Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
• • 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
  • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
  • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/206—Filters comprising particles embedded in a solid matrix
• • 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
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3016—Polarising elements involving passive liquid crystal 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
  • G02F1/13363—Birefringent elements, e.g. for optical compensation
• • 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
  • C09K2019/523—Organic solid particles

Definitions

• the present invention relates to an optically anisotropic film and a display device.
• Optically anisotropic films are used in various applications such as display devices, cameras, and sensors.
• an optical anisotropy compensation panel is disclosed that comprises one or more optically anisotropic layers based on an arranged guest-host system.
• optically anisotropic films have been required to be excellent in all of orientation, light resistance, and heat and humidity durability.
• Light resistance means that when the optically anisotropic film is irradiated with light, the optical properties (for example, in-plane retardation, etc.) of the optically anisotropic film are unlikely to change before and after the light irradiation.
• heat-and-moisture durability means that when the optically anisotropic film is stored under high temperature and high humidity, the optical properties (eg, degree of polarization, etc.) of the optically anisotropic film are unlikely to change before and after storage.
• the present inventors studied an optically anisotropic film using the material described in Patent Document 1, and found that it did not meet the current requirements and that further improvement was necessary.
• the optically anisotropic film according to [1] which has absorption in the infrared region.
• the angle between the slow axis of the optically anisotropic film at a wavelength of 550 nm and the direction of maximum absorption at the maximum absorption wavelength in the infrared region of the optically anisotropic film is 0 to 10° or 80 to 100°.
• the optically anisotropic film contains the liquid crystal compound, The optically anisotropic film according to any one of [1] to [6], wherein the liquid crystal compound is lyotropic liquid crystal.
• a display device comprising the optically anisotropic film according to any one of [1] to [7].
• a display device can be provided.
• a numerical range expressed using " ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as a lower limit value and an upper limit value.
• Re( ⁇ ) and Rth( ⁇ ) represent in-plane retardation and thickness direction retardation at wavelength ⁇ , respectively.
• the wavelength ⁇ is 550 nm.
• Re ( ⁇ ) and Rth ( ⁇ ) are values measured at wavelength ⁇ using AxoScan OPMF-1 (manufactured by Optoscience).
• AxoScan OPMF-1 manufactured by Optoscience.
• Re( ⁇ ) R0( ⁇ )
• the average refractive index values of the main optical films are illustrated below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).
• angular relationships include the range of error allowed in the technical field to which the present invention belongs. For example, it means that the angle is within a strict angle of ⁇ 5°, and the error from the exact angle is preferably within a range of ⁇ 3°.
• the bonding direction of the divalent group (for example, -COO-) described herein is not particularly limited.
• L in XLY is -COO-, it is bonded to the X side. If the position connected to the Good too.
• (meth)acrylic is a concept that includes both “acrylic” and “methacrylic”.
• (Meth)acryloyl group” is a concept that includes both “acryloyl group” and “methacryloyl group.”
• the visible light region means a wavelength range of 400 to 700 nm.
• the infrared region refers to a wavelength range of 700 to 2500 nm (preferably a wavelength range of more than 700 nm and 2500 nm or less).
• the optically anisotropic film of the present invention is an optically anisotropic film containing a liquid crystal compound or a polymer and an aggregate of an organic compound (hereinafter also referred to as a "specific aggregate”).
• the tropic film has no absorption in the visible light region, and the average value of the ratio of the length of the long axis of the specific aggregate to the length of the short axis of the specific aggregate (hereinafter also referred to as "average aspect ratio"). is 2.0 or more, and the average length of the long axis of the specific aggregate is 10 nm or more.
• a characteristic feature of the optically anisotropic film of the present invention is that it contains specific aggregates. Since the specific aggregate has a predetermined average aspect ratio and a predetermined major axis length, it is presumed that it is excellent in all of orientation, light resistance, and moist heat durability. These effects are particularly likely to occur in the infrared region.
• the orientation represents the absorption anisotropy of the optically anisotropic film, and the higher the absorption anisotropy, the better the orientation. Specifically, as described later, the higher the degree of orientation, the better the orientation. Applicable.
• the fact that at least one of the effects of better orientation, better light resistance, and better wet heat durability can be obtained is also referred to as "more excellent" the effects of the present invention.
• the optically anisotropic film contains a liquid crystal compound or a polymer.
• the liquid crystal compound may be either a low molecular liquid crystal compound or a high molecular liquid crystal compound (liquid crystal polymer).
• a low-molecular liquid crystal compound is a compound that does not have repeating units in its chemical structure
• a liquid crystalline polymer is a compound that has repeating units in its chemical structure. The above repeating unit will be described later.
• the liquid crystal compound may be either thermotropic liquid crystal or lyotropic liquid crystal, and preferably lyotropic liquid crystal.
• Lyotropic liquid crystal property refers to the property of causing a phase transition between an isotropic phase and a liquid crystal phase by changing the concentration in a solution state dissolved in a solvent.
• the liquid crystalline compound exhibiting lyotropic liquid crystallinity is preferably water-soluble since the expression of liquid crystallinity can be easily controlled.
• the water-soluble liquid crystal compound refers to a liquid crystal compound that dissolves in water at 1% by mass or more, preferably a liquid crystal compound that dissolves in water at 5% by mass or more.
• Thermotropic liquid crystal property refers to the property of causing a phase transition between an isotropic phase and a liquid crystal phase by changing the temperature.
• the liquid crystal compound may exhibit any of nematic, smectic, and columnar properties.
• the liquid crystalline compound exhibit no absorption in the visible light region (wavelength range of 400 to 700 nm). Specifically, it means that the average transmittance in the visible light range is 90% or more. The above average transmittance is preferably 95% or more. The upper limit may be less than 100%.
• the average transmittance can be measured using, for example, a UV-660 UV-visible near-infrared spectrophotometer equipped with a UV-3100PC (manufactured by SHIMADZU) or an automatic absolute reflectance measurement unit ARMN-735 manufactured by JASCO Corporation. Can be measured.
• liquid crystal compound examples include rod-like compounds and plate-like compounds.
• the liquid crystalline compound only a rod-like compound, only a plate-like compound may be used, or a combination of a rod-like compound and a plate-like compound may be used.
• the rod-like compound and the plate-like compound will be explained in detail.
• Rod-shaped compound refers to a compound having a structure in which ring structures (e.g., aromatic rings and non-aromatic rings) are connected one-dimensionally via a single bond or a divalent linking group, and a solvent It refers to a group of compounds that have the property of being oriented so that their long axes are parallel to each other.
• the rod-like compound is preferably a lyotropic liquid crystal compound.
• the rod-like compound has a maximum absorption wavelength in a wavelength range of 300 nm or less. That is, the rod-like compound preferably has a maximum absorption peak in a wavelength range of 300 nm or less.
• the maximum absorption wavelength of the rod-shaped compound means the wavelength at which the absorbance reaches its maximum value in the absorption spectrum (measurement range: wavelength range of 230 to 400 nm) of the rod-shaped compound. When there are multiple maximum values in the absorbance of the absorption spectrum of the rod-like compound, the longest wavelength in the measurement range is selected.
• the rod-like compound preferably has a maximum absorption wavelength in the wavelength range of 230 to 300 nm, and preferably has a maximum absorption wavelength in the wavelength range of 250 to 290 nm. It is more preferable to have.
• the maximum absorption wavelength of the rod-like compound is preferably located in a range of 230 nm or more, and more preferably in a range of 250 nm or more.
• the method for measuring the maximum absorption wavelength is as follows. A rod-shaped compound (5 to 50 mg) is dissolved in pure water (1000 mL), and the absorption spectrum of the resulting solution is measured using a spectrophotometer (MPC-3100 (manufactured by SHIMADZU)).
• the rod-like compound has a hydrophilic group, since the orientation of the specific aggregate in the optically anisotropic film is better.
• the rod-like compound may have one or more hydrophilic groups.
• the hydrophilic group include an acid group or a salt thereof, an onium base, a hydroxy group or a salt thereof, a sulfonamide group (H 2 N-SO 2 -) or a salt thereof, and a group containing a polyoxyalkylene group, An acid group or a salt thereof is preferred.
• Onium bases are groups derived from onium salts, such as ammonium bases (*-N + (R Z ) 3 A - ), phosphonium bases (*-P + (R Z ) 3 A - ), and sulfonium bases. Examples include bases (*-S + (R Z ) 2 A ⁇ ).
• R Z each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
• a ⁇ represents an anion (eg, halide ion, etc.). * represents the bonding position.
• a salt of a hydroxy group is represented by *-O ⁇ M + , where M + represents a cation and * represents the bonding position.
• Examples of the cation represented by M + include cations in salts of acid groups described below.
• Examples of the group containing a polyoxyalkylene group include a group represented by R Z -(OL Z ) n -*.
• RZ is as described above.
• LZ represents an alkylene group. * represents the bonding position.
• n represents an integer of 2 or more.
• Examples of acid groups or salts thereof include sulfo groups (-SO 3 H) or salts thereof (-SO 3 - M + .
• M + represents a cation
• -COO - M + , M + represents a cation
• a sulfo group or a salt thereof is preferred since it provides better orientation of specific aggregates in the optically anisotropic film.
• the above-mentioned salt refers to one in which the hydrogen ion of an acid is replaced with another cation such as a metal.
• a salt of an acid group refers to one in which the hydrogen ion of an acid group such as a -SO 3 H group is replaced with another cation.
• cations in salts of acid groups include Na + , K + , Li + , Rb + , Cs + , Ba 2+ , Ca 2+ , Examples include Mg 2+ , Sr 2+ , Pb 2+ , Zn 2+ , La 3+ , Ce 3+ , Y 3+ , Yb 3+ , Gd 3+ , and Zr 4+ .
• alkali metal ions are preferred, Na + , K + or Li + are more preferred, and K + is even more preferred, since the orientation of specific aggregates in the optically anisotropic film is better.
• a liquid crystalline polymer having a repeating unit represented by formula (X) is preferable, since the orientation of specific aggregates in the optically anisotropic film is more excellent.
• the liquid crystalline polymer preferably exhibits lyotropic liquid crystallinity. That is, the liquid crystalline polymer is preferably a lyotropic liquid crystalline compound.
• R x1 is a divalent aromatic ring group having a substituent containing a hydrophilic group, a divalent non-aromatic ring group having a substituent containing a hydrophilic group, or a group represented by formula (X1) represents.
• * represents the bonding position.
• Formula (X1) *-R x3 -L x3 -R x4 -* R x3 and R x4 are each independently a divalent aromatic ring group that may have a substituent containing a hydrophilic group, or 2 that may have a substituent containing a hydrophilic group.
• L x3 represents a single bond, -O-, -S-, an alkylene group, an alkenylene group, or an alkynylene group.
• the divalent aromatic ring group and the divalent non-aromatic ring group represented by R x1 have a substituent containing a hydrophilic group.
• the hydrophilic group contained in the substituent containing a hydrophilic group is as described above, and an acid group or a salt thereof is preferable.
• a group represented by formula (H) is preferable.
• * represents the bonding position.
• R H -L H -* R H represents a hydrophilic group.
• the definition of the hydrophilic group is as described above.
• LH represents a single bond or a divalent linking group.
• the divalent linking group is not particularly limited, and includes, for example, divalent hydrocarbon groups (for example, alkylene groups having 1 to 10 carbon atoms, alkenylene groups having 1 to 10 carbon atoms, and alkynylene groups having 1 to 10 carbon atoms).
• divalent hydrocarbon groups for example, alkylene groups having 1 to 10 carbon atoms, alkenylene groups having 1 to 10 carbon atoms, and alkynylene groups having 1 to 10 carbon atoms.
• divalent aliphatic hydrocarbon groups such as, divalent aromatic hydrocarbon ring groups such as arylene groups
• divalent heterocyclic groups -O-, -S-, -SO 2 -, -NH -, -CO-, or a combination thereof (for example, -CO-O-, -O-divalent hydrocarbon group -, -(O-divalent hydrocarbon group) m -O-(m represents an integer of 1 or more), -divalent hydrocarbon group -O-CO-, etc.).
• the number of substituents containing a hydrophilic group included in the divalent aromatic ring group is not particularly limited, but 1 to 3 is preferable, and 1 to 3 is preferable in terms of better orientation of specific aggregates in the optically anisotropic film. is more preferable.
• the number of substituents containing a hydrophilic group included in the divalent non-aromatic ring group is not particularly limited, but 1 to 3 is preferable, and 1 is preferable in terms of better orientation of specific aggregates during light absorption anisotropy. More preferred.
• the aromatic ring constituting the divalent aromatic ring group having a substituent containing a hydrophilic group represented by R x1 may have a monocyclic structure or a polycyclic structure.
• Examples of the aromatic ring constituting the divalent aromatic ring group include aromatic hydrocarbon rings and aromatic heterocycles. That is, examples of R x1 include a divalent aromatic hydrocarbon ring group having a substituent containing a hydrophilic group, and a divalent aromatic heterocyclic group having a substituent containing a hydrophilic group.
• examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring.
• Examples of the structure of only the divalent aromatic hydrocarbon ring portion of the divalent aromatic hydrocarbon ring group having a substituent containing a hydrophilic group include the following groups. * represents the bonding position.
• Examples of the aromatic heterocycle include a pyridine ring, a thiophene ring, a pyrimidine ring, a thiazole ring, a furan ring, a pyrrole ring, an imidazole ring, and an indole ring.
• Examples of the structure of only the divalent aromatic heterocyclic group portion of the divalent aromatic heterocyclic group which may have a substituent include the following groups. * represents the bonding position.
• the non-aromatic ring constituting the divalent non-aromatic ring group having a substituent containing a hydrophilic group represented by R x1 may have a monocyclic structure or a polycyclic structure.
• Examples of the non-aromatic rings constituting the divalent non-aromatic ring group include aliphatic rings and non-aromatic heterocycles, and the orientation of specific aggregates in the light-absorbing anisotropic film In terms of superior properties, aliphatic rings are preferred, cycloalkanes are more preferred, and cyclohexane is even more preferred.
• examples of R A divalent cycloalkylene group having a substituent containing a group is preferred.
• the aliphatic ring may be a saturated aliphatic ring or an unsaturated aliphatic ring.
• Examples of the structure of only the divalent aliphatic ring moiety of the divalent aliphatic ring group having a substituent containing a hydrophilic group include the following groups. * represents the bonding position.
• the heteroatom contained in the non-aromatic heterocycle is not particularly limited, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom.
• the number of heteroatoms contained in the non-aromatic heterocycle is not particularly limited, and examples thereof include 1 to 3. Examples of the structure of only the divalent non-aromatic heterocyclic group portion of the divalent non-aromatic heterocyclic group having a substituent containing a hydrophilic group include the following groups. * represents the bonding position.
• a divalent aromatic ring group having a substituent containing a hydrophilic group and a divalent non-aromatic ring group having a substituent containing a hydrophilic group represented by R x1 are substituents containing a hydrophilic group. It may have a substituent other than the group.
• Substituents are not particularly limited, and include, for example, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, aromatic heterocyclic oxy groups, acyl groups, alkoxycarbonyl groups, and aryloxycarbonyl groups.
• acyloxy group acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, arylthio group, aromatic heterocyclic thio group, ureido group, halogen atom, cyano group, hydrazino group, heterocyclic group (e.g., heterocyclic group) (aryl group), silyl group, and a combination thereof.
• the above substituent may be further substituted with a substituent.
• R x3 and R x4 are each independently a divalent aromatic ring group that may have a substituent containing a hydrophilic group, or 2 that may have a substituent containing a hydrophilic group.
• the definition of the substituent containing the hydrophilic group that the divalent aromatic ring group represented by R x3 and R x4 may have is as described above.
• the definition of the aromatic ring constituting the divalent aromatic ring group which may have a substituent containing a hydrophilic group represented by R x3 and R x4 is the above-mentioned aromatic ring represented by R x1 . This is the same as the definition of an aromatic ring constituting a divalent aromatic ring group having a substituent containing a hydrophilic group.
• the definition of the substituent containing the hydrophilic group that the divalent non-aromatic ring group represented by R x3 and R x4 may have is as described above.
• the definition of the non-aromatic ring constituting the divalent non-aromatic ring group which may have a substituent containing a hydrophilic group represented by R x3 and R x4 is the above-mentioned R x1 . This is the same as the definition of the non-aromatic ring constituting the divalent non-aromatic ring group having a substituent containing a hydrophilic group.
• At least one of R x3 and R x4 represents a divalent aromatic ring group having a substituent containing a hydrophilic group, or a divalent non-aromatic ring group having a substituent containing a hydrophilic group
• R Both x3 and R x4 may represent a divalent aromatic ring group having a substituent containing a hydrophilic group, or a divalent non-aromatic ring group having a substituent containing a hydrophilic group.
• the definition of the divalent aromatic ring group having a substituent containing a hydrophilic group represented by R x3 and R x4 is the divalent aromatic ring group having a substituent containing a hydrophilic group represented by R x1 described above.
• divalent non-aromatic ring group having a substituent containing a hydrophilic group represented by R x3 and R x4 is as follows: It is the same as the definition of valent non-aromatic ring group.
• L x3 represents a single bond, -O-, -S-, an alkylene group, an alkenylene group, or an alkynylene group.
• the number of carbon atoms in the alkylene group is not particularly limited, but it is preferably 1 to 3, and more preferably 1, from the viewpoint of better orientation of the specific aggregate in the optically anisotropic film.
• the number of carbon atoms in the alkenylene group and the alkynylene group is not particularly limited, but is preferably from 2 to 5, more preferably from 2 to 4, in terms of better orientation of specific aggregates in the optically anisotropic film.
• R x2 represents a divalent non-aromatic ring group, a divalent aromatic ring group, or a group represented by formula (X2).
• * represents the bonding position.
• Formula (X2) *-Z x1 -Z x2 -* Z x1 and Z x2 each independently represent a divalent non-aromatic ring group or a divalent aromatic ring group. * represents the bonding position.
• the non-aromatic ring constituting the divalent non-aromatic ring group represented by R x2 may have a monocyclic structure or a polycyclic structure.
• Examples of the non-aromatic ring constituting the divalent non-aromatic ring group include an aliphatic ring and a non-aromatic heterocycle, and the orientation of the specific aggregate in the optically anisotropic film is In terms of superiority, aliphatic rings are preferred, cycloalkanes are more preferred, and cyclohexane is even more preferred. That is, examples of R x2 include a divalent aliphatic cyclic group and a divalent non-aromatic heterocyclic group, with a divalent cycloalkylene group being preferred.
• the aliphatic ring may be a saturated aliphatic ring or an unsaturated aliphatic ring.
• Examples of the divalent aliphatic cyclic group include the following groups. * represents the bonding position.
• the heteroatom contained in the non-aromatic heterocycle is not particularly limited, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom.
• the number of heteroatoms contained in the non-aromatic heterocycle is not particularly limited, and examples thereof include 1 to 3.
• Examples of the divalent non-aromatic heterocyclic group include the following groups. * represents the bonding position.
• the divalent non-aromatic ring group may have a substituent.
• the type of substituent is not particularly limited, and for example, a divalent aromatic ring group having a substituent containing a hydrophilic group represented by R x1 , and a divalent non-containing group having a substituent containing a hydrophilic group. Examples of substituents other than the hydrophilic group-containing substituent that an aromatic ring group may have may be mentioned.
• the aromatic ring constituting the divalent aromatic ring group represented by R x2 may have a monocyclic structure or a polycyclic structure.
• the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocycle.
• the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring.
• the aromatic heterocycle include a pyridine ring, a thiophene ring, a pyrimidine ring, a thiazole ring, a furan ring, a pyrrole ring, an imidazole ring, and an indole ring.
• the divalent aromatic ring group may have a substituent.
• the type of substituent is not particularly limited, and for example, a divalent aromatic ring group having a substituent containing a hydrophilic group represented by R x1 , and a divalent non-containing group having a substituent containing a hydrophilic group. Examples of substituents other than the hydrophilic group-containing substituent that an aromatic ring group may have may be mentioned.
• Z x1 and Z x2 each independently represent a divalent non-aromatic ring group or a divalent aromatic ring group.
• the definitions of the divalent non-aromatic ring group represented by Z x1 and Z x2 and the divalent aromatic ring group are the divalent non-aromatic ring group represented by R x2 described above, and It has the same meaning as the definition of divalent aromatic ring group.
• L x1 and L x2 each independently represent -CONH-, -COO-, -O-, or -S-. Among them, -CONH- is preferable because it has better orientation of specific aggregates.
• the repeating unit represented by formula (X) is preferably a repeating unit represented by formula (X4).
• the content of the repeating unit represented by the formula (X) contained in the liquid crystalline polymer having the repeating unit represented by the formula (X) is not particularly limited, but the content of the repeating unit represented by the formula (X) is not particularly limited. It is preferably mol% or more, more preferably 80 mol% or more. The upper limit is 100 mol% or less.
• the molecular weight of the liquid crystalline polymer having repeating units represented by formula (X) is not particularly limited, but the number of repeating units represented by formula (X) in the liquid crystalline polymer is preferably 2 or more, and 10 to 100,000. More preferably, 100 to 10,000 is even more preferable. Further, the number average molecular weight of the liquid crystalline polymer having a repeating unit represented by formula (X) is not particularly limited, but is preferably from 5,000 to 50,000, more preferably from 10,000 to 30,000. Further, the molecular weight distribution of the liquid crystalline polymer having a repeating unit represented by formula (X) is not particularly limited, but is preferably from 1.0 to 12.0, more preferably from 1.0 to 7.0.
• a plate-like compound is a compound in which an aromatic ring (e.g., an aromatic hydrocarbon ring or an aromatic heterocycle) is two-dimensionally spread through a single bond or an appropriate linking group. This refers to a group of compounds that have the property of forming column-shaped aggregates by associating the planes of the compounds in a solvent.
• the plate-like compound is a lyotropic liquid crystal compound.
• the plate-like compound has a maximum absorption wavelength in a wavelength range exceeding 300 nm. That is, it is preferable that the plate-like compound has a maximum absorption peak in a wavelength range exceeding 300 nm.
• the maximum absorption wavelength of the above-mentioned plate-like compound means the wavelength at which its absorbance takes a maximum value in the absorption spectrum (measurement range: wavelength range of 230 to 400 nm) of the plate-like compound. When there are multiple maximum values in the absorbance of the absorption spectrum of the plate-like compound, the longest wavelength in the measurement range is selected.
• the plate-like compound preferably has a maximum absorption wavelength in a wavelength range of 320 to 400 nm, more preferably a maximum absorption wavelength in a wavelength range of 330 to 360 nm.
• the maximum absorption wavelength of the plate-like compound is preferably located in a range of 320 nm or more, and more preferably in a range of 330 nm or more.
• the method for measuring the maximum absorption wavelength is as follows. A plate-shaped compound (0.01 to 0.05 mmol) is dissolved in pure water (1000 mL), and the absorption spectrum of the resulting solution is measured using a spectrophotometer (MPC-3100 (manufactured by SHIMADZU)).
• the plate-like compound preferably has a hydrophilic group, since the orientation of the specific aggregate in the optically anisotropic film is better.
• the definition of the hydrophilic group is the same as the definition of the hydrophilic group that the rod-shaped compound may have.
• the plate-like compound may have one or more hydrophilic groups. When the plate-like compound has a plurality of hydrophilic groups, the number is preferably 2 to 4, more preferably 2.
• a compound represented by formula (Y) is preferable since it has better orientation of specific aggregates in the optically anisotropic film.
• the compound represented by formula (Y) is preferably a lyotropic liquid crystal compound.
• Formula (Y) R y2 -L y3 -L y1 -R y1 -L y2 -L y4 -R y3 R y1 represents a divalent monocyclic group which may have a substituent or a divalent fused polycyclic group which may have a substituent. Examples of the ring included in the divalent monocyclic group include a monocyclic hydrocarbon ring and a monocyclic heterocycle.
• the monocyclic hydrocarbon ring may be a monocyclic aromatic hydrocarbon ring or a monocyclic non-aromatic hydrocarbon ring.
• the monocyclic heterocycle may be a monocyclic aromatic heterocycle or a monocyclic non-aromatic heterocycle.
• As the divalent monocyclic group a divalent monocyclic aromatic hydrocarbon ring group, or a divalent monocyclic aromatic Heterocyclic groups are preferred.
• the number of ring structures contained in the divalent condensed polycyclic group is not particularly limited, but 3 to 10 is preferable, and 3 to 6 is more preferable in terms of better orientation of the specific aggregate of the optically anisotropic film. , 3 to 4 are more preferred.
• Examples of the ring contained in the divalent condensed polycyclic group include a hydrocarbon ring and a heterocycle.
• the hydrocarbon ring may be an aromatic hydrocarbon ring or a non-aromatic hydrocarbon ring.
• the heterocycle may be an aromatic heterocycle or a non-aromatic heterocycle.
• the divalent condensed polycyclic group is preferably composed of an aromatic hydrocarbon ring and a heterocycle, since the orientation of the specific aggregate of the optically anisotropic film is more excellent.
• the divalent condensed polycyclic group is preferably a conjugated linking group. That is, it is preferably a conjugated divalent condensed polycyclic group.
