WO2022215757A1 - 光吸収異方性層、積層体および赤外光センサーシステム - Google Patents

光吸収異方性層、積層体および赤外光センサーシステム Download PDF

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WO2022215757A1
WO2022215757A1 PCT/JP2022/017497 JP2022017497W WO2022215757A1 WO 2022215757 A1 WO2022215757 A1 WO 2022215757A1 JP 2022017497 W JP2022017497 W JP 2022017497W WO 2022215757 A1 WO2022215757 A1 WO 2022215757A1
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group
light absorption
anisotropic layer
wavelength
liquid crystalline
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French (fr)
Japanese (ja)
Inventor
真裕美 野尻
彩子 村松
直也 柴田
友樹 平井
遼司 姫野
慎一 森嶌
隆志 加藤
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN202280027028.7A priority Critical patent/CN117396784A/zh
Priority to JP2023513065A priority patent/JPWO2022215757A1/ja
Publication of WO2022215757A1 publication Critical patent/WO2022215757A1/ja
Priority to US18/481,056 priority patent/US20240142682A1/en
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/04—Disazo dyes from a coupling component "C" containing a directive amino group
    • C09B31/043—Amino-benzenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/16—Trisazo dyes
    • C09B31/18—Trisazo dyes from a coupling component "D" containing a directive amine group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/039—Disazo dyes characterised by the tetrazo component
    • C09B35/34—Disazo dyes characterised by the tetrazo component the tetrazo component being heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S7/00—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00
    • G01S7/48—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00 of systems according to group G01S17/00
    • G01S7/481—Constructional features, e.g. arrangements of optical elements
    • 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
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3058—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state comprising electrically conductive elements, e.g. wire grids, conductive particles

Definitions

  • the present invention relates to a light absorption anisotropic layer, a laminate and an infrared light sensor system.
  • polarizers for the visible wavelength range are in demand for applications such as recognition light sources for touch panels, security cameras, sensors, counterfeit prevention, and communication equipment. . It is used for optical waveguides, switching, sensing, and anti-reflection of infrared wavelengths by applying the polarization function of infrared wavelengths.
  • the most commonly used polarizer in which iodine is contained in polyvinyl alcohol (PVA) and stretched and oriented has insufficient polarizing performance in the infrared wavelength region of 850 nm or more.
  • a wire grid type polarizing plate (light absorption anisotropic layer) as disclosed in Patent Document 1 is becoming more popular because it can be processed into a film type and is stable as a product. Since the optical properties cannot be maintained without nano-level unevenness on the surface, it cannot be applied to applications that touch the surface, and it is difficult to apply anti-reflection processing or anti-glare processing. In addition, since nano-level processing is required, it is difficult to fabricate a large area and is very expensive.
  • the PVA stretching type polarizer (optical absorption anisotropic layer) as in Patent Document 2 has a thickness of several tens of ⁇ m or more and lacks flexibility, so it is not suitable for processing into a curved surface shape and is not suitable for bending.
  • the light absorption anisotropic layer should have a high efficiency of generating polarized light for unpolarized light in the infrared wavelength range. Therefore, a high S/N ratio is required to generate polarized light.
  • the present invention provides a light-absorbing anisotropic layer, a laminate, and a sensor system comprising the same, which have a high S/N ratio for generating polarized light with respect to light rays in the infrared wavelength range, are lightweight and excellent in handleability, and the like. intended to provide
  • the present inventors have made intensive studies to solve this problem, and found that it contains a dichroic dye having a maximum absorption at a wavelength of 700 to 1500 nm and an average absorbance at 850 nm of 0.24 to 0.50.
  • a light absorption anisotropic layer having a thickness of 5 ⁇ m or less.
  • [4] The light absorption anisotropic layer according to any one of [1] to [3], which is formed from a composition containing the dichroic dye and a liquid crystalline polymer.
  • [5] The light absorption anisotropic layer according to [2] or [4], wherein the content of the dichroic dye is 1 to 50% by mass relative to the content of the liquid crystalline compound.
  • [6] The light absorption anisotropic layer of [4], wherein the aqueous solution of the liquid crystalline polymer exhibits lyotropic liquid crystallinity.
  • the angle formed by the absorption axis at the maximum absorption wavelength of the dichroic dye having a maximum absorption at a wavelength of 400 to 700 nm and the absorption axis at the maximum absorption wavelength of the dichroic dye is 10 to 90°. , the light absorption anisotropic layer according to [13].
  • a laminate comprising the light absorption anisotropic layer A according to any one of [1] to [18] and a light absorption anisotropic layer B, wherein the light absorption anisotropic layer B contains a dichroic dye having a maximum absorption at a wavelength of 400 to 700 nm, and the luminosity correction single transmittance of the light absorption anisotropic layer B at a wavelength of 400 to 700 nm is 30 to 50%. .
  • a laminate comprising the light absorption anisotropic layer A according to any one of [1] to [18] and an optically anisotropic layer, wherein the light absorption anisotropic layer A A laminate wherein the in-plane retardation of the optically anisotropic layer at the wavelength ⁇ A is 10 to ⁇ A /4 nm, where ⁇ A is the maximum absorption wavelength.
  • a laminate comprising the light absorption anisotropic layer A according to any one of [1] to [18] and an optically anisotropic layer, wherein the surface of the entire laminate at a wavelength of 550 nm A laminate having an internal retardation of 0 to 50 nm.
  • a light absorption anisotropic layer, a laminate, and a sensor system comprising the same have a high S/N ratio for generating polarized light with respect to light rays in the infrared wavelength range, and are lightweight and excellent in handleability. can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of a sensor system of the present invention
  • FIG. 1 is a schematic cross-sectional view showing an example of a sensor system of the present invention
  • FIG. 1 is a schematic cross-sectional view showing an example of a sensor system of the present invention
  • FIG. 1 is a schematic cross-sectional view showing an example of a display device of the present invention
  • a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
  • parallel and orthogonal do not mean parallel and orthogonal in a strict sense, but mean a range of ⁇ 5° from parallel or orthogonal.
  • liquid crystalline composition and “liquid crystalline compound” also conceptually includes those that no longer exhibit liquid crystallinity due to curing or the like.
  • the substituent W used in this specification represents the following groups.
  • Examples of the substituent W include a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and an alkylcarbonyl group having 1 to 10 carbon atoms.
  • an alkyloxycarbonyl group having 1 to 10 carbon atoms an alkylcarbonyloxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylaminocarbonyl group, an alkoxy group having 1 to 20 carbon atoms, and 1 carbon atom ⁇ 20 alkenyl groups, alkynyl groups having 1 to 20 carbon atoms, aryl groups having 1 to 20 carbon atoms, heterocyclic groups (also referred to as heterocyclic groups), cyano groups, hydroxy groups, nitro groups, carboxy groups, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
  • LW represents a single bond or a divalent linking group
  • SPW represents a divalent spacer group
  • Q represents Q1 or Q2 in formula (LC) described below
  • * represents a binding position.
  • Divalent linking groups represented by LW include —O—, —(CH 2 ) g —, —(CF 2 ) g —, —Si(CH 3 ) 2 —, and —(Si(CH 3 ) 2 O).
  • the divalent spacer group represented by SPW includes a linear, branched or cyclic alkylene group having 1 to 50 carbon atoms, or a heterocyclic group having 1 to 20 carbon atoms.
  • the hydrogen atom of the alkylene group and the hydrogen atom of the heterocyclic group are a halogen atom, a cyano group, -Z H , -OH, -OZ H , -COOH, -C(O)Z H , -C(O) OZ H , -OC(O)Z H , -OC(O)OZ H , -NZ H Z H ', -NZ H C(O) Z H ', -NZ H C(O) OZ H ', -C (O) NZHZH ', -OC (O) NZHZH ', -NZHC (O) NZH'OZH '', -SH , -SZH , -C (S) ZH , —C(O)SZ H and —SC(O)Z H (hereinafter collectively abbreviated as “SP-H”).
  • Z H and Z H ' are each independently an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or -L-CL (L represents a single bond or a divalent linking group. Specific examples of the divalent linking group are the same as LW and SPW described above.
  • CL represents a crosslinkable group, and includes groups represented by Q1 or Q2 in formula (LC) described below. Crosslinkable groups represented by (P1) to (P30) are preferred.).
  • the anisotropic light absorption layer of the present invention contains a dichroic dye having a maximum absorption at a wavelength of 700 to 1500 nm, and the average absorbance of the anisotropic light absorption layer at the maximum absorption wavelength of the dichroic dye is 0.5. 24 to 0.5, and the thickness is 5 ⁇ m or less.
  • the anisotropic light absorption layer having absorption in the infrared region is also referred to as an anisotropic light absorption layer A.
  • the average absorbance of the light absorption anisotropic layer in the invention means the absorbance for unpolarized light.
  • the maximum absorption wavelength of the dichroic dye can be obtained by measuring the light absorption anisotropic layer A with an ultraviolet-visible-near-infrared spectrophotometer V-660.
  • the average absorbance of the anisotropic light absorption layer A at the maximum absorption wavelength is obtained by irradiating the anisotropic light absorption layer A with unpolarized light of the maximum absorption wavelength, and measuring the absorbance at the maximum absorption wavelength by ultraviolet-visible-near-infrared spectroscopy. Measure with photometer V-660.
  • the average absorbance at the maximum absorption wavelength of the dichroic dye in the light absorption anisotropic layer of the present invention is preferably 0.3 or more, more preferably 0.35 or more, and even more preferably 0.4 or more.
  • the present inventors We speculate as follows.
  • the light absorption anisotropic layer A contains a dichroic dye that satisfies the above requirements and the average absorbance is within the above range, absorption of infrared light by the dichroic dye occurs appropriately, and the infrared wavelength It is believed that the signal-to-noise ratio that produces polarized light for light in the region will be higher.
  • the thickness is 5 ⁇ m or less, it is considered to be lightweight and excellent in handleability.
  • the effect of the present invention is better.”
  • the light absorption anisotropic layer A may be produced by various known techniques as long as the above conditions are satisfied.
  • the anisotropy of light absorption can be realized by orienting a substance (dichroic dye) having different absorbance depending on the direction.
  • a method for orienting the dichroic dye there is a method for orienting the dichroic dye using the orientation of the liquid crystalline compound.
  • the above method is preferably used in the present invention from the viewpoint of the wet heat durability of the light absorption anisotropic layer A.
  • the dichroic dye itself exhibits liquid crystallinity, it is also possible to align the dichroic dye using only the liquid crystalline dichroic dye.
  • the light absorption anisotropic layer contains a liquid crystalline compound.
  • the absorption axis is parallel to the alignment axis of the liquid crystalline compound. is preferred.
  • the above state is advantageous in terms of cost and orientation since the structure is simple.
  • a preferred embodiment 1 is a method of orienting a water-soluble dichroic dye by utilizing the orientability of a lyotropic liquid crystal.
  • Preferred mode 2 is a method of orienting a water-insoluble infrared-absorbing dye by utilizing the orientation of thermotropic liquid crystals.
  • the anisotropic light absorption layer A When the anisotropic light absorption layer A is used by being laminated with a polarizer for visible wavelengths, it is preferable that the anisotropic light absorption layer A has substantially no absorption in the visible light region.
  • the average absorbance of the light absorption anisotropic layer A at a wavelength of 400 to 700 nm is preferably 0.2 or less.
  • the lower limit of the average absorbance is not particularly limited, it may be 0.0 or more.
  • the light absorption anisotropic layer A may have an average absorbance of 0.2 to 0.5 at a wavelength of 750 nm. Further, the light absorption anisotropic layer A may have an average absorbance of 0.2 to 0.5 at a wavelength of 1100 nm. The light absorption anisotropic layer A may simultaneously meet the requirements for average absorbance at the above wavelengths.
  • the anisotropic light absorption layer A of the present invention is also preferably formed using a composition containing a lyotropic liquid crystalline compound.
  • a lyotropic liquid crystal compound is a compound exhibiting lyotropic liquid crystallinity.
  • the lyotropic liquid crystallinity is a property of causing a phase transition between an isotropic phase and a liquid crystal phase by changing the temperature and concentration in a solution state dissolved in a solvent. When the solvent is removed by drying, the lyotropic liquid crystal compound can form an organic film with a high degree of orientation by transitioning from the liquid crystal phase to the crystal phase. A high-contrast, high-performance polarizing plate can be obtained.
  • the lyotropic liquid crystalline compound is preferably water-soluble, since it is easy to control the development of liquid crystallinity.
  • the water-soluble lyotropic liquid crystalline compound means a lyotropic liquid crystalline compound that dissolves in water at 1% by mass or more, preferably a lyotropic liquid crystalline compound that dissolves in water at 5% by mass or more.
  • the type of the lyotropic liquid crystalline compound in the composition is not particularly limited as long as the light absorption anisotropic layer A can be formed.
  • the dichroic dye may exhibit lyotropic liquid crystallinity
  • the composition may contain a lyotropic liquid crystalline compound other than the dichroic dye.
  • the light absorption anisotropic layer A formed using the composition contains the dichroic dye.
  • the composition contains a lyotropic liquid crystalline compound other than the dichroic dye
  • the light absorption anisotropic layer A formed using the composition contains the dichroic dye and the lyotropic liquid crystalline compound including.
  • the light absorption anisotropic layer A can be formed by applying a composition in which a dichroic dye exhibiting lyotropic liquid crystallinity is dispersed in water or an organic solvent, and orienting the composition in a lyotropic liquid crystal phase. It is also possible to form the light absorption anisotropic layer A by coating a composition containing a lyotropic liquid crystalline compound separately from the dichroic dye. Above all, the composition preferably contains a lyotropic liquid crystalline polymer in that the light absorption anisotropic layer A of the present invention can be formed with good productivity. In other words, it is preferable that the aqueous solution of the liquid crystalline polymer exhibits lyotropic liquid crystallinity. Preferred properties of the dichroic dye in Embodiment 1 are described in detail below.
  • a dichroic dye means a substance that absorbs differently depending on the direction.
  • a dichroic dye having a maximum absorption at a wavelength of 700 to 1500 nm is used in order to obtain a polarizing plate that functions in the infrared region.
  • the dichroic dye may exhibit liquid crystallinity (for example, lyotropic liquid crystallinity) or may not exhibit liquid crystallinity. In other words, it is preferable that the aqueous solution of the dichroic dye exhibits lyotropic liquid crystallinity.
  • the dichroic dye exhibits liquid crystallinity, it may exhibit either nematic properties or smectic properties.
  • the dichroic dye preferably has a hydrophilic group.
  • Hydrophilic groups include acid groups or salts thereof, onium groups, hydroxy groups or salts thereof, sulfonamide groups (H 2 N—SO 2 —), and polyoxyalkylene groups. Among them, an acid group or a salt thereof is preferable.
  • Onium bases are groups derived from onium salts, such as ammonium bases (*-N + (R Z ) 3 A ⁇ ), phosphonium bases (*-P + (R Z ) 4 A ⁇ ), and sulfonium bases. A base (*-S + (R Z ) 2 A ⁇ ) is included.
  • Each R Z independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
  • a ⁇ represents an anion (eg, halogen ion). * represents a binding position.
  • a salt of a hydroxy group is represented by *-O - M + , where M + represents a cation and * represents a binding position. Examples of cations represented by M + include cations in salts of acid groups described later.
  • Examples of polyoxyalkylene groups include groups represented by R Z —(OL Z ) n —*. RZ is as described above.
  • L Z represents an alkylene group. * represents a binding position.
  • Acid groups or salts thereof include, for example, a sulfo group (--SO 3 H) or a salt thereof (--SO 3 ⁇ M + .
  • M + represents a cation.
  • a carboxyl group (--COOH) or a salt thereof.
  • —COO ⁇ M + where M + represents a cation
  • a sulfo group or a salt thereof is preferred in terms of better orientation of the dichroic dye in the light absorption anisotropic layer.
  • the above-mentioned salt refers to a substance in which hydrogen ions of an acid are replaced with other cations such as metals.
  • a salt of an acid group means one in which a hydrogen ion of an acid group such as —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+ , Mg 2+ , Sr 2+ , Pb 2+ , Zn 2+ , La 3+ , Ce 3+ , Y 3+ , Yb 3+ , Gd 3+ or Zr 4+ .
  • alkali metal ions are preferable, Na + or Li + is more preferable, and Li + is even more preferable, because the orientation of the dichroic dye in the light absorption anisotropic layer is more excellent.
  • a dichroic dye has a maximum absorption wavelength in the wavelength range of 700 to 1500 nm. That is, the dichroic dye is an infrared absorbing dichroic dye. Examples of infrared absorbing dichroic dyes include near-infrared absorbing dichroic dyes.
  • the type of dichroic dye (particularly, a near-infrared absorbing dichroic dye having a hydrophilic group) is not particularly limited, and includes known materials.
  • Dichroic dyes include, for example, 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, hydrophilic cyanine dyes having a group, oxonol dyes having a hydrophilic group, squarylium dyes having a hydrophilic group, rylene dyes having a hydrophilic group, diimmonium dyes having a hydrophilic group, diphenylamines having a hydrophilic group triphenylamine dyes having a hydrophilic group, quinone dyes having a hydrophilic group, and azo dyes having a hydrophilic group.
  • Dyes exemplified above 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, hydrophilic groups cyanine dyes with hydrophilic groups, oxonol dyes with hydrophilic groups, squarylium dyes with hydrophilic groups, rylene dyes with hydrophilic groups, diimmonium dyes with hydrophilic groups, diphenylamine dyes with hydrophilic groups , a triphenylamine dye having a hydrophilic group, a quinone dye having a hydrophilic group, and an azo dye having a hydrophilic group) are as described above.
  • lyotropic liquid crystalline polymer- A lyotropic liquid crystalline polymer is oriented in a predetermined direction by applying a shearing force, using an alignment film, etc., by utilizing the fact that a solution dissolved in water or an organic solvent at a predetermined concentration exhibits liquid crystallinity. be able to. It is preferable that the lyotropic liquid crystalline polymer is water-soluble from the viewpoint of easy control of liquid crystalline expression.
  • the water-soluble lyotropic liquid crystalline polymer means a lyotropic liquid crystalline polymer that dissolves in water at 1% by mass or more, preferably a lyotropic liquid crystalline polymer that dissolves in water at 5% by mass or more.
  • a specific structure of the lyotropic liquid crystalline polymer is a structure in which ring structures (aromatic rings, non-aromatic rings, etc.) are one-dimensionally linked via a single bond or a divalent linking group.
  • a compound having The lyotropic liquid crystalline polymer as described above often has the property of aligning in a solvent such that the long axes are aligned parallel to each other.
  • the lyotropic liquid crystalline polymer preferably has a maximum absorption wavelength in the wavelength range of 300 nm or less. That is, the lyotropic liquid crystalline polymer preferably has a maximum absorption peak in the wavelength range of 300 nm or less.
