Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
  • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays

Definitions

• the present invention relates to a liquid crystal composition, an optically absorbing anisotropic film, a method for producing an optically absorbing anisotropic film, an optical laminate, and an image display device.
• Patent Document 1 describes an optically absorptive anisotropic film formed using a liquid crystal composition containing a polymer liquid crystal compound and a dichroic substance ([Claim 1]).
• the inventors have studied the liquid crystal composition and the optically absorbing anisotropic film described in Patent Document 1 and have found that there is room for improvement in achieving both the solubility of the liquid crystal composition and the degree of orientation of the optically absorbing anisotropic film.
• the present invention aims to provide a liquid crystal composition with excellent solubility that can produce an optically absorptive anisotropic film with a high degree of orientation, an optically absorptive anisotropic film, a method for producing an optically absorptive anisotropic film, an optical laminate, and an image display device.
• the inventors have discovered that by using a dichroic substance having a specific acid-cleavable group together with a liquid crystal compound, the solubility of the liquid crystal composition is improved and the degree of orientation of the optically absorptive anisotropic film produced is also increased, thereby completing the present invention. That is, the present inventors have found that the above problems can be solved by the following configuration.
• a liquid crystal composition containing a dichroic substance represented by formula (1) described later and a liquid crystal compound [2] The liquid crystal composition according to [1], wherein X in formula (1) described later represents an acid-cleavable group represented by any one of formulas (A1) to (A5) described later. [3] The liquid crystal composition according to [2], wherein X in formula (1) below represents an acid-cleavable group represented by formula (A2) below. [4] The liquid crystal composition according to [3], wherein two R A2 in formula (A2) described later each independently represents a linear or branched monovalent aliphatic hydrocarbon group. [5] The liquid crystal composition according to [4], wherein R A2 in formula (A2) below has a molecular weight of 300 or less.
• the present invention can provide a liquid crystal composition with excellent solubility that can produce an optically absorptive anisotropic film with a high degree of orientation, an optically absorptive anisotropic film, a method for producing an optically absorptive anisotropic film, an optical laminate, and an image display device.
• a numerical range expressed using "to” means a range that includes the numerical values before and after "to" as the lower and upper limits.
• the upper or lower limit value of a certain numerical range in a stepwise described numerical range may be replaced with the upper or lower limit value of another stepwise described numerical range.
• the upper or lower limit value of a certain numerical range in a numerical range described in the present specification may be replaced with a value shown in the examples.
• each component may be used alone or in combination of two or more substances corresponding to each component.
• the content of the component refers to the total content of the substances used in combination, unless otherwise specified.
• “(meth)acrylate” is a notation representing “acrylate” or “methacrylate”
• “(meth)acrylic” is a notation representing “acrylic” or “methacrylic”
• “(meth)acryloyl” is a notation representing "acryloyl” or “methacryloyl”.
• the bonding direction of a divalent group (e.g., -O-CO-) represented in this specification is not particularly limited.
• L2 when L2 is -O-CO- in the bond of " L1 - L2 - L3 ", when the position bonded to L1 side is *1 and the position bonded to L3 side is *2, L2 may be *1-O-CO-*2 or *1-CO-O-*2.
• Re( ⁇ ) and Rth( ⁇ ) respectively represent the in-plane retardation and the retardation in the thickness direction at a wavelength ⁇ , which is set to 550 nm unless otherwise specified.
• Re( ⁇ ) and Rth( ⁇ ) are values measured at a wavelength ⁇ using an AxoScan (manufactured by Axometrics).
• AxoScan manufactured by Axometrics.
• Re( ⁇ ) R0( ⁇ )
• examples of the substituent include the substituents described in the following Substituent Group A.
• the phrase "optionally substituted” includes embodiments having one or more substituents as well as embodiments having no substituents.
• substituents include: A halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, preferably a chlorine atom, a fluorine atom, more preferably a fluorine atom); Alkyl groups (preferably linear, branched or cyclic alkyl groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and particularly preferably 1 to 8 carbon atoms, such as linear alkyl groups having 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl), branched alkyl groups having 3 to 6 carbon atoms (e.g., isopropyl, isobutyl, tert-butyl, sec-butyl, neopentyl, isohexyl, 3-methylpenty
• a halogen atom e.
• the liquid crystal composition of the present invention contains a dichroic substance represented by the formula (1) described below and a liquid crystal compound.
• the acid-cleavable group possessed by the dichroic substance represented by formula (1) described later i.e., the acid-cleavable group represented by any of formulas (A1) to (A6) described later, is a flexible substituent or a bulky substituent, and therefore crystallization of the dichroic substance is suppressed, thereby improving the solubility of the liquid crystal composition.
• a coating film formed by applying a liquid crystal composition is subjected to a treatment for cleaving an acid-cleavable group, whereby flexible or bulky substituents are eliminated, promoting the crystallization of the dichroic substance and improving the degree of orientation of the optically absorptive anisotropic film produced.
• the dichroic substance and liquid crystal compound contained in the liquid crystal composition of the present invention, as well as any optional components, will be described in detail below.
• the liquid crystal composition of the present invention contains a dichroic material represented by the following formula (1).
• the dichroic substance means a dye whose absorbance varies depending on the direction.
• the dichroic material may or may not exhibit liquid crystallinity.
• Y represents an n-valent dye skeleton structure.
• the dye skeleton structure refers to a structure having a maximum absorption wavelength in the visible light region (wavelength range of 380 nm to 780 nm).
• the maximum absorption wavelength can be calculated from the absorption spectrum obtained by measuring the absorbance in the visible light region using an ultraviolet-visible spectrophotometer (e.g., UV-1800 (manufactured by Shimadzu Corporation)).
• UV-1800 ultraviolet-visible spectrophotometer
• a suitable example of such a dye skeleton structure is the structure of the dichroic material represented by formula (2) described below, excluding -(L B -X).
• n represents an integer of 1 or more.
• n is preferably an integer of 2 or more, more preferably an integer of 2 to 4, even more preferably 2 or 3, and particularly preferably 2.
• L 1 B represents a divalent aliphatic hydrocarbon group having one or more carbon atoms, and one or more of the -CH 2 - groups constituting the aliphatic hydrocarbon group may be substituted with -CO-, -O-, -S-, -NH- or -N(Q)-.
• Q represents a substituent.
• n represents an integer of 2 or more, multiple L 1 B may be the same or different.
• Examples of the divalent aliphatic hydrocarbon group having one or more carbon atoms include linear or branched alkylene groups having 1 to 20 carbon atoms, linear or branched alkenylene groups having 1 to 20 carbon atoms, and linear or branched alkynylene groups having 1 to 20 carbon atoms.
• As the linear or branched alkylene group having 1 to 20 carbon atoms an alkylene group having 1 to 12 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable.
• Suitable examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
• linear or branched alkenylene group having 1 to 20 carbon atoms an alkenylene group having 2 to 10 carbon atoms is preferable, and an alkenylene group having 2 to 4 carbon atoms is more preferable, and a suitable example thereof is an ethenylene group.
