal compound is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. Although the lower limit is not particularly limited, 400 or more is preferable, and 500 or more is preferable.
• the molecular weight range is preferably from 400 to 2,000, more preferably from 400 to 1,500, and particularly preferably from 500 to 1,000.
• the molecular weight of the polymerizable liquid crystal compound is the sum of the atomic weights contained in the polymerizable liquid crystal compound.
• polymerizable liquid crystal compound (Specific example of polymerizable liquid crystal compound)
• polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention include, but are not limited to, the polymerizable liquid crystal compounds described below.
• C 6 H 13 means an n-hexyl group.
• the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention preferably comprises the polymerizable liquid crystal compound (2).
• the anisotropic dye film-forming composition of the present invention may contain only one type of polymerizable liquid crystal compound alone, or may contain two or more types in any combination and ratio.
• the content of the liquid crystal compound in the composition for an anisotropic dye film of the present invention is the solid content of the composition for an anisotropic dye film. (100 parts by mass), preferably 35 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 55 parts by mass or more, preferably 99 parts by mass or less, and more preferably 98 parts by mass or less. If the content of the liquid crystal compound in the composition for an anisotropic dye film is in the range from the lower limit to the upper limit, the orientation of the liquid crystal molecules tends to increase.
• the composition for an anisotropic dye film of the present invention may contain one or more polymerizable or non-polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (2). From the viewpoint of obtaining the effects of the present invention by using the polymerizable liquid crystal compound (2) more effectively, the polymerizable liquid crystal in the total amount of 100% by mass of the liquid crystal compounds contained in the composition for an anisotropic dye film of the present invention
• the proportion of compound (2) is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15 to 100% by mass.
• composition for an anisotropic dye film of the present invention contains a polymerizable liquid crystal compound, and the mass concentration in the composition for an anisotropic dye film is the compound of the present invention represented by the above formula (1). It is preferable to contain so as to achieve the mass concentration described later with respect to the concentration.
• the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention preferably has an isotropic phase appearance temperature of 160° C. or lower, more preferably 140° C. or lower. , 115° C. or less is more preferable, 110° C. or less is even more preferable, and 105° C. or less is particularly preferable.
• the isotropic phase appearance temperature means the phase transition temperature from liquid crystal to liquid and the phase transition temperature from liquid to liquid crystal. In the present invention, at least one of these phase transition temperatures is preferably equal to or lower than the above upper limit, and more preferably both of these phase transition temperatures are equal to or lower than the above upper limit.
• the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention undergoes alkylation reaction, esterification reaction, amidation reaction, etherification reaction, ipso substitution reaction, and coupling reaction using a metal catalyst.
• alkylation reaction e.g., alkylation reaction, esterification reaction, amidation reaction, etherification reaction, ipso substitution reaction, and coupling reaction using a metal catalyst.
• the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention can be obtained by the method described in Examples below or by the method described in "Liquid Crystal Handbook" (Maruzen Co., Ltd., October 30, 2000). (published by Japan), pages 449-468.
• the anisotropic dye film-forming composition contains molecules of a polymerizable liquid crystal compound.
• the number of ring structures (r n1 ) possessed by the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition and the anisotropic dye film-forming composition is 0.7 to 1.5. is preferred.
• a condensed ring in which two or more rings are condensed is counted as one ring structure.
• the number of ring structures (r n2 ) possessed by the compound of the present invention represented by formula (1) is the sum of A 1 , A 2 , and A 3 in the formula, and specifically, If n is 1, r n2 is 3; if n is 2, r n2 is 4; if n is 3, r n2 is 5. Even if -Y is a cyclic functional group such as a pyrrolidinyl group or a piperidinyl group, the ring structure contained in -Y is the number of ring structures (r n2 ).
• the number of ring structures (r n1 ) possessed by the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition includes ring structures (for example, oxirane rings and oxetane rings) contained in the polymerizable groups in the polymerizable liquid crystal compound. etc.) are not included.