  • the maximum absorption wavelength of the lyotropic liquid crystalline polymer means the wavelength at which the absorbance takes the maximum value in the absorption spectrum of the lyotropic liquid crystalline polymer (measurement range: wavelength range of 230 to 400 nm). If there are multiple maximum absorbance values in the absorption spectrum of the lyotropic liquid crystalline polymer, select the wavelength on the longest wavelength side in the measurement range.
  • the lyotropic liquid crystalline polymer preferably has a maximum absorption wavelength in the range of 230 to 300 nm, and more preferably has a maximum absorption wavelength in the range of 250 to 290 nm, from the viewpoint that the effects of the present invention are excellent.
  • the maximum absorption wavelength of the lyotropic liquid crystalline polymer is preferably located at 250 nm or longer.
  • the method for measuring the maximum absorption wavelength is as follows. A lyotropic liquid crystalline polymer (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 lyotropic liquid crystalline polymer preferably has a hydrophilic group from the point of view that the effects of the present invention are more excellent.
  • the lyotropic liquid crystalline polymer may have only one hydrophilic group, or may have a plurality of hydrophilic groups.
  • Hydrophilic groups include acid groups or salts thereof, onium groups, hydroxy groups, sulfonamide groups (H 2 N—SO 2 —), and polyoxyalkylene groups. Among them, an acid group or a salt thereof is preferable. Acid groups or salts thereof will be described in detail later.
  • Onium bases are groups derived from onium salts, such as ammonium bases (*-N + (R Z ) 3 A ⁇ ), phosphonium bases (*-P + (R Z ) 4 A ⁇ ), and sulfonium bases.
  • a base (*-S + (R Z ) 2 A ⁇ ) is included.
  • Each R Z independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
  • a ⁇ represents an anion (eg, halogen ion). * represents a binding position.
  • Examples of polyoxyalkylene groups include groups represented by R Z —(OL Z ) n —*. RZ is as described above.
  • L Z represents an alkylene group. * represents a binding position.
  • Acid groups or salts thereof include, for example, a sulfo group (--SO 3 H) or a salt thereof (--SO 3 ⁇ M + . M + represents a cation.), and a carboxyl group (--COOH) or a salt thereof. (—COO ⁇ M + . M + represents a cation.), and a sulfo group or a salt thereof is preferred in that the effects of the present invention are more excellent.
  • the above-mentioned salt refers to a substance in which hydrogen ions of an acid are replaced with other cations such as metals.
  • a salt of an acid group means one in which a hydrogen ion of an acid group such as —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+ , Mg 2+ , Sr 2+ , Pb 2+ , Zn 2+ , La 3+ , Ce 3+ , Y 3+ , Yb 3+ , Gd 3+ or Zr 4+ .
  • alkali metal ions are preferable, K + , Na + , or Li + are more preferable, and Li + is even more preferable, because the effects of the present invention are more excellent.
  • a polymer having a repeating unit represented by the formula (X) is preferable because the effects of the present invention are more excellent.
  • 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 In formula (X1), * represents a bonding position.
  • R x3 and R x4 are each independently a divalent aromatic ring group optionally having a substituent containing a hydrophilic group, or optionally having a substituent containing a hydrophilic group 2 represents a valent non-aromatic ring group, and at least one of R x3 and R x4 is a divalent aromatic ring group having a substituent containing a hydrophilic group, or a divalent divalent ring having a substituent containing a hydrophilic group represents a non-aromatic ring 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 include the groups described above, and an acid group or a salt thereof is preferable.
  • a substituent containing a hydrophilic group a group represented by Formula (H) is preferable.
  • * represents a bonding position.
  • R H -L H -* RH 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 examples thereof include divalent hydrocarbon groups (e.g., 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. and divalent aromatic hydrocarbon groups such as arylene groups), divalent heterocyclic groups, -O-, -S-, -NH-, -CO-, Alternatively, a group combining these (e.g., -CO-O-, -O-divalent hydrocarbon group -, -(O-divalent hydrocarbon group) m -O- (m is an integer of 1 or more ), and -divalent hydrocarbon group -O-CO-, etc.).
  • divalent hydrocarbon groups e.g., 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. and divalent aromatic hydrocarbon
  • the number of substituents containing a hydrophilic group possessed by the divalent aromatic ring group is not particularly limited, it is preferably 1 to 3, more preferably 1, from the standpoint that the effects of the present invention are more excellent.
  • the number of substituents containing a hydrophilic group possessed by the divalent non-aromatic ring group is not particularly limited, it is preferably 1 to 3, more preferably 1, from the standpoint that the effects of the present invention are more excellent.
  • 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 an aromatic hydrocarbon ring and an aromatic heterocyclic ring. That is, R x1 includes 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.
  • aromatic hydrocarbon rings include benzene rings and naphthalene rings.
  • Examples of the structure of only the divalent aromatic hydrocarbon ring group portion of the divalent aromatic hydrocarbon ring group having a substituent containing a hydrophilic group include the following groups. * represents a binding position.
  • Aromatic heterocycles include, for example, pyridine, thiophene, pyrimidine, thiazole, furan, pyrrole, imidazole, and indole rings.
  • Examples of the structure of only the divalent aromatic heterocyclic group portion of the divalent aromatic heterocyclic group having a substituent containing a hydrophilic group include the following groups. * represents a binding 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.
  • the non-aromatic ring constituting the divalent non-aromatic ring group includes, for example, an aliphatic ring and a non-aromatic heterocyclic ring. Preferred are cycloalkanes, and even more preferred is cyclohexane. That is, R x1 includes a divalent aliphatic cyclic group having a substituent containing a hydrophilic group, and a divalent non-aromatic heterocyclic group having a substituent containing a hydrophilic group.
  • a divalent cycloalkylene group having a substituent containing group is preferred.
  • the alicyclic ring may be either a saturated alicyclic ring or an unsaturated alicyclic ring.
  • Examples of the structure of only the divalent aliphatic cyclic group portion of the divalent aliphatic cyclic group having a substituent containing a hydrophilic group include the following groups. * represents a binding position.
  • the heteroatom contained in the non-aromatic heterocyclic ring is not particularly limited, and examples thereof include oxygen, nitrogen and sulfur atoms.
  • the number of heteroatoms contained in the non-aromatic heterocyclic ring is not particularly limited, and examples include 1-3. 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 a binding position.
  • a divalent aromatic ring group having a substituent containing a hydrophilic group represented by R x1 and a divalent non-aromatic ring group having a substituent containing a hydrophilic group are substituted with a hydrophilic group. It may have a substituent other than the group.
  • Substituents are not particularly limited, and examples include 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., hetero aryl group), a silyl group, and groups in which these are combined.
  • the said substituent may be further substituted by the substituent.
  • R x3 and R x4 are each independently a divalent aromatic ring group optionally having a substituent containing a hydrophilic group, or optionally having a substituent containing a hydrophilic group 2 represents a valent non-aromatic ring group, and at least one of R x3 and R x4 is a divalent aromatic ring group having a substituent containing a hydrophilic group, or a divalent divalent ring having a substituent containing a hydrophilic group represents a non-aromatic ring group.
  • the definition of the substituent including 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 optionally having a substituent containing a hydrophilic group represented by R x3 and R x4 is the above-described aromatic ring represented by R x1 . 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 including 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 optionally having a substituent containing a hydrophilic group represented by R x3 and R x4 is the above-described R x1 It is the same as the definition of the non-aromatic ring constituting the bivalent 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.
  • the definition of the divalent non-aromatic ring group having a substituent containing a hydrophilic group represented by R x3 and R x4 is 2 having a substituent containing a hydrophilic group represented by R x1 described above. It is synonymous with the definition of a 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, it is preferably 1 to 3, more preferably 1, from the standpoint of better effects of the present invention.
  • the number of carbon atoms in the alkenylene group and the alkynylene group is not particularly limited, it is preferably 2 to 5, more preferably 2 to 4, from the viewpoint of better effects of the present invention.
  • R x2 represents a divalent non-aromatic ring group or a group represented by formula (X2).
  • * represents a bonding position.
  • Formula (X2) *-Z x1 -Z x2 -* Z x1 and Z x2 each independently represent a divalent non-aromatic ring group. * represents a binding 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.
  • the non-aromatic ring constituting the divalent non-aromatic ring group includes, for example, an aliphatic ring and a non-aromatic heterocyclic ring. Preferred are cycloalkanes, and even more preferred is cyclohexane. That is, R x2 includes a divalent aliphatic ring group and a divalent non-aromatic heterocyclic group, preferably a divalent cycloalkylene group.
  • the alicyclic ring may be either a saturated alicyclic ring or an unsaturated alicyclic ring.
  • divalent aliphatic ring groups include the following groups. * represents a binding position.
  • the heteroatom contained in the non-aromatic heterocyclic ring is not particularly limited, and examples thereof include oxygen, nitrogen and sulfur atoms.
  • the number of heteroatoms contained in the non-aromatic heterocyclic ring is not particularly limited, and examples include 1-3.
  • Examples of divalent non-aromatic heterocyclic groups include the following groups. * represents a binding position.
  • the divalent non-aromatic ring group may have a substituent.
  • the type of substituents is not particularly limited, for example, a divalent aromatic ring group having a substituent containing a hydrophilic group represented by R x1 , and a divalent non-substituted divalent having a substituent containing a hydrophilic group
  • the groups exemplified as the substituents other than the hydrophilic group-containing substituents that the aromatic ring group may have may be mentioned.
  • Z x1 and Z x2 each independently represent a divalent non-aromatic ring group.
  • the definition of the divalent non-aromatic ring group represented by Z x1 and Z x2 is the same as the definition of the divalent non-aromatic ring group represented by R x2 described above.
  • L x1 and L x2 each independently represent -CONH-, -COO-, -O-, or -S-. Among them, -CONH- is preferable because the effects of the present invention are more excellent.
  • the repeating unit represented by formula (X) is preferably a repeating unit represented by formula (X4).
  • the content of the repeating unit represented by formula (X) contained in the polymer having the repeating unit represented by formula (X) is not particularly limited, it is 60 mol% with respect to all repeating units in the polymer. 80 mol % or more is more preferable. 100 mol% is mentioned as an upper limit.
  • the molecular weight of the polymer having repeating units represented by formula (X) is not particularly limited, but the number of repeating units represented by formula (X) in the polymer is preferably 2 or more, more preferably 10 to 100,000. , 100 to 10,000 are more preferred. Although the number average molecular weight of the polymer having repeating units represented by formula (X) is not particularly limited, it is preferably 5,000 to 50,000, more preferably 10,000 to 30,000.
  • the molecular weight distribution of the polymer having repeating units represented by formula (X) is not particularly limited, but is preferably 1-12, more preferably 1-7.
  • the number average molecular weight and molecular weight distribution in the present invention are values measured by a gel permeation chromatography (GPC) method.
  • the composition may contain components other than the lyotropic liquid crystalline polymer and the dichroic dye.
  • the composition may contain a salt (salt consisting of a cation and an anion).
  • the dichroic dye has an acid group or a salt thereof, the presence of the salt in the composition makes it easier for the dichroic dye to associate with each other, and easily forms an aggregate having shape anisotropy.
  • the salt does not include the lyotropic liquid crystalline polymer and the dichroic dye. That is, the salt is a compound different from the lyotropic liquid crystalline polymer and the dichroic dye.
  • the salt is not particularly limited, and may be an inorganic salt or an organic salt.
  • Inorganic salts are preferred because the effects of the present invention are more excellent.
  • Examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and transition metal salts, and alkali metal salts are preferred in that the effects of the present invention are more excellent.
  • 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, more preferably a lithium ion. That is, the salt is preferably lithium salt or sodium salt, more preferably lithium salt.
  • Alkali metal salts include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; alkali metal bicarbonates such as lithium, sodium bicarbonate, and potassium bicarbonate; In addition to the above, alkali metal salts may be, for example, phosphates and chlorides.
  • Anions of the above salts include, for example, hydroxide ion, carbonate ion, chloride ion, sulfate ion, nitrate ion, phosphate ion, borate ion, tetrafluoroborate ion, hexafluorophosphate ion, and perchlorate ion.
  • toluenesulfonate oxalate, formate, trifluoroacetate, trifluoromethanesulfonate, hexafluorophosphate, bis(fluoromethanesulfonyl)imide, bis(pentafluoroethanesulfonyl)imide, and bis (trifluoromethanesulfonyl) imide ion.
  • the cation in the acid group salt and the cation in the salt used are preferably of the same type.
  • the composition may contain a hydrophilic solvent.
  • Hydrophilic solvents include water, alcohols and polar solvents such as dimethylformamide. Among them, polar solvents are preferred, and water or alcohol is more preferred.
  • Additives that may be contained in the composition include, in addition to the above, polymerizable compounds, polymerization initiators, wavelength dispersion control agents, optical property modifiers, surfactants, adhesion improvers, slip agents, and alignment control agents. agents, and UV absorbers.
  • composition of composition The composition preferably contains a lyotropic liquid crystalline compound and a dichroic dye.
  • the composition may correspond to a lyotropic liquid crystalline composition.
  • the lyotropic liquid crystalline composition is a composition that has the property of undergoing a phase transition between an isotropic phase and a liquid crystal phase by changing the temperature and concentration in a solution state. That is, the composition can exhibit lyotropic liquid crystallinity by adjusting the concentration of each compound in a solution state containing various components such as a lyotropic liquid crystalline polymer, a dichroic dye, and a solvent. is.
  • the composition corresponds to the lyotropic liquid crystalline composition described above.
  • the content of the lyotropic liquid crystalline compound in the composition is not particularly limited, but is preferably 60 to 100% by mass, more preferably 80 to 99% by mass, based on the total solid content in the composition.
  • the total solid content means the components capable of forming the light absorption anisotropic layer A, excluding the solvent. Even if the properties of the above components are liquid, the compound forming the light absorption anisotropic layer A is calculated as a solid content.
  • the content of the dichroic dye is preferably 80% by mass or less, and 50% by mass with respect to the total mass of the lyotropic liquid crystalline polymer and the dichroic dye. % or less is more preferable.
  • the oriented lyotropic liquid crystalline polymer acts as a host, and the dichroic dye is oriented along the orientation direction of the polymer, resulting in a light absorption anisotropic layer A with a high degree of orientation.
  • the content of the dichroic dye is preferably 1% by mass or more, more preferably 5% by mass or more, relative to the total mass of the lyotropic liquid crystalline polymer and the dichroic dye. In the case of this content, the dichroic dye can obtain a high degree of orientation by forming an aggregate. Moreover, when the composition contains a lyotropic liquid crystalline polymer and a dichroic dye, the content of the dichroic dye is preferably 1 to 50% by mass relative to the content of the lyotropic liquid crystalline compound.
  • the composition may contain only one type of lyotropic liquid crystalline polymer, or may contain two or more types of lyotropic liquid crystalline polymer.
  • the content of the lyotropic liquid crystalline polymer means the total content of the lyotropic liquid crystalline polymer.
  • the composition may contain only one dichroic dye, or may contain two or more dichroic dyes. Containing two or more kinds of dichroic dyes is more preferable because the wavelength region functioning as a polarizing plate is widened and a wider band polarizing plate can be obtained.
  • the content of the dichroic dyes means the total content of the dichroic dyes.
  • the composition may contain a dichroic dye having an absorption maximum at 400 to 700 nm in addition to the dichroic dye. By including a dichroic dye having a maximum absorption at 400 to 700 nm, a polarizing plate that functions even in the visible light region can be obtained.
  • the composition may contain a solvent, as described above.
  • the solid content concentration of the composition is not particularly limited, it is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, based on the total mass of the composition, from the viewpoint that the effects of the present invention are excellent.
  • the composition is preferably a lyotropic liquid crystalline composition.
  • the composition may contain a predetermined amount of solvent and exhibit lyotropic liquid crystallinity (a state in which lyotropic liquid crystallinity is exhibited), or the composition may contain a solvent.
  • the solvent evaporates during the formation of the light absorption anisotropic layer A, resulting in the formation of a coating film.
  • It may be a composition that exhibits lyotropic liquid crystallinity during formation.
  • an alignment film is placed on the support, the compound exhibits lyotropic liquid crystallinity during the drying process after application of the composition, thereby inducing alignment of the compound and light absorption anisotropy. It becomes possible to form the active layer A.
  • the dichroic dye may be used as a dye dispersion, and the composition may be prepared using the dye dispersion.
  • a pigment dispersion can be prepared by mixing the above ingredients.
  • each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then blended successively.
  • a dye dispersion may be prepared by simultaneously dissolving or dispersing all components in a solvent.
  • the preparation of the pigment dispersion preferably includes a process of dispersing the pigment.
  • the mechanical forces used to disperse pigments include compression, squeezing, impact, shearing, and cavitation. Examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, and ultrasonic dispersion.
  • the dichroic dye may be particulate in the composition.
  • the average particle size of the particles is not particularly limited, but is preferably 10 to 1000 nm, more preferably 10 to 500 nm, in terms of the degree of orientation of the dichroic dye being more excellent. is more preferable, and 10 to 200 nm is even more preferable.
  • a method for manufacturing the light absorption anisotropic layer A of the present invention will be described.
  • a method for manufacturing the light absorption anisotropic layer A using the composition described above will be described below.
  • the composition is applied, and the lyotropic liquid crystalline compound (e.g., lyotropic liquid crystalline polymer and dichroic dye) in the coating film is oriented, resulting in light absorption anisotropy.
  • the method of forming layer A is preferred. The procedure of the above method will be described in detail below.
  • the composition is applied.
  • the support used is a member that functions as a substrate for applying the composition.
  • the support may be a so-called temporary support.
  • Examples of the support (temporary support) include a plastic substrate and a glass substrate.
  • 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 about 5 to 1000 ⁇ m, preferably 10 to 250 ⁇ m, more preferably 15 to 90 ⁇ m.
  • the support may be surface-treated for purposes such as imparting coatability and controlling adhesion.
  • surface treatment methods include physical treatments such as sputtering, sandblasting, plasma treatment and corona treatment, application of surface modifiers such as silane coupling agents, saponification treatment with alkali, and the like.
  • An alignment film may be arranged on the support, if necessary.
  • An alignment film is generally composed mainly of a polymer. Polymers for alignment films are described in many documents, and many commercial products are available. Polyvinyl alcohol, polyimide, derivatives thereof, azo derivatives, and cinnamoyl derivatives are preferable as the polymer for the alignment film. Note that the alignment film is preferably subjected to a known rubbing treatment. Moreover, you may use a photo-alignment film as an alignment film. The thickness of the alignment film is preferably 0.01 to 10 ⁇ m, more preferably 0.01 to 1 ⁇ m.
  • coating methods 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 a shearing force it is possible to simultaneously carry out the two processes of orientation and coating of the compound.