• Examples of the ring constituting the divalent condensed polycyclic group include dibenzothiophene-S,S-dioxide (ring represented by formula (Y2)), dinaphtho[2,3-b:2',3'- d] Furan (ring represented by formula (Y3)), 12H-benzo "b” phenoxazine (ring represented by formula (Y4)), dibenzo[b,i]oxanthrene (represented by formula (Y5)) ring), benzo[b]naphtho[2',3':5,6]dioxino[2,3-i]oxanthrene (ring represented by formula (Y6)), acenaphtho[1,2-b]benzo [g] Quinoxaline (ring represented by formula (Y7)), 9H-acenaphtho[1,2-b]imidazo[4,5-g]quinoxaline (ring represented by formula (Y8)), dibenzo[b , def] chrycerin-7,14
• the divalent fused polycyclic group includes a divalent group formed by removing two hydrogen atoms from a ring represented by any one of formulas (Y2) to (Y10), A divalent group formed by removing two hydrogen atoms from the ring represented by Y2) is preferred.
• the divalent monocyclic group and the divalent fused polycyclic group may have a substituent.
• the type of substituent is not particularly limited, and for example, a divalent aromatic ring group having a substituent containing a hydrophilic group represented by R x1 , and a divalent non-containing group having a substituent containing a hydrophilic group. Examples of substituents other than the hydrophilic group-containing substituents of the aromatic ring group may be mentioned.
• R y2 and R y3 each independently represent a hydrogen atom or a hydrophilic group, and at least one of R y2 and R y3 represents a hydrophilic group. Preferably, both R y2 and R y3 represent hydrophilic groups.
• the definitions of the hydrophilic groups represented by R y2 and R y3 are as described above.
• L y1 and L y2 each independently represent a single bond, a divalent aromatic ring group, or a group represented by formula (Y1). However, when R y1 is a divalent monocyclic group, both L y1 and L y2 represent a divalent aromatic ring group or a group represented by formula (Y1).
• * represents the bonding position.
• R y4 and R y5 each independently represent a divalent aromatic ring group.
• n represents 1 or 2.
• the aromatic ring constituting the divalent aromatic ring group represented by L y1 and L y2 may have a monocyclic structure or a polycyclic structure.
• Examples of the aromatic ring constituting the divalent aromatic ring group include aromatic hydrocarbon rings and aromatic heterocycles. That is, the divalent aromatic ring group represented by L y1 and L y2 includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
• the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring.
• Examples of the divalent aromatic hydrocarbon ring group include the following groups. * represents the bonding position.
• Examples of the aromatic heterocycle include a pyridine ring, a thiophene ring, a pyrimidine ring, a thiazole ring, a furan ring, a pyrrole ring, an imidazole ring, and an indole ring.
• Examples of the divalent aromatic heterocyclic group include the following groups. * represents the bonding position.
• the definition of the divalent aromatic ring group represented by R y4 and R y5 is also the same as that of the divalent aromatic ring group represented by L y1 and L y2 .
• L y3 and L y4 each independently represent a single bond, -O-, -S-, an alkylene group, an alkenylene group, an alkynylene group, or a combination thereof.
• groups combining the above-mentioned groups include an -O-alkylene group and an -S-alkylene group.
• the number of carbon atoms in the alkylene group is not particularly limited, but it is preferably 1 to 3, and more preferably 1, since the orientation of the specific aggregate of the optically anisotropic film is better.
• the number of carbon atoms in the alkenylene group and the alkynylene group is not particularly limited, but is preferably from 2 to 5, more preferably from 2 to 4, in terms of better orientation of specific aggregates of the optically anisotropic film.
• liquid crystal compound is a liquid crystal polymer having a repeating unit represented by formula (1).
• PC1 represents the main chain of the repeating unit
• L1 represents a single bond or a divalent linking group
• SP1 represents a spacer group
• MG1 represents a mesogenic group
• T1 represents a terminal group.
• Examples of the main chain of the repeating unit represented by PC1 include groups represented by any of formulas (P1-A) to (P1-D), depending on the diversity and handling of the monomers used as raw materials.
• a group represented by the following formula (P1-A) is preferred in terms of ease of use.
• R 11 to R 14 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms. represents an alkoxy group of 10.
• the alkyl group may be a linear or branched alkyl group, or may be an alkyl group having a cyclic structure (cycloalkyl group). Further, the number of carbon atoms in the alkyl group is preferably 1 to 5.
• the group represented by formula (P1-A) is preferably one unit of a partial structure of a poly(meth)acrylic ester obtained by polymerization of a (meth)acrylic ester.
• the group represented by formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of the epoxy group of a compound having an epoxy group.
• the group represented by formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of the oxetane group of a compound having an oxetane group.
• the group represented by formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by polycondensation of a compound having at least one of an alkoxysilyl group and a silanol group.
• examples of the compound having at least one of an alkoxysilyl group and a silanol group include a compound having a group represented by SiR 14 (OR 15 ) 2 -.
• R 14 has the same meaning as R 14 in formula (P1-D), and each of the plurality of R 15s independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• Examples of the divalent linking group represented by L1 include -CO-, -COO-, -O-, -S-, -CONR 16 -, -SO 2 -, and -NR 16 R 17 -.
• R 16 and R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent (for example, a group exemplified by the above-mentioned substituent W).
• P1 is a group represented by formula (P1-A)
• L1 is preferably a group represented by -COO- or -CONR 16 -.
• PC1 is a group represented by any one of formulas (P1-B) to (P1-D)
• L1 is preferably a single bond.
• the spacer group represented by SP1 is a group containing at least one structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure, and a fluorinated alkylene structure, or a linear group having 2 to 20 carbon atoms.
• a linear or branched alkylene group is preferred.
• the above alkylene group further includes -O-, -S-, -COO-, -O-CO-O-, -CONR- (R represents an alkyl group having 1 to 10 carbon atoms), or -SO 2 - may be included.
• the spacer group represented by SP1 is at least one type selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure, and a fluorinated alkylene structure, from the viewpoint of easy expression of liquid crystallinity and availability of raw materials.
• a group containing a structure is more preferable.
• the oxyethylene structure represented by SP1 is preferably a group represented by *-(CH 2 -CH 2 O) n1 -*.
• n1 represents an integer from 1 to 20, and * represents the bonding position.
• n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 6, and even more preferably an integer of 2 to 4.
• the oxypropylene structure represented by SP1 is preferably a group represented by *-(CH(CH 3 )-CH 2 O) n2 -*.
• n2 represents an integer of 1 to 3, and * represents the bonding position.
• the polysiloxane structure represented by SP1 is preferably a group represented by *-(Si(CH 3 ) 2 -O) n3 -*.
• n3 represents an integer from 6 to 10
• * represents the bonding position.
• the fluorinated alkylene structure represented by SP1 is preferably a group represented by *-(CF 2 -CF 2 ) n4 -*.
• n4 represents an integer from 6 to 10, and * represents the bonding position.
• the mesogenic group represented by MG1 is a group representing the main skeleton of liquid crystal molecules that contributes to liquid crystal formation.
• Liquid crystal molecules exhibit liquid crystallinity, which is an intermediate state (mesophase) between a crystalline state and an isotropic liquid state.
• mesogenic group There are no particular restrictions on the mesogenic group, and for example, the description in "Flussige Kristallein Kunststoff II” (VEBDeutsche Verlagfur Grundstoff Industrie, Leipzig, published in 1984), especially pages 7 to 16, and the liquid crystal handbook editor. Compiled by Committee, Liquid Crystal Handbook (Maruzen, published in 2000) ), especially the description in Chapter 3.
• the mesogenic group for example, a group having at least one type of cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group is preferable.
• the mesogenic group preferably has an aromatic hydrocarbon group, more preferably has 2 to 4 aromatic hydrocarbon groups, and more preferably has 3 aromatic hydrocarbon groups because the effects of the present invention are better. It is more preferable to have the following.
• the mesogenic group the following formula (M1-A) is used from the viewpoints of expression of liquid crystallinity, adjustment of liquid crystal phase transition temperature, availability of raw materials, synthesis suitability, and higher degree of orientation of the optically anisotropic film.
• a group represented by the following formula (M1-B) is preferable, and a group represented by the formula (M1-B) is more preferable.
• A1 is a divalent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group. These groups may be substituted with an alkyl group, a fluorinated alkyl group, an alkoxy group, or a substituent.
• the divalent group represented by A1 is preferably a 4- to 6-membered ring. Further, the divalent group represented by A1 may be a monocyclic ring or a condensed ring group. * represents the binding position with SP1 or T1.
• the divalent aromatic hydrocarbon group represented by A1 includes a phenylene group, a naphthylene group, a fluorene-diyl group, an anthracene-diyl group, and a tetracene-diyl group. From this point of view, a phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable.
• the divalent heterocyclic group represented by A1 may be either aromatic or non-aromatic, but is preferably a divalent aromatic heterocyclic group from the viewpoint of further improving the degree of orientation.
• Atoms other than carbon constituting the divalent aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom.
• the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different.
• divalent aromatic heterocyclic groups include pyridylene group (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene group (quinoline-diyl group), etc.
• isoquinolylene group isoquinoline-diyl group
• oxazole-diyl group isoquinoline-diyl group
• thiazole-diyl group isoxadiazole-diyl group
• benzothiazole-diyl group benzothiadiazole-diyl group
• phthalimido-diyl group isoquinoline-diyl group
• thienothiazole-diyl group isoxazole-diyl group
• thiazole-diyl group isoxadiazole-diyl group
• benzothiazole-diyl group isnzothiadiazole-diyl group
• phthalimido-diyl group isoquinoline-diyl group
• thienothiazole-diyl group isoxadiazole-diyl group
• benzothiadiazole-diyl group isoquino
• divalent alicyclic group represented by A1 examples include a cyclopentylene group and a cyclohexylene group.
• a1 represents an integer from 1 to 10.
• the plural A1s may be the same or different.
• A2 and A3 are each independently a divalent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group. Specific examples and preferred embodiments of A2 and A3 are the same as A1 in formula (M1-A), so their explanation will be omitted.
• a2 represents an integer from 1 to 10, and when a2 is 2 or more, multiple A2s may be the same or different, and multiple A3s may be the same or different. Often, multiple LA1s may be the same or different.
• A2 is preferably an integer of 2 or more, and more preferably 2, from the viewpoint of increasing the degree of orientation of the light absorption anisotropic layer.
• LA1 is a divalent linking group.
• the plurality of LA1s are each independently a single bond or a divalent linking group, and at least one of the plurality of LA1s is a divalent linking group.
• a2 is 2, it is preferable that one of the two LA1s is a divalent linking group and the other is a single bond, since the degree of orientation of the light absorption anisotropic layer becomes higher.
• the terminal group represented by T1 includes a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, -SH, a carboxyl group, a boronic acid group, -SO 3 H, -PO 3 H 2 , -NR 11 R 12 ( R 11 and R 12 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group), an alkyl group having 1 to 10 carbon atoms, Alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 10 carbon atoms, alkoxycarbonyloxy group having 1 to 10 carbon atoms, acyloxy group having 1 to 10 carbon atoms, acylamino group having 1 to 10 carbon atoms, 1 carbon number -10 alkoxycarbonyl group, alkoxycarbonylamino group having 1 to 10 carbon atom
• Examples of the crosslinkable group-containing group include -L-CL.
• L represents a single bond or a divalent linking group.
• Examples of the divalent linking group include the substituent represented by L1.
• CL represents a crosslinkable group, preferably a crosslinkable group represented by any one of formulas (P-1) to (P-30), and more preferably an acryloyl group or a methacryloyl group.
• T1 may be a combination of two or more of these groups.
• R P in the following formula represents a hydrogen atom or an alkyl group. * represents the bonding position.
• T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably a methoxy group. These terminal groups may be further substituted with these groups or the polymerizable group described in JP-A-2010-244038.
• the number of atoms in the main chain of T1 is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 10, and particularly preferably 1 to 7. When the number of atoms in the main chain of T1 is 20 or less, the orientation of the specific aggregate in the optically anisotropic film is further improved.
• the "main chain” in T1 means the longest molecular chain bonded to M1, and hydrogen atoms are not counted in the number of atoms in the main chain of T1.
• the number of atoms in the main chain is 4, and when T1 is a sec-butyl group, the number of atoms in the main chain is 3.
• the content of the repeating unit (1) is preferably 40 to 100% by mass, more preferably 50 to 95% by mass, based on all repeating units of the rodlike compound (liquid crystalline rodlike polymer).
• the liquid crystalline polymer preferably contains a repeating unit having electron-donating and/or electron-withdrawing properties at the end. More specifically, the liquid crystalline polymer includes a repeating unit (21) having a mesogenic group and an electron-withdrawing group having a ⁇ p value of greater than 0 present at the terminal thereof, and a repeating unit (21) having a mesogenic group and an electron-withdrawing group having a ⁇ p value greater than 0 at the terminal thereof. It is more preferable to include a repeating unit (22) having a group having a value of 0 or less.