• an alkynylene group having 2 to 10 carbon atoms is preferable, and an alkynylene group having 2 to 4 carbon atoms is more preferable, and a suitable example thereof is an ethynylene group.
• one or more of the -CH 2 - groups constituting the aliphatic hydrocarbon group may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-.
• substituent represented by Q include the substituents described in the above-mentioned substituent group A, and among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group or a halogen atom is preferable.
• X represents an acid-cleavable group represented by any one of the following formulae (A1) to (A6).
• n represents an integer of 2 or more, multiple Xs may be the same or different.
• * represents the bonding position with L B.
• R A1 represents a hydrogen atom or a monovalent hydrocarbon group, some of the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms, and some of the carbon atoms may be substituted with silicon or oxygen, provided that the two R A1 in the above formulae (A1) and (A5) may be the same or different and may be bonded to each other to form a ring.
• R represents a monovalent hydrocarbon group, some of the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms, and some of the carbon atoms may be substituted with silicon or oxygen, provided that multiple R in the above formulae ( A2 ) to (A6) may be the same or different and may be bonded to each other to form a ring.
• examples of the monovalent hydrocarbon group represented by R A2 and one embodiment of R A1 include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group.
• examples of the monovalent chain hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; and alkynyl groups such as ethynyl, propynyl, and butynyl groups.
• Examples of the monovalent alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group; and cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a norbornenyl group.
• Examples of the monovalent aromatic hydrocarbon group include aryl groups such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, a methylnaphthyl group, an anthryl group, and a methylanthryl group; and aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and an anthrylmethyl group.
• a monovalent chain hydrocarbon group is preferred, and an alkyl group is more preferred.
• an embodiment in which some of the hydrogen atoms of the hydrocarbon group are substituted with halogen atoms includes, for example, a fluorinated alkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, specifically, -(CH 2 ) m1 (CF 2 ) m2 CF 2 X.
• m1 and m2 each independently represent an integer of 0 to 19, and X represents a hydrogen atom or a fluorine atom.
• m1 is preferably an integer of 1 to 10
• m2 is preferably an integer of 0 to 9.
• examples of embodiments in which a portion of the carbon atoms is substituted with silicon or oxygen include embodiments in which a portion of the carbon atoms of an alkyl group is substituted with silicon or oxygen, and specific examples include -( CH2 ) m3Si ( CH3 ) 3 and -( CH2 ) m3Si (OSi( CH3 ) 3)3 , where m3 represents an integer of 1 to 10.
• X in the above formula (1) represents an acid-cleavable group represented by any one of the above formulas (A1) to (A5), and more preferably represents an acid-cleavable group represented by the above formula (A2).
• the two R A2 in the above formula (A2) each independently represent a linear or branched monovalent aliphatic hydrocarbon group, because this improves the solubility of the liquid crystal composition.
• the two R A2 in the above formula (A2) do not bond to each other to form a ring.
• the linear monovalent aliphatic hydrocarbon group include linear alkyl groups having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group.
• branched monovalent aliphatic hydrocarbon group examples include branched alkyl groups having 3 to 6 carbon atoms, such as an isopropyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a neopentyl group, an isohexyl group, and a 3-methylpentyl group.
• the molecular weight of R A2 in the above formula (A2) is preferably 300 or less, and more preferably 10 to 150, because this further increases the degree of orientation of the optically absorptive anisotropic film to be produced.
• a suitable example of the dichroic material represented by the above formula (1) is a compound represented by the following formula (2).
• X and L B are each defined as in the above formula (1), provided that the two Xs may be the same or different, and the two L Bs may be the same or different.
• n1 and n2 each independently represent an integer of 0 to 4.
• n1 and n2 are each preferably an integer of 0 to 2, and more preferably 0 or 1.
• k represents an integer of 1 to 4.
• k is preferably an integer of 2 to 4, and more preferably 2 or 3.
• Ar 1 represents an (n1+2)-valent aromatic hydrocarbon group or an (n1+2)-valent heterocyclic group, provided that when k represents an integer of 2 to 4, the multiple Ar 1s may be the same or different.
• examples of the (n1+2)-valent aromatic hydrocarbon group include groups in which the number of hydrogen atoms corresponding to the valence is removed from an aromatic hydrocarbon ring, i.e., the number of hydrogen atoms bonded to carbon atoms constituting the aromatic hydrocarbon ring is removed, the number of which corresponds to the valence.
• examples of an (n1+2)-valent heterocyclic group include groups in which the number of hydrogen atoms corresponding to the valence is removed from a heterocycle, i.e., the number of hydrogen atoms bonded to carbon atoms or heteroatoms constituting the heterocycle is removed corresponding to the valence.
• examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring.
• examples of the heterocyclic ring include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring.
• Ar2 represents an (n2+2)-valent aromatic hydrocarbon group or an (n2+2)-valent heterocyclic group.
• aromatic hydrocarbon group and the heterocyclic group include the same as those explained in relation to Ar1 .
• R 1 and R 2 each independently represent a substituent, provided that when n1 represents an integer of 2 to 4, the multiple R 1s may be the same or different, and when n2 represents an integer of 2 to 4, the multiple R 2s may be the same or different.
• substituent include those described in the above-mentioned substituent group A, and among them, an alkyl group or a halogen atom is preferable.
• substituent represented by Y include the substituents described in the above-mentioned substituent group A, and among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferable.
• Suitable examples of the dichroic substance represented by formula (1), particularly the compound represented by formula (2), include the compounds represented by formulas B-1 to B-15 below, in which Me represents a methyl group and TMS represents a trimethylsilyl group (-Si( CH3 ) 3 ).
• the content of the dichroic material represented by the above formula (1) is preferably 4 to 80 mass %, more preferably 5 to 40 mass %, and even more preferably 6 to 20 mass %, relative to the total mass of the solid content of the liquid crystal composition.
• the liquid crystal composition of the present invention may contain a dichroic substance other than the dichroic substance represented by the above formula (1).
• the other dichroic substances are not particularly limited, and examples thereof include visible light absorbing substances (dichroic dyes), luminescent substances (fluorescent substances, phosphorescent substances), ultraviolet absorbing substances, infrared absorbing substances, nonlinear optical substances, carbon nanotubes, and inorganic substances (e.g., quantum rods), and any conventionally known dichroic substances (dichroic dyes) can be used.
• a dichroic azo dye compound means an azo dye compound whose absorbance varies depending on the direction.
• the dichroic azo dye compound may or may not exhibit liquid crystallinity. When the dichroic azo dye compound exhibits liquid crystallinity, it may exhibit either nematic or smectic properties.
• the temperature range in which the liquid crystal phase is exhibited is preferably room temperature (about 20 to 28°C) to 300°C, and more preferably 50 to 200°C from the viewpoints of handling and manufacturing suitability.
• three or more dichroic azo dye compounds may be used in combination.