  • the lyotropic liquid crystalline compound may be continuously oriented simultaneously with the coating by continuous coating.
  • Continuous coating includes curtain coating, extrusion coating, roll coating, and slide coating.
  • a method of applying a shearing force is suitably used as described above.
  • the coating film formed on the support may be subjected to heat treatment, if necessary.
  • the conditions for heating the coating film are not particularly limited, but the heating temperature is preferably 50 to 250° C., and the heating time is preferably 10 seconds to 10 minutes. Moreover, after heating a coating film, you may cool a coating film as needed.
  • the cooling temperature is preferably 20 to 200°C, more preferably 20 to 150°C.
  • Another means for orienting the lyotropic liquid crystalline compound in the coating film is the method of using an orientation film as described above.
  • the alignment direction can be controlled by subjecting the alignment film to alignment treatment in advance in a predetermined direction.
  • the method of using an alignment film is preferable in the case of aligning in a direction oblique to the conveying direction.
  • the concentration of the solvent in the composition to be used is not particularly limited, and the concentration of the solvent may be such that the composition exhibits lyotropic liquid crystallinity. good too.
  • composition is a lyotropic liquid crystalline composition
  • concentration of the solvent in the composition is high (when the composition itself exhibits an isotropic phase)
  • orientation of the compound is induced on the orientation film, and the light absorption anisotropic layer A can be formed.
  • a treatment for fixing the alignment state of the lyotropic liquid crystalline compound may be performed.
  • a method for fixing the alignment state of the lyotropic liquid crystalline compound is not particularly limited, and a method of heating the coating film as described above and then cooling it can be mentioned.
  • a method for fixing the alignment state of the lyotropic liquid crystalline compound includes a method of contacting a solution containing polyvalent metal ions with the formed coating film. be done. When the solution containing polyvalent metal ions is brought into contact with the formed coating film, polyvalent metal ions are supplied into the coating film.
  • the polyvalent metal ions supplied into the coating film become cross-linking points between the acid groups of the lyotropic liquid crystalline compound or salts thereof, forming a cross-linked structure in the coating film and fixing the alignment state of the lyotropic liquid crystalline compound.
  • the type of polyvalent metal ion used is not particularly limited, and alkaline earth metal ions are preferred, and calcium ions are more preferred, in that the orientation state of the lyotropic liquid crystalline compound is easily fixed.
  • a preferred method (preferred embodiment 2) for forming the light absorption anisotropic layer A will be described below.
  • Techniques for aligning a dichroic dye in a desired orientation include a technique for producing a polarizer using a dichroic dye and a technique for producing a guest-host liquid crystal cell.
  • the method for producing a dichroic polarizing element described in JP-A-11-305036 and JP-A-2002-090526, and the guest described in JP-A-2002-099388 and JP-A-2016-027387 The technique used in the manufacturing method of the host-type liquid crystal display device can also be used in manufacturing the light absorption anisotropic layer A used in the present invention.
  • the orientation of the molecules of the dichroic dye can be oriented as desired along with the orientation of the host liquid crystal.
  • a guest dichroic dye is mixed with a liquid crystalline compound (for example, a thermotropic liquid crystalline compound) that serves as a host liquid crystal, and the host liquid crystal is oriented, along with the orientation of the liquid crystal molecules.
  • the light absorption anisotropic layer A used in the present invention can be produced by orienting the molecules of the dichroic dye and fixing the orientation state.
  • the orientation of the dichroic dye can be fixed by proceeding with the polymerization of the host liquid crystal, the dichroic dye, or the optionally added polymerizable component.
  • the light absorption anisotropic layer A is formed using a composition containing a liquid crystalline compound (e.g., thermotropic liquid crystalline compound) and a dichroic dye (e.g., water-insoluble dichroic dye) is preferably formed.
  • a liquid crystalline compound e.g., thermotropic liquid crystalline compound
  • a dichroic dye e.g., water-insoluble dichroic dye
  • the water-insoluble dichroic dye and the thermotropic liquid crystalline compound are described below.
  • the dichroic dye is water-insoluble is preferably used.
  • the dichroic dye may exhibit liquid crystallinity (for example, thermotropic liquid crystallinity) or may not exhibit liquid crystallinity.
  • Dichroic dyes are not particularly limited as long as they have a maximum absorption wavelength of 700 to 1500 nm.
  • Preferred examples include cyanine, anthraquinone, azo, squarylium, pyrrolopyrrole, phthalocyanine, oxonol, perylene, diimmonium, and croconium. be done. Particularly preferred are cyanine, anthraquinone, azo, squarylium, pyrrolopyrrole and phthalocyanine. Among them, pyrrolopyrrole is preferred.
  • dichroic dyes for example, Shin Okawara, Ken Matsuoka, Tsunesuke Hirashima, Teijiro Kitao, Functional dyes, Kodansha, 1992, Sumio Tokita supervision, Electronics-related materials, CMC, 1998 Also included are the dyes mentioned.
  • the dichroic dye, such as cyanine means a cyanine dye.
  • a cyanine-based dye will be simply referred to as cyanine.
  • cyanine Specific examples of cyanines used in the present invention are shown below. However, the cyanines used in the present invention are not limited to these.
  • anthraquinone Specific examples of cyanines used in the present invention are shown below. However, the anthraquinone used in the present invention is not limited to these.
  • azo (Azo) Specific examples of azo used in the present invention are shown below. However, the azo used in the present invention is not limited to these.
  • squarylium Specific examples of squarylium used in the present invention are shown below. However, the squarylium used in the present invention is not limited to these.
  • pyrrolopyrrole Specific examples of pyrrolopyrrole used in the present invention are shown below. However, the pyrrolopyrrole used in the present invention is not limited to these.
  • phthalocyanine Specific examples of the phthalocyanine used in the present invention are shown below. However, the present invention is not limited to these.
  • the dichroic dye it is also possible to use a dichroic dye whose absorption axis is not parallel to the alignment axis of the liquid crystal.
  • a dichroic dye for example, when it is used together with a dichroic dye having another maximum wavelength in the same layer, a design in which the direction of the absorption axis is intentionally changed depending on the wavelength becomes possible.
  • Specific examples of the dichroic dye whose absorption axis is not parallel to the alignment axis of the liquid crystal are shown below, but the dichroic dye used in the present invention is not limited to these.
  • dichroic dyes are compatible with a wide infrared wavelength range, it is also preferable to use two or more types of dyes having different maximum absorption wavelengths in combination.
  • the amount of dichroic dye used is preferably 3 to 40% by mass, more preferably 5 to 35% by mass, based on the total weight of the liquid crystalline compound.
  • the composition used for forming the light absorption anisotropic layer A preferably contains a liquid crystalline compound (preferably a thermotropic liquid crystalline compound).
  • a liquid crystalline compound preferably a thermotropic liquid crystalline compound
  • the dichroic dye can be oriented with a high degree of orientation while suppressing precipitation of the dichroic dye.
  • the liquid crystalline compound is a liquid crystalline compound that does not exhibit dichroism, and is a compound different from the dichroic dye.
  • the composition contains a liquid crystalline compound (preferably a thermotropic liquid crystalline compound)
  • the light absorption anisotropic layer A contains a liquid crystalline compound.
  • thermotropic liquid crystal is a liquid crystal that exhibits a transition to a liquid crystal phase due to a change in temperature.
  • the thermotropic liquid crystal may exhibit either a nematic phase or a smectic phase. It is preferable that at least a nematic phase is exhibited from the viewpoint of
  • the temperature range showing the nematic phase is preferably room temperature (23° C.) to 450° C., because the degree of orientation of the light absorption anisotropic layer A becomes higher and the haze becomes more difficult to observe. and from the viewpoint of manufacturing aptitude, it is more preferably 40 to 400°C.
  • Liquid crystalline compounds can generally be classified into a rod-like type (rod-like liquid crystalline compound) and a disk-like type (disc-like liquid crystalline compound) according to their shape.
  • a liquid crystalline compound that does not show dichroism in the visible light region is preferable.
  • both low-molecular liquid crystalline compounds and high-molecular liquid crystalline compounds can be used, but from the viewpoint of increasing the degree of orientation of the dichroic dye, high-molecular liquid crystalline compounds are more preferable.
  • the term "low-molecular-weight liquid crystalline compound” refers to a liquid crystalline compound having no repeating unit in its chemical structure.
  • the term "polymeric liquid crystalline compound” refers to a liquid crystalline compound having a repeating unit in its chemical structure.
  • Examples of low-molecular-weight liquid crystalline compounds include liquid crystalline compounds described in JP-A-2013-228706.
  • polymer liquid crystalline compounds include thermotropic liquid crystalline polymers described in JP-A-2011-237513.
  • the polymer liquid crystalline compound may have a crosslinkable group (for example, an acryloyl group and a methacryloyl group) at its terminal.
  • a rod-like liquid crystal compound may be used individually by 1 type, and may use 2 or more types together.
  • the rod-like liquid crystalline compound preferably contains a macromolecular liquid crystalline compound, and more preferably contains both a macromolecular liquid crystalline compound and a low molecular liquid crystalline compound, from the viewpoint of further enhancing the effects of the present invention.
  • the rod-like liquid crystalline compound preferably contains a liquid crystalline compound represented by formula (LC) or a polymer thereof.
  • the liquid crystalline compound represented by formula (LC) or a polymer thereof is a compound exhibiting liquid crystallinity.
  • the liquid crystal phase exhibited by the liquid crystalline compound may be either a nematic phase or a smectic phase, or may exhibit both a nematic phase and a smectic phase, and preferably exhibits at least a nematic phase.
  • the smectic phase may be a higher order smectic phase.
  • the higher-order smectic phases referred to herein include smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase, and smectic L.
  • a smectic B phase, a smectic F phase, or a smectic I phase is preferred.
  • the smectic liquid crystal phase exhibited by the liquid crystalline compound is such a high-order smectic liquid crystal phase, the light absorption anisotropic layer A having a higher degree of orientational order can be produced.
  • the light absorption anisotropic layer A produced from a high-order smectic liquid crystal phase with a high degree of orientational order has a Bragg peak (derived from Bragg reflection) derived from a high-order structure such as a hexatic phase or a crystal phase. peak) is obtained.
  • the Bragg peak is a peak derived from the plane periodic structure of molecular orientation, and the light absorption anisotropic layer A having a periodic interval of 3.0 to 5.0 ⁇ is preferable.
  • Q1 and Q2 each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms.
  • R P is a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.
  • an alkoxy group having 1 to 20 carbon atoms an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a heterocyclic group (also referred to as a heterocyclic group) , cyano group, hydroxy group, nitro group, carboxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group) ), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocycl
  • a preferred embodiment of the crosslinkable group includes a radically polymerizable group or a cationic polymerizable group.
  • the radically polymerizable group includes a vinyl group represented by the above formula (P-1), a butadiene group represented by the above formula (P-2), and a (meth)acrylic group represented by the above formula (P-4).
  • a (meth)acrylamide group represented by the above formula (P-5), a vinyl acetate group represented by the above formula (P-6), a fumarate group represented by the above formula (P-7), A styryl group represented by the formula (P-8), a vinylpyrrolidone group represented by the formula (P-9), maleic anhydride represented by the formula (P-11), or the formula (P -12) is preferred.
  • the cationically polymerizable group includes a vinyl ether group represented by the above formula (P-18), an epoxy group represented by the above formula (P-19), or an oxetanyl group represented by the above formula (P-20). , is preferred.
  • S1 and S2 each independently represent a divalent spacer group, and preferred embodiments of S1 and S2 include the same structure as SPW in formula (W1) above. omitted.
  • MG represents a mesogenic group to be described later.
  • the mesogenic group represented by MG is a group showing 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. There are no particular restrictions on the mesogenic group. ed., Handbook on Liquid Crystals (published by Maruzen, 2000), especially the description in Chapter 3.
  • the mesogenic group represented by MG preferably contains 2 to 10 cyclic structures, more preferably 3 to 7 cyclic structures. Specific examples of cyclic structures include aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups.
  • the mesogenic group represented by MG has the following formula (MG-A) or A group represented by formula (MG-B) is preferred, and a group represented by formula (MG-B) is more preferred.
  • A1 is a divalent group selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups. These groups may be substituted with a substituent such as the substituent W.
  • the divalent group represented by A1 is preferably a 4- to 15-membered ring. Also, the divalent group represented by A1 may be monocyclic or condensed. * represents the binding position with S1 or S2.
  • 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. etc., a phenylene group or a naphthylene group is 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 non-carbon ring-constituting atoms, these may be the same or different.
  • divalent aromatic heterocyclic groups include, for example, pyridylene group (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene group (quinoline-diyl group ), isoquinolylene group (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazole-diyl group, benzothiadiazole-diyl group, phthalimide-diyl group, thienothiazole-diyl group , thiazolothiazole-diyl group, thienothiophene-diyl group, thienooxazole-diyl group, and structures (II-1) to (II-4) below.
  • D 1 represents -S-, -O-, or -NR 11 -
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Y 1 represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms
  • Z 1 , Z 2 and Z 3 each independently represent a hydrogen atom or a carbon atom 1 to 20 aliphatic hydrocarbon groups, 3 to 20 carbon atom alicyclic hydrocarbon groups, monovalent C 6 to 20 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups
  • -NR 12 represents R 13 or SR 12
  • Z 1 and Z 2 may combine with each other to form an aromatic ring or an aromatic heterocyclic ring
  • R 12 and R 13 each independently represent a hydrogen atom or a carbon number Representing an alkyl group of 1 to 6, J 1 and J 2 each independently represent -O-, -NR 21
  • Y 1 when Y 1 is an aromatic hydrocarbon group having 6 to 12 carbon atoms, it may be monocyclic or polycyclic. When Y 1 is an aromatic heterocyclic group having 3 to 12 carbon atoms, it may be monocyclic or polycyclic.
  • substituents for R 21 include those described in paragraphs [0035] to [0045] of JP-A-2008-107767. can be consulted, the contents of which are incorporated herein.
  • R ' represents a substituent, and as the substituent, for example, the description in paragraphs [0035] to [0045] of JP-A-2008-107767 can be referred to, and -NZ A1 Z A2 (Z A1 and Z A2 are respectively independently represents a hydrogen atom, an alkyl group or an aryl group.) is preferred.
  • divalent alicyclic group represented by A1 include a cyclopentylene group and a cyclohexylene group, and the carbon atoms are -O-, -Si(CH 3 ) 2 -, -N( Z)—(Z represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, a cyano group, or a halogen atom.), —C(O)—, —S—, —C (S)—, —S(O)—, and SO 2 —, optionally substituted by a combination of two or more of these groups.
  • a1 represents an integer of 2-10 (preferably an integer of 2-4).
  • a plurality of A1's may be the same or different.
  • A2 and A3 are each independently a divalent group selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups. Specific examples and preferred embodiments of A2 and A3 are the same as those of A1 in Formula (MG-A), and thus description thereof is omitted.
  • a2 represents an integer of 1 to 10 (preferably an integer of 1 to 3), a plurality of A2 may be the same or different, and a plurality of LA1 may be the same or different. . It is more preferable that a2 is 2 or more from the viewpoint that the effect of the present invention is more excellent.
  • LA1 is a single bond or a divalent linking group.
  • LA1 is a divalent linking group
  • a2 is 2 or more
  • at least one of the plurality of LA1 is a divalent linking group.
  • the divalent linking group represented by LA1 is the same as LW, and thus the description thereof is omitted.
  • MG include the following structures, in which hydrogen atoms on aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups may be substituted with the substituent W described above. good.
  • liquid crystal compound represented by the formula (LC) is a low-molecular-weight liquid crystal compound
  • preferred embodiments of the cyclic structure of the mesogenic group MG include a cyclohexylene group, a cyclopentylene group, a phenylene group, a naphthylene group, and a fluorene- diyl group, pyridine-diyl group, pyridazine-diyl group, thiophene-diyl group, oxazole-diyl group, thiazole-diyl group, and thienothiophene-diyl group, wherein the number of cyclic structures is 2 to 10; Preferably, 3 to 7 are more preferable.
  • Preferred embodiments of the substituent W of the mesogenic structure include a halogen atom, a halogenated alkyl group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an alkoxy group having 1 to 10 carbon atoms, and an alkylcarbonyl group having 1 to 10 carbon atoms.
  • an alkyloxycarbonyl group having 1 to 10 carbon atoms an alkylcarbonyloxy group having 1 to 10 carbon atoms, an amino group, an alkylamino group having 1 to 10 carbon atoms, an alkylaminocarbonyl group, the above formula (W1) where LW is is a single bond, SPW is a divalent spacer group, and Q is a crosslinkable group represented by the above formulas (P-1) to (P-30); is a vinyl group, butadiene group, (meth)acryl group, (meth)acrylamide group, vinyl acetate group, fumarate ester group, styryl group, vinylpyrrolidone group, maleic anhydride, maleimide group, vinyl ether group, epoxy group, or , oxetanyl groups are preferred.
  • the divalent spacer groups S1 and S2 are the same as those of SPW above, so description thereof will be omitted.
  • the number of carbon atoms in the spacer group is preferably 6 or more carbon atoms, more preferably 8 or more. preferable.
  • liquid crystalline compound represented by the formula (LC) is a low-molecular-weight liquid crystalline compound
  • a plurality of low-molecular-weight liquid crystalline compounds may be used in combination. Combined use is more preferable.
  • low-molecular-weight liquid crystal compounds include compounds represented by the following formulas (LC-1) to (LC-77), but low-molecular-weight liquid crystal compounds are not limited to these.
  • the polymer liquid crystalline compound is preferably a homopolymer or copolymer containing repeating units described later, and may be any polymer such as random polymer, block polymer, graft polymer, and star polymer.
  • the polymeric liquid crystalline compound preferably contains a repeating unit represented by formula (1) (hereinafter also referred to as “repeating unit (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 the mesogenic group MG in the above formula (LC).
  • T1 represent terminal groups.
  • the main chain of the repeating unit represented by PC1 includes, for example, groups represented by formulas (P1-A) to (P1-D), and among them, the diversity of raw material monomers and ease of handling From the viewpoint of being, a group represented by the following formula (P1-A) is preferable.
  • R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or , represents an alkoxy group having 1 to 10 carbon atoms.
  • the alkyl group may be a linear or branched alkyl group, or may be an alkyl group having a cyclic structure (cycloalkyl group).
  • 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 the partial structure of poly(meth)acrylic acid ester obtained by polymerization of (meth)acrylic acid ester.
  • the group represented by formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of an 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 an oxetane group of a compound having an oxetane group.
  • the group represented by formula (P1-D) is preferably a siloxane unit of polysiloxane obtained by condensation polymerization of a compound having at least one of an alkoxysilyl group and a silanol group.
  • the compound having at least one of an alkoxysilyl group and a silanol group includes a compound having a group represented by the formula SiR 14 (OR 15 ) 2 —.