• the composition for an anisotropic dye film of the present invention preferably contains the polymerizable liquid crystal compound at a mass concentration of 1 or more times the mass concentration of the compound of the present invention represented by formula (1). If the mass concentration of the polymerizable liquid crystal compound is 1 or more times the mass concentration of the compound of the present invention represented by formula (1), a high dichroic ratio tends to be obtained, and the mechanical strength of the anisotropic dye film is improved. It is preferable from the viewpoint that it can be improved. More preferably, the mass concentration of the polymerizable liquid crystal compound in the composition for an anisotropic dye film of the present invention is at least 1.5 times the mass concentration of the compound of the present invention represented by formula (1).
• the mass concentration of the polymerizable liquid crystal compound in the anisotropic dye film composition of the present invention is preferably 1000 times or less the mass concentration of the compound of the present invention represented by formula (1). It is more preferably 700 times or less, and even more preferably 500 times or less.
• the anisotropic dye film-forming composition of the present invention may contain a polymerization initiator, if necessary.
• a polymerization initiator is a compound that can initiate a polymerization reaction of a polymerizable liquid crystal compound.
• a photopolymerization initiator that generates active radicals by the action of light is preferred.
• Examples of usable polymerization initiators include titanocene derivatives; biimidazole derivatives; halomethylated oxadiazole derivatives; halomethyl-s-triazine derivatives; alkylphenone derivatives; iodonium salts; sulfonium salts; anthraquinone derivatives; acetophenone derivatives; thioxanthone derivatives; Among these photopolymerization initiators, alkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferred.
• titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluoro phenyl-1-yl), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl- 1-yl), dicyclopentadienyl titanium di(2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium di(2,4-difluorophenyl-1-yl), di(methylcyclopenta dienyl) titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl-1-yl), di(methyl
• Biimidazole derivatives include, for example, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′-methoxyphenyl )-4,5-diphenylimidazole dimer and the like.
• halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2′-(6′′-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.
• halomethyl-s-triazine derivatives examples include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine and the like.
• alkylphenone derivatives include diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamyl Benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino -3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone and the like.
• oxime ester derivatives examples include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, O-acetyl-1-[6-(2-methylbenzoyl)-9 -Ethyl-9H-carbazol-3-yl]ethanone oxime, oxime ester derivatives described in JP-A-2000-80068, JP-A-2006-36750, International Publication No. 2009/131189, etc. be done.
• Benzoins include, for example, benzoin, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.
• benzophenone derivatives include benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, methyl o-benzoylbenzoate, 4 -phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.
• Acylphosphine oxide derivatives include, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,4, 6-trimethylbenzoyl)phenylphosphine oxide and the like.
• iodonium salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4-nonylphenyl)iodonium hexafluorophosphate. etc.
• sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate.
• anthraquinone derivatives examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
• Acetophenone derivatives include, for example, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, ⁇ -hydroxy-2-methylphenylpropanone, 1-hydroxy -1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, 1, 1,1-trichloromethyl-(p-butylphenyl)ketone and the like.
• Thioxanthone derivatives include, for example, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.
• benzoic acid ester derivatives include ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.
• acridine derivatives examples include 9-phenylacridine and 9-(p-methoxyphenyl)acridine.
• phenazine derivatives examples include 9,10-dimethylbenzphenazine and the like.
• Anthrone derivatives include, for example, benzanthrone.
• the polymerization initiator may be used singly or in combination of two or more.
• a commercial item can also be used as a polymerization initiator.
• Commercially available products include, for example, IRGACURE (registered trademark; the same shall apply hereinafter) 250, IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO 7, IRGACURE 419 , OXE-01, OXE-02 (both manufactured by BASF); Seikuol (registered trademark) BZ, Z, and BEE (manufactured by Seiko Chemical Co., Ltd.); Kayacure (registered trademark) BP100, and UVI-6992 (manufactured by Dow Chemical Co., Ltd.); ADEKA OPTOMER SP-152 and SP-170 (manufactured by ADEKA Corporation); TAZ-A and TAZ-PP (manufactured by Nihon SiberHeg
• the content of the polymerization initiator in the composition for forming an anisotropic dye film of the present invention disturbs the alignment of the polymerizable liquid crystal compound. From the viewpoint of difficulty, it is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. be.