• a first dichroic azo dye compound a second dichroic azo dye compound, and at least one dye compound (a third dichroic azo dye compound) having a maximum absorption wavelength in the wavelength range of 380 nm or more and less than 455 nm in combination.
• the dichroic azo dye compound preferably has a crosslinkable group.
• the crosslinkable group include a (meth)acryloyl group, an epoxy group, an oxetanyl group, and a styryl group, and among these, a (meth)acryloyl group is preferable.
• the content of the other dichroic substances is not particularly limited, but is preferably 10 to 80% by mass, more preferably 15 to 60% by mass, and even more preferably 20 to 40% by mass, based on the total mass of the solid content of the liquid crystal composition.
• the liquid crystal composition of the present invention contains a liquid crystal compound, which makes it possible to align the dichroic substance with a higher degree of orientation while suppressing precipitation of the dichroic substance.
• a liquid crystal compound either a polymer liquid crystal compound or a low molecular weight liquid crystal compound can be used, and the polymer liquid crystal compound is preferred from the viewpoint of increasing the degree of orientation.
• a polymer liquid crystal compound and a low molecular weight liquid crystal compound may be used in combination.
• the term "polymeric liquid crystal compound” refers to a liquid crystal compound having a repeating unit in the chemical structure.
• the term "low molecular weight liquid crystal compound” refers to a liquid crystal compound that does not have a repeating unit in its chemical structure.
• the polymer liquid crystal compound include the thermotropic liquid crystal polymer described in JP-A-2011-237513 and the polymer liquid crystal compound described in paragraphs [0012] to [0042] of WO 2018/199096.
• the low molecular weight liquid crystal compound include the liquid crystal compounds described in paragraphs [0072] to [0088] of JP-A-2013-228706, and among them, liquid crystal compounds exhibiting smectic properties are preferable.
• Such liquid crystal compounds include those described in paragraphs [0019] to [0140] of WO 2022/014340, the descriptions of which are incorporated herein by reference.
• the liquid crystal compound is preferably one that does not exhibit dichroism in the visible light region.
• the content of the liquid crystal compound is preferably 25 to 2000 parts by mass, more preferably 100 to 1300 parts by mass, and even more preferably 200 to 900 parts by mass, relative to 100 parts by mass of the content of the dichroic substance described above (including the content of other dichroic substances if they are contained). When the content of the liquid crystal compound is within the above range, the degree of orientation of the dichroic substance is further improved.
• the liquid crystal compound may be contained alone or in combination of two or more. When two or more liquid crystal compounds are contained, the content of the liquid crystal compounds means the total content of the liquid crystal compounds.
• the liquid crystal composition of the present invention preferably contains a thermal acid generator, because when preparing an optically absorptive anisotropic film, specifically, when a coating film formed by coating the liquid crystal composition is formed, this makes it easier to cleave the acid-cleavable group of the dichroic material represented by the above formula (1).
• the thermal acid generator is not particularly limited as long as it is a compound that generates an acid by heat, and examples thereof include onium salts such as sulfonium salts, ammonium salts, and phosphonium salts, and ester compounds such as carboxylate compounds, sulfonate compounds, and phosphate compounds.
• Examples of the acid generated from the thermal acid generator upon heating include sulfonic acid, phosphoric acid, and carboxylic acid, with sulfonic acid being preferred and aromatic sulfonic acid being more preferred.
• the pKa of the acid generated from the thermal acid generator is preferably from -15 to 3, and more preferably from -10 to 0.
• the acid generation temperature of the thermal acid generator is preferably from 40 to 300°C, more preferably from 80 to 260°C, further preferably from 100 to 220°C, and particularly preferably from 120 to 200°C.
• the acid generation temperature is determined as the lowest exothermic peak temperature when the thermal acid generator is heated to 500° C. at 5° C./min in a pressure-resistant capsule.
• An example of an instrument used to measure the acid generation temperature is Q2000 (manufactured by TA Instruments).
• the acid generation temperature of the thermal acid generator is preferably lower than the boiling point of the solvent contained in the thermosetting photosensitive composition.
• thermal acid generators include the San-Aid SI series manufactured by Sanshin Chemical Industry Co., Ltd., the CPI series manufactured by San-Apro Co., Ltd., and the K-PURE TAG series manufactured by King Co., Ltd. Also usable are known thermal acid generators described in JP-A Nos. 2003-277353, 2-001470, 2-255646, 3-011044, 2003-183313, 2003-277352, 58-037003, and 58-198532.
• the content of the thermal acid generator is preferably 1 to 10 mass % relative to the total mass of the solid content of the liquid crystal composition of the present invention, and more preferably 2 to 5 mass %.
• the liquid crystal composition of the present invention contains a photoacid generator, because this makes it easier to cleave the acid-cleavable group of the dichroic material represented by the above formula (1) when preparing an optically absorptive anisotropic film, specifically, when forming a coating film by applying the liquid crystal composition.
• the photoacid generator is not particularly limited, and is preferably a compound that responds to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid.
• the photoacid generator is not directly sensitive to actinic rays having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer, so long as it responds to actinic rays having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer.
• a photoacid generator that generates an acid with a pKa of 4 or less is preferred, a photoacid generator that generates an acid with a pKa of 3 or less is more preferred, and a photoacid generator that generates an acid with a pKa of 2 or less is even more preferred.
• pKa basically refers to the pKa in water at 25°C. If it cannot be measured in water, it refers to the pKa measured after changing to a solvent suitable for measurement. Specifically, the pKa listed in the Chemical Handbook and the like can be used as a reference.
• the acid with a pKa of 3 or less sulfonic acid or phosphonic acid is preferred, and sulfonic acid is more preferred.
• photoacid generators examples include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, onium salt compounds, imide sulfonate compounds, and oxime sulfonate compounds are preferred, and onium salt compounds and oxime sulfonate compounds are more preferred. Photoacid generators can be used alone or in combination of two or more types.
• the content of the photoacid generator is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass, based on the total mass of the solid content of the liquid crystal composition of the present invention.
• the liquid crystal composition of the present invention may contain a polymerization initiator.
• the polymerization initiator is not particularly limited, but is preferably a compound having photosensitivity, that is, a photopolymerization initiator.
• a photopolymerization initiator various compounds can be used without any particular limitation. Examples of the photopolymerization initiator include ⁇ -carbonyl compounds (see U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (see U.S. Pat. No. 2,448,828), ⁇ -hydrocarbon-substituted aromatic acyloin compounds (see U.S. Pat. No.
• o-acyloxime compounds JP 2016-27384 A [0065]
• acylphosphine oxide compounds JP 63-40799 A, JP 5-29234 A, JP 10-95788 A and JP 10-29997 A.
• commercially available products can be used, such as IRGACURE-184, IRGACURE-907, IRGACURE-369, IRGACURE-651, IRGACURE-819, IRGACURE-OXE-01, and IRGACURE-OXE-02, all of which are manufactured by BASF.
• the content of the polymerization initiator is preferably 0.01 to 30 mass %, and more preferably 0.1 to 15 mass %, based on the total mass of the solid content of the liquid crystal composition.