• the liquid crystalline polymer contains the repeating unit (21) and the repeating unit (22), compared to the case where the liquid crystalline polymer contains only either the repeating unit (21) or the repeating unit (22), The orientation of the optically anisotropic film formed is improved. Although the details of this reason are not clear, it is generally estimated as follows. In other words, the opposite dipole moments generated between the repeating unit (21) and the repeating unit (22) interact intermolecularly, and the interaction in the direction of the short axis of the mesogenic group becomes stronger, resulting in a liquid crystal. It is presumed that the orientation direction of the liquid crystals becomes more uniform, and as a result, the degree of order of the liquid crystal increases. This improves the orientation of the specific aggregates, and is therefore presumed to improve the orientation of the optically anisotropic film formed. Note that the repeating units (21) and (22) may be repeating units represented by the formula (1) above.
• the repeating unit (21) has a mesogenic group and an electron-withdrawing group having a ⁇ p value of greater than 0, which is present at the end of the mesogenic group.
• the electron-withdrawing group is located at the end of the mesogenic group and has a ⁇ p value greater than 0.
• Examples of the electron-withdrawing group include a group represented by EWG in the formula (LCP-21) described below, and specific examples thereof are also the same.
• the ⁇ p value of the electron-withdrawing group is preferably 0.3 or more, and more preferably 0.4 or more, since it is larger than 0 and improves the orientation of the optically anisotropic film.
• the upper limit of the ⁇ p value of the electron-withdrawing group is preferably 1.2 or less, more preferably 1.0 or less, from the viewpoint of excellent alignment uniformity.
• the ⁇ p value is the Hammett's substituent constant ⁇ p value (also simply referred to as the " ⁇ p value"), which is a numerical expression of the effect of a substituent on the acid dissociation equilibrium constant of substituted benzoic acid, and is a numerical representation of the effect of a substituent on the acid dissociation equilibrium constant of substituted benzoic acid. This is a parameter indicating the strength of electron-withdrawing and electron-donating properties.
• the Hammett substituent constant ⁇ p value in this specification means the substituent constant ⁇ when the substituent is located at the para position of benzoic acid.
• Hammett substituent constant ⁇ p value of each group in this specification the value described in the document "Hansch et al., Chemical Reviews, 1991, Vol, 91, No. 2, 165-195" is adopted.
• the pKa of benzoic acid is determined using the software "ACD/ChemSketch (ACD/Labs 8.00 Release Product Version: 8.08)
• Hammett's substituent constant ⁇ p value can be calculated based on the difference between pKa and pKa of the benzoic acid derivative having a substituent at the para position.
• the repeating unit (21) is not particularly limited as long as it has a mesogenic group in the side chain and an electron-withdrawing group with a ⁇ p value larger than 0 present at the end of the mesogenic group, but it can be used in the optically anisotropic film.
• a repeating unit represented by the following formula (LCP-21) is preferable in that the orientation of the specific aggregate is more excellent.
• PC21 represents the main chain of the repeating unit, more specifically represents the same structure as PC1 in the above formula (1), and L21 represents a single bond or a divalent linking group.
• SP21A and SP21B each independently represent a single bond or a spacer group, and a specific example of the spacer group is SP1 in the above formula (1).
• MG21 represents a mesogenic structure, more specifically a mesogenic group represented by MG1 in the above formula (1)
• EWG represents an electron-withdrawing group having a ⁇ p value greater than 0.
• SP21A includes at least one structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure, and a fluorinated alkylene structure.
• SP21B a single bond or a linear or branched alkylene group having 2 to 20 carbon atoms is preferable.
• the above alkylene group may further contain -O-, -CO-O-, or -O-CO-O-.
• the spacer group represented by SP21B is preferably a single bond, since the orientation of the optically anisotropic film becomes higher.
• EWG represents an electron-withdrawing group with a ⁇ p value greater than 0 ( ⁇ p value greater than 0).
• R E represents an alkyl group having 1 to 20 carbon atoms (preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms).
• R F each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms).
• EWG is preferably a group represented by *-COO- RE , a (meth)acryloyloxy group, a cyano group, or a nitro group.
• the content of the repeating unit (21) is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less, based on all repeating units of the liquid crystalline polymer.
• the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, based on all repeating units of the liquid crystalline polymer.
• a repeating unit (21) that does not contain a crosslinkable group in EWG and a repeating unit (21) that contains a polymerizable group in EWG are used together. It's okay. This further improves the curability of the optically anisotropic film.
• crosslinkable groups include vinyl group, butadiene group, (meth)acryloyl group, (meth)acrylamide group, vinyl acetate group, fumaric acid ester group, styryl group, vinylpyrrolidone group, maleic anhydride, maleimide group, and vinyl ether.
• a group, an epoxy group or an oxetanyl group are preferred.
• the content of the repeating unit (21) containing a polymerizable group in the EWG is 1 to 1 to 30% by mass is preferred.
• the repeating unit (22) has a mesogenic group and a group having a ⁇ p value of 0 or less, which is present at the end of the mesogenic group. Since the liquid crystalline polymer has the repeating unit (22), the liquid crystalline polymer and the specific aggregate can be uniformly aligned.
• the mesogenic group is a group representing the main skeleton of a liquid crystal molecule that contributes to liquid crystal formation, and is as described above for the mesogenic group represented by MG1 in formula (1), and its specific examples are also the same. The above group is located at the end of the mesogenic group and has a ⁇ p value of 0 or less.
• the above groups include hydrogen atoms whose ⁇ p value is 0, and groups represented by T22 (electronic (donating group).
• groups represented by T22 electroactive (donating group).
• specific examples of groups (electron donating groups) with a ⁇ p value smaller than 0 are the same as T22 in formula (LCP-22) described below.
• the ⁇ p value of the above group is 0 or less, and is preferably smaller than 0, more preferably -0.1 or less, and even more preferably -0.2 or less, since the uniformity of orientation is more excellent.
• the lower limit is preferably -0.9 or more, more preferably -0.7 or more.
• the repeating unit (22) is not particularly limited as long as it has a mesogenic group in the side chain and a group having a ⁇ p value of 0 or less that is present at the end of the mesogenic group, but is represented by the above formula (LCP-21). It is preferable to use a repeating unit that does not correspond to the repeating unit represented by the following formula (LCP-22).
• PC22 represents the main chain of the repeating unit, more specifically represents the same structure as PC1 in the above formula (1), and L22 represents a single bond or a divalent linking group.
• SP22 represents a spacer group, more specifically represents the same structure as SP1 in the above formula (1)
• MG22 represents the same structure as SP1 in the above formula (1).
• It represents a mesogenic structure, more specifically a structure similar to the mesogenic group MG1 in the above formula (1)
• T22 represents an electron donating group having a Hammett's substituent constant ⁇ p value of 0 or less.
• T22 represents an electron donating group with a ⁇ p value of 0 or less (preferably less than 1).
• the electron-donating group having a ⁇ p value of 0 or less include a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkylamino group having 1 to 10 carbon atoms.
• the "main chain" in T22 means the longest molecular chain bonded to MG22, and hydrogen atoms are not counted in the number of atoms in the main chain of T22. For example, when T22 is an n-butyl group, the number of atoms in the main chain is 4, and when T22 is a sec-butyl group, the number of atoms in the main chain is 3.
• repeating unit (21) and the repeating unit (22) have a part of the structure in common. It is presumed that the more similar the structures of the repeating units are, the more uniformly the liquid crystals are aligned. This increases the orientation of the optically anisotropic film.
• SP21A of formula (LCP-21) and SP22 of formula (LCP-22) have the same structure in that the orientation of the optically anisotropic film becomes higher;
• MG21 of formula (LCP-22) has the same structure, and L21 of formula (LCP-21) and L22 of formula (LCP-22) have the same structure, It is preferable that at least one condition is satisfied, it is more preferable that two or more conditions are satisfied, and it is even more preferable that all conditions are satisfied.
• the content of the repeating unit (22) is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more, based on all the repeating units of the liquid crystalline polymer.
• the upper limit is preferably 99% by mass or less, more preferably 97% by mass or less, based on all repeating units of the liquid crystalline polymer.
• the liquid crystalline compounds may be used alone or in combination of two or more.
• the content of the liquid crystal compound is preferably more than 50% by mass, more preferably 55% by mass or more, based on the total mass of the optically anisotropic film.
• the upper limit is not particularly limited, but is preferably 98% by mass or less, more preferably 95% by mass or less.
• the polymer is a compound different from the liquid crystal compound described above.
• known polymers can be used, such as polycarbonate resins, polyolefin resins (especially cycloolefin polymers), cellulose resins, and acrylic resins.
• a polymer when the optically anisotropic film is a stretched film, a polymer can be used to produce the stretched film.
• the polymers may be used alone or in combination of two or more.
• the content of the polymer is preferably more than 50% by mass, more preferably 55% by mass or more, based on the total mass of the optically anisotropic film.
• the upper limit is not particularly limited, but is preferably 98% by mass or less, more preferably 95% by mass or less.
• the optically anisotropic film contains specific aggregates.
• the specific aggregate is an aggregate of organic compounds produced by aggregation of organic compounds.
• the organic compound is a compound different from the liquid crystal compound and polymer described above.
• the organic compound is not particularly limited as long as it is a compound other than liquid crystal compounds and polymers, but dichroic dyes are preferred.
• the optically anisotropic film may contain an organic compound as long as it contains a specific aggregate. In other words, the optically anisotropic film may contain an organic compound that is not an aggregate.
• the average value of the ratio of the length L of the long axis of the specific aggregate to the length D of the short axis of the specific aggregate is 2.0 or more, preferably 3.5 or more. , more preferably 10 or more.
• the upper limit may be 100 or less, preferably 50 or less, and more preferably 20 or less.
• the average length L of the long axis of the specific aggregate is 10 nm or more, preferably 200 nm or more, more preferably 500 nm or more, and even more preferably 1000 nm or more.
• the upper limit may be 100 ⁇ m or less, preferably 20 ⁇ m or less, and more preferably 10 ⁇ m or less.
• the average length D of the minor axis of the specific aggregate is appropriately selected so as to fall within the range of the preferred embodiments of the above L and the above L/D.
• the above L, the above D, and the above L/D can be measured by observing a specific aggregate using a SEM (Scanning Electron Microscope). For example, first, an image of the surface of the optically anisotropic film is obtained using a SEM. Next, using image processing software "ImageJ", an image is created by binarizing the brightness of the acquired image. Among the plurality of high-intensity regions of the created binarized image, those having an area equal to or larger than a circle with a diameter of 50 nm (1963 nm 2 ) are extracted as specific aggregates.
• each extracted specific aggregate is approximated to an ellipse using the image processing software, and the length of the major axis of the approximated ellipse is defined as the length of the major axis of the specific aggregate, L, and the length of the minor axis of the approximated ellipse. The length is measured as the length D of the minor axis of the specific aggregate.
• the above measurements were performed at three locations in a 13.58 ⁇ m 2 area that did not overlap with each other, and the D, L, and L/D of 5 specific aggregates were calculated at each location, and the calculated 15 aggregates were calculated.
• Calculate the average value of the above ratio by arithmetic averaging L/D of calculate the average length L of the major axis by arithmetic averaging the calculated 15 L, and calculate the calculated 15 D by arithmetic.
• the average length D of the short axis is calculated by averaging.
• the optically anisotropic film to be measured may be brought into contact with the solution before the measurement.
• components other than the specific aggregates contained in the optically anisotropic film for example, liquid crystalline compounds, etc.
• Examples of the above solution include an aqueous sodium chloride solution.
• the specific aggregate is preferably a J-aggregate, more preferably a J-aggregate of a dichroic dye.
• a J-aggregate is an aggregate of organic compounds (eg, dichroic dyes, etc.). More specifically, the J-aggregate refers to a state in which organic compound molecules are associated with each other at a certain slip angle.
• the J-aggregate has an absorption band with a narrower half-width on the long wavelength side and a higher extinction coefficient than when it is a single molecule of an organic compound in a solution state.
• the sharpened absorption band will be referred to as the J band.
• the J band is described in detail in literature (for example, Photographic Science and Engineering Vol 18, No. 323-335 (1974)). Whether it is a J aggregate or not can be easily determined by measuring its maximum absorption wavelength.
• the absorption peak of the J band is shifted to the longer wavelength side with respect to the absorption peak of one molecule of an organic compound, and the difference between the wavelength of the absorption peak of the J band and the wavelength of the absorption peak of one molecule of an organic compound is , 10 to 300 nm is preferable, and 30 to 250 nm is more preferable.
• the absorption spectrum of the specific aggregate in the infrared region is subjected to waveform separation
• the absorption spectrum is preferably composed of a plurality of peaks derived from the J aggregate.
• the number of peaks (the number of local maximum values) derived from the J aggregate upon waveform separation is preferably 2 or more, more preferably 3 or more.
• the upper limit is preferably 10 or less.