  • R 14 has the same definition as R 14 in (P1-D), and each of a plurality of R 15 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • the divalent linking group represented by L1 is the same divalent linking group as LW in the above formula (W1), and preferred embodiments are -C(O)O-, -OC(O)-, - O—, —S—, —C(O)NR 16 —, —NR 16 C(O)—, —S(O) 2 —, and —NR 17 —.
  • R 16 and R 17 each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms (for example, the substituent W described above).
  • the left-hand bond is attached to PC1 and the right-hand bond is attached to SP1.
  • L1 is preferably a group represented by -C(O)O- or -C(O)NR 16 -.
  • PC1 is a group represented by formulas (P1-B) to (P1-D)
  • L1 is preferably a single bond.
  • the spacer group represented by SP1 represents the same group as S1 and S2 in the above formula (LC), and is selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure and an alkylene fluoride structure from the viewpoint of the degree of orientation. or a linear or branched alkylene group having 2 to 20 carbon atoms.
  • the above alkylene groups are -O-, -S-, -O-CO-, -CO-O-, -O-CO-O-, -CO-NR- (R has 1 to 10 carbon atoms represents an alkyl group.) or —S(O) 2 —.
  • the spacer group represented by SP1 is at least one selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure and an alkylene fluoride structure, from the viewpoints of easy liquid crystallinity and availability of raw materials.
  • a group containing a seed structure is more preferred.
  • the oxyethylene structure represented by SP1 is preferably a group represented by *--(CH 2 --CH 2 O) n1 --*.
  • n1 represents an integer of 1 to 20
  • * represents the binding position with L1 or MG1.
  • n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 6, and most preferably 2 to 4, from the viewpoint of better effects of the present invention.
  • 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
  • * represents the binding position with L1 or MG1.
  • the polysiloxane structure represented by SP1 is preferably a group represented by *-(Si(CH 3 ) 2 -O) n3 -*.
  • n3 represents an integer of 6 to 10
  • * represents the binding position with L1 or MG1.
  • the fluorinated alkylene structure represented by SP1 is preferably a group represented by *-(CF 2 -CF 2 ) n4 -*.
  • n4 represents an integer of 6 to 10, * represents the binding position with L1 or MG1.
  • Terminal groups represented by T1 include a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy 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, carbon 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, and 1 to 1 carbon atoms alkoxycarbonyl group having 10 carbon atoms, alkoxycarbonylamino group
  • crosslinkable group-containing group examples include the -L-CL described above.
  • L represents a single bond or a divalent linking group. Specific examples of the linking group are the same as LW and SPW described above.
  • CL represents a crosslinkable group, including the groups represented by Q1 or Q2 described above, preferably the crosslinkable groups represented by the above formulas (P-1) to (P-30).
  • T1 may be a group in which two or more of these groups are combined. 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, from the viewpoint of better effects of the present invention.
  • the number of atoms in the main chain of T1 is preferably from 1 to 20, more preferably from 1 to 15, even more preferably from 1 to 10, and particularly preferably from 1 to 7, from the viewpoint of better effects of the present invention.
  • the number of atoms in the main chain of T1 is 20 or less, the degree of orientation of the light absorption anisotropic layer is further improved.
  • the "main chain" in T1 means the longest molecular chain that binds to M1, and hydrogen atoms are not counted in the number of atoms in the main chain of T1. For example, when T1 is an n-butyl group, 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 the total repeating units (100% by mass) of the polymer liquid crystalline compound. If the content of the repeating unit (1) is 40% by mass or more, an excellent light absorption anisotropic layer A can be obtained due to good orientation. Further, when the content of the repeating unit (1) is 100% by mass or less, an excellent light absorption anisotropic layer A can be obtained due to good orientation.
  • the repeating unit (1) may be contained singly or in combination of two or more in the polymer liquid crystalline compound. When two or more kinds of repeating units (1) are contained, the content of repeating units (1) means the total content of repeating units (1).
  • ) is preferably 4 or more, more preferably 4.25 or more, still more preferably 4.5 or more, from the viewpoint of further improving the degree of orientation of the light absorption anisotropic layer A.
  • the upper limit of the difference is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less, from the viewpoint of adjustment of the liquid crystal phase transition temperature and synthesis suitability.
  • the logP value is an index expressing the hydrophilicity and hydrophobicity of a chemical structure, and is sometimes called a hydrophilicity/hydrophobicity parameter. LogP values can be calculated using software such as ChemBioDraw Ultra or HSPiP (Ver.4.1.07).
  • logP 1 means the logP values of PC1, L1 and SP1 as described above.
  • logP value of PC1, L1 and SP1 means the logP value of the structure in which PC1, L1 and SP1 are integrated, and is not the sum of the logP values of PC1, L1 and SP1.
  • logP 1 is calculated by inputting a series of structural formulas from PC1 to SP1 in formula (1) into the software.
  • the portion of the group represented by PC1 is the structure of the group itself represented by PC1 (for example, the above-mentioned formula (P1-A ) to formula (P1-D), etc.) may be used, or the structure of a group that can be PC1 after polymerizing the monomer used to obtain the repeating unit represented by formula (1) good too.
  • PC1 when PC1 is obtained by polymerization of ethylene glycol, it is ethylene glycol, and when PC1 is obtained by polymerization of propylene glycol, it is propylene glycol.
  • a silanol a compound represented by the formula Si(R 2 ) 3 (OH).
  • a plurality of R 2 each independently represent a hydrogen atom or an alkyl group. However, , at least one of a plurality of R 2 represents an alkyl group).
  • logP 1 and logP 2 described above are preferably 4 or more, and may be lower than logP 2 or higher than logP 2 .
  • the logP value of common mesogenic groups tends to be in the range of 4-6.
  • the value of logP 1 is preferably 1 or less, more preferably 0 or less.
  • the value of logP 1 is preferably 8 or more, more preferably 9 or more.
  • the logP value of SP1 in the above formula ( 1 ) is 3. 7 or more is preferable, and 4.2 or more is more preferable.
  • Examples of structures with a logP value of 1 or less include an oxyethylene structure and an oxypropylene structure.
  • Structures with a logP value of 6 or more include a polysiloxane structure and an alkylene fluoride structure.
  • the polymer liquid crystalline compound preferably contains an electron-donating and/or electron-withdrawing repeating unit at the end. More specifically, a repeating unit (21) having a mesogenic group and an electron-withdrawing group having a ⁇ p value of greater than 0 present at the end thereof, and a mesogenic group and a ⁇ p value of 0 or less present at the end of the repeating unit (21) and a repeating unit (22) having a group.
  • the polymer liquid crystalline compound contains the repeating unit (21) and the repeating unit (22), it is more advantageous than the case where the polymer liquid crystalline compound contains only one of the repeating unit (21) and the repeating unit (22).
  • the degree of orientation of the light absorption anisotropic layer A formed by using is improved. Although the details of the reason for this are not clear, it is roughly estimated as follows. That is, the opposite dipole moments generated in the repeating unit (21) and the repeating unit (22) interact intermolecularly, thereby strengthening the interaction in the short axis direction of the mesogenic group, and the liquid crystal It is presumed that the orientation direction of the liquid crystal becomes more uniform, and as a result, the degree of order of the liquid crystal increases. As a result, the orientation of the dichroic dye is improved, so it is presumed that the degree of orientation of the light absorption anisotropic layer A to be formed is increased.
  • the repeating units (21) and (22) may be repeating units represented by the formula (1).
  • the repeating unit (21) has a mesogenic group and an electron-withdrawing group having a ⁇ p value of greater than 0 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 of greater than zero.
  • Examples of electron-withdrawing groups include groups represented by EWG in formula (LCP-21) described later, and specific examples thereof are the same.
  • the ⁇ p value of the electron-withdrawing group is preferably 0.3 or more, more preferably 0.4 or more, from the viewpoint of being greater than 0 and increasing the degree of orientation of the light absorption anisotropic layer A.
  • 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 Hammett's substituent constant ⁇ p value (also abbreviated simply as " ⁇ p value”), which numerically represents the effect of a substituent on the acid dissociation equilibrium constant of a substituted benzoic acid. It is a parameter that indicates the strength of electron-withdrawing and electron-donating properties.
  • Hammett's substituent constant ⁇ p value in this specification means the substituent constant ⁇ when the substituent is located at the para-position of benzoic acid.
  • Hammett's substituent constant ⁇ p value of each group in the present specification adopts the value described in the document "Hansch et al., Chemical Reviews, 1991, Vol, 91, No. 2, 165-195".
  • the repeating unit (21) is not particularly limited as long as it has a mesogenic group in a side chain and an electron-withdrawing group having a ⁇ p value greater than 0 present at the end of the mesogenic group, but the light absorption anisotropic layer From the viewpoint of increasing the degree of orientation of A, a repeating unit represented by the following formula (LCP-21) is preferable.
  • PC21 represents the main chain of the repeating unit, more specifically represents the same structure as PC1 in formula (1) above, and L21 represents a single bond or a divalent linking group.
  • SP21A and SP21B each independently represents 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 the mesogenic group MG in the above formula (LC), and EWG represents an electron-withdrawing group with a ⁇ p value of greater than zero.
  • the spacer group represented by SP21A and SP21B represents the same group as in the above formulas S1 and S2, and has at least one structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure and an alkylene fluoride structure. containing group, or a linear or branched alkylene group having 2 to 20 carbon atoms. However, the above alkylene group may contain -O-, -O-CO-, -CO-O-, or -O-CO-O-.
  • the spacer group represented by SP1 is at least one selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure and an alkylene fluoride structure, from the viewpoints of easy development of liquid crystallinity and availability of raw materials. It preferably contains a seed structure.
  • SP21B is preferably a single bond or a linear or branched alkylene group having 2 to 20 carbon atoms.
  • the above alkylene group may contain -O-, -O-CO-, -CO-O-, or -O-CO-O-.
  • the spacer group represented by SP21B is preferably a single bond from the viewpoint of increasing the degree of orientation of the light absorption anisotropic layer A.
  • the repeating unit 21 preferably has a structure in which the electron-withdrawing group EWG in formula (LCP-21) directly connects to the mesogenic group MG21 in formula (LCP-21).
  • the intermolecular interaction due to the appropriate dipole moment in the polymer liquid crystalline compound works more effectively, and the orientation direction of the liquid crystal is changed. It is presumed to be more uniform, and as a result, it is believed that the liquid crystal has a higher degree of order and a higher degree of orientation.
  • Electron-withdrawing groups having a ⁇ p value greater than 0 include an ester group (specifically, a group represented by *—C(O) ORE ), a (meth)acryloyl group, and a (meth)acryloyloxy group.
  • 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 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 a group represented by *-C(O)O-RE, a (meth)acryloyloxy group, a cyano group, or a nitro groups are preferred.
  • the content of the repeating unit (21) is such that the polymer liquid crystalline compound and the dichroic dye can be uniformly oriented while maintaining the high degree of orientation of the light absorption anisotropic layer A. It is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 45% by mass or less, based on the total repeating units (100% by mass).
  • the lower limit of the content of the repeating unit (21) is preferably 1% by mass or more based on the total repeating units (100% by mass) of the polymer liquid crystalline compound, from the viewpoint that the effect of the present invention is more exhibited. , more preferably 3% by mass or more.
  • each repeating unit contained in the polymer liquid crystalline compound is calculated based on the charged amount (mass) of each monomer used to obtain each repeating unit.
  • the repeating unit (21) may be contained alone or in combination of two or more in the polymer liquid crystalline compound.
  • the polymer liquid crystalline compound contains two or more repeating units (21)
  • advantages such as improved solubility of the polymer liquid crystalline compound in a solvent and easy adjustment of the liquid crystal phase transition temperature are obtained. be.
  • the total amount is preferably within the above range.
  • the repeating units (21) in which the EWG does not contain a crosslinkable group and the repeating units (21) in which the EWG contains a polymerizable group may be used in combination. Thereby, the curability of the light absorption anisotropic layer A is further improved.
  • crosslinkable groups include vinyl group, butadiene group, (meth)acryl group, (meth)acrylamide group, vinyl acetate group, fumarate ester group, styryl group, vinylpyrrolidone group, maleic anhydride, maleimide group, and vinyl ether. groups, epoxy groups or oxetanyl groups are preferred.
  • the content of the repeating unit (21) containing a polymerizable group in the EWG should be adjusted so that all the repeating units ( 100% by mass), it is preferably 1 to 30% by mass.
  • repeating unit (21) An example of the repeating unit (21) is shown below, but the repeating unit (21) is not limited to the following repeating units.
  • the present inventors have extensively studied the composition (content ratio) and the electron-donating and electron-withdrawing properties of the terminal groups of the repeating unit (21) and the repeating unit (22).
  • the group has a strong electron-withdrawing property (that is, when the ⁇ p value is large)
  • the degree of orientation of the light absorption anisotropic layer A can be increased by reducing the content of the repeating unit (21), and the repeating unit
  • the electron-withdrawing property of the electron-withdrawing group 21) is weak (that is, when the ⁇ p value is close to 0)
  • the degree of orientation of the light absorption anisotropic layer A can be improved by increasing the content of the repeating unit (21). was found to be higher.
  • the degree of orientation of the anisotropic layer A is higher.
  • the ⁇ p value of the electron-withdrawing group (EWG in the formula (LCP-21)) in the repeating unit (21) and the content ratio of the repeating unit (21) in the polymer liquid crystal compound (mass basis ) is preferably from 0.020 to 0.150, more preferably from 0.050 to 0.130, and even more preferably from 0.055 to 0.125. If the above product is within the above range, the degree of orientation of the light absorption anisotropic layer A will be higher.
  • the repeating unit (22) has a mesogenic group and a group having a ⁇ p value of 0 or less present at the end of the mesogenic group.
  • the mesogenic group is a group showing the main skeleton of the liquid crystal molecule that contributes to liquid crystal formation, and the details are as described for MG in formula (LCP-22) below, and the specific examples are the same.
  • the group is positioned at the end of the mesogenic group and has a ⁇ p value of 0 or less.
  • Examples of the above groups include a hydrogen atom with a ⁇ p value of 0, and a group represented by T22 in the following formula (LCP-22) with a ⁇ p value smaller than 0 (electron donor group).
  • specific examples of the group having a ⁇ p value of less than 0 (electron-donating group) are the same as T22 in formula (LCP-22) described later.
  • the ⁇ p value of the group is 0 or less, preferably less than 0, more preferably ⁇ 0.1 or less, and even more preferably ⁇ 0.2 or less from the viewpoint of better alignment uniformity.
  • the lower limit of the ⁇ p value of the group 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 present at the end of the mesogenic group, but the uniformity of the liquid crystal alignment is improved. From the viewpoint of increasing the cost, it is preferably a repeating unit represented by the following formula (PCP-22) instead of the repeating unit represented by the above formula (LCP-21).
  • PC22 represents the main chain of the repeating unit, more specifically represents the same structure as PC1 in formula (1) above, 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 is It represents a mesogenic structure, more specifically, a structure similar to the mesogenic group MG in the above formula (LC), and T22 represents an electron-donating group having a Hammett's substituent constant ⁇ p value of less than zero.
  • T22 represents an electron-donating group with a ⁇ p value of less than zero.
  • electron-donating groups having a ⁇ p value of less than 0 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 that binds 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 (22) An example of the repeating unit (22) is shown below, but the repeating unit (22) is not simply limited to the following repetitions.
  • the repeating unit (21) and the repeating unit (22) share a part of the structure. It is presumed that the more similar the structures of the repeating units are, the more uniformly the liquid crystals are aligned. Thereby, the degree of orientation of the light absorption anisotropic layer A becomes higher.
  • SP21A of formula (LCP-21) and SP22 of formula (LCP-22) have the same structure, and formula (LCP -21) and MG22 of formula (LCP-22) have the same structure, and L21 of formula (LCP-21) and L22 of formula (LCP-22) have the same structure, At least one of them is preferably satisfied, two or more are more preferable, and all are particularly preferable.
  • the content of the repeating unit (22) is preferably 50% by mass or more, more preferably 55% by mass or more, based on the total repeating units (100% by mass) of the polymer liquid crystal compound, from the viewpoint of excellent alignment uniformity. More preferably, 60% by mass or more is even more preferable.
  • the upper limit of the content of the repeating unit (22) is preferably 99% by mass or less, more preferably 97% by mass, based on the total repeating units (100% by mass) of the polymer liquid crystalline compound. The following are more preferred.
  • the repeating unit (22) may be contained alone or in combination of two or more in the polymer liquid crystalline compound.
  • the polymer liquid crystalline compound contains two or more repeating units (22), advantages such as improved solubility of the polymer liquid crystalline compound in a solvent and easy adjustment of the liquid crystal phase transition temperature are obtained. be.
  • the total amount is preferably within the above range.
  • the polymer liquid crystalline compound can contain a repeating unit (3) that does not contain a mesogen.
  • the repeating unit (3) containing no mesogen is a repeating unit having a molecular weight of 280 or less.
  • the solvent can easily enter the polymer liquid crystalline compound, so that the solubility is improved.
  • the repeating unit (3) is believed to reduce the degree of orientation. However, since the molecular weight of the repeating unit is small, the orientation of the repeating unit (1), the repeating unit (21), or the repeating unit (22) containing the mesogenic group is less likely to be disturbed, and a decrease in the degree of orientation can be suppressed. Presumed.
  • the repeating unit (3) is preferably a repeating unit having a molecular weight of 280 or less.
  • the molecular weight of the repeating unit (3) does not mean the molecular weight of the monomer used to obtain the repeating unit (3), but the repeating unit (3 ) means the molecular weight of The molecular weight of the repeating unit (3) is preferably 280 or less, more preferably 180 or less, even more preferably 100 or less.
  • the lower limit of the molecular weight of the repeating unit (3) is usually 40 or more, more preferably 50 or more.
  • repeating unit (3) examples include a repeating unit that does not contain a crosslinkable group (e.g., an ethylenically unsaturated group) (hereinafter also referred to as “repeating unit (3-1)”), and a crosslinkable group. (hereinafter also referred to as “repeating unit (3-2)”).
  • a crosslinkable group e.g., an ethylenically unsaturated group
  • monomers used for polymerization of the repeating unit (3-1) include acrylic acid [72.1], ⁇ -alkylacrylic acids (e.g., methacrylic acid [86.1], itaconic acid [130.1 ]), esters and amides derived therefrom (e.g., Ni-propylacrylamide [113.2], Nn-butylacrylamide [127.2], Nt-butylacrylamide [127.2 ], N,N-dimethylacrylamide [99.1], N-methylmethacrylamide [99.1], acrylamide [71.1], methacrylamide [85.1], diacetoneacrylamide [169.2], acryloyl morpholine [141.2], N-methylol acrylamide [101.1], N-methylol methacrylamide [115.1], methyl acrylate [86.0], ethyl acrylate [100.1], hydroxyethyl acrylate [116.