• a polymerization accelerator may be used in combination with the polymerization initiator.
• the polymerization accelerator used include N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester; mercapto compounds having a heterocyclic ring such as imidazole; and mercapto compounds such as aliphatic polyfunctional mercapto compounds.
• the polymerization accelerator may also be used singly or in combination of two or more.
• a sensitizing dye may be used in combination for the purpose of increasing sensitivity.
• a suitable sensitizing dye is used according to the wavelength of the exposure light source.
• xanthene dyes described in JP-A-4-221958 and JP-A-4-219756 coumarin dyes having a heterocycle described in JP-A-3-239703 and JP-A-5-289335; 3-ketocoumarin dyes described in JP-A-3-239703, JP-A-5-289335, etc.
• the anisotropic dye film-forming composition of the present invention may contain a solvent, if necessary.
• the solvent that can be used for the anisotropic dye film-forming composition of the present invention is not particularly limited as long as it can sufficiently disperse or dissolve the dye or other additives in the polymerizable liquid crystal compound.
• alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, propylene ester solvents such as glycol methyl ether acetate and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and h
• the solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound and the dye, and more preferably a solvent capable of completely dissolving the polymerizable liquid crystal compound and the dye.
• the solvent is preferably inert to the polymerization reaction of the polymerizable liquid crystal compound.
• the solvent preferably has a boiling point in the range of 50 to 200° C. from the viewpoint of applying the composition for forming an anisotropic dye film of the present invention, which will be described later.
• the anisotropic dye film-forming composition of the present invention contains a solvent
• the content of the solvent in the anisotropic dye film-forming composition is 50 to 98% by mass is preferable.
• the solid content in the anisotropic dye film-forming composition of the present invention is preferably 2 to 50% by mass.
• the viscosity of the anisotropic dye film-forming composition does not become too high, and the obtained polarizing film has a uniform thickness. , there is a tendency that unevenness is less likely to occur in the polarizing film.
• the solid content of the anisotropic dye film-forming composition of the present invention can be determined in consideration of the thickness of the polarizing film to be produced.
• the viscosity of the anisotropic dye film composition of the present invention is not particularly limited as long as a uniform film with no thickness unevenness is produced by the coating method described below.
• the viscosity of the composition for forming an anisotropic dye film of the present invention is 0.1 mPa ⁇ s or more from the viewpoint of achieving thickness uniformity over a large area, productivity such as coating speed, and in-plane uniformity of optical properties. is preferably 500 mPa ⁇ s or less, more preferably 100 mPa ⁇ s or less, and even more preferably 50 mPa ⁇ s or less.
• composition for forming an anisotropic dye film of the present invention may optionally contain, as components other than the dye and the polymerizable liquid crystal compound, a polymerization inhibitor, a polymerization aid, and a polymerization initiator in addition to the polymerization initiator described above.
• the composition for forming an anisotropic dye film of the present invention can be improved in coatability, stability, etc., or the composition formed from the composition for forming an anisotropic dye film of the present invention can be In some cases, the stability of the anisotropic dye film can be improved.
• the method for producing the anisotropic dye film composition of the present invention is not particularly limited.
• a dye containing the compound of the present invention, a polymerizable liquid crystal compound, a solvent, other additives, etc. are mixed as necessary, and the mixture is stirred and shaken at 0 to 80° C. to dissolve the dye. If it is poorly soluble, a homogenizer, a bead mill disperser, or the like may be used.
• the method for producing the composition for an anisotropic dye film of the present invention may include a filtration step for the purpose of removing foreign substances and the like in the composition.
• composition for forming an anisotropic dye film of the present invention may or may not be a liquid crystal at any temperature. preferably exhibits liquid crystallinity.
• the composition obtained by removing the solvent from the anisotropic dye film-forming composition of the present invention preferably has an isotropic phase appearance temperature of less than 160°C, preferably 140°C. It is more preferably less than 115°C, even more preferably less than 110°C, and particularly preferably less than 105°C.