• the Lorentz function is applied to the obtained absorption spectrum for the range where the absorbance is 0.05 or more. Perform fitting by linear combination of . Next, in the above fitting, the number of Lorentz functions used was sequentially increased until the coefficient of determination R2 reached 0.98 or more when performing a correlation analysis between the measured value and the simulated value in 1 nm increments. Do it repeatedly. From the multiple absorption spectra obtained, in order to remove peaks derived from the organic compounds constituting the specific aggregate, we exclude spectra that have a maximum absorption wavelength within ⁇ 10 nm of the maximum absorption wavelength in the infrared region of the organic compound. do.
• the specific aggregate does not exhibit absorption in the visible light region (wavelength range of 400 to 700 nm). Specifically, it means that the average transmittance in the visible light range is 90% or more. The above average transmittance is preferably 95% or more. The upper limit may be less than 100%. The average transmittance can be measured in the same manner as the average transmittance of a liquid crystal compound.
• the specific aggregate preferably has a maximum absorption wavelength in the wavelength range of 700 to 2500 nm. That is, it is preferable that the specific aggregate has absorption in the infrared region.
• the specific aggregate may have a plurality of maximum absorption wavelengths in the wavelength range of 700 to 2500 nm. Note that when the specific aggregate is a J-aggregate, the maximum absorption wavelength of the J-aggregate is preferably located in a wavelength range of 700 to 2,500 nm. As described later, the maximum absorption wavelength of the specific aggregate in the wavelength range of 700 to 2,500 nm preferably corresponds to the maximum absorption wavelength of the optically anisotropic film in the wavelength range of 700 to 2,500 nm.
• Dichroic dye refers to an organic compound whose absorbance differs depending on the direction.
• the dichroic dye may exhibit liquid crystallinity (for example, lyotropic liquid crystallinity, thermotropic liquid crystallinity, etc.) or may not exhibit liquid crystallinity.
• the dichroic dye When the dichroic dye exhibits liquid crystallinity, it may exhibit any of nematic, smectic, and columnar properties.
• the dichroic dye preferably has a maximum absorption wavelength in the wavelength range of 700 to 2500 nm.
• the method for measuring the maximum absorption wavelength of the above-mentioned dichroic dye is a solution in which the object to be measured (5 to 50 mg) is dissolved in a solution (for example, water, methanol, dimethyl sulfoxide, etc.) (1000 mL) in which the object to be measured is dissolved.
• the absorption spectrum is measured using a spectrophotometer (MPC-3100 (manufactured by SHIMADZU)), and the maximum absorption wavelength is read from the obtained absorption spectrum.
• the dichroic dye has a hydrophilic group.
• the hydrophilic group include the hydrophilic groups that the above-mentioned liquid crystalline compound may have.
• dichroic dye is not particularly limited, and known materials may be used.
• dichroic dyes include phthalocyanine dyes, naphthalocyanine dyes, metal complex dyes, boron complex dyes, cyanine dyes, oxonol dyes, squarylium dyes, rylene dyes, diimonium dyes, and diphenylamines.
• examples include triphenylamine-based dyes, triphenylamine-based dyes, quinone-based dyes, and azo-based dyes.
• these dyes have longer absorption wavelengths by extending the existing ⁇ -conjugated system, and exhibit a wide variety of absorption wavelengths depending on their structure.
• phthalocyanine dyes having a hydrophilic group phthalocyanine dyes having a hydrophilic group
• naphthalocyanine dyes having a hydrophilic group metal complex dyes having a hydrophilic group
• boron complex dyes having a hydrophilic group cyanine dyes having a hydrophilic group.
• oxonol dyes having a hydrophilic group squarylium dyes having a hydrophilic group, rylene dyes having a hydrophilic group, diimonium dyes having a hydrophilic group, diphenylamine dyes having a hydrophilic group, hydrophilic groups
• triphenylamine dyes having the following, quinone dyes having a hydrophilic group, or azo dyes having a hydrophilic group examples of the hydrophilic group possessed by the dyes exemplified above include hydrophilic groups that may be possessed by the above-mentioned liquid crystalline compound.
• Phthalocyanine dyes and naphthalocyanine dyes are dyes that have a planar structure and a wide ⁇ -conjugated plane. It is preferable that the phthalocyanine dye has a structure represented by formula (1A). The naphthalocyanine dye preferably has a structure represented by formula (1B).
• M 1 represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide.
• Metal atoms include Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu. , Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi.
• metal oxides include VO, GeO, and TiO.
• metal hydroxides include Si(OH) 2 , Cr(OH) 2 , Sn(OH) 2 and AlOH.
• metal halides examples include SiCl2 , VCl, VCl2 , VOCl, FeCl, GaCl, ZrCl, and AlCl.
• metal atoms such as Fe, Co, Cu, Ni, Zn, Al, and V, metal oxides such as VO, or metal hydroxides such as AlOH are preferable, and metal oxides such as VO are more preferable. preferable.
• a compound represented by the following formula (1A-1) is preferable.
• R a1 and R a2 each independently represent a substituent.
• substituent W examples include groups exemplified by the substituent W described below.
• R a1 represents a substituent containing a hydrophilic group (hereinafter also referred to as "specific substituent")
• R a2 represents a substituent that does not contain a hydrophilic group.
• the hydrophilic group that the specific substituent has is as described above.
• R a11 represents a hydrophilic group.
• the hydrophilic group include the hydrophilic groups that the above-mentioned liquid crystalline compound may have.
• L a1 represents a single bond or a divalent connecting group when q is 1, and represents a q+1-valent connecting group when q is 2 or more.
• divalent linking groups include divalent hydrocarbon groups (for example, alkylene groups (preferably carbon atoms 1 to 10, more preferably 1 to 5), alkenylene groups (preferably carbon atoms 2 to 10, more preferably 2 to 5), and a divalent aliphatic hydrocarbon group such as an alkynylene group (preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms), and a divalent aromatic hydrocarbon ring such as an arylene group.
• divalent hydrocarbon groups for example, alkylene groups (preferably carbon atoms 1 to 10, more preferably 1 to 5), alkenylene groups (preferably carbon atoms 2 to 10, more preferably 2 to 5), and a divalent aliphatic hydrocarbon group such as an alkynylene group (preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms), and a divalent aromatic hydrocarbon ring such as an arylene group.
• q represents a hydrogen atom or an alkyl group.
• Examples of the trivalent linking group include a residue formed by removing three hydrogen atoms from a hydrocarbon, a group represented by -N ⁇ , and a group formed by removing three hydrogen atoms from a heterocyclic compound. and a group combining the above-mentioned residue and the above-mentioned divalent linking group.
• Examples of the tetravalent linking group include a residue formed by removing four hydrogen atoms from a hydrocarbon, a residue formed by removing four hydrogen atoms from a heterocyclic compound, and the above-mentioned residues. and the above-mentioned divalent linking group.
• q represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.
• Examples of the substituent not having a hydrophilic group represented by R a2 include an alkyl group, an aryl group, and a heteroaryl group.
• r a1 represents an integer of 1 or more, preferably an integer of 1 to 12, more preferably an integer of 1 to 4.
• s a1 represents an integer of 0 or more, preferably an integer of 0 to 4, and more preferably 0.
• naphthalocyanine dye a compound represented by the following formula (1B-1) is preferred.
• R a3 and R a4 each independently represent a substituent.
• substituent W examples include groups exemplified by the substituent W described below. It is preferable that R a3 represents a specific substituent, and R a4 represents a substituent that does not contain a hydrophilic group.
• the hydrophilic group that the specific substituent has is as described above.
• the specific substituent represented by R a3 has the same meaning as the specific substituent represented by R a1 .
• the substituent not containing a hydrophilic group represented by R a4 has the same meaning as the substituent not containing a hydrophilic group represented by R a2 .
• r a2 represents an integer of 1 or more, preferably an integer of 1 to 12, more preferably an integer of 1 to 4.
• s a2 represents an integer of 0 or more, preferably an integer of 0 to 4, and more preferably 0.
• the following Compound Example 1 is preferred.
• p and k each independently represent an integer of 0 to 12, and the sum of p and k is an integer of 1 to 12. Among these, it is preferable that p is an integer of 1 to 4 and k is 0.
• Quinone dyes are dyes that have broad absorption. It is preferable that the quinone dye has a structure represented by formula (2).
• R b represents a hydrogen atom or a substituent.
• the substituent represented by R b include groups exemplified by the substituent W described below.
• Ar 1 and Ar 2 each independently represent an aromatic ring or a heterocycle, and a heterocycle is more preferable from the viewpoint of increasing the absorption wavelength.
• quinone dyes having a hydrophilic group include indanthrone dyes described in Japanese Patent Publication No. 2006-508034.
• R b1 each independently represents a substituent.
• substituent W examples include groups exemplified by the substituent W described below, and preferred are specific substituents, such as a group represented by formula (Z), where q in formula (Z) is 1 and Certain substituents are more preferred.
• r b1 represents an integer of 1 to 12, preferably an integer of 1 to 4.
• n an integer from 1 to 12
• each sulfonic acid may be in free form or salt form, or may contain both free form and salt form in any proportion. You can stay there.
• Cyanine dyes are dyes that have strong absorption in the infrared region.
• a compound represented by formula (3) or a compound represented by formula (4) is preferable.
• Ar 3 to Ar 4 each independently represent a heterocyclic group which may have a substituent, and R c1 represents a hydrogen atom or a substituent. At least one of Ar 3 and Ar 4 preferably represents a heterocyclic group having a specific substituent.
• heterocycle constituting the heterocyclic group examples include an indolenine ring, a benzindolenine ring, an imidazole ring, a benzimidazole ring, a naphthoimidazole ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a thiazoline ring, an oxazole ring, Examples include a benzoxazole ring, a naphthoxazole ring, an oxazoline ring, a selenazole ring, a benzoselenazole ring, a naphthoselenazole ring, and a quinoline ring, and an indolenine ring, a benzindolenine ring, a benzothiazole ring, or a naphthothiazole ring. is preferred.
• the specific substituent may be substituted on
• r c1 represents an integer of 1 to 7, preferably an integer of 3 to 5.
• the type of substituent represented by R c1 is not particularly limited, and includes known substituents, such as an alkyl group that may have a substituent, an aryl group that may have a substituent, or A heteroaryl group which may have a substituent is preferred.
• substituents that an alkyl group, an aryl group, and a heteroaryl group may have include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, and an aromatic heterocyclic oxy group.
• acyl group alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, aromatic heterocyclic thio group, ureido group, a halogen atom, a cyano group, a nitro group, a heterocyclic group (for example, a heteroaryl group), a silyl group, and a group combining these (hereinafter, these groups are also collectively referred to as "substituent W"). ) etc. Note that the above substituent may be further substituted with a substituent W.
• Ar 5 to Ar 6 each independently represent a heterocyclic group which may have a substituent
• Ar 7 represents a cyclic skeleton having 5 to 7 carbon atoms
• W is Hydrogen atom, halogen atom, methyl group, phenyl group optionally having a substituent, benzyl group optionally having a substituent, pyridyl group, morpholyl group, piperidyl group, pyrrolidyl group, optionally having a substituent represents a phenylamino group, a phenoxy group that may have a substituent, an alkylthio group that may have a substituent, or a phenylthio group that may have a substituent.
• At least one of Ar 5 and Ar 6 preferably represents a heterocyclic group having a specific substituent.
• the heterocycle constituting the heterocyclic group include an indolenine ring, a benzindolenine ring, an imidazole ring, a benzimidazole ring, a naphthoimidazole ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a thiazoline ring, an oxazole ring, Examples include a benzoxazole ring, a naphthoxazole ring, an oxazoline ring, a selenazole ring, a benzoselenazole ring, a naphthoselenazole ring, and a quinoline ring, and an indolenine ring, a benzindolenine ring, a benzothiazole ring, or
• Examples of the phenyl group, benzyl group, phenylamino group, phenoxy group, alkylthio group, and the substituent that the phenylthio group represented by W include the groups exemplified by the above-mentioned substituent W, and hydrophilic groups. and specific substituents.
• the number of carbon atoms in the alkylthio group represented by W is not particularly limited, but is preferably from 1 to 5, more preferably from 1 to 3.
• the compound represented by formula (4) is preferably an inner salt type having a cation and an anion in one molecule, or an intermolecular salt type.
• examples include organic salts such as chlorate, antimony fluoride, phosphorus fluoride, boron fluoride, trifluoromethanesulfonate, bis(trifluoromethane)sulfonic acid imide salt, and naphthalenesulfonic acid.
• organic salts such as chlorate, antimony fluoride, phosphorus fluoride, boron fluoride, trifluoromethanesulfonate, bis(trifluoromethane)sulfonic acid imide salt, and naphthalenesulfonic acid.
• Specific examples include indocyanine green and water-soluble dyes described in JP-A No. 63-033477.
• the compound represented by formula (4) is preferably a compound represented by formula (4-1).
• R c2 to R c5 each independently represent a hydrogen atom or a substituent. At least one of R c2 to R c5 is a substituent having -SO 3 - (for example, an alkyl group having -SO 3 - . The number of carbon atoms in the alkyl group is preferably 1 to 10), -COO - (For example, an alkyl group having -COO - . The alkyl group preferably has 1 to 10 carbon atoms.), -SO 3 - or -COO - . R c each independently represents a hydrogen atom or a substituent.