  • acrylic acid [72.1] ⁇ -alkylacrylic acids (e.g.,
  • vinyl acetate [86.1] maleic acid or esters derived from fumaric acid (e.g., dimethyl maleate [144.1], diethyl fumarate [172.2]), maleimides (e.g., N-phenylmaleimide [173.2]), maleic acid [ 116.1], fumaric acid [116.1], p-styrenesulfonic acid [184.1], acrylonitrile [53.1], methacrylonitrile [67.1], dienes (e.g., butadiene [54.1 ], cyclopentadiene [66.1], isoprene [68.1]), aromatic vinyl compounds (e.g., styrene [104.2], p-chlorostyrene [138.6], t-butylstyrene [160.3 ], ⁇ -methylstyrene [118.2]), N-vinylpyrrolidone [111.1], N-vinyloxazolidone [113.1], N-vinylsucc
  • the numerical value in [ ] means the molecular weight of a monomer.
  • the above monomers may be used singly or in combination of two or more.
  • acrylic acid, ⁇ -alkylacrylic acids, esters and amides derived therefrom, acrylonitrile, methacrylonitrile, and aromatic vinyl compounds are preferred.
  • Examples of monomers other than those described above include Research Disclosure No. 1955 (July, 1980) can be used.
  • repeating unit (3-1) Specific examples of the repeating unit (3-1) and their molecular weights are shown below, but the present invention is not limited to these specific examples.
  • the crosslinkable group examples include the crosslinkable groups represented by the above formulas (P-1) to (P-30), vinyl group, butadiene group, (meth ) acrylic group, (meth)acrylamide group, vinyl acetate group, fumarate ester group, styryl group, vinylpyrrolidone group, maleic anhydride, maleimide group, vinyl ether group, epoxy group, or oxetanyl group is more preferred.
  • the repeating unit (3-2) is preferably a repeating unit represented by the following formula (3).
  • PC32 represents the main chain of the repeating unit, more specifically represents the same structure as PC1 in the above formula (1)
  • L32 represents a single bond or a divalent linking group, More specifically, it has the same structure as L1 in formula (1) above
  • P32 represents a crosslinkable group represented by formulas (P-1) to (P-30) above.
  • repeating unit (3-2) and their weight average molecular weights (Mw) are shown below, but the present invention is not limited to these specific examples.
  • the content of the repeating unit (3) is preferably less than 14% by mass, more preferably 7% by mass or less, and further preferably 5% by mass or less, based on the total repeating units (100% by mass) of the polymer liquid crystalline compound.
  • the lower limit of the content of the repeating unit (3) is preferably 2% by mass or more, more preferably 3% by mass or more, based on the total repeating units (100% by mass) of the polymer liquid crystalline compound. If the content of the repeating unit (3) is less than 14% by mass, the degree of orientation of the light absorption anisotropic layer A is further improved. If the content of the repeating unit (3) is 2% by mass or more, the solubility of the polymer liquid crystalline compound is further improved.
  • the repeating unit (3) may be contained alone or in combination of two or more in the polymer liquid crystalline compound. When two or more repeating units (3) are included, the total amount is preferably within the above range.
  • the polymer liquid crystalline compound can contain a repeating unit (4) having a flexible structure with a long molecular chain (SP4 in formula (4) described later) from the viewpoint of improving adhesion and surface uniformity.
  • SP4 in formula (4) described later
  • the reason for this is presumed as follows. That is, by including such a flexible structure with long molecular chains, the molecular chains constituting the polymer liquid crystalline compound are easily entangled with each other, and the cohesive failure of the light absorption anisotropic layer A (specifically, , destruction of the light-absorbing anisotropic layer A itself) can be suppressed. As a result, it is presumed that the adhesion between the light absorption anisotropic layer A and the underlying layer (for example, the substrate or the alignment film) is improved.
  • the decrease in planar uniformity is caused by the low compatibility between the dichroic dye and the polymer liquid crystalline compound.
  • compatibility between the dichroic dye and the polymer liquid crystalline compound is insufficient, it is considered that surface defects (orientation defects) occur with the precipitated dichroic dye as the nucleus.
  • the polymer liquid crystalline compound contains a flexible structure with a long molecular chain, the deposition of the dichroic dye is suppressed, and the light absorption anisotropic layer A with excellent planar uniformity is obtained.
  • excellent planar uniformity means that the liquid crystalline composition containing the polymer liquid crystalline compound is repelled on the underlying layer (for example, the base material or the alignment film) to cause less alignment defects.
  • the repeating unit (4) is a repeating unit represented by the following formula (4).
  • PC4 represents the main chain of the repeating unit, more specifically represents the same structure as PC1 in the above formula (1)
  • L4 represents a single bond or a divalent linking group, More specifically, it represents the same structure as L1 in the above formula (1) (preferably a single bond)
  • SP4 represents an alkylene group having a main chain of 10 or more atoms
  • T4 represents a terminal group, and more Specifically, it represents the same structure as T1 in the above formula (1).
  • PC4 The specific example and preferred mode of PC4 are the same as PC1 in formula (1), so the description thereof is omitted.
  • a single bond is preferable as L4 from the viewpoint that the effects of the present invention are more exhibited.
  • SP4 represents an alkylene group having a main chain of 10 or more atoms.
  • R 21 to R 28 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a linear or branched alkyl group having
  • the number of atoms in the main chain of SP4 is 10 or more, preferably 15 or more, more preferably 19 or more, from the viewpoint of obtaining a light absorption anisotropic layer A having at least one of excellent adhesion and surface uniformity. preferable.
  • the upper limit of the number of atoms in the main chain of SP4 is preferably 70 or less, more preferably 60 or less, and even more preferably 50 or less, from the viewpoint of obtaining a light absorption anisotropic layer A with an excellent degree of orientation.
  • the "main chain” in SP4 means a partial structure necessary for directly connecting L4 and T4, and the "number of atoms in the main chain” means the number of atoms constituting the above partial structure. means.
  • the "main chain" in SP4 is the partial structure with the shortest number of atoms connecting L4 and T4.
  • the number of atoms in the main chain is 10
  • SP4 is a 4,6-dimethyldodecanyl group
  • the number of atoms in the main chain is 12.
  • the frame represented by the dotted square corresponds to SP4
  • the number of atoms in the main chain of SP4 is 11. .
  • the alkylene group represented by SP4 may be linear or branched.
  • the number of carbon atoms in the alkylene group represented by SP4 is preferably 8 to 80, more preferably 15 to 80, even more preferably 25 to 70, and 25 to 60 is particularly preferred.
  • One or more —CH 2 — constituting the alkylene group represented by SP4 is replaced with the above-mentioned “SP-C” from the viewpoint of obtaining a light absorption anisotropic layer A with excellent adhesion and surface uniformity. It is preferable that Further, when there are a plurality of —CH 2 — constituting the alkylene group represented by SP4, from the viewpoint of obtaining the light absorption anisotropic layer A excellent in adhesion and surface uniformity, one of the plurality of —CH 2 — More preferably, only the part is replaced by the above "SP-C".
  • R 21 to R 28 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a linear or branched alkyl group having 1 to 10 carbon atoms.
  • SP4 is an oxyalkylene structure in which one or more —CH 2 — constituting the alkylene group is replaced by —O—, and one or more —CH 2 —CH 2 — constituting the alkylene group is —O—.
  • a hydrogen atom contained in one or more —CH 2 — constituting the alkylene group represented by SP4 may be replaced by the aforementioned “SP—H”.
  • one or more hydrogen atoms contained in —CH 2 — may be replaced with “SP—H”.
  • T4 represents a terminal group similar to T1, as described above, and includes a hydrogen atom, a methyl group, a hydroxy group, a carboxy group, a sulfonic acid group, a phosphate group, a boronic acid group, an amino group, a cyano group, a nitro group, A phenyl group optionally having a substituent, or -L-CL (L represents a single bond or a divalent linking group. Specific examples of the divalent linking group are the same as LW and SPW described above.
  • CL represents a crosslinkable group, including the groups represented by Q1 or Q2 above, preferably crosslinkable groups represented by formulas (P-1) to (P-30).
  • the above CL includes vinyl group, butadiene group, (meth)acryl group, (meth)acrylamide group, vinyl acetate group, fumarate ester group, styryl group, vinylpyrrolidone group, maleic anhydride, maleimide group, vinyl ether group,
  • An epoxy group or an oxetanyl group is preferred.
  • the epoxy group may be an epoxycycloalkyl group, and the number of carbon atoms in the cycloalkyl group portion of the epoxycycloalkyl group is preferably 3 to 15, more preferably 5 to 12, from the viewpoint of better effects of the present invention. , 6 (ie when the epoxycycloalkyl group is an epoxycyclohexyl group) are more preferred.
  • Examples of the substituent of the oxetanyl group include alkyl groups having 1 to 10 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferable from the standpoint of more excellent effects of the present invention.
  • the alkyl group as a substituent of the oxetanyl group may be linear or branched, but is preferably linear from the viewpoint of more excellent effects of the present invention.
  • Examples of the substituent of the phenyl group include boronic acid group, sulfonic acid group, vinyl group, and amino group, and boronic acid group is preferable from the viewpoint of more excellent effects of the present invention.
  • repeating unit (4) include the following structures, but the present invention is not limited thereto.
  • n1 represents an integer of 2 or more
  • n2 represents an integer of 1 or more.
  • the content of the repeating unit (4) is preferably 2 to 20% by mass, more preferably 3 to 18% by mass, based on the total repeating units (100% by mass) of the polymer liquid crystalline compound. If the content of the repeating unit (4) is 2% by mass or more, the light absorption anisotropic layer A having excellent adhesion can be obtained. Further, when the content of the repeating unit (4) is 20% by mass or less, the light absorption anisotropic layer A having excellent planar uniformity can be obtained.
  • the repeating unit (4) may be contained alone or in combination of two or more in the polymer liquid crystalline compound. When two or more repeating units (4) are contained, the content of the repeating units (4) means the total content of the repeating units (4).
  • the polymer liquid crystalline compound may contain repeating units (5) introduced by polymerizing a polyfunctional monomer.
  • the repeating unit (5) introduced by polymerizing the polyfunctional monomer should be replaced with all the repeating units (100 mass %), preferably 10% by mass or less.
  • the reason why the planar uniformity can be improved while suppressing the decrease in the degree of orientation by including the repeating unit (5) in an amount of 10% by mass or less is presumed as follows.
  • the repeating unit (5) is a unit introduced into the polymer liquid crystalline compound by polymerizing a polyfunctional monomer.
  • the polymer liquid crystalline compound contains a polymer having a three-dimensional crosslinked structure formed by the repeating unit (5).
  • the content of the repeating unit (5) is small, the content of the polymer containing the repeating unit (5) is considered to be very small.
  • the presence of a small amount of the high molecular weight material having the three-dimensional crosslinked structure suppresses the repelling of the composition for forming the light absorption anisotropic layer A, and the light absorption anisotropic layer having excellent planar uniformity is obtained. It is presumed that a layer A was obtained. In addition, it is presumed that the effect of suppressing the decrease in the degree of orientation could be maintained because the content of the high molecular weight substance was small.
  • the repeating unit (5) introduced by polymerizing the polyfunctional monomer is preferably a repeating unit represented by the following formula (5).
  • PC5A and PC5B represent the main chain of the repeating unit, and more specifically represent the same structure as PC1 in formula (1) above, and L5A and L5B are single bonds or divalent linking groups.
  • L5A and L5B are single bonds or divalent linking groups.
  • SP5A and SP5B represent spacer groups, more specifically the same structure as SP1 in the above formula (1)
  • MG5A and MG5B represent a mesogenic structure, more specifically a structure similar to the mesogenic group MG in formula (LC) above, and a and b represent integers of 0 or 1.
  • PC5A and PC5B may be the same group or different groups, but from the viewpoint of further improving the degree of orientation of the light absorption anisotropic layer A, they are preferably the same group. .
  • Both L5A and L5B may be a single bond, the same group, or different groups. From the point of view, all are preferably a single bond or the same group, more preferably the same group.
  • Both SP5A and SP5B may be a single bond, the same group, or different groups, but the degree of orientation of the light absorption anisotropic layer A is further improved. From the point of view, all are preferably a single bond or the same group, more preferably the same group.
  • the same group in formula ( 5 ) means that the chemical structure is the same regardless of the bonding direction of each group.
  • * (* represents the binding position with L5A, ** represents the binding position with MG5A), and SP5B is *-O-CH 2 -CH 2 -** (* represents the binding position with MG5B). and ** represents the bonding position with L5B.) is also the same group.
  • Each of a and b is independently an integer of 0 or 1, and preferably 1 from the viewpoint of further improving the degree of orientation of the light absorption anisotropic layer A. Although a and b may be the same or different, both are preferably 1 from the viewpoint of further improving the degree of orientation of the light absorption anisotropic layer A.
  • the sum of a and b is preferably 1 or 2 from the viewpoint of further improving the degree of orientation of the light absorption anisotropic layer A (that is, the repeating unit represented by formula (5) has a mesogenic group ), and more preferably 2.
  • the partial structure represented by -(MG5A) a -(MG5B) b - preferably has a cyclic structure from the viewpoint of further improving the degree of orientation of the light absorption anisotropic layer A.
  • the number of cyclic structures in the partial structure represented by -(MG5A2) a -(MG5B) b - is preferably 2 or more in order to further improve the degree of orientation of the light absorption anisotropic layer A. 2 to 8 are more preferred, 2 to 6 are even more preferred, and 2 to 4 are particularly preferred.
  • Each of the mesogenic groups represented by MG5A and MG5B independently preferably contains one or more cyclic structures, more preferably 2 to 4, from the viewpoint of further improving the degree of orientation of the anisotropic light absorption layer A. It is more preferred to contain 2 to 3, and it is particularly preferred to contain 2.
  • Specific examples of the cyclic structure include aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups, among which aromatic hydrocarbon groups and alicyclic groups are preferred.
  • MG5A and MG5B may be the same group or different groups, but from the viewpoint of further improving the degree of orientation of the light absorption anisotropic layer A, they are preferably the same group. .
  • the mesogenic group represented by MG5A and MG5B is represented by the above formula (LC) from the viewpoint of the development of liquid crystallinity, the adjustment of the liquid crystal phase transition temperature, the availability of raw materials and the synthesis suitability, and the viewpoint that the effect of the present invention is more excellent. It is preferably the mesogenic group MG.
  • PC5A and PC5B are the same group
  • L5A and L5B are both single bonds or the same group
  • SP5A and SP5B are both single bonds or the same group
  • MG5A and MG5B are preferably the same group.
  • the content of the repeating unit (5) is preferably 10% by mass or less, more preferably 0.001 to 5% by mass, based on the total repeating unit content (100% by mass) of the polymer liquid crystalline compound. 0.05 to 3% by mass is more preferable.
  • the repeating unit (5) may be contained alone or in combination of two or more in the polymer liquid crystalline compound. When two or more kinds of repeating units (5) are included, the total amount is preferably within the above range.
  • the polymer liquid crystalline compound may be a star polymer.
  • a star polymer in the present invention means a polymer having three or more polymer chains extending from a nucleus, and specifically, a polymer represented by the following formula (6).
  • the star-shaped polymer represented by the formula (6) as the macromolecular liquid crystalline compound can form the light absorption anisotropic layer A with a high degree of orientation while being highly soluble (excellent solubility in a solvent).
  • nA represents an integer of 3 or more, preferably an integer of 4 or more. Although the upper limit of nA is not limited to this, it is usually 12 or less, preferably 6 or less.
  • Each of the plurality of PIs independently has a polymer chain containing any of the repeating units represented by the above formulas (1), (21), (22), (3), (4), and (5). show. However, at least one of the plurality of PIs represents a polymer chain containing the repeating unit represented by formula (1) above.
  • A represents an atomic group that forms the nucleus of the star polymer. Specific examples of A include [0052] to [0058] paragraphs of Japanese Patent Application Laid-Open No.
  • the number of thiol groups in the polyfunctional thiol compound from which A is derived is preferably 3 or more, more preferably 4 or more.
  • the upper limit of the number of thiol groups in the polyfunctional thiol compound is usually 12 or less, preferably 6 or less. Specific examples of polyfunctional thiol compounds are shown below.
  • the polymer liquid crystalline compound may be a thermotropic liquid crystal and a crystalline polymer from the viewpoint of improving the degree of orientation.
  • thermotropic liquid crystal is a liquid crystal that exhibits a transition to a liquid crystal phase due to a change in temperature, and preferred embodiments are the same as above.
  • a crystalline polymer is a polymer that exhibits a transition to a crystalline layer upon temperature change.
  • the crystalline polymer may exhibit a glass transition as well as a transition to a crystalline layer.
  • the degree of orientation of the light absorption anisotropic layer A becomes higher, and the haze becomes more difficult to observe, so that when heated, the crystal phase transitions to the liquid crystal phase (glass in the middle).
  • a compound is preferred.
  • the presence or absence of crystallinity of the polymer liquid crystalline compound is evaluated as follows. Two optical absorption anisotropic layers A of an optical microscope (Nikon ECLIPSE E600 POL) are arranged perpendicular to each other, and a sample stage is set between the two optical absorption anisotropic layers. Then, a small amount of polymer liquid crystalline compound is placed on a slide glass, and the slide glass is set on a hot stage placed on a sample table. While observing the state of the sample, the temperature of the hot stage is raised to a temperature at which the polymer liquid crystalline compound exhibits liquid crystallinity, thereby bringing the polymer liquid crystalline compound into a liquid crystal state.
  • the behavior of the liquid crystal phase transition is observed while gradually lowering the temperature of the hot stage, and the temperature of the liquid crystal phase transition is recorded.
  • the polymer liquid crystalline compound exhibits a plurality of liquid crystal phases (for example, a nematic phase and a smectic phase)
  • all the transition temperatures are also recorded.
  • DSC differential scanning calorimeter
  • the method for obtaining the crystalline polymer is not particularly limited, but as a specific example, a method using a polymeric liquid crystalline compound containing the repeating unit (1) is preferable. A method using a preferred embodiment of the liquid crystalline compound is more preferred.
  • the crystallization temperature of the polymer liquid crystal compound is preferably ⁇ 50° C. or more and less than 150° C., because the degree of orientation of the light absorption anisotropic layer A becomes higher and haze becomes more difficult to observe. , more preferably 120°C or less, more preferably -20°C or more and less than 120°C, and particularly preferably 95°C or less. From the viewpoint of reducing haze, the crystallization temperature of the polymer liquid crystalline compound is preferably less than 150°C.
  • the crystallization temperature is the exothermic peak temperature due to crystallization in the DSC described above.