• the liquid crystal composition of the present invention preferably contains a solvent.
• the solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetylacetone, etc.), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, cyclopentyl methyl ether, dibutyl ether, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, tetralin, trimethylbenzene, etc.), halogenated carbons (e.g., benzene, toluene
• the content of the solvent is preferably 60 to 99.5% by mass, more preferably 70 to 99% by mass, and particularly preferably 75 to 98% by mass, relative to the total mass (100% by mass) of the liquid crystal composition.
• the liquid crystal composition of the present invention may contain an interface modifier.
• the interfacial improver is not particularly limited, and a polymer-based interfacial improver or a low molecular weight interfacial improver can be used, and the compounds described in paragraphs [0253] to [0293] of JP2011-237513A can be used.
• a silicon-based polymer can be used.
• fluorine (meth)acrylate polymers described in, for example, paragraphs [0018] to [0043] of JP-A-2007-272185 can also be used.
• Examples of the interface improver include compounds described in paragraphs [0079] to [0102] of JP-A-2007-069471, polymerizable liquid crystal compounds represented by formula (4) described in JP-A-2013-047204 (particularly compounds described in paragraphs [0020] to [0032]), polymerizable liquid crystal compounds represented by formula (4) described in JP-A-2012-211306 (particularly compounds described in paragraphs [0022] to [0029]), and liquid crystal alignment promoters represented by formula (4) described in JP-A-2002-129162 (particularly compounds described in paragraphs [0032] to [0040]).
• the content of the interfacial modifier is preferably 0.005 to 15% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.015 to 3% by mass, based on the total mass of the solid content of the liquid crystal composition.
• the total amount of the multiple interfacial modifiers is within the above-mentioned range.
• the liquid crystal composition of the present invention preferably contains an alignment agent.
• the alignment agent include those described in paragraphs [0042] to [0076] of JP-T-2013-543526, paragraphs [0089] to [0097] of JP-T-2016-523997, and paragraphs [0153] to [0170] of JP-A-2020-076920. These may be used alone or in combination of two or more.
• the above-mentioned alignment agent is preferably an onium compound represented by the following formula (B1), because the degree of alignment of the light absorptive anisotropic layer formed is high.
• ring A represents a quaternary ammonium ion consisting of a nitrogen-containing heterocycle.
• X represents an anion.
• L1 represents a divalent linking group.
• L2 represents a single bond or a divalent linking group.
• Y 1 represents a divalent linking group having a 5- or 6-membered ring as a partial structure.
• Z represents a divalent linking group having an alkylene group having 2 to 20 carbon atoms as a partial structure.
• P1 and P2 each independently represent a monovalent substituent having a polymerizable ethylenically unsaturated bond.
• Ring A represents a quaternary ammonium ion consisting of a nitrogen-containing heterocycle.
• ring A include a pyridine ring, a picoline ring, a 2,2'-bipyridyl ring, a 4,4'-bipyridyl ring, a 1,10-phenanthroline ring, a quinoline ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazine ring, a triazole ring, and a tetrazole ring, and are preferably a quaternary imidazolium ion or a quaternary pyridinium ion.
• X represents an anion.
• X include halogen anions (e.g., fluorine ion, chloride ion, bromide ion, iodine ion, etc.), sulfonate ions (e.g., methanesulfonate ion, trifluoromethanesulfonate ion, methylsulfate ion, vinylsulfonate ion, allylsulfonate ion, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, p-vinylbenzenesulfonate ion, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion, etc.), sulfate ion, carbonate ion, nitrate ion, thi
• halogen anions sulfonate ions, and hydroxide ions.
• chloride ions bromide ions, iodide ions, methanesulfonate ions, vinylsulfonate ions, p-toluenesulfonate ions, and p-vinylbenzenesulfonate ions are preferred.
• L 1 represents a divalent linking group.
• L 1 include an alkylene group, -O-, -S-, -CO-, -SO 2 -, -NRa- (wherein Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), an alkenylene group, a divalent linking group having 1 to 20 carbon atoms formed by combining with an alkynylene group or an arylene group.
• L 1 is preferably -AL-, -O-AL-, -CO-O-AL-, or -O-CO-AL- having 1 to 10 carbon atoms, more preferably -AL- or -O-AL- having 1 to 10 carbon atoms, and most preferably -AL- or -O-AL- having 1 to 5 carbon atoms.
• AL represents an alkylene group.
• L 2 represents a single bond or a divalent linking group.
• L 2 include an alkylene group, -O-, -S-, -CO-, -SO 2 -, -NRa- (wherein Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), an alkenylene group, a divalent linking group having 1 to 10 carbon atoms formed by combining an alkynylene group or an arylene group, a single bond, -O-, -O-CO-, -CO-O-, -O-AL-O-, -O-AL-O-CO-, -O-AL-CO-O-, -CO-O-AL-O-, -CO-O-AL-O-, -CO-O-AL-O-CO-, -CO-O-AL-CO-, -CO-O-AL-CO-, -CO-O-AL-CO-, -CO-O-AL-CO-O-,
• AL represents an alkylene group.
• L2 is preferably a single bond, -AL-, -O-AL-, or -NRa-AL-O- having 1 to 10 carbon atoms, more preferably a single bond, -AL-, -O-AL-, or -NRa-AL-O- having 1 to 5 carbon atoms, and most preferably a single bond, or -O-AL- or -NRa-AL-O- having 1 to 5 carbon atoms.
• Y1 represents a divalent linking group having a 5-membered or 6-membered ring as a partial structure.
• Y1 include a cyclohexyl ring, an aromatic ring, or a heterocyclic ring.
• the aromatic ring include a benzene ring, an indene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, a biphenyl ring, and a pyrene ring, and the benzene ring, the biphenyl ring, and the naphthalene ring are particularly preferred.
• the heteroatoms constituting the heterocycle are preferably nitrogen, oxygen and sulfur atoms, and examples thereof include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazan ring, tetrazole ring, pyran ring, dioxane ring, dithiane ring, thiine ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine
• the heterocycle is preferably a 6-membered ring.
• the divalent linking group having a 5-membered or 6-membered ring as a partial structure represented by Y1 may further have a substituent (for example, the above-mentioned substituent W).
• the divalent linking group represented by Y1 is preferably a divalent linking group having two or more 5- or 6-membered rings, and more preferably has a structure in which two or more rings are linked by a linking group.
• Z represents a divalent linking group having an alkylene group having 2 to 20 carbon atoms as a partial structure, and consisting of a combination of -O-, -S-, -CO-, and -SO2-, and the alkylene group may have a substituent.
• the divalent linking group include an alkyleneoxy group and a polyalkyleneoxy group.
• the number of carbon atoms in the alkylene group represented by Z is more preferably 2 to 16, even more preferably 2 to 12, and particularly preferably 2 to 8.
• P1 and P2 each independently represent a monovalent substituent having a polymerizable ethylenically unsaturated group.