• R c examples include the groups exemplified by the substituent W, with an alkyl group being preferred.
• the number of carbon atoms in the alkyl group is preferably 1 to 5.
• Ar c1 and Ar c2 each independently represent an aromatic hydrocarbon ring (for example, a benzene ring and a naphthalene ring),
• Ar 7 represents a cyclic skeleton having 5 to 7 carbon atoms
• W represents a hydrogen atom, a halogen Atom, methyl group, phenyl group that may have a substituent, benzyl group that may have a substituent, pyridyl group, morpholyl group, piperidyl group, pyrrolidyl group, phenylamino group that may have a substituent , represents a phenoxy group that may have a substituent, an alkylthio group that may have a substituent, or a phenylthio group that may have a substituent,
• R c2 to R c5 represent an integer from 1 to 3.
• substituents represented by R c2 to R c5 include groups exemplified by substituent W and specific substituents.
• the phenyl group, benzyl group, phenylamino group, phenoxy group, alkylthio group, and the substituent that the phenylthio group represented by W may include the groups exemplified by the substituent W, and specific substituents. Examples include groups.
• Examples of the compound represented by formula (3) and the compound represented by formula (4) include Compound Examples 3 to 6.
• Squarylium pigments are pigments that have square acid as their central skeleton.
• a compound represented by formula (5) is preferable.
• Ar 8 and Ar 9 each independently represent a heterocyclic group which may have a specific substituent.
• Ar 8 and Ar 9 the above-mentioned heterocycle represented by Ar 6 is preferable.
• the compound represented by formula (5) also takes the form of an inner salt or an intermolecular salt, and takes the form of a salt similar to that of cyanine dyes.
• squarylium dye a compound represented by formula (5-1) or a compound represented by formula (5-2) is preferable.
• Ar e1 represents a heterocyclic group which may have a specific substituent.
• Ar e2 may have a specific substituent and represents a heterocyclic group containing N + .
• At least one of the heterocyclic group represented by Ar e1 and the heterocyclic group represented by Ar e2 preferably has a specific substituent.
• Ar e3 represents a heterocyclic group which may have a specific substituent.
• Ar e4 may have a specific substituent and represents a heterocyclic group containing N + .
• At least one of the heterocyclic group represented by Ar e3 and the heterocyclic group represented by Ar e4 preferably has a specific substituent.
• Azo dyes are dyes that absorb visible light, and are mainly used in water-soluble inks, but dyes that can absorb into the infrared region by broadening their absorption range are commercially available.
• the azo dye for example, C.I. I. Acid Black 2 (manufactured by Orient Chemical Industry Co., Ltd.), C.I. I. Direct Black 19 (manufactured by Aldrich Industries) is mentioned.
• the azo dye can also form a complex with a metal atom. Examples of the complex containing an azo dye include a compound represented by formula (6).
• M 2 represents a metal atom, such as cobalt and nickel.
• a 1 and B 1 each independently represent an aromatic ring which may have a specific substituent. At least one of A 1 and B 1 preferably represents an aromatic ring having a specific substituent. Examples of the aromatic ring include a benzene ring and a naphthalene ring.
• X + represents a cation. Cations include H + , alkali metal cations, and ammonium cations. Examples of complexes containing azo dyes include the dyes described in JP-A-59-011385.
• Examples of the metal complex dye include a compound represented by formula (7) and a compound represented by formula (8).
• M 3 represents a metal atom.
• R g1 to R g2 each independently represent a hydrogen atom or a substituent.
• X 1 to X 2 each independently represent an oxygen atom, a sulfur atom, or -NR g3 -.
• R g3 represents a hydrogen atom, an alkyl group, or an aryl group. At least one of R g1 to R g2 preferably represents a specific substituent.
• Examples of the metal atom represented by M 3 include Pd, Ni, Co, and Cu, with Ni being preferred.
• the types of substituents represented by R g1 to R g2 are not particularly limited, and include the groups exemplified for the above-mentioned substituent W and specific substituents.
• M 4 represents a metal atom
• R h1 to R h2 each independently represent a hydrogen atom or a substituent
• X 3 to X 4 each independently represent an oxygen atom or a sulfur atom.
• R h3 represents a hydrogen atom, an alkyl group, or an aryl group.
• At least one of R h1 to R h2 preferably represents a specific substituent.
• Examples of the metal atom represented by M 4 include Pd, Ni, Co, and Cu, with Ni being preferred.
• the types of substituents represented by R h1 to R h2 are not particularly limited, and include the groups exemplified for the above-mentioned substituent W and specific substituents.
• Examples of the boron complex dye include a compound represented by formula (9).
• R i1 to R i2 each independently represent a hydrogen atom, an alkyl group, or a phenyl group
• R i3 each independently represents an electron-withdrawing group
• Ar 10 is Each independently represents an aryl group that may have a substituent
• at least one of the two Ar 10 represents an aryl group that has a substituent
• each Ar 11 independently represents an aryl group that may have a substituent.
• Y represents a sulfur atom or an oxygen atom.
• the electron-withdrawing group represented by R i3 is not particularly limited, and represents a substituent with a positive Hammett's ⁇ p value (sigma para value), such as a cyano group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group. , a sulfamoyl group, a sulfinyl group, and a heterocyclic group. These electron-withdrawing groups may be further substituted.
• Hammett's substituent constant ⁇ value will be explained. Hammett's rule was developed by L. Hammett in 1935 to quantitatively discuss the influence of substituents on the reaction or equilibrium of benzene derivatives. P.
• the electron-withdrawing group is preferably a substituent having a Hammett's substituent constant ⁇ p value of 0.20 or more.
• the ⁇ p value is preferably 0.25 or more, more preferably 0.30 or more, and even more preferably 0.35 or more.
• the upper limit is not particularly limited, but is preferably 0.80 or less.
• cyano group (0.66), carboxyl group (-COOH: 0.45), alkoxycarbonyl group (-COOMe: 0.45), aryloxycarbonyl group (-COOPh: 0.44), carbamoyl group (-CONH 2 : 0.36), alkylcarbonyl group (-COMe: 0.50), arylcarbonyl group (-COPh: 0.43), alkylsulfonyl group (-SO 2 Me: 0.72), and , an arylsulfonyl group (-SO 2 Ph: 0.68).
• the aryl group which may have a substituent represented by Ar 10 is preferably a phenyl group which may have a substituent.
• the aromatic hydrocarbon ring in the aromatic hydrocarbon ring which may have a substituent represented by Ar 11 is preferably a benzene ring or a naphthalene ring.
• substituents that the aromatic hydrocarbon ring and aromatic heterocycle represented by Ar 11 may have include the groups exemplified for the substituent W mentioned above and specific substituents.
• the diimonium dye is a dye that has absorption on the relatively long wavelength side (wavelength range of 950 to 1100 nm) even in the near-infrared region, and a compound represented by formula (10) is preferable.
• R j1 to R j8 each independently represent an alkyl group that may have a substituent or an aromatic ring group that may have a substituent. At least one of R j1 to R j8 preferably represents an alkyl group having a specific substituent or an aromatic ring group having a specific substituent.
• Q - represents an anion, such as a halide ion, perchlorate ion, antimony fluoride ion, phosphorus fluoride ion, boron fluoride ion, trifluoromethanesulfonate ion, bis(trifluoromethane)sulfonic acid imide ion, and naphthalene. Examples include sulfonic acid ions.
• oxonol dye a compound represented by formula (11) is preferable.
• Y 1 and Y 2 each independently represent a group of nonmetallic atoms forming an aliphatic ring or a heterocycle, and M + is a proton, a monovalent alkali metal cation, or Represents an organic cation, L1 represents a methine chain consisting of 5 or 7 methine groups, and the methine group at the center of the methine chain has a substituent represented by the following formula A, *-S A -T A formula (A)
• S A represents a single bond or an alkylene group
• T A represents an alkyl group
• the total number of carbon atoms contained in S A and T A is 3 or more
• * indicates the methine group at the center of the methine chain. represents the binding site with.
• a compound represented by formula (12) is more preferable.
• M + and L 1 are the same as M + and L 1 in formula (11).
• R m1 , R m2 , R m3 and R m4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and X each independently represents an oxygen atom, a sulfur atom, or a selenium atom. represents an atom.
• oxonol dye a compound represented by formula (13) is more preferable.
• M + , L 1 and X are the same as M + , L 1 and X in formula (11).
• R n1 and R n3 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R n2 and R n4 each independently represent an alkyl group, a halogen atom, or an alkenyl group.
• a compound represented by formula (14), a compound represented by formula (15), or a compound represented by formula (16) is preferable.
• Y o1 and Y o2 are each independently an oxygen atom or -NR w1 -, R w1 represents a hydrogen atom or a substituent, and Z o1 to Z o4 are each independently, represents an oxygen atom or -NR W2 -, R w2 represents a hydrogen atom or a substituent, R o1 to R o8 each independently represent a hydrogen atom or a substituent, and R o1 to R o8 and R z At least one represents a specific substituent. Note that R W1 and R W2 may be bonded to each other to form a ring that may have a substituent.
• Y p1 and Y p2 are each independently an oxygen atom or -NR w3 -, R w3 represents a hydrogen atom or a substituent, and Z p1 to Z p4 are each independently, represents an oxygen atom or -NR W4 -, R w4 represents a hydrogen atom or a substituent, R p1 to R p12 each independently represent a hydrogen atom or a substituent, R p1 to R p12 and R z At least one represents a specific substituent.
• R W3 and R W4 may be bonded to each other to form a ring that may have a substituent.
• the substituents may be bonded to each other to form a ring (for example, an aromatic ring).
• Y q1 and Y q2 are each independently an oxygen atom or -NR w5 -, R w5 represents a hydrogen atom or a substituent, and Z q1 to Z q4 are each independently, represents an oxygen atom or -NR W6 -, R w6 represents a hydrogen atom or a substituent, R q1 to R q16 each independently represent a hydrogen atom or a substituent, R q1 to R q16 and R z At least one represents a specific substituent.
• R W5 and R W6 may be bonded to each other to form a ring that may have a substituent. When the ring to be formed has two or more substituents, the substituents may be bonded to each other to form a ring (for example, an aromatic ring).
• the content of the specific aggregate is not particularly limited, and is preferably 1 to 30% by mass, more preferably 3 to 15% by mass, based on the total mass of the optically anisotropic film.
• the optically anisotropic film may contain salt.
• a plate-like compound has an acid group or a salt thereof, if the salt is included in the optically anisotropic film, the planes in the plate-like compound are more likely to associate with each other, forming a column-shaped aggregate.
• Cheap does not include the above-mentioned organic compound, specific aggregate, or above-mentioned liquid crystal compound. That is, the salt is a compound different from the organic compound, the specific aggregate, and the liquid crystal compound.
• the salt is not particularly limited, and may be either an inorganic salt or an organic salt, and inorganic salts are preferred since they provide better orientation of specific aggregates in the optically anisotropic film.
• inorganic salts include alkali metal salts, alkaline earth metal salts, and transition metal salts, and alkali metal salts are preferable because they provide better orientation of specific aggregates in the optically anisotropic film.
• An alkali metal salt is a salt whose cation is an alkali metal ion, and the alkali metal ion is preferably a lithium ion or a sodium ion, and more preferably a lithium ion.
• the salt is preferably a lithium salt or a sodium salt, and more preferably a lithium salt.
• alkali metal salts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; lithium hydrogen carbonate, and hydrogen carbonate.
• alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate.
• alkali metal salts include phosphates and chlorides.
• Examples of the anions of the above salts include hydroxide ion, carbonate ion, chloride ion, sulfate ion, nitrate ion, phosphate ion, borate ion, tetrafluoroborate ion, hexafluorophosphate ion, and perchlorate ion.
• the cation in the salt of the acid group and the cation in the salt used above are preferably of the same type.
• the optically anisotropic film has no absorption in the visible light region.
• the average transmittance in the wavelength range of 400 to 700 nm is 90% or more, preferably 95% or more.
• the upper limit may be less than 100%.
• the average transmittance can be measured, for example, in the same manner as the average transmittance of a liquid crystal compound.
• the optically anisotropic film preferably has absorption in the infrared region.
• the optically anisotropic film preferably has a maximum absorption wavelength in a wavelength range of 700 to 2500 nm. Since the optically anisotropic film has a maximum absorption wavelength in the above range, it can absorb near-infrared rays in the wavelength range of 700 to 2,500 nm. Note that, as described above, the maximum absorption wavelength of the optically anisotropic film preferably corresponds to the maximum absorption wavelength of a specific aggregate contained in the optically anisotropic film.