  • the weight-average molecular weight (Mw) of the polymer liquid crystalline compound is preferably 1,000 to 500,000, more preferably 2,000 to 300,000, from the viewpoint of more excellent effects of the present invention. If the Mw of the liquid crystalline polymer compound is within the above range, the liquid crystalline polymer compound can be easily handled.
  • the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably 10,000 or more, more preferably 10,000 to 300,000.
  • the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably less than 10,000, more preferably 2,000 or more and less than 10,000.
  • the weight average molecular weight and number average molecular weight in the present invention are values measured by a gel permeation chromatography (GPC) method.
  • the content of the rod-like liquid crystalline compound is preferably 10 to 97 parts by mass, more preferably 40 to 95 parts by mass, with respect to the total mass of the light absorption anisotropic layer A (100 parts by mass), from the viewpoint that the effects of the present invention are more excellent. is more preferred, and 60 to 95 parts by mass is even more preferred.
  • the content of the macromolecular liquid crystalline compound is preferably 10 to 99 parts by weight, preferably 30 to 99 parts by weight, based on the total weight (100 parts by weight) of the rod-like liquid crystalline compound. 95 parts by mass is more preferable, and 40 to 90 parts by mass is even more preferable.
  • the content of the low-molecular-weight liquid crystalline compound is preferably 1 to 90 parts by weight, preferably 5 to 90 parts by weight, based on the total weight (100 parts by weight) of the rod-like liquid crystalline compound. 70% by mass is more preferred, and 10 to 60 parts by mass is even more preferred.
  • the mass ratio of the content of the low molecular liquid crystalline compound to the content of the high molecular liquid crystalline compound is preferably from 5/95 to 70/30, more preferably from 10/90 to 50/50, from the viewpoint of more excellent effects of the present invention.
  • the content of the liquid crystalline compound is preferably 25 to 2000 parts by mass, more preferably 100 to 1300 parts by mass with respect to 100 parts by mass of the dichroic dye content in the total mass of the light absorption anisotropic layer A. 200 to 1000 is more preferable, and 200 to 900 parts by mass is particularly preferable. That is, the content of the dichroic dye is particularly preferably 1 to 50% by mass relative to the content of the liquid crystalline compound. When the content of the liquid crystalline compound is within the above range, the degree of orientation of the light absorption anisotropic layer A is further improved.
  • the liquid crystalline compound may be contained individually by 1 type, and may be contained 2 or more types. When two or more kinds of liquid crystalline compounds are contained, the content of the liquid crystalline compounds means the total content of the liquid crystalline compounds.
  • the dichroic substance contained in the composition for forming the light absorption anisotropic layer A is not particularly limited, and is a visible light absorbing substance (dichroic dye), a light emitting substance (fluorescent substance, phosphorescent substance), and an ultraviolet absorbing substance. , infrared absorbing substances, nonlinear optical substances, carbon nanotubes, inorganic substances (for example, quantum rods), etc., and conventionally known dichroic substances (dichroic dyes) can be used.
  • a dichroic dye that absorbs visible light for example, a dichroic dye that has a maximum absorption at a wavelength of 400 to 700 nm.
  • a dichroic dye that has a maximum absorption at a wavelength of 400 to 700 nm for example, a dichroic dye that has a maximum absorption at a wavelength of 400 to 700 nm.
  • Other dichroic substances include, for example, paragraphs [0067] to [0071] of JP-A-2013-228706, paragraphs [0008] to [0026] of JP-A-2013-227532, and JP-A-2013-209367.
  • the maximum absorption wavelength is 560 nm or more and 700 nm or less (more preferably 560 to 650 nm, particularly preferably 560 to 640 nm), the first dichroic dye having a maximum absorption wavelength in the range of 455 nm or more and less than 560 nm (more preferably 455 to 555 nm, particularly preferably 455 to 550 nm)
  • the light absorption anisotropic layer A can be applied to applications having polarization performance from the visible light region to the infrared region.
  • the light absorption anisotropic layer A of the present invention preferably has a luminosity correction single transmittance of 30 to 50% at a wavelength of 400 to 700 nm.
  • the luminosity-corrected single transmittance is the average transmittance weighted by the luminosity of the human eye for unpolarized light with a wavelength of 400 to 700 nm.
  • the luminosity-corrected single transmittance can be obtained by performing luminosity correction on the transmittance for each wavelength measured with a spectrophotometer using a 2-degree field of view (C light source) of JIS Z 8701.
  • the dichroic substance may have a crosslinkable group.
  • the crosslinkable group include a (meth)acryloyl group, an epoxy group, an oxetanyl group, a styryl group, etc. Among them, a (meth)acryloyl group is preferable.
  • the accompanying layers include an alignment layer (alignment film), particularly preferably a photo-alignment layer (photo-alignment film), a protective layer, a refractive index adjusting layer, and the like. It is preferable to have For details, reference can be made to the description of International Publication 2019-131943.
  • the light absorption anisotropic layer A preferably has a maximum absorption wavelength in the wavelength range of 700 to 1500 nm. Since the light absorption anisotropic layer A has a maximum absorption wavelength in the above range, it can absorb near infrared rays in the wavelength range of 700 to 1500 nm. As a result, it can be used as a light absorption anisotropic layer having absorption in the near-infrared region.
  • the light absorption anisotropic layer A of the present invention is preferably a film having different absorbances depending on the direction with respect to light having a wavelength of 700 to 1500 nm.
  • the anisotropic light absorption layer A preferably has a first maximum absorption wavelength in the wavelength range of 700 nm or more and less than 900 nm, and a second maximum absorption wavelength in the wavelength range of 900 to 1500 nm.
  • the absorption characteristics of the light absorption anisotropic layer A as described above can be achieved by using a dichroic substance having a maximum absorption wavelength in the above wavelength range.
  • the dichroic dye may have various orientations.
  • the alignment state includes, for example, homogeneous alignment and homeotropic alignment. More specifically, the orientation states include, for example, nematic orientation (a state in which a nematic phase is formed), smectic orientation (a state in which a smectic phase is formed), twisted orientation, and cholesteric orientation (a state in which a cholesteric phase is formed). ), and hybrid orientations.
  • a liquid crystalline compound for example, the lyotropic liquid crystalline compound described above. That is, when the light absorption anisotropic layer contains a liquid crystalline compound, the dichroic dye can also be oriented in accordance with the above-described predetermined orientation state of the liquid crystalline compound.
  • the light absorption anisotropic layer A preferably has an absorption axis at the maximum absorption wavelength in the in-plane direction.
  • the dichroic dye having absorption at the maximum absorption wavelength is homogeneously oriented in the light absorption anisotropic layer (the long axis direction of the dichroic dye is oriented with respect to the light absorption anisotropic layer surface. horizontally and in the same orientation).
  • the light absorption anisotropic layer A preferably has an absorption axis at the maximum absorption wavelength along the thickness direction.
  • the dichroic substance dye having absorption at the maximum absorption wavelength is homeotropically oriented in the light absorption anisotropic layer (the long axis direction of the dichroic substance dye is the surface of the light absorption anisotropic layer). can be achieved by aligning them perpendicular to the
  • the absorption axis of the light absorption anisotropic layer A at a wavelength of 250 nm and the light absorption at the maximum absorption wavelength of the dichroic dye It is also preferable that the angle formed by the absorption axis of the anisotropic layer A is 0 to 5°.
  • the direction of the absorption axis of the light absorption anisotropic layer A at the maximum absorption wavelength of the dichroic dye is obtained in the measurement of the degree of orientation in the case of homogeneous orientation described below.
  • the absorption axis at a wavelength of 250 nm can also be measured in the same manner as the degree of orientation described below.
  • the light absorption anisotropic layer A has an absorption axis at the maximum absorption wavelength along the thickness direction and contains a dichroic dye having a maximum absorption at a wavelength of 400 to 700 nm
  • the maximum absorption at a wavelength of 400 to 700 nm is 10 to 90° is also preferred.
  • the direction of the absorption axis at the maximum absorption wavelength of the dichroic dye corresponds to the azimuthal angle and polar angle with the highest transmittance obtained in the following measurement of the degree of orientation in the case of homeotropic orientation.
  • the absorption axis of the light absorption anisotropic layer A at the maximum absorption wavelength of the dichroic dye having a maximum absorption at a wavelength of 400 to 700 nm can be measured in the same manner as the degree of orientation described below.
  • the degree of orientation of the dichroic dye in the light absorption anisotropic layer A is not particularly limited, it is preferably 0.80 or more, and 0.85 or more in terms of better absorption characteristics of the light absorption anisotropic layer A. It is more preferably 0.90 or more, and particularly preferably 0.95 or more. Although the upper limit is not particularly limited, 1.00 can be mentioned.
  • the degree of orientation is the degree of orientation measured by the maximum absorption wavelength of the dichroic dye in the light absorption anisotropic layer A. When the dichroic dye forms a J-aggregate in the light absorption anisotropic layer A, the degree of orientation is measured using the maximum absorption wavelength derived from the J-aggregate.
  • the degree of orientation is calculated by the following method.
  • a linear polarizer inserted on the light source side of an optical microscope (manufactured by Nikon Corporation, product name "ECLIPSE E600 POL")
  • the light absorption anisotropic layer was set on the sample stage, and a multichannel spectroscope (Ocean Optics)
  • the absorbance of the light absorption anisotropic layer A is measured using the product name "QE65000" manufactured by Epson Co., Ltd., and the value is calculated by the following formula.
  • the degree of orientation is calculated by the following method. Using AxoScan OPMF-1 (manufactured by Optoscience), the transmittance of the light absorption anisotropic layer A for P-polarized light at the maximum absorption wavelength of the dichroic dye is measured.
  • the transmittance at the azimuth angle and polar angle with the highest transmittance is Tm(0).
  • Tm(40) be the transmittance at an angle in which the polar angle is tilted by 40°.
  • the absorbance is calculated from the obtained Tm(0) and Tm(40) by the following formula, and A(0) and A(40) are calculated.
  • A -log(Tm)
  • Tm represents transmittance
  • A represents absorbance.
  • the film thickness of the light absorption anisotropic layer A is 5 ⁇ m or less, and preferably 3 ⁇ m or less from the viewpoint of better bending properties.
  • the lower limit is not particularly limited, it is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, from the viewpoint of handleability.
  • the film thickness of the light absorption anisotropic layer A is measured by using an ultra-high resolution non-contact director and surface shape measurement system BW-A501 manufactured by Nikon Corporation for arbitrary 10 points of the light absorption anisotropic layer A. It is the average value obtained by arithmetically averaging the obtained values.
  • the light absorption anisotropic layer A preferably has an ordered structure derived from a crystal phase or a higher-order liquid crystal phase in terms of the degree of orientation.
  • the presence of the ordered structure can be confirmed by performing X-ray diffraction measurement using the light absorption anisotropic layer A as a sample and observing a crystalline Bragg peak (a peak derived from Bragg reflection) by X-ray diffraction.
  • the light absorption anisotropic layer A of the present invention may be combined with other members to form a laminate.
  • a laminate for example, a light absorption anisotropic layer A and a dichroic dye having a maximum absorption at a wavelength of 400 to 700 nm are contained, and the visibility correction single transmittance at a wavelength of 400 to 700 nm is 30 to 50%.
  • a laminate having a certain light absorption anisotropic layer B can be mentioned.
  • the absorption axis at the maximum absorption wavelength of the anisotropic light absorption layer B and the maximum absorption of the anisotropic light absorption layer A is parallel.
  • the absorption axis at the wavelength is parallel.
  • the absorption axis at the maximum absorption wavelength of the anisotropic light absorption layer B and the absorption axis at the maximum absorption wavelength of the anisotropic light absorption layer A may not be parallel.
  • the layers are preferably laminated so that the absorption axis of the anisotropic light absorption layer B and the absorption axis of the anisotropic light absorption layer A form an angle of 10 to 90°.
  • the laminate is a circularly polarizing plate in which a light absorption anisotropic layer B that absorbs visible light and an optically anisotropic layer that exhibits the properties of a ⁇ /4 wavelength plate for visible light are combined. It may be a laminate in which the light absorption anisotropic layer A has a function of polarizing infrared light while satisfying the function of preventing reflection of light.
  • Another embodiment of the laminate includes a laminate having the light-absorbing anisotropic layer A of the present invention and an optically anisotropic layer and capable of generating circularly polarized infrared light.
  • the optically anisotropic layer of the laminate capable of generating circularly polarized infrared light has an in-plane retardation of 10 at the maximum absorption wavelength ⁇ A (unit: nm) of the optically anisotropic layer A.
  • ⁇ A /4 nm is preferred.
  • the anisotropic light absorption layer A of the present invention when used in an image display device, the anisotropic light absorption layer A and the It is also preferable to use it as a laminate having the optically anisotropic layer used.
  • the in-plane retardation of the entire laminate at a wavelength of 550 nm is preferably 0 to 50 nm.
  • the sum of out-of-plane retardations of each member of the laminate at a wavelength of 550 nm is preferably -50 to 50 nm.
  • the laminate may have a light absorption anisotropic layer B.
  • the laminate may be in a mode having the light absorption anisotropic layer A and the wire grid polarizer. Since the wire grid polarizer is a reflective polarizer, the reflected light may adversely affect it as stray light. By laminating so that the angle between the absorption axis of the light absorption anisotropic layer A and the absorption axis of the wire grid polarizer is 1° or less, stray light can be reduced, which is preferable.
  • the light absorption anisotropic layer B used in the laminate of the present invention contains a dichroic dye having a maximum absorption at a wavelength of 400 to 700 nm, and has a luminosity correction single transmittance of 30 to 50% at a wavelength of 400 to 700 nm. It is below.
  • stretched PVA resin containing iodine stretched polyvinyl alcohol dyed with iodine
  • a stretched PVA resin containing an organic dichroic dye described in JP-A-2019-86622 can also be used as the light absorption anisotropic layer B.
  • the dichroic dyes used in the light absorption anisotropic layer B it is preferable to use a plurality of dichroic dyes in combination from the viewpoint of broadband.
  • the first dichroic dye having a maximum absorption wavelength in the range of 560 nm or more and 700 nm or less (more preferably 560 to 650 nm, particularly preferably 560 to 640 nm), maximum absorption A second dichroic dye having a maximum absorption wavelength in the range of 455 nm or more and less than 560 nm (more preferably 455 to 555 nm, particularly preferably 455 to 550 nm), and 380 nm or more and less than 455 nm (more preferably 385 to It is more preferable to use a third dichroic dye having a maximum absorption wavelength in the range of 454 nm).
  • the laminate of the invention preferably has an optically anisotropic layer.
  • the optically anisotropic layer refers to any film that produces a phase difference in transmitted light. and a retardation film.
  • the alignment direction of the liquid crystalline compound contained in the optically anisotropic layer there are no particular restrictions on the alignment direction of the liquid crystalline compound contained in the optically anisotropic layer, and examples thereof include horizontal alignment, vertical alignment, and twisted alignment with respect to the film surface.
  • specific functions of the optically anisotropic layer include, for example, a ⁇ /4 plate and a ⁇ /2 plate.
  • the optically anisotropic layer may consist of a plurality of layers.
  • optically anisotropic layer comprising a plurality of optically anisotropic layers
  • the description in paragraphs [0008] to [0053] of JP-A-2014-209219 can be referred to.
  • an optically anisotropic layer and the above-described light absorption anisotropic layer A may be provided in contact with each other, or another layer may be provided therebetween.
  • Such a layer includes an adhesive layer or adhesive layer for securing adhesion.
  • the laminate of the present invention is used as a circularly polarizing plate for visible light, it is preferable to use a ⁇ /4 plate as the optically anisotropic layer described above. More preferably it has a plate.
  • the " ⁇ / 4 plate” is a plate having a ⁇ / 4 function, specifically, the function of converting linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light) is a plate with
  • the ⁇ /4 plate has a single layer structure include, specifically, a stretched polymer film and a retardation film having an optically anisotropic layer having a ⁇ /4 function on a support.
  • a broadband ⁇ /4 plate formed by laminating a ⁇ /4 plate and a ⁇ /2 plate can be mentioned.
  • the polarizing plate of the present invention can be produced by the method described for the light absorption anisotropic layer A and the laminate.
  • a film for protecting the light absorption anisotropic layer A and the like may be provided on one or both sides of the polarizing plate via an adhesive, a pressure-sensitive adhesive, or the like.
  • a protective film By using a protective film, a physically stable and highly flexible film can be obtained.
  • protective films include triacetyl cellulose films, acrylic films, polycarbonate films, and cycloolefin films that are used as conventional protective films for polarizing plates. Among them, a protective film that is transparent, has little birefringence, and hardly generates a retardation is preferable.
  • the base material When a film made of a thermoplastic resin is used as the base material, the base material may be used as the protective film as it is because the film already has a high surface hardness and is less susceptible to humidity. Further, when producing a polarizing plate, a polymerizable resin composition or the like is applied to the light absorption anisotropic layer A or the surface of the laminate, and a hard coat layer, an antiglare layer, a low reflection layer, etc. are formed. may be provided. When a protective film is provided on the polarizing plate, the above protective film may be laminated on one or both sides of the polarizing plate via an adhesive and dried. The drying conditions can be appropriately changed depending on the concentration of the adhesive used and the moisture permeability of the protective film.
  • the polarizing plate of the present invention can also be used as a laminated substrate by bonding to inorganic substrates such as prisms and glass, and organic substrates such as plastic plates. It is also possible to form a curved surface layered substrate by laminating a polarizing plate according to the curved surface of a glass or plastic plate.
  • the polarizing plate may be used in combination with other layers or films, for example, when applied to a display device such as a liquid crystal display device.
  • Other layers or films include various functional layers for viewing angle improvement and/or contrast improvement, and layers or films with brightness enhancement properties.
  • Various functional layers include, for example, layers or films that control retardation.
  • the polarizing plate may have various known functional layers such as an antireflection layer, an antiglare layer, and a hard coat layer on the protective layer or the exposed surface of the film.
  • a coating method is preferable as a method for producing a layer having various functions.
  • a layer having various functionalities may be produced by bonding films having various functionalities to the laminate via an adhesive or pressure-sensitive adhesive.
  • the light absorption anisotropic layer A and the laminate of the present invention can be used as a polarizing element (polarizing plate) in the infrared wavelength region, for example, can be used as a linear polarizing plate or a circular polarizing plate, and infrared light can be linearly polarized or It can be used for all kinds of applications that take advantage of the feature of being able to convert to circularly polarized light. Specific applications include display devices, sensors, lenses, switching elements, isolators, and cameras. , and can be used for receiving only necessary infrared polarized light or infrared circularly polarized light by being attached to an infrared light receiving section.
  • infrared circular polarizer for preventing reflection of infrared light.
  • infrared sensor system to be described later, by linearly polarized light or circularly polarized light (polarized light) for the emission (projection) and incidence (reception) of infrared light, not only information on light intensity but also phase can be obtained. Information such as changes can also be obtained.