• the anisotropic dye film of the present invention is formed using the anisotropic dye film-forming composition of the present invention. Accordingly, the anisotropic dye film of the present invention includes a dye and one or both of a polymerizable liquid crystal compound and a polymer having units based on the polymerizable liquid crystal compound, and the dye includes the compound of the present invention.
• the anisotropic dye film of the present invention formed using the composition for an anisotropic dye film of the present invention preferably has a total mass concentration of the polymerizable liquid crystal compound and the polymer having units based on the polymerizable liquid crystal compound of , 1 time or more, more preferably 1.5 times or more, still more preferably 2 times or more, particularly preferably 3 times or more, and preferably 1000 times or less, the mass concentration of the compound of the present invention represented by formula (1) , more preferably 700 times or less, more preferably 500 times or less.
• the anisotropic dye film of the present invention contains, as other components, a non-polymerizable liquid crystal compound, a polymerization initiator, a polymerization inhibitor, a polymerization aid, a polymerizable non-liquid crystal compound, a non-polymerizable non-liquid crystal compound, a surfactant, and leveling. agents, coupling agents, pH adjusters, dispersants, antioxidants, organic/inorganic fillers, organic/inorganic nanosheets, organic/inorganic nanofibers, metal oxides, and the like.
• the anisotropic dye film of the present invention can function as a polarizing film that obtains linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption. (or transparent material) can be functionalized as various anisotropic dye films such as refractive anisotropy and conduction anisotropy.
• the orientation characteristics of the anisotropic dye film can be expressed using a dichroic ratio.
• a dichroic ratio of 8 or more functions as a polarizing element, preferably 15 or more, more preferably 20 or more, even more preferably 25 or more, particularly preferably 30 or more, and particularly preferably 40 or more. The higher the dichroic ratio of the anisotropic dye film, the better. When the dichroic ratio is equal to or higher than the lower limit, it is useful as an optical element, particularly a polarizing element, which will be described later.
• the performance of the polarizing element is high, it is easy to simplify the layer structure, and it is easy to exhibit sufficient functions even with a thin film structure, and it can be used suitably for uses in which it is deformed, including folding and bending. Also, the cost can be kept low.
• the dichroic ratio (D) referred to in the present invention is represented by the following formula when the dyes are uniformly oriented.
• D Az/Ay
• Az is the absorbance observed when the polarization direction of the light incident on the anisotropic dye film is parallel to the orientation direction of the anisotropic dye.
• Ay is the absorbance observed when the polarization direction of the light incident on the anisotropic dye film is perpendicular.
• Each absorbance (Az, Ay) is not particularly limited as long as the same wavelength is used, and any wavelength may be selected depending on the purpose.
• the transmittance of the anisotropic dye film of the present invention is preferably 25% or higher, more preferably 35% or higher, and particularly preferably 40% or higher, at the intended wavelength.
• the transmittance of the anisotropic dye film in the visible light wavelength region is preferably 25% or more. , more preferably 35% or more, and particularly preferably 40% or more.
• the transmittance of the anisotropic dye film of the present invention may have an upper limit depending on the application. For example, when increasing the degree of polarization, the transmittance is preferably 50% or less.
• the transmittance is within the above range, it is useful as an optical element to be described later, particularly as an optical element for a liquid crystal display used for color display or for an antireflection film combining an anisotropic dye film and a retardation film. Useful.
• the dry film thickness of the anisotropic dye film is preferably 10 nm or more, more preferably 100 nm or more, and even more preferably 500 nm or more.
• the thickness of the anisotropic dye film is preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less. When the film thickness of the anisotropic dye film is within the above range, it tends to be possible to obtain a uniform dye orientation and a uniform film thickness in the film.
• the anisotropic dye film of the invention is preferably prepared by a wet film-forming method using the composition for forming an anisotropic dye film of the invention.