• Examples of the monovalent substituent having a polymerizable ethylenically unsaturated group include the following formulae (M-1) to (M-8). That is, the monovalent substituent having a polymerizable ethylenically unsaturated group may be a substituent consisting of only an ethenyl group, as in (M-8).
• R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.
• R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.
• P1 is preferably (M-1).
• P2 is preferably (M-1) or (M-8), and in compounds in which ring A is a quaternary imidazolium ion, P2 is preferably (M-8) or (M-1), and in compounds in which ring A is a quaternary pyridinium ion, P2 is preferably (M-1).
• Examples of the onium compound represented by the above formula (B1) include the onium salts described in paragraphs 0052 to 0058 of JP-A-2012-208397, the onium salts described in paragraphs 0024 to 0055 of JP-A-2008-026730, and the onium salts described in JP-A-2002-37777.
• the alignment agent is preferably a boronic acid compound represented by the following formula (B2), because the degree of alignment of the optically absorptive anisotropic layer formed is high.
• R1 and R2 each independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group, or an optionally substituted heterocyclic group. Furthermore, R3 represents a substituent.
• Examples of the aliphatic hydrocarbon group represented by one embodiment of R1 and R2 include a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.), a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms (e.g., a cyclohexyl group, etc.), and an alkenyl group having 2 to 20 carbon atoms (e.g., a vinyl group, etc.).
• a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms e.g., a methyl group, an ethyl group, an isopropyl group, etc.
• a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms e.g., a cyclo
• Examples of the aryl group represented by one embodiment of R 1 and R 2 include a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms (e.g., a phenyl group, a tolyl group, etc.), a substituted or unsubstituted naphthyl group having 10 to 20 carbon atoms, and the like.
• examples of the heterocyclic group represented by one embodiment of R1 and R2 include substituted or unsubstituted 5- or 6-membered ring groups containing at least one heteroatom (e.g., a nitrogen atom, an oxygen atom, a sulfur atom, etc.), and specific examples thereof include a pyridyl group, an imidazolyl group, a furyl group, a piperidyl group, and a morpholino group.
• R 1 and R 2 may be linked to each other to form a ring; for example, the isopropyl groups of R 1 and R 2 may be linked to form a 4,4,5,5-tetramethyl-1,3,2-dioxaborolane ring.
• R 1 and R 2 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a ring formed by combining these, and more preferably a hydrogen atom.
• the substituent represented by R3 is preferably a substituent containing a functional group capable of bonding to a (meth)acrylic group.
• the functional group capable of bonding to a (meth)acrylic group include a vinyl group, an acrylate group, a methacrylate group, an acrylamide group, a styryl group, a vinyl ketone group, a butadiene group, a vinyl ether group, an oxiranyl group, an aziridinyl group, and an oxetane group.
• a vinyl group, an acrylate group, a methacrylate group, a styryl group, an oxiranyl group, or an oxetane group is preferred, and a vinyl group, an acrylate group, an acrylamide group, or a styryl group is more preferred.
• R3 is preferably a substituted or unsubstituted aliphatic hydrocarbon group, aryl group or heterocyclic group having a functional group capable of bonding to a (meth)acrylic group.
• the aliphatic hydrocarbon group include substituted or unsubstituted linear or branched alkyl groups having 1 to 30 carbon atoms (e.g., methyl, ethyl, isopropyl, n-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, sec-butyl, tert-butyl, butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohe
• aryl group examples include substituted or unsubstituted phenyl groups having 6 to 50 carbon atoms (e.g., a phenyl group, a tolyl group, a styryl group, a 4-benzoyloxyphenyl group, a 4-phenoxycarbonylphenyl group, a 4-biphenyl group, a 4-(4-octyloxybenzoyloxy)phenoxycarbonylphenyl group, etc.), and substituted or unsubstituted naphthyl groups having 10 to 50 carbon atoms (e.g., an unsubstituted naphthyl group, etc.).
• substituted or unsubstituted phenyl groups having 6 to 50 carbon atoms e.g., a phenyl group, a tolyl group, a styryl group, a 4-benzoyloxyphenyl group, a 4-phenoxycarbonylphenyl group, a
• heterocyclic groups include substituted or unsubstituted 5- or 6-membered ring groups containing at least one heteroatom (e.g., a nitrogen atom, an oxygen atom, a sulfur atom, etc.), and examples thereof include pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazole benzimidazole, anthranil, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline,
• Examples of the boronic acid compound represented by the above formula (B2) include the boronic acid compounds represented by general formula (I) described in paragraphs 0023 to 0032 of JP-A No. 2008-225281. As the compound represented by the above formula (B2), the compounds exemplified below are also preferred.
• the content of the alignment agent is preferably 0.2 to 20 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the total of the liquid crystal compound and dichroic substance contained in the liquid crystal composition.
• the liquid crystal composition of the present invention may contain other components in addition to the above-mentioned components, such as an adhesion improver and a plasticizer.
• the optically absorptive anisotropic film of the present invention is an optically absorptive anisotropic film formed by using the above-mentioned liquid crystal composition of the present invention, and is preferably an optically absorptive anisotropic film obtained by fixing the alignment state of the above-mentioned liquid crystal composition of the present invention.
• the alignment state of the liquid crystal composition may be any of horizontal alignment, vertical alignment, tilt alignment, and twist alignment.
• the optically absorptive anisotropic film of the present invention is preferably an optically absorptive anisotropic film obtained by fixing the liquid crystal compound contained in the above-mentioned liquid crystal composition of the present invention in a horizontally aligned state.
• horizontal alignment means that the major surface of the optically absorptive anisotropic film (or, when the optically absorptive anisotropic film is formed on a member such as a support or an alignment film, the surface of the member) is parallel to the long axis direction of the liquid crystal compound.
• the angle between the long axis direction of the liquid crystal compound and the major surface of the optically absorptive anisotropic film is less than 10°.
• the angle between the major axis direction of the liquid crystal compound and the main surface of the optically absorptive anisotropic film is preferably 0 to 5°, more preferably 0 to 3°, and even more preferably 0 to 2°.
• the optically absorptive anisotropic film of the present invention is preferably an optically absorptive anisotropic film obtained by fixing the liquid crystal compound contained in the above-mentioned liquid crystal composition of the present invention in a vertically aligned state.
• the angle ⁇ between the central axis of transmittance of the optically absorptive anisotropic film and the normal direction to the surface of the optically absorptive anisotropic film is preferably 0° or more and 45° or less, more preferably 0° or more and less than 45°, even more preferably 0° or more and 35° or less, and particularly preferably 0° or more and less than 35°.
• the central axis of transmittance of the optically absorptive anisotropic film means the direction showing the highest transmittance when the transmittance is measured by changing the inclination angle (polar angle) and inclination direction (azimuth angle) relative to the normal direction of the optically absorptive anisotropic film surface.
• the Mueller matrix at a wavelength of 550 nm is measured using AxoScan (OPMF-2, manufactured by Axometrics).