  • polarized light By projecting and receiving polarized light, the influence of light from the outside can be reduced and the S/N ratio can be increased.
  • the infrared light sensor system of the present invention is not particularly limited as long as it has the light absorption anisotropic layer A or laminate of the present invention described above.
  • Examples of infrared light sensor systems include sensor systems for detecting objects and measuring the distance to objects, and sensors for measuring the surface and internal conditions of objects by detecting reflected or transmitted light. sensor system, etc.
  • the infrared light sensor system is preferably mounted on a device or the like.
  • Devices and the like equipped with infrared light sensor systems are not particularly limited, and examples thereof include portable devices such as smartphones, smart watches, and smart glasses, and stationary devices such as televisions and smart speakers.
  • the infrared light sensor system may be mounted on automobiles, drones, buildings, transportation infrastructure, and the like.
  • the infrared light sensor system of the present invention preferably has at least one of an infrared light source and an infrared light receiving section, more preferably both.
  • the light absorption anisotropic layer A and the laminate of the present invention are preferably used on the emission side of the infrared light source and the incidence side of the infrared light receiving section.
  • any infrared light source can be applied, and typically infrared emitting LED (light emitting diode) devices, infrared lasers, and various lamps having an emission band in the near infrared region. is mentioned.
  • LED light emitting diode
  • a photodetection element such as a photodiode or a phototransistor sensitive to the non-visible light region can be applied as the infrared light receiving section.
  • a photodiode or phototransistor sensitive to the near-infrared region is preferable.
  • An organic photodiode (OPD) or an organic phototransistor (OPT) may be applied as the photodetector.
  • the target to be detected by the light receiving unit is not particularly limited. degree, fingerprint, and iris. That is, the infrared light sensor system of the present invention can detect the shape of the object, the surface condition of the object, the user's eye movement, eye position, expression, face shape, vein pattern, blood flow, pulse, blood oxygen saturation, fingerprint , and the iris may be detected or recognized.
  • a mode of the infrared light sensor system of the present invention will be described with reference to the drawings.
  • Each figure is a schematic diagram and does not show the specific number, arrangement, distance, etc. of the actual mode, and the number, arrangement, distance, etc. can be changed as appropriate.
  • the infrared light sensor system 100a shown in FIG. a light absorption anisotropic layer A1a and a light absorption anisotropic layer A1b are respectively arranged.
  • the infrared emitted light 11 is emitted from the infrared light source 101 through the light absorption anisotropic layer A1a, and the infrared light reflected from the measurement object 105 has light absorption anisotropic layer A1a.
  • the incident infrared light 12 is received by the infrared receiving section 102 through the anisotropic layer A1b.
  • the measurement target 105 can be detected or recognized by receiving the infrared light reflected from the measurement target 105 as the infrared incident light 12 by the infrared light receiving unit 102 .
  • the anisotropic light absorption layer A1a and the anisotropic light absorption layer A1b can be used as a polarizing element (polarizing plate) in the infrared wavelength region. Therefore, the infrared light emitted from the infrared light sensor system 100a may be polarized light (for example, linearly polarized light).
  • the anisotropic light absorption layer A1a and the anisotropic light absorption layer A1b function as a polarizer and a polarizing filter, and the polarization direction may be determined depending on the purpose.
  • the infrared sensor system 100 may include a mechanism (for example, a rotation mechanism) for changing the polarization directions of the anisotropic light absorption layer A1a and the anisotropic light absorption layer A1b. Further, the infrared sensor system 100a may further include a light absorption anisotropic layer B that absorbs visible light as described in the laminate. Preferred aspects of the laminate are as described above.
  • the infrared light sensor system 100a shown in FIG. 1 may further comprise an optically anisotropic layer. That is, it may be in the form of the infrared light sensor system 100b shown in FIG.
  • the infrared light sensor system 100b shown in FIG. 2 includes an infrared light source 101 and an infrared light receiving section 102.
  • the light absorption anisotropic layer A 1a and the optically anisotropic layer 2a are arranged on the measurement side of the infrared light source 101 (the measurement target 105 side),
  • the anisotropic light absorption layer A1b and the anisotropic optical layer 2b are arranged on the side of the section 102 where the measurement is performed (the side of the object to be measured 105).
  • External light is received by the infrared receiving section 102 as infrared incident light 12 through the optically anisotropic layer 2b and the light absorption anisotropic layer A1b.
  • the measurement target 105 can be detected or recognized by receiving the infrared light reflected from the measurement target 105 as the incident infrared light 12 by the infrared receiving unit 102 .
  • the mode in which the light absorption anisotropic layer A1a and the optically anisotropic layer 2a, and the light absorption anisotropic layer A1b and the optically anisotropic layer 2b are arranged corresponds to the mode of the laminate.
  • the laminate can produce infrared circularly polarized light, and the laminate also functions as a circular polarizing filter.
  • the direction of the circularly polarized light may be determined according to the purpose, and the infrared light sensor system 100b may have a mechanism for changing the direction of the circularly polarized light of the laminate. Preferred aspects of the laminate are as described above.
  • the unit 102 may be provided in a separate housing. That is, it may be in the form of the infrared light sensor system 100c shown in FIG.
  • the infrared light sensor system 100c shown in FIG. The infrared radiation device on which the layer 2a is arranged, the infrared light receiving section 102, and the light absorption anisotropic layer A1b and the optically different light absorption layer A1b are arranged on the measurement side of the infrared light receiving section 102 (measurement object 105 side). and an infrared incidence device in which the anisotropic layer 2b is arranged.
  • the infrared light 11 is emitted from the infrared light source 101 through the light absorption anisotropic layer A1a and the optically anisotropic layer 2a and emitted from the infrared emission device.
  • the infrared light reflected from the object 105 to be measured enters the infrared incident device, passes through the optically anisotropic layer 2b and the light absorption anisotropic layer A1b, and is received by the infrared receiving section 102 as incident infrared light 12.
  • the measurement target 105 can be detected or recognized by receiving the infrared light reflected from the measurement target 105 as the infrared incident light 12 by the infrared light receiving unit 102 .
  • the mode in which the light absorption anisotropic layer A1a and the optically anisotropic layer 2a, and the light absorption anisotropic layer A1b and the optically anisotropic layer 2b are arranged corresponds to the mode of the laminate.
  • the laminate can produce infrared circularly polarized light, and the laminate also functions as a circular polarizing filter.
  • the direction of the circularly polarized light may be determined according to the purpose, and the infrared light sensor system 100c may have a mechanism for changing the direction of the circularly polarized light of the laminate.
  • Preferred aspects of the laminate are as described above.
  • the infrared light sensor system of the present invention may be used in an image display device or the like.
  • Light-emitting panels or image display devices having the above-described infrared light sensor system are, for example, wearable devices such as head-mounted displays, mobile display devices such as smartphones and tablets, and stationary display devices such as televisions and lighting. can be applied.
  • the image display device 104 shown in FIG. An infrared light source 101 and an infrared light receiving section 102 are provided on the optically anisotropic layer 2 side of the .
  • the light absorption anisotropic layer A1a is arranged between the infrared light source 101 and the optically anisotropic layer 2, and the infrared light receiving section 102 and the optically anisotropic layer 2 are arranged.
  • a light absorption anisotropic layer A1b is arranged in between.
  • the visible light from the visible light emitting panel 103 is emitted to the viewing side (measurement target 105 side) so that the image can be viewed, and the infrared emitted light 11 is absorbed from the infrared light source 101.
  • the light is emitted through the anisotropic layer A1a, the optically anisotropic layer 2 and the light absorption anisotropic layer B3.
  • the infrared emitted light 11 is reflected by the measurement object 105, and the reflected infrared light passes through the light absorption anisotropic layer B3, the optically anisotropic layer 2, and the optically anisotropic layer 2b as infrared incident light 12.
  • Light is received by the infrared light receiving unit 102 .
  • the measurement target 105 can be detected or recognized by receiving the infrared light reflected from the measurement target 105 as the incident infrared light 12 by the infrared receiving unit 102 .
  • Preferred embodiments of the anisotropic light absorption layer A1a and the anisotropic light absorption layer A1b in the image display device are as described above.
  • composition 1 for forming a light absorption anisotropic layer A having the following composition was prepared.
  • the composition 1 for forming the light absorption anisotropic layer A was a composition exhibiting lyotropic liquid crystallinity.
  • Composition 1 for forming light absorption anisotropic layer A ⁇ ⁇ 10 parts by mass of the rod-like compound I-1 ⁇ 0.5 parts by mass of the above dichroic dye II-1 ⁇ 0.5 parts by mass of the above dichroic dye II-2 ⁇ 89 parts by mass of water ⁇ ⁇
  • composition 1 for forming the light absorption anisotropic layer A prepared above and 20 g of zirconia beads with a diameter of 2 mm were filled in a zirconia 45 mL container, and a planetary ball mill P-7 classic line manufactured by FRISCH was used at a rotation speed of 300 rpm. Milling was performed for 50 minutes.
  • the composition 1 for forming the light-absorbing anisotropic layer A milled as described above was applied onto a glass substrate (substrate) with a wire bar (moving speed: 100 cm/s) and air-dried.
  • the resulting coating film was immersed in a 1 mol/L aqueous solution of calcium chloride for 5 seconds, washed with ion-exchanged water, and blown to dry to fix the orientation state.
  • An absorption anisotropic layer 1 was produced.
  • the film thickness was measured using an ultra-high resolution non-contact three-dimensional surface profile measurement system BW-A501 manufactured by Nikon Corporation.
  • the degree of orientation of the dichroic dye was 0.85 at the maximum absorption wavelength.
  • the average absorbance at a wavelength of 400 to 700 nm was 0.2 or less, and the average absorbance at a wavelength of 750 nm was 0.31.
  • Example 2 Anisotropic light absorption layer 2 was prepared in the same manner as in Example 1, except that composition 1 for forming light absorption anisotropic layer A was replaced with composition 2 for forming light absorption anisotropic layer A below. did.
  • the film thickness of the light absorption anisotropic layer 2 was 1.2 ⁇ m.
  • the degree of orientation of the dichroic dye was 0.81 at the maximum absorption wavelength. Also, the average absorbance at a wavelength of 400 to 700 nm was 0.2 or less, and the average absorbance at a wavelength of 750 nm was 0.26.
  • composition 2 for forming light absorption anisotropic layer A ⁇ ⁇ 10 parts by mass of the rod-shaped compound I-1 ⁇ 0.31 parts by mass of the dichroic dye II-1 ⁇ 0.31 parts by mass of the dichroic dye II-2 ⁇ 0.31 parts by mass of the long wavelength dye III-1 parts, water 89.1 parts by mass ⁇
  • An anisotropic light absorption layer 7 was produced in the same manner as in Example 1, except that the composition 1 for forming an anisotropic light absorption layer A was replaced with the composition 7 for forming an anisotropic light absorption layer described below. .
  • the film thickness of the light absorption anisotropic layer 7 was 1.2 ⁇ m.
  • the particle size measurement was performed using Nanotrac UPA-EX manufactured by MicrotracBEL. ⁇ 200 nm.
  • Example 3> (Preparation of transparent support) -Preparation of core layer cellulose acylate dope- The following composition was charged 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 having a degree of acetyl substitution of 2.88 ⁇ 12 parts by mass of polyester compound B described in 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 ⁇
  • Matting agent solution ⁇ Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass ⁇ Methylene chloride (first solvent) 76 parts by mass ⁇ Methanol (second solvent) 11 parts by mass Rate dope 1 part by mass ⁇
  • AEROSIL R972 manufactured by Nippon Aerosil Co., Ltd.
  • cellulose acylate film 1 After the core layer cellulose acylate dope and the outer layer cellulose acylate dope were filtered through a filter paper having an average pore size of 34 ⁇ m and a sintered metal filter having an average pore size of 10 ⁇ m, the core layer cellulose acylate dope and the outer layer cellulose acylate dope were formed on both sides thereof. 3 layers were simultaneously cast on a drum at 20° C. from a casting port (band casting machine). Next, the film was peeled off with a solvent content of approximately 20% by mass, fixed at both ends in the width direction of the film with tenter clips, and dried while being stretched in the horizontal direction at a draw ratio of 1.1.
  • the film was further dried by transporting it between rolls of a heat treatment apparatus to prepare an optical film (transparent support) having a thickness of 40 ⁇ m.
  • the in-plane retardation of the obtained cellulose acylate film 1 was 0 nm.
  • a coating solution 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 is formed is dried with hot air at 140° C. for 120 seconds, and then the coating film is irradiated with polarized ultraviolet rays (10 mJ/cm 2 , using an ultra-high pressure mercury lamp) to form a photo-alignment film.
  • PA1 was formed to obtain a TAC (triacetylcellulose) film with a photo-alignment film.
  • the film thickness of the photo-alignment film PA1 was 0.5 ⁇ m.
  • a composition 3 for forming a light absorption anisotropic layer A having the following composition was continuously applied with a wire bar to form a coating layer 3.
  • the coating layer 3 was heated at 140° C. for 15 seconds, and the coating layer P1 was cooled to room temperature (23° C.). Then, it was heated at 80° C. for 60 seconds and cooled again to room temperature.
  • the light absorption anisotropic layer 3 was formed on the photo-alignment film PA1 by irradiating for 2 seconds under irradiation conditions of an illuminance of 200 mW/cm 2 using an LED lamp (center wavelength 365 nm).
  • the dichroic dye IR-1 corresponds to a water-insoluble dichroic dye.
  • the film thickness of the light absorption anisotropic layer 3 was 2.0 ⁇ m.
  • composition 3 for forming light absorption anisotropic layer A ⁇ Dichroic dye C-1 0.65 parts by mass Dichroic dye M-1 0.15 parts by mass Dichroic dye Y-1 0.52 parts by mass Dichroic dye IR-1 0.38 Parts by mass Liquid crystalline compound L-1 2.67 parts by mass Liquid crystalline compound L-4 1.15 parts by mass Adhesion improver A-1 0.17 parts by mass Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.17 parts by mass Surfactant F-1 0.020 parts by mass Cyclopentanone 91.95 parts by mass Benzyl alcohol 2.36 parts by mass ⁇
  • a coating liquid B1 having the following composition was continuously applied onto the light absorption anisotropic layer 3 with a wire bar. Then, it was dried with hot air at 80°C for 5 minutes and irradiated with ultraviolet rays (300 mJ/cm 2 , using an ultra-high pressure mercury lamp) to form an oxygen blocking layer B1 made of polyvinyl alcohol (PVA) with a thickness of 1.0 ⁇ m.
  • Laminate A that is, laminate 3 comprising cellulose acylate film 1 (transparent support), photo-alignment film PA1, light absorption anisotropic layer 3, and oxygen blocking layer B1 adjacent to each other in this order was obtained.
  • Example 4 An anisotropic light absorption layer 4 was prepared in the same manner as in Example 1, except that the composition 1 for forming the anisotropic light absorption layer A was replaced with the composition 4 for forming the anisotropic light absorption layer A below. did.
  • the film thickness of the light absorption anisotropic layer 4 was 1.2 ⁇ m.
  • the degree of orientation of the dichroic dye was 0.85 at the maximum absorption wavelength. Also, the average absorbance at a wavelength of 400 to 700 nm was 0.2 or less, and the average absorbance at a wavelength of 750 nm was 0.22.
  • composition 4 for forming light absorption anisotropic layer A ⁇ ⁇ 10 parts by mass of the rod-like compound I-1 ⁇ 0.35 parts by mass of the above dichroic dye II-1 ⁇ 0.35 parts by mass of the above dichroic dye II-2 ⁇ 89.3 parts by mass of water ⁇ ⁇
  • the particle size measurement was performed using Nanotrac UPA-EX manufactured by MicrotracBEL. ⁇ 200 nm.
  • Anisotropic light absorption layer 5 was prepared in the same manner as in Example 1, except that Composition 1 for forming light absorption anisotropic layer A was replaced with Composition 5 for forming light absorption anisotropic layer A below. did.
  • the film thickness of the light absorption anisotropic layer 5 was 1.2 ⁇ m.
  • the degree of orientation of the dichroic dye was 0.85 at the maximum absorption wavelength.
  • the average absorbance at a wavelength of 400 to 700 nm was 0.2 or less, and the average absorbance at a wavelength of 750 nm was 0.13.
  • composition 5 for forming light absorption anisotropic layer A ⁇ ⁇ 10 parts by mass of the rod-like compound I-1 ⁇ 0.18 parts by mass of the above dichroic dye II-1 ⁇ 0.18 parts by mass of the above dichroic dye II-2 ⁇ 89.6 parts by mass of water ⁇ ⁇
  • the particle size measurement was performed using Nanotrac UPA-EX manufactured by MicrotracBEL. ⁇ 200 nm.
  • composition 6 for forming light absorption anisotropic layer A.
  • the dichroic dye IR-3 corresponds to a water-insoluble dichroic dye.
  • composition 6 for forming light absorption anisotropic layer A ⁇ ⁇ Polymerizable liquid crystalline compound L-5 29.3 parts by mass ⁇ Dichroic dye IR-3 2.2 parts by mass ⁇ Polymerization initiator Irgacure 369 (manufactured by BASF Japan) 2.0 parts by mass ⁇ Leveling agent BYK361N (Bic Chemie Japan Co., Ltd.) 0.1 parts by mass Cyclopentanone 66.4 parts by mass ⁇ ---
  • Irgacure 369 is a trade name, and the compound name is 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one.
  • polyvinyl alcohol polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.
  • a thickness of 89 nm was applied on the glass substrate.
  • a polyvinyl alcohol film was obtained.
  • the surface of the polyvinyl alcohol film was subjected to rubbing treatment to obtain a laminate of the alignment film and the glass substrate.
  • a solution of composition 6 for forming light absorption anisotropic layer A was applied to the rubbed surface of the obtained laminate by a spin coating method.
  • the laminate coated with the solution was dried on a hot plate for 1 minute and then irradiated with ultraviolet rays of 2400 mJ/cm 2 while being heated to obtain an anisotropic light absorption layer 6 .
  • the film thickness of the light absorption anisotropic layer 6 was 1.2 ⁇ m.
  • the degree of orientation of the dichroic dye was 0.53 at the maximum absorption wavelength. Also, the average absorbance at wavelengths of 400 to 700 nm was 0.2 or less.
  • Example 12 Anisotropic light absorption layer 12 was prepared in the same manner as in Example 3, except that composition 3 for forming light absorption anisotropic layer A was replaced with composition 12 for forming light absorption anisotropic layer A having the following composition. and a laminate 12 was produced.
  • the dichroic substance dye IR-2 corresponds to a water-insoluble dichroic dye.
  • the film thickness of the light absorption anisotropic layer 12 was 1.2 ⁇ m.