• the wet film-forming method referred to in the present invention is a method of coating and orienting a composition for an anisotropic dye film on a substrate by some method. Therefore, the composition for an anisotropic dye film should have fluidity, and may or may not contain a solvent. It is more preferable to contain a solvent from the viewpoint of the viscosity and film uniformity at the time of application.
• the orientation of the liquid crystals and dyes in the anisotropic dye film may be oriented by shearing during the coating process, or may be oriented during the solvent drying process.
• liquid crystals, dyes, and the like may be aligned and laminated on a substrate through a process of reorienting liquid crystals, dyes, and the like by heating after application and drying.
• the dye or the liquid crystal compound self-associates (a molecular association state such as a liquid crystal state) to cause alignment in a minute area.
• an anisotropic dye film having desired properties By applying an external field to this state, it is possible to obtain an anisotropic dye film having desired properties by orienting the dye in a certain direction in a macroscopic region.
• the external field includes the influence of an orientation treatment layer previously applied on the substrate, shear force, magnetic field, electric field, heat, and the like, and these may be used singly or in combination. If necessary, a heating step may be performed.
• the process of applying the anisotropic dye film composition on the substrate to form a film, the process of applying an external field for orientation, and the process of drying the solvent may be carried out sequentially or simultaneously.
• Examples of the method for applying the anisotropic dye film-forming composition onto the substrate in the wet film-forming method include a coating method, a dip coating method, an LB film-forming method, and a known printing method. There is also a method of transferring the anisotropic dye film thus obtained to another substrate.
• composition for forming an anisotropic dye film onto the substrate using a coating method.
• the orientation direction of the anisotropic dye film may be different from the coating direction.
• the orientation direction of the anisotropic dye film means, for example, the transmission axis (polarization axis) or absorption axis of polarized light in the case of a polarizing film, and the fast or slow axis in the case of a retardation film. It is about the phase axis.
• the method of applying the composition for an anisotropic dye film to obtain an anisotropic dye film is not particularly limited. ), the method described on pages 253 to 277 of Kunihiro Ichimura, the method described on pages 118 to 149 of "Creation and Application of Molecular Cooperative Materials” (CMC Publishing Co., Ltd., March 3, 1998), supervised by Kunihiro Ichimura, steps Slot die coating method, spin coating method, spray coating method, bar coating method, roll coating method, blade coating method, curtain coating method, fountain method, dip method, etc. on a substrate having a structure (which may be subjected to orientation treatment in advance) A method of coating with Among them, the use of the slot die coating method and the bar coating method is preferable because an anisotropic dye film with high uniformity can be obtained.
• the die coater used for the slot die coating method is generally equipped with a so-called slit die, which is a coating machine that discharges the coating liquid.
• Slit dies are described, for example, in JP-A-2-164480, JP-A-6-154687, JP-A-9-131559, “Fundamentals and Applications of Dispersion, Coating and Drying” (2014, Technosystem Co., Ltd., ISBN9784924728707C305), “Wet coating technology for displays and optical members” (2007, Information Organization, ISBN9784901677752), “Precision coating and drying technology in the electronics field” (2007, Technical Information Institute, ISBN9784861041389), etc.
• These known slit dies can coat flexible members such as films and tapes and hard members such as glass substrates.
• Examples of the substrate used for forming the anisotropic dye film of the present invention include glass, triacetate, acrylic, polyester, polyimide, polyetherimide, polyetheretherketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, A triacetyl cellulose or urethane-based film or the like can be used.
• a known method (rubbing method, orientation Alignment is achieved by a method of forming grooves (fine groove structure) on the film surface, a method using polarized ultraviolet light and a polarized laser (photo-alignment method), an alignment method by forming an LB film, an alignment method by oblique vapor deposition of an inorganic substance, etc.).
• a treatment (orientation film) may be applied.
• alignment treatment by a rubbing method and a photo-alignment method can be mentioned preferably.
• Materials used in the rubbing method include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, acrylic resin, and the like.
• Examples of materials used in the photo-alignment method include polycinnamate-based materials, polyamic acid/polyimide-based materials, and azobenzene-based materials.