• the azimuth angle at which the transmittance central axis is tilted is first found, and then, within a plane including the normal direction of the optically absorptive anisotropic film along that azimuth angle (a plane including the transmittance central axis and perpendicular to the film surface), the polar angle, which is the angle with respect to the normal direction of the optically absorptive anisotropic film surface, is changed from -70 to 70° in 1° increments, and the Mueller matrix at a wavelength of 550 nm is measured, and the transmittance of the optically absorptive anisotropic film is derived.
• the central axis of transmittance means the direction of the absorption axis (the long axis direction of the molecule) of the dichroic material contained in the optically absorptive anisotropic film.
• the thickness of the optically absorptive anisotropic film of the present invention is preferably 1.5 ⁇ m or more, more preferably 2 to 10 ⁇ m, and even more preferably 2 to 8 ⁇ m, for the reason that the degree of orientation becomes higher.
• the thickness of the optically absorptive anisotropic film is measured by cutting the film with a microtome to prepare a cross-section of the film, and then observing the cross-section with a scanning electron microscope from the normal direction to the cross-section.
• a preferred example of a method for producing the optically absorptive anisotropic film of the present invention includes a coating film formation step of coating the above-mentioned liquid crystal composition of the present invention to form a coating film, a cleavage step of generating an acid in the coating film by light irradiation or heating after the coating film formation step to cleave the acid-cleavable group (X in the above formula (1)) of the dichroic material represented by the above formula (1), an alignment step of orienting the dichroic material whose acid-cleavable group has been cleaved after the cleavage step, and a curing step of fixing the orientation state of the dichroic material to obtain the optically absorptive anisotropic film after the alignment step.
• a coating film formation step of coating the above-mentioned liquid crystal composition of the present invention to form a coating film
• a cleavage step of generating an acid in the coating film by light irradiation or heating after the coating
• the coating film forming step is a step of forming a coating film by coating the above-mentioned liquid crystal composition of the present invention.
• a liquid crystal composition containing the above-mentioned solvent or by using a liquid crystal composition that has been made into a liquid such as a molten liquid by heating or the like, it becomes easy to apply the liquid crystal composition.
• methods for applying the liquid crystal composition include known methods such as roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spraying, and inkjet.
• the cleavage step is a step in which an acid is generated in the coating film by irradiation with light or heating, and the acid-cleavable group (X in the above formula (1)) of the dichroic material represented by the above formula (1) is cleaved.
• the method of generating an acid in the coating film is not particularly limited, but examples thereof include a method of adding an acid to the coating film; a method of forming a coating film using a liquid crystal composition containing an acid generator, and heating or irradiating the coating film with light to generate an acid; and the like.
• the acid is preferably an acid having a pKa of 3 or less, specifically, sulfonic acid or phosphonic acid is preferable, and sulfonic acid is more preferable.
• the temperature to which the coating film is heated is not particularly limited since it varies depending on the type of thermal acid generator, but is preferably 40 to 300°C, more preferably 80 to 260°C, even more preferably 100 to 220°C, and particularly preferably 120 to 200°C.
• the conditions for irradiating the coating film with light are not particularly limited, and examples include a method of irradiating with ultraviolet light.
• a light source a lamp that emits ultraviolet light, such as a high-pressure mercury lamp or a metal halide lamp, can be used.
• the irradiation amount is preferably 10 mJ/cm 2 to 50 J/cm 2 , more preferably 20 mJ/cm 2 to 5 J/cm 2 , even more preferably 30 mJ/cm 2 to 3 J/cm 2 , and particularly preferably 50 to 1000 mJ/cm 2 .
• the orientation step is a step of orienting the dichroic material (after cleavage of the acid cleavable group, if any) contained in the coating film.
• the orientation step may include a drying treatment. By the drying treatment, components such as a solvent can be removed from the coating film.
• the drying treatment may be performed by leaving the coating film at room temperature for a predetermined time (for example, natural drying), or may be performed by heating and/or blowing air.
• the dichroic material contained in the liquid crystal composition may be aligned by the above-mentioned coating film forming process or drying treatment.
• the coating film is dried to remove the solvent from the coating film, thereby obtaining a coating film having optical absorption anisotropy (i.e., an uncured optical absorption anisotropic film).
• the orientation step preferably includes a heat treatment, which allows the dichroic material contained in the coating film to be oriented, so that the coating film after the heat treatment can be suitably used as an optically absorptive anisotropic film.
• the heat treatment is preferably performed at 10 to 250° C., more preferably at 25 to 190° C.
• the heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.
• the orientation step may include a cooling treatment carried out after the heating treatment.
• the cooling treatment is a treatment for cooling the coated film after heating to about room temperature (20 to 25°C). This makes it possible to fix the orientation of the dichroic material contained in the coated film.
• the cooling means is not particularly limited and can be carried out by a known method. By the above steps, an optically absorptive anisotropic film can be obtained.
• the method for aligning the dichroic material contained in the coating film includes drying treatment and heating treatment, but is not limited thereto and can be carried out by any known alignment treatment.
• the curing step is a step for fixing the oriented state of the dichroic material after the orientation step, thereby obtaining an optically absorptive anisotropic film.
• the curing step is carried out, for example, by heating and/or light irradiation (exposure), and among these, the curing step is preferably carried out by light irradiation.
• the light source used for curing can be various light sources such as infrared light, visible light, or ultraviolet light, but ultraviolet light is preferable. In addition, ultraviolet light may be irradiated while heating during curing, or ultraviolet light may be irradiated through a filter that transmits only specific wavelengths.
• the exposure may be carried out under a nitrogen atmosphere. When the curing of the optically absorptive anisotropic film proceeds by radical polymerization, it is preferable to carry out the exposure under a nitrogen atmosphere, since this reduces the inhibition of polymerization caused by oxygen.
• the optical layered body of the present invention has the above-mentioned optically absorptive anisotropic film of the present invention.
• the optical layered body of the present invention may have a substrate for supporting the optically absorptive anisotropic film of the present invention.
• the optical layered body of the present invention may further include a ⁇ /4 plate on the optically absorptive anisotropic film.
• the optical layered body of the present invention may further include an alignment layer between the substrate and the optically absorptive anisotropic film.
• the optical layered body of the present invention may further include a barrier layer between the optically absorptive anisotropic film and the ⁇ /4 plate.
• the substrate can be selected depending on the application of the light absorption anisotropic film, and examples thereof include glass and polymer films.
• the light transmittance of the substrate is preferably 80% or more.
• a polymer film is used as the substrate, it is preferable to use an optically isotropic polymer film. Specific examples and preferred aspects of the polymer are described in paragraph [0013] of JP-A-2002-22942.
• a polymer that is easily capable of exhibiting birefringence such as conventionally known polycarbonate or polysulfone
• optically absorptive anisotropic film The optically absorptive anisotropic film has been described above, and therefore its description will be omitted.
• ⁇ /4 plate refers to a plate having a lambda/4 function, specifically, a plate having the function of converting linearly polarized light of a certain wavelength into circularly polarized light (or circularly polarized light into linearly polarized light).