  • composition 12 for forming light absorption anisotropic layer A ⁇ Dichroic dye IR-2 0.39 parts by weight Liquid crystal compound L-1 2.71 parts by weight Liquid crystal compound L-4 1.16 parts by weight Adhesion improver A-1 0.17 Parts by mass Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.17 parts by mass Surfactant F-1 0.020 parts by mass Cyclopentanone 93.00 parts by mass Benzyl alcohol 2.38 parts by mass - ⁇
  • Example 13 Anisotropic light absorption layer 13 was prepared in the same manner as in Example 3, except that composition 3 for forming light absorption anisotropic layer A was replaced with composition 13 for forming light absorption anisotropic layer A having the following composition. And laminate 13 was produced. The film thickness of the light absorption anisotropic layer 13 was 1.2 ⁇ m.
  • composition 13 for forming light absorption anisotropic layer A 0.39 parts by mass of the dichroic dye IR-3 2.70 parts by mass of the liquid crystalline compound L-1 1.16 parts by mass of the liquid crystalline compound L-4 0.16 parts by mass of the liquid crystalline compound L-4 17 parts by mass polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.17 parts by mass Surfactant F-1 0.020 parts by mass Cyclopentanone 92.86 parts by mass Benzyl alcohol 2.38 parts by mass ⁇ ⁇
  • Anisotropic light absorption layer 14 was prepared in the same manner as in Example 3, except that composition 3 for forming light absorption anisotropic layer A was replaced with composition 14 for forming light absorption anisotropic layer A having the following composition. and laminate 14 were produced.
  • the film thickness of the light absorption anisotropic layer 14 was 1.2 ⁇ m.
  • the orientation axis of the liquid crystalline compound and the absorption axis of the dichroic dye were parallel.
  • the maximum absorption wavelengths were 840 nm and 1100 nm, and the average absorbance at 1100 nm was 0.22.
  • composition 14 for forming light absorption anisotropic layer A ⁇ - 0.39 parts by mass of the dichroic dye IR-3 - 1.00 parts by mass of the dichroic dye IR-4 - 2.70 parts by mass of the liquid crystalline compound L-1 -
  • the liquid crystalline compound L-4 1. 16 parts by mass 0.17 parts by mass of the adhesion improver A-1 Polymerization initiator 0.17 parts by mass IRGACUREOXE-02 (manufactured by BASF) 0.17 parts by mass 0.020 parts by mass of the surfactant F-1 parts Cyclopentanone 92.86 parts by mass Benzyl alcohol 2.38 parts by mass ⁇ ⁇
  • Example 15 In the formation of the light absorption anisotropic film 3 of Example 3, the following composition 15 for forming the light absorption anisotropic layer A was continuously applied on the photo-alignment film PA1 by means of a wire bar. A layer 15 was formed. Next, the coating layer 15 was heated at 120° C. for 60 seconds and then quickly cooled down to room temperature (23° C.) to form a dry film. In the dried film, the liquid crystalline compound was smectic B phase.
  • the light absorption anisotropic layer 15 was formed on the photo-alignment film PA1 by irradiating for 2 seconds under irradiation conditions of illuminance of 200 mW/cm 2 using an LED lamp (center wavelength 365 nm).
  • the film thickness of the light absorption anisotropic layer 15 was 1.2 ⁇ m.
  • a Bragg peak (a peak derived from Bragg reflection) was observed by X-ray diffraction measurement.
  • a laminate of Example 15 was obtained in the same manner as in Example 3 except that the anisotropic light absorption film 15 was used instead of the anisotropic light absorption film 3 .
  • a composition 15 for forming an anisotropic light absorption layer A was prepared with the following composition, heated and dissolved at 50° C. for 3 hours while stirring, and filtered through a 0.45 ⁇ m filter.
  • ⁇ Composition 15 for forming light absorption anisotropic layer A ⁇ - 7.6 parts by mass of the above dichroic dye IR-2 - 75.5 parts by mass of the following liquid crystal compound M4 - 0.8 parts by mass of the polymerization initiator IRGACURE819 (manufactured by BASF) - 0.8 parts by mass of the above surfactant F-1. 6 parts by mass Cyclopentanone 274.5 parts by mass Tetrahydrofuran 640.5 parts by mass ⁇ ⁇
  • Example 16> In the formation of the light absorption anisotropic layer 3 of Example 3, the following composition H1 for forming the light absorption anisotropic layer A was continuously applied on the photo-alignment film PA1 with a wire bar. A layer H1 was formed. Then, the coating layer H1 was heated at 100° C. for 5 minutes and cooled to 60° C. to form a dry film. In the dried film, the liquid crystalline compound was in a nematic phase. After that, an anisotropic light absorption layer H1 was formed on the photo-alignment film PA1 by irradiating for 2 seconds under irradiation conditions of an illuminance of 200 mW/cm 2 using an LED lamp (center wavelength 365 nm).
  • the film thickness of the light absorption anisotropic layer H1 was 2.5 ⁇ m. Also, in the X-ray diffraction measurement, only a broad halo was observed in the wide-angle region.
  • a laminate of Example 16 was obtained in the same manner as in Example 3, except that the anisotropic light absorption film H1 was used instead of the anisotropic light absorption film 3.
  • composition H1 for forming an anisotropic light absorption layer A was prepared according to the following composition, heated and dissolved at 50° C. for 3 hours with stirring, and filtered through a 0.45 ⁇ m filter.
  • ⁇ Composition H1 for forming light absorption anisotropic layer A ⁇ - 7.6 parts by mass of the above dichroic dye IR-2 - 75.5 parts by mass of the following liquid crystalline compound H1 - 0.8 parts by mass of the polymerization initiator IRGACURE819 (manufactured by BASF) - 0.8 parts by mass of the above surfactant F-1. 6 parts by mass Cyclopentanone 274.5 parts by mass Tetrahydrofuran 640.5 parts by mass ⁇ ⁇
  • Liquid crystal compound H1 (a mixture of the following three types of compounds. The mixing ratio (mass ratio) is described on the upper left of the compound.)
  • An alignment film coating solution having the following composition was continuously applied to the support using a #14 wire bar. Then, the support on which the coating film was formed was dried with hot air at 60° C. for 60 seconds and then with hot air at 100° C. for 120 seconds. Subsequently, the coating film after drying was continuously rubbed to form an alignment film. At this time, the longitudinal direction of the long film was parallel to the conveying direction, and the rotation axis of the rubbing roller with respect to the longitudinal direction of the film was 0° clockwise.
  • Modified polyvinyl alcohol in the following structural formula, the ratio is a molar ratio
  • the following composition H2 for forming an anisotropic light-absorbing light-absorbing layer A was continuously applied with a wire bar to form a coating layer H2.
  • the coating layer H2 was heated with hot air at 15° C. for 90 seconds and then with hot air at 80° C. for 60 seconds to form a dry film.
  • the liquid crystalline compound was in a nematic phase.
  • an anisotropic light absorption layer H2 was formed on the alignment film by irradiating for 2 seconds under irradiation conditions of an illuminance of 200 mW/cm 2 using an LED lamp (center wavelength of 365 nm).
  • the film thickness of the light absorption anisotropic layer H2 was 3.2 ⁇ m.
  • the liquid crystalline compound D-1 is a discotic liquid crystal (DLC) compound, the average tilt angle of the disk surface of the DLC compound with respect to the film surface is 90°, and the DLC compound is oriented perpendicular to the film surface. It was confirmed. Also, in the X-ray diffraction measurement, only a broad halo was observed in the wide-angle region.
  • a laminate of Example 17 was obtained in the same manner as in Example 3, except that the anisotropic light absorption film H2 was used instead of the anisotropic light absorption film 3.
  • composition H2 for forming the light absorption anisotropic layer A was prepared with the following composition, heated and dissolved at 50° C. for 3 hours while stirring, and filtered through a 0.45 ⁇ m filter.
  • Composition H2 for forming light absorption anisotropic layer A ⁇
  • the following liquid crystalline compound D-1 100 parts by mass
  • Photopolymerization initiator Irgacure 907 manufactured by BASF
  • fluorine-containing compound F-2 air interface alignment agent 0.25 parts by mass ⁇ 0.9 parts by mass of the following additive T-1 ⁇ 760 parts by mass of methyl ethyl ketone ⁇ ⁇
  • Liquid crystalline compound D-1 (mixture of the following two compounds)
  • Infrared absorption dye IR-5 (maximum absorption wavelength: 867 nm)
  • ⁇ Reference example> (Preparation of polarizer 1 with single-sided protective film)
  • the surface of the support of a cellulose triacetate film TJ25 (manufactured by Fujifilm; thickness 25 ⁇ m) was saponified with an alkali. Specifically, the support was immersed in a 1.5 N sodium hydroxide aqueous solution at 55° C. for 2 minutes, washed in a water washing bath at room temperature, and further treated with 0.1 N sulfuric acid at 30° C. neutralized using After neutralization, the support was washed in a water washing bath at room temperature and dried with warm air at 100° C. to obtain a polarizer protective film 1 .
  • a polyvinyl alcohol-based film (VF-XS manufactured by Kuraray Co., Ltd.) with a thickness of 75 ⁇ m, a degree of polymerization of 2400, and a degree of saponification of 99% or more with hot water at 40 ° C.
  • the dyed film was stretched in a solution containing 3% by weight of boric acid and, after stretching, immersed in an aqueous solution containing 5% by weight of potassium iodide.
  • the film immersed in an aqueous potassium iodide solution for 15 seconds was dried in a drier at 70° C.
  • polarizer 1 having a thickness of 25 ⁇ m.
  • the polarizer protective film 1 was adhered to one surface of the polarizer 1 using the PVA adhesive to prepare a polarizer 1 with a single-sided protective film.
  • the visibility correction single transmittance of the polarizer 1 was 42%.
  • Example 7 An adhesive (SK-2057, manufactured by Soken Chemical Co., Ltd.) is applied to the polarizer side of the polarizer 1 with a single-sided protective film to form an adhesive layer, and the light absorption anisotropic layer 1 is adhered.
  • a laminated body 7 was obtained by laminating so as to be in close contact with the agent layer. The direction of the absorption axis of the polarizer and the absorption axis of the dichroic dye in the light absorption anisotropic layer 1 was adjusted to 0°.
  • Example 8 An adhesive (SK-2057, manufactured by Soken Chemical Co., Ltd.) is applied to the coated surface side of the laminate 8-1 described later to form an adhesive layer, and the light absorption anisotropic layer 1 is used as the adhesive layer.
  • a laminated body 8 was obtained by bonding so as to be in close contact with each other. The direction of the absorption axis of the laminate 8-1 and the absorption axis of the dichroic dye in the light absorption anisotropic layer 1 was adjusted to 0°.
  • the liquid crystalline compound L-1 2.68 parts by mass
  • the liquid crystal compound L-4 1.15 parts by mass
  • Example 9 A laminate was obtained in the same manner as in Example 8, except that the absorption axis of the laminate 8-1 and the absorption axis of the dichroic dye in the light absorption anisotropic layer 1 were oriented at 90°. 9 was made.
  • Example 10 An adhesive (SK-2057, manufactured by Soken Chemical Co., Ltd.) is applied to the surface of a wire grid polarizer (UVT300A, manufactured by Moxtek) on which the wire grid is not formed to form an adhesive layer.
  • a laminate 10 was obtained by laminating the polar layer 1 and the pressure-sensitive adhesive layer so as to be in close contact with each other. The direction of the absorption axis of the polarizer and the absorption axis of the dichroic dye in the light absorption anisotropic layer 1 was adjusted to 0°.
  • Example 11 An adhesive (SK-2057, manufactured by Soken Kagaku Co., Ltd.) is applied to the coating surface side of the optically anisotropic layer A described later to form an adhesive layer, and the light absorption anisotropic layer 1 is coated with the adhesive.
  • a laminated body 11 was obtained by laminating the layers so as to be in close contact with each other. The direction of the slow axis of the optically anisotropic layer A and the absorption axis of the dichroic dye of the optically anisotropic layer 1 was adjusted to 0°.
  • UV absorber solution C-1 (Preparation of UV absorber solution C-1) The following composition was put into another mixing tank and stirred while heating to dissolve each component to prepare UV absorber solution C-1.
  • UV absorber solution C-1 ⁇ ⁇ Ultraviolet absorber (UV-1 below) 10.0 parts by mass ⁇ Ultraviolet absorber (UV-2 below) 10.0 parts by mass ⁇ Methylene chloride 55.7 parts by mass ⁇ Methanol 10 parts by mass ⁇ Butanol 1.3 parts by mass ⁇ Cellulose ester solution A-1 12.9 parts by mass ⁇
  • the cast dope film was dried on a drum by blowing dry air at 34° C. at 150 m 3 /min, and the film was peeled off from the drum with a residual solvent content of 150%. At the time of peeling, the film was stretched by 15% in the transport direction (longitudinal direction). Thereafter, both ends of the film in the width direction (direction perpendicular to the casting direction) are conveyed while being held by a pin tenter (the pin tenter described in FIG. 3 of JP-A-4-1009), and the film is stretched in the width direction. No treatment. Further, the film was further dried by transporting it between rolls of a heat treatment apparatus to produce a cellulose acylate film (T1).
  • T1 cellulose acylate film
  • the produced long cellulose acylate film (T1) had a residual solvent amount of 0.2%, a thickness of 60 ⁇ m, and Re (in-plane retardation) and Rth (thickness retardation) at a wavelength of 550 nm, respectively. 8 nm and 40 nm.
  • the cellulose acylate film (T1) was passed through a dielectric heating roll at a temperature of 60°C to raise the film surface temperature to 40°C, and then an alkaline solution having the composition shown below was applied to the band surface of the film.
  • a coating amount of 14 mL/m 2 was applied using a coater and conveyed for 10 seconds under a steam far-infrared heater manufactured by Noritake Co., Ltd. heated to 110°C. Subsequently, using the same bar coater, 3 ml/m 2 of pure water was applied.
  • the film was transported to a drying zone at 70° C. for 10 seconds and dried to prepare a cellulose acylate film saponified with an alkali.
  • Alignment film coating liquid (A) having the following composition was continuously applied to the alkali-saponified surface of the cellulose acylate film (T1) using a #14 wire bar. It was dried with hot air at 60°C for 60 seconds and then with hot air at 100°C for 120 seconds. The degree of saponification of the modified polyvinyl alcohol used was 88%.
  • the alignment film prepared above was continuously subjected to rubbing treatment.
  • the longitudinal direction of the long film and the conveying direction were parallel, and the angle formed by the longitudinal direction of the film (conveying direction) and the rotation axis of the rubbing roller was 72.5° (longitudinal direction of the film (conveying direction ) is 90°, and the rotation axis of the rubbing roller is at ⁇ 17.5° when the counterclockwise direction is represented by a positive value with the film width direction as the reference (0°) observed from the alignment film side.
  • the position of the rotation axis of the rubbing roller corresponds to the position rotated counterclockwise by 72.5° with respect to the longitudinal direction of the film.).
  • An optically anisotropic layer coating solution (A) containing a discotic liquid crystal (DLC) compound having the following composition was continuously applied onto the alignment film prepared above with a #5.0 wire bar.
  • the transport speed (V) of the film was set to 26 m/min.
  • UV (ultraviolet) irradiation exposure amount: 70 mJ/cm 2 ) was performed to fix the orientation of the liquid crystalline compound.
  • the thickness of the optically anisotropic layer A was 2.0 ⁇ m.
  • the average inclination angle of the disk surface of the DLC compound with respect to the film surface was 90°, and it was confirmed that the DLC compound was oriented perpendicular to the film surface.
  • the angle of the slow axis is parallel to the rotation axis of the rubbing roller, and the film longitudinal direction (conveyance direction) is 90° (the film width direction is 0°.
  • the film width direction is the reference (0°) when observed from the alignment film side. ) and the counterclockwise direction is represented by a positive value), the result was -17.5°.
  • the obtained optically anisotropic layer A corresponded to a ⁇ /2 plate, and Re and Rth at a wavelength of 550 nm were Re(550): 238 nm and Rth(550): -119 nm, respectively.
  • a high contrast means a high S/N ratio for generating polarized light for rays in the infrared wavelength range.
  • the slow axis of the light absorption anisotropic layer is synonymous with the orientation axis of the liquid crystalline compound, and the orientation axis of the liquid crystalline compound was evaluated as the absorption axis direction at a wavelength of 250 nm. Further, the following "the alignment axis of the liquid crystalline compound and the absorption axis of the dichroic dye are parallel" means that the angle formed by the alignment axis of the liquid crystalline compound and the absorption axis of the dichroic dye is 0 to 5°.
  • A1/A2 is more than 1: the alignment axis of the liquid crystalline compound and the absorption axis of the dichroic dye are parallel
  • A1/A2 is less than 1: the alignment axis of the liquid crystalline compound and the absorption axis of the dichroic dye are orthogonal
  • wet heat durability evaluation As the wet heat durability test condition, a test was conducted in which the sample was left for 500 hours in an environment of 85° C. relative humidity of 85%. The degree of polarization and transmittance of the anisotropic light absorption layer before the test and the degree of polarization and transmittance of the anisotropic light absorption layer after the test were measured, and wet heat durability was evaluated according to the following criteria. The results are shown in Table 1 below. A: The amount of change in the degree of polarization and transmittance after the test relative to the degree of polarization and transmittance before the test is less than 20%. B: The amount of change in the degree of polarization and transmittance after the test relative to the degree of polarization and transmittance before the test. 20% or more of any
  • maximum absorption wavelength represents the maximum absorption wavelength of the dichroic dye. However, in the reference example, it represents the maximum absorption wavelength of iodine.
  • average absorbance of the light absorption anisotropic layer at a wavelength of 850 nm represents the average absorbance of the light absorption anisotropic layer at a wavelength of 850 nm.
  • parallel in the “evaluation of absorption axis” column means that A1/A2 is more than 1
  • perpendicular means that A1/A2 is less than 1.
  • anisotropic layer X is a generic term for polarizer 1, laminate 8-1, wire grid polarizer, and optically anisotropic layer A.
  • the light absorption anisotropic layer of the present invention has high contrast in the infrared region and good wet heat durability. Moreover, it was confirmed that the light absorption anisotropic layer of the present invention is excellent in wet heat durability. Further, from the results of Table 2, in addition to the light absorption anisotropic layer A containing a dichroic dye in the infrared region (700 to 1500 nm), the light absorption containing a dichroic dye having a maximum absorption at a wavelength of 400 to 700 nm It was found that even with the anisotropic layer B, good contrast was exhibited.
  • the optically anisotropic layer of the present invention has a thickness of 5 ⁇ m or less, and is lightweight and excellent in handleability.
  • the light absorption anisotropic layers of the present invention (Examples 1 to 6 and 12 to 15) and the laminates of the present invention (Examples 7 to 11) generate polarized light for rays in the infrared wavelength region. Since the S/N ratio is high, it can be suitably used for an infrared light sensor system.

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