• the angle between the slow axis of the optically anisotropic film at a wavelength of 550 nm and the direction of maximum absorption at the maximum absorption wavelength in the infrared region of the optically anisotropic film is 0 to 10° or 80 to 100°. is preferred, and more preferably 0 to 5° or 85 to 95°.
• the angle formed above can be measured by the following method.
• the slow axis of the optically anisotropic film at a wavelength of 550 nm can be measured using AxoScan manufactured by Axometrics.
• the direction in which the optically anisotropic film has the highest absorption at the maximum absorption wavelength in the infrared region is determined by ultraviolet-visible near-infrared spectrophotometry using an automatic absolute reflectance measuring unit ARMN-735 manufactured by JASCO Corporation (JASCO).
• ARMN-735 manufactured by JASCO Corporation
• V-660 instrument the absorption spectrum was measured while rotating the sample in 5° increments, and the absorbance was measured in the direction in which the absorbance was greatest. The angle between the slow axis and the direction in which the absorbance is greatest can be determined.
• the optically anisotropic film preferably has an absorption axis in the in-plane direction at the maximum absorption wavelength in the infrared region of the optically anisotropic film. Such an embodiment can be achieved by orienting specific aggregates having absorption corresponding to the maximum absorption wavelength.
• the degree of orientation of the optically anisotropic film is not particularly limited, but in terms of better absorption properties of the optically anisotropic film, it is preferably 0.60 or more, preferably 0.80 or more, and even more preferably 0.90 or more. .
• the upper limit is not particularly limited, but may be 1.00 or less.
• the degree of orientation is the degree of orientation measured by the maximum absorption wavelength in the infrared region of the optically anisotropic film, and corresponds to the degree of orientation measured by the maximum absorption wavelength of the specific aggregate.
• the maximum absorption wavelength derived from the J-aggregate of the specific aggregate is used to correspond to the degree of orientation. Specifically, it is calculated using the following method.
• the absorbance of the optically anisotropic film was measured using an ultraviolet-visible near-infrared spectrophotometer V-660 equipped with an automatic absolute reflectance measurement unit ARMN-735 manufactured by JASCO Corporation. This is the calculated value.
• the polarized light used is the polarized light having the maximum absorption wavelength in the infrared region of the optically anisotropic film.
• Orientation degree: S [(Az0/Ay0)-1]/[(Az0/Ay0)+2] Az0: Absorbance of the optically anisotropic film for polarized light in the absorption axis direction
• Ay0 Absorbance of the optically anisotropic film for polarized light in the transmission axis direction
• the dichroic ratio of the optically anisotropic film is preferably 0 or more, more preferably 10 or more, and even more preferably 30 or more.
• the upper limit may be 100 or less.
• the thickness of the optically anisotropic film is preferably 10 ⁇ m or less, more preferably 0.5 to 8.0 ⁇ m, and even more preferably 0.5 to 6.0 ⁇ m.
• the film thickness of the optically anisotropic film was obtained by measuring the film at 10 arbitrary points of the optically anisotropic film using Nikon Corporation's ultra-high resolution non-contact measurement system and surface profile measurement system BW-A501. This is the average value obtained by taking the arithmetic mean of the calculated values.
• the method for producing the optically anisotropic film of the present invention is not particularly limited, and for example, the optically anisotropic film may be produced by applying a composition containing the above-mentioned components and orienting the liquid crystalline compound and specific aggregates in the coating film.
• a method including a step of forming a sexual film is preferred. Below, the steps of the above method will be explained in detail.
• composition used in the above method includes a liquid crystal compound and an organic compound or specific aggregate.
• the content of each component is adjusted to match the content of each component in the optically anisotropic film described above.
• the composition may also include a solvent.
• the type of solvent is not particularly limited, but an aqueous medium is preferred.
• the aqueous medium is water or a mixture of water and a water-soluble organic solvent.
• a water-soluble organic solvent is a solvent having a solubility in water of 5% by mass or more at 20°C. Examples of water-soluble organic solvents include alcohol compounds, ketone compounds, ether compounds, amide compounds, nitrile compounds, and sulfone compounds.
• the solid content concentration of the composition is not particularly limited, but it is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, based on the total mass of the composition, in order to obtain better effects of the present invention.
• the content of the liquid crystal compound in the composition is not particularly limited, but is preferably 60 to 99% by mass, more preferably 80 to 97% by mass, based on the total solid content in the composition.
• the content of the organic compound or specific aggregate in the composition is not particularly limited, but is preferably 2 to 20% by mass, more preferably 5 to 10% by mass, based on the total solid content in the composition.
• the total solid content means components that can form an optically anisotropic film, excluding the solvent. Note that even if the above components are in liquid form, they are calculated as solid content.
• the method of applying the composition is not particularly limited, and the composition is usually applied onto a support in many cases.
• the support used is a member that functions as a base material for applying the composition.
• the support may be a so-called temporary support.
• Examples of the support (temporary support) include a plastic substrate or a glass substrate.
• Examples of materials constituting the plastic substrate include polyester resins such as polyethylene terephthalate, polycarbonate resins, (meth)acrylic resins, epoxy resins, polyurethane resins, polyamide resins, polyolefin resins, cellulose resins, silicone resins, and polyvinyl alcohol.
• the thickness of the support may be 5 to 1000 ⁇ m, preferably 10 to 250 ⁇ m, and more preferably 15 to 90 ⁇ m.
• the alignment film generally has a polymer as its main component. Polymers for alignment films are described in many documents, and many commercially available products are available. As the polymer for alignment film, polyvinyl alcohol, polyimide or its derivative, azo derivative or cinnamoyl derivative is preferable. Note that the alignment film is preferably subjected to a known rubbing treatment. Furthermore, a photo-alignment film may be used as the alignment film. The thickness of the alignment film is preferably 0.01 to 10 ⁇ m, more preferably 0.01 to 1 ⁇ m.
• the coating method examples include known methods, such as curtain coating, extrusion coating, roll coating, dip coating, spin coating, print coating, spray coating, and slide coating.
• a coating method that applies shear to the composition such as wire bar coating
• two treatments, coating and orientation of various compounds can be performed simultaneously. That is, by subjecting the composition to shearing treatment, the liquid crystal compound and the specific aggregate can be oriented. Further, by continuous coating, the liquid crystal compound may be continuously aligned at the same time as the coating. Continuous coating includes curtain coating, extrusion coating, roll coating, and slide coating.
• the method for orienting each compound in the applied composition is not particularly limited, and any known method may be employed.
• a method of applying shearing may be used as described above.
• another method for aligning each compound in the applied composition includes a method using an alignment film, as described above.
• the alignment direction can be controlled.
• a method using an alignment film is preferable.
• the concentration of the solvent in the composition used is not particularly limited, and the concentration of the solvent may be such that the composition exhibits lyotropic liquid crystallinity, or the concentration may be lower than that. Good too.
• composition is a lyotropic liquid crystal composition
• concentration of the solvent in the composition is high (when the composition itself exhibits an isotropic phase)
• exhibiting lyotropic liquid crystallinity alignment of each compound is induced on the alignment film, making it possible to form an optically anisotropic film.
• composition contains a thermotropic liquid crystal compound
• a method of heat-treating the formed composition layer may be mentioned.
• the method for manufacturing an optically anisotropic film of the present invention may include steps other than the above steps. As another step, it is preferable to further include a step of fixing the liquid crystal compound.
• the method of fixing the alignment state of the liquid crystalline compound is not particularly limited, and examples include a method of heating the coating film as described above and then cooling it.
• a method for fixing the alignment state of the liquid crystal compound is to use optical anisotropy formed with a solution containing polyvalent metal ions. Examples include a method of contacting with a membrane. When a solution containing polyvalent metal ions is brought into contact with the formed optically anisotropic film, the polyvalent metal ions are supplied into the optically anisotropic film.
• the polyvalent metal ions supplied into the optically anisotropic film serve as crosslinking points between the acid groups or their salts possessed by the liquid crystalline compound, forming a crosslinked structure in the optically anisotropic film, which improves the orientation of the liquid crystalline compound.
• the state is fixed.
• the type of polyvalent metal ion used is not particularly limited, and alkaline earth metal ions are preferred, and calcium ions are more preferred, since the orientation state of the liquid crystal compound and/or specific aggregate is easily fixed.
• an unstretched film containing a specific aggregate and a polymer is formed, and the obtained unstretched film is stretched and oriented to obtain a stretched film.
• Examples include a method of forming an optically anisotropic film.
• a method for forming an unstretched film is to apply a composition containing a specific aggregate or an organic compound capable of forming the aggregate, a polymer, and a solvent, and then remove the solvent to form an unstretched film.
• the stretching method include known methods such as longitudinal uniaxial stretching, transverse uniaxial stretching, simultaneous biaxial stretching or sequential biaxial stretching which is a combination thereof.
• the specific aggregate or the organic compound capable of forming the aggregate used in producing the stretched film is as described above.
• Examples of the polymer used in producing the stretched film include the polymers mentioned above.
• the optically anisotropic film of the present invention is applicable to various uses.
• the optically anisotropic film of the present invention can be used as a retardation film.
• it can be used as an infrared retardation film that can absorb any wavelength in the wavelength range of 700 to 2,500 nm.
• the optically anisotropic film of the present invention may be used in combination with other members.
• a protective film may be placed on one or both sides of the optically anisotropic film of the present invention.
• the protective film When disposing the protective film, it may be disposed via an adhesive or a pressure-sensitive adhesive.
• the protective film include triacetylcellulose film, acrylic film, polycarbonate film, and cycloolefin film.
• the protective film it is preferable to use a film that is transparent, has little birefringence, and is less likely to cause retardation.
• the optically anisotropic film of the present invention may be combined with other layers such as a hard coat layer, an antiglare layer, and an antireflection layer. These other layers may be placed via an adhesive or adhesive.
• the optically anisotropic film of the present invention can also be used by being attached to an inorganic substrate such as a prism or glass, or a plastic plate.
• an inorganic substrate such as a prism or glass, or a plastic plate.
• the inorganic substrate and the plastic substrate have a curved surface, it is also possible to form a curved surface by laminating the optically anisotropic film of the present invention in accordance with the curved surface.
• the optically anisotropic film of the present invention may be combined with various functional layers for improving viewing angles, various functional layers for improving contrast, and layers having brightness improving properties.
• various functional layers mentioned above include a layer that controls retardation.
• the optically anisotropic film of the present invention combined with such various functional layers can be applied to various display devices such as liquid crystal display devices.
• the optically anisotropic film of the present invention can be used for liquid crystal projectors, calculators, watches, notebook computers, word processors, liquid crystal televisions, polarized lenses, polarized glasses, car navigation systems, sensors, lenses, switching elements, isolators, cameras, It is also applicable to indoor and outdoor measuring instruments and display devices for cars, etc.
• the optically anisotropic film of the present invention is suitably applied to display devices. That is, the present invention also relates to a display device including the optically anisotropic film of the present invention.
• the optically anisotropic film of the present invention is suitably applied to cameras (particularly polarized multispectral cameras) and sensors.
• the optically anisotropic film of the present invention may be combined with an infrared light source. That is, the present invention also relates to a device including the optically anisotropic film of the present invention and an infrared light source. Examples of such devices include distance measuring devices such as LIDAR (Light Detection and Ranging).
• Compounds A1 to A5 were synthesized by known methods.
• Compounds A1 to A5 are all dichroic dyes.
• Compound A3 is D-1 described in WO2020/175448.
• Liquid crystalline compounds B1 and B2 both exhibited lyotropic liquid crystallinity, and liquid crystalline compounds B3 to B5 all exhibited thermotropic liquid crystallinity. Furthermore, none of the liquid crystal compounds B1 to B5 had absorption in the visible light region.
• Liquid crystal compound B1 was a liquid crystal polymer (in the formula, n is 2 or more), and had a number average molecular weight: 25,000 and a molecular weight distribution: 5.1.
• Liquid crystalline compound B3 had a number average molecular weight of 9,000 and a molecular weight distribution of 1.9.
• Composition 1 having the following composition was prepared. ⁇ Composition 1 ⁇ ⁇ Liquid crystal compound (plate compound) B1 10 parts by mass ⁇ Organic compound (dichroic dye) A1 0.5 part by mass ⁇ Water 89.5 parts by mass ⁇ ⁇
• composition 1 prepared above was applied onto a glass substrate as a base material using a wire bar (travel speed: 100 cm/s) and air-dried. Next, the obtained composition layer was immersed in a 1 mol/L calcium chloride aqueous solution for 5 seconds, washed with ion-exchanged water, and dried with air to fix the orientation state, resulting in a film thickness of 1.2 ⁇ m. Optically anisotropic film 1 was produced. The film thickness was measured using the ultra-high resolution non-contact measurement system BW-A501 manufactured by Nikon Corporation in the manner described above.
• Example 2 and Comparative Example 2 Optically anisotropic films 2 and 6 having a film thickness of 1.2 ⁇ m were prepared in the same manner as in Example 1, except that the compounds shown in Table 1 below were used.