• ⁇ /4 plate having a single layer structure include a stretched polymer film and a retardation film having an optically anisotropic layer having ⁇ /4 function provided on a support
• ⁇ /4 plate having a multilayer structure include a broadband ⁇ /4 plate formed by laminating a ⁇ /4 plate and a ⁇ /2 plate.
• the ⁇ /4 plate and the optically absorptive anisotropic film may be provided in contact with each other, or another layer may be provided between the ⁇ /4 plate and the optically absorptive anisotropic film.
• Such layers include an adhesive layer or a bonding layer for ensuring adhesion, and a barrier layer.
• the barrier layer is provided between the optically absorptive anisotropic film and the ⁇ /4 plate.
• the barrier layer can be provided, for example, between the optically absorptive anisotropic film and the other layer.
• the barrier layer is also called a gas barrier layer (oxygen barrier layer), and has the function of protecting the light absorption anisotropic film from gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers.
• the optical layered body of the present invention may have an alignment layer between the substrate and the optically absorptive anisotropic film.
• the alignment film may be any layer as long as it can provide a desired alignment state for the dichroic material contained in the liquid crystal composition of the present invention on the alignment film.
• the alignment layer can be provided by a method such as rubbing an organic compound (preferably a polymer) on the film surface, oblique deposition of an inorganic compound, formation of a layer having microgrooves, or accumulation of an organic compound (e.g., ⁇ -tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearate) by the Langmuir-Blodgett method (LB film).
• LB film Langmuir-Blodgett method
• an alignment layer formed by a rubbing treatment is preferred from the viewpoint of ease of control of the pretilt angle of the alignment layer, and a photo-alignment layer formed by irradiation with light is also preferred from the viewpoint of uniformity of alignment.
• ⁇ Rubbing Treatment Alignment Film Polymer materials used for the alignment film formed by rubbing treatment are described in many documents, and many commercial products are available. In the present invention, polyvinyl alcohol or polyimide and derivatives thereof are preferably used.
• the thickness of the alignment film is preferably 0.01 to 10 ⁇ m, and more preferably 0.01 to 1 ⁇ m.
• Photo-alignment materials used in the alignment film formed by light irradiation are described in many documents.
• azo compounds described in JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007-121721, JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, Japanese Patent No. 3883848, and Japanese Patent No. 4151746, and compounds described in JP-A-2002-229039 are used.
• Preferred examples include aromatic ester compounds of the above, maleimide and/or alkenyl-substituted nadimide compounds having a photo-orientable unit described in JP-A-2002-265541 and JP-A-2002-317013, photo-crosslinkable silane derivatives described in Japanese Patent Nos. 4205195 and 4205198, and photo-crosslinkable polyimides, polyamides, or esters described in JP-T-2003-520878, JP-T-2004-529220, or JP-T-4162850. More preferred are azo compounds, photo-crosslinkable polyimides, polyamides, or esters.
• a photo-alignment film formed from the above-mentioned material is irradiated with linearly polarized or non-polarized light to produce a photo-alignment film.
• “irradiation with linearly polarized light” and “irradiation with non-polarized light” are operations for causing a photoreaction in a photoalignment material.
• the wavelength of the light used varies depending on the photoalignment material used, and is not particularly limited as long as it is a wavelength necessary for the photoreaction.
• the peak wavelength of the light used for photoirradiation is preferably 200 nm to 700 nm, and more preferably ultraviolet light with a peak wavelength of 400 nm or less.
• Light sources used for light irradiation include commonly used light sources, such as lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps, various lasers [e.g., semiconductor lasers, helium-neon lasers, argon ion lasers, helium-cadmium lasers, and YAG (yttrium aluminum garnet) lasers], light-emitting diodes, and cathode ray tubes.
• lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps
• various lasers e.g., semiconductor lasers, helium-neon lasers, argon ion lasers, helium-cadmium lasers, and YAG (yttrium aluminum garnet) lasers
• light-emitting diodes e.g.,
• Means for obtaining linearly polarized light include using a polarizing plate (e.g., an iodine polarizing plate, a dichroic dye polarizing plate, and a wire grid polarizing plate), using a prism-based element (e.g., a Glan-Thompson prism) or a reflective polarizer that utilizes the Brewster angle, or using light emitted from a polarized laser light source. Also, a filter or wavelength conversion element may be used to selectively irradiate only light of the required wavelength.
• a polarizing plate e.g., an iodine polarizing plate, a dichroic dye polarizing plate, and a wire grid polarizing plate
• a prism-based element e.g., a Glan-Thompson prism
• a reflective polarizer that utilizes the Brewster angle
• a filter or wavelength conversion element may be used to selectively irradiate only light of the required
• the light is irradiated from the top or back surface of the alignment film perpendicularly or obliquely to the alignment film surface.
• the incident angle of the light varies depending on the photoalignment material, but is preferably 0 to 90° (perpendicular), more preferably 40 to 90°.
• the non-polarized light is obliquely irradiated onto the alignment film, preferably at an incident angle of 10 to 80°, more preferably at an incident angle of 20 to 60°, and even more preferably at an incident angle of 30 to 50°.
• the irradiation time is preferably from 1 to 60 minutes, and more preferably from 1 to 10 minutes.
• patterning is required, a method of irradiating light using a photomask the number of times required to create a pattern, or a method of writing a pattern using laser light scanning can be used.
• the optical laminate of the present invention can be used as a polarizing element (polarizing plate), for example, as a linear polarizing plate or a circular polarizing plate.
• polarizing plate polarizing element
• the laminate of the present invention does not have an optically anisotropic layer such as the ⁇ /4 plate
• the laminate can be used as a linear polarizing plate.
• the laminate of the present invention has the above-mentioned ⁇ /4 plate
• the laminate can be used as a circularly polarizing plate.
• the image display device of the present invention has the above-mentioned optically absorptive anisotropic film or the above-mentioned laminate.
• the display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as "EL") display panel, and a plasma display panel.
• EL organic electroluminescence
• a liquid crystal cell or an organic EL display panel is preferred, and a liquid crystal cell is more preferred.
• the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, or an organic EL display device using an organic EL display panel as a display element, and more preferably a liquid crystal display device.
• a preferred embodiment of the liquid crystal display device which is one example of the image display device of the present invention, is a liquid crystal display device having the above-mentioned light absorption anisotropic film and a liquid crystal cell, and more preferably a liquid crystal display device having the above-mentioned laminate (not including a ⁇ /4 plate) and a liquid crystal cell.
• the optically absorptive anisotropic films (laminates) provided on both sides of the liquid crystal cell it is preferable to use the optically absorptive anisotropic film (laminate) of the present invention as the front side polarizing element, and it is more preferable to use the optically absorptive anisotropic film (laminate) of the present invention as the front side and rear side polarizing elements.
• the liquid crystal cell constituting the liquid crystal display device will be described in detail below.
• the liquid crystal cell used in the liquid crystal display device is preferably in a VA (Vertical Alignment) mode, an OCB (Opticaly Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode, but is not limited to these.