• an alignment treatment layer it is considered that the liquid crystal compound and the dye are oriented due to the influence of the alignment treatment of the alignment treatment layer and the shear force applied to the anisotropic dye film composition during coating.
• the supply method and supply interval of the anisotropic dye film composition when applying the anisotropic dye film composition are not particularly limited. If the anisotropic dye film is thin, continuous anisotropic It is desirable to apply while supplying the composition for the dye film.
• the speed at which the anisotropic dye film composition is applied is usually 0.001 m/min or more, preferably 0.01 m/min or more, more preferably 0.1 m/min or more, and still more preferably It is 1.0 m/min or more, and particularly preferably 5.0 m/min or more.
• the speed at which the anisotropic dye film composition is applied is usually 400 m/min or less, preferably 200 m/min or less, more preferably 100 m/min or less, and still more preferably 50 m/min or less. . When the coating speed is within the above range, the anisotropy of the anisotropic dye film can be obtained, and there is a tendency for uniform coating.
• the coating temperature of the anisotropic dye film composition is usually 0°C or higher and 100°C or lower, preferably 80°C or lower, and more preferably 60°C or lower.
• the humidity during application of the anisotropic dye film composition is preferably 10% RH or more and preferably 80 RH% or less.
• the anisotropic dye film may be subjected to insolubilization treatment.
• Insolubilization means a treatment for controlling the elution of the compound from the anisotropic dye film and increasing the stability of the film by reducing the solubility of the compound in the anisotropic dye film.
• film polymerization, overcoating, and the like are preferable from the viewpoints of ease of subsequent processes, durability of the anisotropic dye film, and the like.
• the light source of the active energy ray with a wavelength of 190 to 450 nm is not particularly limited.
• Lamp light sources such as arcs and fluorescent lamps; laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers and semiconductor lasers;
• An optical filter can also be used when using it by irradiating the light of a specific wavelength.
• the exposure dose of active energy rays is preferably 10 to 10,000 J/m 2 .
• the polymerization is carried out using heat, it is preferably carried out in the range of 50 to 200°C, more preferably in the range of 60 to 150°C.
• Polymerization may be performed using light, heat, and/or radiation, but using photopolymerization or using photopolymerization and thermal polymerization in combination shortens the film formation process time and uses simple equipment. Therefore, it is preferable.
• optical element of the invention includes the anisotropic dye film of the invention.
• the optical element in the present invention utilizes the anisotropy of light absorption to obtain linearly polarized light, circularly polarized light, elliptical polarized light, etc., a polarizing element, a phase difference element, and has functions such as refractive anisotropy and conduction anisotropy. represents an element. These functions can be appropriately adjusted by selecting the anisotropic dye film forming process and the composition containing the substrate and the organic compound (dye and transparent material).
• the optical element of the present invention is used as a polarizing element.
• the optical element of the present invention can be suitably used for applications such as flexible displays because a polarizing element can be obtained by forming an anisotropic dye film on a substrate by coating or the like.
• the optical element may be provided with other layers in order to maintain and improve the function of the anisotropic dye film.
• Other layers include, for example, a layer having a function of blocking a specific wavelength and a layer having a function of blocking a specific substance (oxygen Barrier films such as barrier films, water vapor barrier films, etc.); layers containing wavelength cut filters and materials that absorb specific wavelengths, which are used to change the color gamut or improve optical properties; be done.
• a polarizing element (hereinafter sometimes referred to as "the polarizing element of the present invention") can be manufactured.
• the polarizing element of the present invention may have any other film (layer) as long as it has the anisotropic dye film of the present invention.
• it can be produced by providing an alignment film on a substrate and forming the anisotropic dye film of the present invention on the surface of the alignment film.
• the polarizing element is not limited to an anisotropic dye film, and includes an overcoat layer that has functions such as improving the polarizing performance and improving the mechanical strength; an adhesive layer or an antireflection layer; an alignment film; and a function as a retardation film.
• a layer having an optical function such as a function as a brightness enhancement film, a function as a reflection or antireflection film, a function as a transflective film, a function as a diffusion film, and the like.