• Example 3> (Preparation of transparent support) -Preparation of core layer cellulose acylate dope- The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution to be used as a core layer cellulose acylate dope.
• Core layer cellulose acylate dope ⁇ - 100 parts by mass of cellulose acetate with a degree of acetyl substitution of 2.88 - 12 parts by mass of polyester compound B described in the examples of JP-A-2015-227955 - 2 parts by mass of compound F - 430 parts by mass of methylene chloride (first solvent) parts methanol (second solvent) 64 parts by mass ⁇
• outer layer cellulose acylate dope 10 parts by mass of the following matting agent solution was added to 90 parts by mass of the core layer cellulose acylate dope to prepare a cellulose acetate solution to be used as the outer layer cellulose acylate dope.
• Matting agent solution - 2 parts by mass of silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) - 76 parts by mass of methylene chloride (first solvent) - 11 parts by mass of methanol (second solvent) -
• the above core layer cellulose ash Rate dope 1 part by mass ⁇
• cellulose acylate film 1- After filtering the core layer cellulose acylate dope and the outer layer cellulose acylate dope through a filter paper with an average pore size of 34 ⁇ m and a sintered metal filter with an average pore size of 10 ⁇ m, the core layer cellulose acylate dope and the outer layer cellulose acylate dope are placed on both sides of the core layer cellulose acylate dope. Three layers of the above were simultaneously cast from a casting port onto a drum at 20°C (band casting machine).
• the film was peeled off with a solvent content of approximately 20% by mass, and both ends of the film in the width direction were fixed with tenter clips, and the film was dried while being stretched in the transverse direction at a stretching ratio of 1.1 times. Thereafter, the film was further dried by being conveyed between rolls of a heat treatment device to produce an optical film (transparent support) having a thickness of 40 ⁇ m, which was designated as cellulose acylate film 1.
• the in-plane retardation (wavelength: 550 nm) of the obtained cellulose acylate film 1 was 0 nm.
• a coating liquid PA1 for forming a photo-alignment film was continuously applied onto the cellulose acylate film 1 using a wire bar.
• the support on which the coating film has been formed is dried with hot air at 140°C for 120 seconds, and then the coating film is irradiated with polarized ultraviolet light (10 mJ/cm 2 , using an ultra-high pressure mercury lamp) to form a photo-alignment film.
• PA1 was formed to obtain a TAC (triacetyl cellulose) film with a photo-alignment film.
• the film thickness of the photo-alignment film PA1 was 0.5 ⁇ m.
• composition for forming optically anisotropic film ⁇ ⁇ Organic compound (dichroic dye) A2 0.38 parts by mass ⁇ Liquid crystal compound B3 2.67 parts by mass ⁇ Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.17 parts by mass ⁇ Surfactant F-1 below 0.020 parts by mass ⁇ Cyclopentanone 91.95 parts by mass ⁇ Benzyl alcohol 2.36 parts by mass------ ⁇
• Coating liquid B1 having the following composition was continuously applied onto the optically anisotropic film 3 using a wire bar. Thereafter, it was dried with warm air at 80° C. for 5 minutes and irradiated with ultraviolet light (300 mJ/cm 2 , using an ultra-high pressure mercury lamp) to form an oxygen barrier layer B1 made of polyvinyl alcohol (PVA) with a thickness of 1.0 ⁇ m.
• a laminate A was obtained, that is, a laminate including a cellulose acylate film 1 (transparent support), a photoalignment film PA1, an optically anisotropic film 3, and an oxygen barrier layer B1 adjacent to each other in this order.
• Example 4 A laminate including an optically anisotropic film 4 was produced according to the same procedure as in Example 3, except that organic compound (dichroic dye) A2 was changed to organic compound (dichroic dye) A3.
• the above coating solution was spin-coated onto a glass substrate with a polyimide alignment layer (SE-130, manufactured by Nissan Chemical Industries, Ltd.) that had been subjected to a rubbing process to form a coating film, heated at 210°C for 1 minute, and then heated to 100°C. It was rapidly cooled. After that, the atmosphere was purged with nitrogen so that the oxygen concentration was 1.0% by volume or less, and the coating film was irradiated with ultraviolet rays at an irradiation dose of 500 mJ/cm 2 using a high-pressure mercury lamp to produce an optically anisotropic film 5. did.
• a polyimide alignment layer SE-130, manufactured by Nissan Chemical Industries, Ltd.
• a 4% by mass aqueous solution of PVA103 (manufactured by Kuraray Co., Ltd.) was spin-coated on the optically anisotropic film 5 prepared above, and heated at 100°C for 2 minutes to form a thick layer on the optically anisotropic film 5.
• a PVA (polyvinyl alcohol) layer with a thickness of 1.0 ⁇ m was formed to obtain a laminate having the optically anisotropic film 5 and the PVA layer. Note that the oxygen permeability of the PVA layer was 10 mL/m 2 ⁇ day ⁇ atm or less.
• VF-PS polyvinyl alcohol film
• a swelling treatment was applied to give a stretching ratio of 1.30 times.
• aqueous solution containing 20 g/L of boric acid (manufactured by Societa Chimica Larderellos.pa.).
• the film after immersion was stretched for 5 minutes in a 50° C. aqueous solution containing 30.0 g/L of boric acid while being stretched 5.0 times.
• the obtained film was washed by immersing it in water at 25° C. for 20 seconds while maintaining its tension. The washed film was dried at 70° C. for 9 minutes.
• an alkali-treated triacetylcellulose film (TD-80U, manufactured by Fuji Film Co., Ltd.) was laminated using a 4% by mass solution of polyvinyl alcohol (NH-26, manufactured by Nippon Vinegar Vipoval Co., Ltd.) in water as an adhesive.
• An optically anisotropic film 7 provided with a protective film was obtained.
• All of the optically anisotropic films 1 to 4 had absorption in the infrared region.
• the dichroic ratio and degree of orientation were measured for each of the optically anisotropic films 1 to 7.
• the dichroic ratio and degree of orientation were measured using an ultraviolet-visible near-infrared spectrophotometer V-660 equipped with an automatic absolute reflectance measuring unit ARMN-735 manufactured by JASCO Corporation.
• the absorbance was measured and calculated using the following formula. Note that the polarized light used in the following measurements was polarized light having a maximum absorption wavelength in the wavelength range of 400 to 2500 nm for each optically anisotropic film.
• the maximum absorption wavelength also corresponds to the maximum absorption wavelength of the J aggregate of the specific aggregate in each optically anisotropic film.
• Ay0 Absorbance for polarized light in the transmission axis direction of the optically anisotropic film
• the absorption axis of the optically anisotropic film is the wavelength of the optically anisotropic film. This corresponds to the absorption axis of the maximum absorption wavelength in the range of 400 to 2500 nm.
• the angle (specific angle) between the slow axis of the optically anisotropic film at a wavelength of 550 nm and the direction of maximum absorption at the maximum absorption wavelength in the infrared region of the optically anisotropic film was measured by the following method.
• the slow axis of the optically anisotropic film at a wavelength of 550 nm was measured using AxoScan manufactured by Axometrics, and the direction in which the optically anisotropic film had the largest absorption at the maximum absorption wavelength in the infrared region was determined by JASCO Corporation (JASCO).
• an image was created by binarizing the brightness of the obtained SEM observation image of the surface of each optically anisotropic film using image processing software "ImageJ".
• imageJ image processing software
• those having an area equal to or larger than a circle with a diameter of 50 nm (1963 nm 2 ) were extracted as specific aggregates.
• to binarize the brightness of the surface SEM observation image create a brightness histogram of the SEM observed image, extract the brightness with the highest frequency in the created brightness histogram, and select a brightness that is 1.2 times the extracted brightness. was used as the threshold value.
• each extracted specific aggregate is approximated to an ellipse, and the length of the major axis of the approximated ellipse is the length of the major axis of the specific aggregate, and the length of the minor axis of the approximated ellipse is The short axis length of the specific aggregate was taken as D.
• the above measurement was performed at three locations in a 13.58 ⁇ m 2 area that did not overlap with each other, and the D, L, and ratio (L/D) of 5 specific aggregates were calculated at each location, and the calculated 15 L /D is arithmetic averaged to calculate the average value of the above ratio (average L/D), and the calculated 15 L are arithmetic averaged to calculate the average length L of the major axis, and the calculated 15 L/D are calculated.
• the average length D of the short axis was calculated by taking the arithmetic average of D.
• the organic compound to be measured (5 to 50 mg) is dissolved in a solution (e.g., water, methanol, dimethyl sulfoxide). ) (1000 mL), the absorption spectrum was measured using a spectrophotometer (UV-3100PC (manufactured by SHIMADZU), and the maximum absorption wavelength was read from the obtained absorption spectrum.
• a solution e.g., water, methanol, dimethyl sulfoxide.
• UV-3100PC manufactured by SHIMADZU
• optically anisotropic films 1 to 5 the maximum absorption wavelength (J band) was observed on the longer wavelength side than the maximum absorption wavelength (dye ⁇ max) of the dichroic dye used. It was also confirmed that the specific aggregates in optically anisotropic films 1 to 5 were J aggregates. Since the J band was not observed in the specific aggregate in the optically anisotropic film 6, it was an H association, and the specific aggregate was not included in the optically anisotropic film 7.
• Each of the optically anisotropic films had an absorption axis in the in-plane direction at the maximum absorption wavelength in the wavelength range of 400 to 2,500 nm.
• FIG. 1 shows the absorption spectrum of the optically anisotropic film of Example 1 when the waveform of the peak derived from the J aggregate was separated.
• the measured peaks can be separated into waveforms of peaks 1 to 5, with peak 1 corresponding to the absorption spectrum of the organic compound constituting the specific aggregate.
• the absorption peak derived from the J-aggregate is normalized so that the absorbance at the maximum absorption wavelength ( ⁇ max) in the infrared region is 1.0, the range where the absorbance is 0.05 or more is determined by a linear combination of Lorentz functions. I did the fitting.
• fitting was repeated by sequentially increasing the number of Lorentz functions used until the coefficient of determination R 2 became 0.98 or more.
• the number of Lorentz functions required for fitting was evaluated as follows. In the case of the following A evaluation, it corresponds to the fact that the absorption spectrum is composed of a plurality of peaks derived from the J aggregate.
• each sample was set in a xenon irradiator (SX75 manufactured by Suga Test Instruments Co., Ltd.) so that the surface of the optically anisotropic film opposite to the substrate was the irradiation surface.
• a 200 hour irradiation test was conducted using a 275 filter.
• the Re(550) of the optically anisotropic film before the test and the Re(550) of the optically anisotropic film after the test were measured, and the light resistance was evaluated based on the following criteria. The results are shown in Table 1 below. Note that Re(550) represents the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm.
• Amount of change (%) ⁇ (Re(550) before test - Re(550) after test)/Re(550) before test ⁇ 100
• the test conditions for heat and humidity durability were as follows: a test in which the product was left in an environment of 85° C. and 85% relative humidity for 500 hours. The degree of polarization of the optically anisotropic film before the test and the degree of polarization of the optically anisotropic film after the test were measured, and the wet heat durability was evaluated based on the following criteria. The results are shown in Table 1 below. Note that the amount of change during the following evaluation is calculated by the following formula.
• Amount of change (%) ⁇ (degree of polarization before test - degree of polarization after test) / degree of polarization before test ⁇ ⁇ 100
• C The degree of polarization before the test. The degree of polarization change is 60% or more after the test for The absorbance of the optically anisotropic film was measured using 660, and calculated using the following formula.
• the polarized light used in the measurement had a maximum absorption wavelength in the wavelength range of 400 to 2500 nm of the optically anisotropic film.
• This maximum absorption wavelength also corresponds to the maximum absorption wavelength of the J aggregate composed of dichroic dyes in each optically anisotropic film.
• Degree of polarization [Ty0-Tz0]/[Ty0+Tz0]
• Tz0 Transmittance of the optically anisotropic film to polarized light in the absorption axis direction
• Ty0 Transmittance of the optically anisotropic film to polarized light in the transmission axis direction
• the absorption axis of the optically anisotropic film is the optically anisotropic film. This corresponds to the absorption axis of the maximum absorption wavelength in the wavelength range of 400 to 2500 nm.
• the average transmittance in the visible light region was measured using UV-3100PC (manufactured by SHIMADZU).
• the "L” column of “Specific aggregate” indicates the average length of the long axis of the specific aggregate.
• the “L/D” column of “Specific aggregate” indicates the average aspect ratio of the specific aggregate.
• the “J peak waveform separation” column shows the evaluation results of the waveform separation of the peak derived from the J aggregate described above.
• the " ⁇ max” column in the “Optically anisotropic film” column represents the maximum absorption wavelength of the optically anisotropic film.
• the “dye ⁇ max” column in the “specific aggregate” column represents the maximum absorption wavelength exhibited by the solution in which the organic compound used in each example was dissolved.

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