• the layers having various functions described above may be laminated by coating, lamination, or the like, and used as a laminate.
• each layer can be formed on the anisotropic dye film or on the opposite side of the substrate provided with the anisotropic dye film.
• the order of forming each layer may be before or after forming the anisotropic dye film.
• These layers having optical functions can be formed by the following methods.
• a layer having a function as a retardation film can be formed by applying or bonding a retardation film to another layer that constitutes the polarizing element.
• the retardation film is, for example, subjected to the stretching treatment described in JP-A-2-59703, JP-A-4-230704, etc., or the treatment described in JP-A-7-230007. can be formed by
• a layer functioning as a brightness enhancement film can be formed by applying or bonding a brightness enhancement film to another layer that constitutes a polarizing element.
• the brightness enhancement film is formed by, for example, forming micropores by a method as described in JP-A-2002-169025 and JP-A-2003-29030, or two or more layers having different central wavelengths of selective reflection. of cholesteric liquid crystal layers.
• a layer functioning as a reflective film or a semi-transmissive reflective film can be formed, for example, by coating or adhering a metal thin film obtained by vapor deposition or sputtering to another layer constituting the polarizing element. can be done.
• a layer functioning as a diffusion film can be formed, for example, by coating another layer constituting the polarizing element with a resin solution containing fine particles.
• a layer having a function as a retardation film or an optical compensation film contains a liquid crystalline compound such as a discotic liquid crystalline compound, a nematic liquid crystalline compound, a smectic liquid crystalline compound, a cholesteric liquid crystalline compound, or another layer constituting a polarizing element. It can be formed by coating and orienting. At that time, an alignment film may be provided on the substrate, and a retardation film or an optical compensation film may be formed on the surface of the alignment film.
• anisotropic dye film of the present invention When the anisotropic dye film of the present invention is used as an anisotropic dye film or the like in various display elements such as a liquid crystal device (LCD) and an organic electroluminescence device (OLED), electrodes constituting these display devices
• LCD liquid crystal device
• OLED organic electroluminescence device
• the anisotropic dye film of the present invention may be formed directly on the surface of a substrate or the like, or the substrate having the anisotropic dye film of the present invention formed thereon may be used as a constituent member of these display elements.
• a sandwich cell (cell gap: 8.0 ⁇ m, 10.0 ⁇ m, film-formed polyimide) in which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems) is formed on glass as a substrate
• a polyimide alignment film LX1400, manufactured by Hitachi Chemical DuPont Microsystems
• the composition for an anisotropic dye film was injected in an isotropic phase into an anisotropic dye film and cooled to 80° C. at 5° C./min to obtain an anisotropic dye film. While cooling to 0°C at °C/min, the dichroic ratio was measured at each temperature. Among them, the dichroic ratio at the temperature and wavelength showing the maximum dichroic ratio was determined as the dichroic ratio of the anisotropic dye film.
• the dichroic ratio of the anisotropic dye film measured above is 20 or more, it is practically sufficient and preferable, 30 or more is more preferable, and 40 or more is even more preferable.
• the isotropic phase appearance temperature (phase transition temperature from liquid crystal to liquid and phase transition temperature from liquid to liquid crystal) was determined by differential scanning calorimetry.
• 0.2 parts by mass of 4-methoxyphenol as a polymerization inhibitor was added to 100 parts by mass of the polymerizable liquid crystal compound (I-1).
• the phase transition temperature of the polymerizable liquid crystal compound (I-1) from liquid crystal to liquid was 111.0°C, and the phase transition temperature from liquid to liquid crystal was 109.4°C. It was confirmed by polarizing microscope observation and X-ray structure analysis that this temperature is the isotropic phase appearance temperature.
• the dye (II-1) in a 10 ppm chloroform solution had a maximum absorption wavelength ( ⁇ max) of 593 nm and a gram extinction coefficient of 131.9 Lg ⁇ 1 cm ⁇ 1 .
• the solubility of dye (II-1) in cyclopentanone was measured. 3 mg of dye (II-1) was added to 103 mg of cyclopentanone, and the mixture was stirred at 80° C. for 5 minutes. After that, it was allowed to stand at room temperature for 1 hour, and the resulting mixture was filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, caliber 0.45 ⁇ m) to remove pigment (II-1). A saturated solution of cyclopentanone was obtained. This solution was diluted with 746 mg of tetrahydrofuran, and the concentration was determined using HPLC (L-2300 series manufactured by Hitachi High Technologies).
• a solution was prepared by dissolving 0.1% by mass of dye (II-1) in tetrahydrofuran, and a calibration curve was drawn at an absorption wavelength of 254 nm. Using this calibration curve, the concentration of saturated cyclopentanone solution was measured. Table 1 shows the results.
• the dye (II-2) in a 10 ppm chloroform solution had a maximum absorption wavelength ( ⁇ max) of 596 nm and a gram extinction coefficient of 153.2 Lg ⁇ 1 cm ⁇ 1 .
• (III-1-c) (III-1-b) (113.5 g, 427.7 mmol) and ethyl acetate (1100 mL) were mixed under an argon stream, and then palladium carbon (5% Pd—C, water content 55% by mass, 11.4 g). was added and stirred at 25° C. for 60 hours under a hydrogen atmosphere. After purging the inside of the container with argon, the catalyst was filtered off. The catalyst was extracted with dichloromethane, and the organic layers were combined, concentrated, and purified by silica gel chromatography (dichloromethane) to obtain 99.5 g of (III-1-c).
• (III-1-f) (III-1-c) (47.3 g, 201 mmol) and 12N hydrochloric acid (375 mL) were mixed under a nitrogen stream, cooled to 0° C. and stirred for 1 hour. An aqueous solution obtained by mixing sodium nitrite (17.3 g, 251 mmol) and water (130 mL) was added thereto, and the mixture was stirred at 5°C for 1 hour to prepare a diazonium solution. (III-1-e) (37.2 g, 241 mmol) and methanol were mixed, and after cooling to 0° C., the above diazonium solution was added dropwise over 40 minutes. The mixture was heated to 25° C. and stirred for 3 hours, the precipitated solid was collected by filtration, and the obtained crude product was washed with hexane to obtain 48.1 g of (III-1-f).
• the dye (III-1) in a 10 ppm chloroform solution had a maximum absorption wavelength ( ⁇ max) of 563 nm and a gram extinction coefficient of 134.8 Lg ⁇ 1 cm ⁇ 1 .
• Example 1 Add 20.00 parts of the polymerizable liquid crystal compound (I-1) and 0.23 parts of the dye (II-1) to 2959.1 parts of chloroform, stir to dissolve, and then remove the solvent. Thus, an anisotropic dye film-forming composition 1 was obtained. rn 1 /rn 2 of the composition 1 for forming an anisotropic dye film is 1. It was confirmed that the anisotropic dye film-forming composition 1 exhibited liquid crystallinity by observing birefringence at 40° C. with a polarizing microscope equipped with a hot stage.
• an anisotropic dye film 1 was produced using a sandwich cell with a cell gap of 8.0 ⁇ m in order to determine the dichroic ratio by the method described above. .
• the dichroic ratio of the anisotropic dye film 1 was determined. Table 1 shows the results.
• Example 2 The anisotropic dye film-forming composition 2 and the anisotropic A sexual pigment film 2 was obtained. rn 1 /rn 2 of composition 2 for forming an anisotropic dye film is 1. It was confirmed that the anisotropic dye film-forming composition 2 exhibited liquid crystallinity by observing birefringence at 40° C. with a polarizing microscope equipped with a hot stage. The dichroic ratio of the anisotropic dye film 2 was determined. Table 1 shows the results.
• the dye (II-1) used in Example 1 and the dye (II-2) used in Example 2 have high solubility in cyclopentanone, and the resulting anisotropic dye film has It showed a good dichroic ratio.
• Comparative Examples 1 and 2 showed a good dichroic ratio but low solubility in cyclopentanone.

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