• VA Vertical Alignment
• OCB Opticaly Compensated Bend
• IPS In-Plane-Switching
• TN Transmission Nematic
• rod-shaped liquid crystal molecules are aligned substantially horizontally when no voltage is applied, and further aligned in a twisted manner at an angle of 60 to 120°.
• TN mode liquid crystal cells are most commonly used as color TFT (Thin Film Transistor) liquid crystal display devices, and are described in many publications.
• VA mode liquid crystal cell rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied.
• the VA mode liquid crystal cells include (1) a narrow-sense VA mode liquid crystal cell (described in JP-A-2-176625) in which rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied and substantially horizontally when voltage is applied, (2) a VA mode multi-domain (MVA mode) liquid crystal cell (described in SID97, Digest of tech.
• n-ASM mode liquid crystal cell in which rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied and are aligned in a twisted multi-domain when voltage is applied (described in Japan Liquid Crystal Discussion Society Preprints 58-59 (1998)), and (4) a SURVIVAL mode liquid crystal cell (announced at LCD International 98).
• the liquid crystal display may be of any of a PVA (Patterned Vertical Alignment) type, an optical alignment type, and a PSA (Polymer-Sustained Alignment) type. Details of these modes are described in detail in Japanese Patent Application Laid-Open No.
• the rod-shaped liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied.
• the black display is achieved when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are perpendicular to each other.
• JP-A-10-54982 JP-A-11-202323, JP-A-9-292522, JP-A-11-133408, JP-A-11-305217, JP-A-10-307291, and the like.
• An organic EL display device which is one example of the image display device of the present invention, may have, for example, a light absorption anisotropic film, a ⁇ /4 plate, and an organic EL display panel in this order from the viewing side. It is preferable to mention. More preferably, the laminate includes, from the viewing side, the above-mentioned laminate having a ⁇ /4 plate and an organic EL display panel in this order. In this case, the laminate includes, from the viewing side, a substrate An alignment film which is provided as required, a light absorbing anisotropic film, a barrier layer which is provided as required, and a ⁇ /4 plate are arranged in this order.
• An organic EL display panel is a display panel configured using organic EL elements in which an organic light-emitting layer (organic electroluminescence layer) is sandwiched between electrodes (cathode and anode).
• the configuration is not particularly limited, and a known configuration may be adopted.
• compound B-1a (6.4 g) was dissolved in methanol (50 mL), water (20 mL), and hydrochloric acid (10 mL), heated at 80° C. for 8 hours, cooled to room temperature, and the resulting solid was collected by suction filtration to obtain compound B-1b (4.0 g) represented by the above formula B-1b.
• compound B-1b (3.5 g) was dissolved in water (35 mL) and hydrochloric acid (2.0 mL) and cooled in an ice bath, sodium nitrite (1.9 g) was added, and the mixture was stirred for 120 minutes.
• compound B-1c (4.0 g), compound B-1d (2.0 g), potassium carbonate (1.5 g), and potassium iodide (0.4 g) were dissolved in N,N-dimethylacetamide (DMAc) (50 mL) and stirred for 8 hours at 85° C. After stirring, hydrochloric acid (1.0 g), water (10 mL), and methanol (50 mL) were added, and the resulting solid was suction filtered to obtain dichroic substance B-1 (4.5 g).
• DMAc N,N-dimethylacetamide
• compound B-1b (3.5 g) was dissolved in water (35 mL) and hydrochloric acid (2.0 mL), cooled in an ice bath, and sodium nitrite (1.9 g) was added. Stirring was continued for 120 minutes. Amidosulfuric acid (0.5 g) was further added, and a solution of phenol (3.5 g), 48% aqueous potassium hydroxide solution (4.0 g) and water (24 mL) was added and stirred at room temperature for 1 hour. After stirring, the mixture was neutralized with hydrochloric acid, and the resulting solid was collected by suction filtration to obtain compound B-2a (3.6 g) represented by the above formula B-2a.
• compound B-2a (3.6 g), paraoctyloxybenzoic acid (1.0 g), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (1.0 g), and 4-N,N-dimethylaminopyridine (0.4 g) were dissolved in N,N-dimethylacetamide (DMAc) (30 mL) and stirred for 8 hours at 50° C. After stirring, methanol (50 mL) was added, and the resulting solid was suction filtered and purified using a silica gel column to obtain compound B-2b (1.1 g) represented by the above formula B-2b.
• DMAc N,N-dimethylacetamide
• Levulinic acid (10 g), 2-(N-methylanilino)ethanol (8.0 g), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (6.0 g), and 4-N,N-dimethylaminopyridine (1.0 g) were dissolved in N,N-dimethylacetamide (DMAc) (30 mL) and stirred for 2 hours at 50° C. 10 mL of methanol was added to terminate the reaction, and 50 mL of ethyl acetate and 50 mL of water were added to carry out a liquid separation operation.
• DMAc N,N-dimethylacetamide
• paraacetanilide (10 g) was dissolved in water (300 mL) and 12 mol/L (liter) hydrochloric acid (17 mL) and cooled in an ice bath, sodium nitrite (3.3 g) was added, and the mixture was stirred for 30 minutes. After further addition of amidosulfuric acid (0.5 g), a solution of phenol (4.0 g), 48% aqueous potassium hydroxide solution (4.0 g), and water (24 mL) was added, and the mixture was stirred at room temperature for 1 hour. After stirring, the mixture was neutralized with hydrochloric acid, and the resulting solid was collected by suction filtration to obtain compound B-4a (12 g) represented by the above formula B-4a.
• compound B-4a (40 g) was suspended in methanol (700 mL), water (240 mL), and hydrochloric acid (46 g), heated at 85° C. for 8 hours, cooled to room temperature, sodium nitrite (11.9 g) was added, and the mixture was stirred for 30 minutes. After further addition of amidosulfuric acid (1.0 g), a solution of N,N-dimethylaniline (70 g), acetic acid (4.7 g), and methanol (320 mL) was added, and the mixture was stirred at room temperature for 1 hour. The obtained solid was collected by suction filtration to obtain compound B-4b (48 g) represented by the above formula B-4b.
• compound B-4b (5.0 g), compound B-1d (3.0 g), potassium carbonate (2.0 g), and potassium iodide (0.4 g) were dissolved in N,N-dimethylacetamide (DMAc) (20 mL) and stirred for 8 hours at 85° C. After stirring, hydrochloric acid (1.0 g), water (9 mL), and methanol (20 mL) were added, and the resulting solid was suction filtered to obtain dichroic substance B-4 (5.6 g).
• DMAc N,N-dimethylacetamide
• compound B-2a (3.6 g), compound B-5a (2.0 g), potassium carbonate (1.0 g), and potassium iodide (0.3 g) were dissolved in N,N-dimethylacetamide (DMAc) (30 mL) and stirred for 8 hours at 85° C. After stirring, hydrochloric acid (1.0 g), water (8 mL), and methanol (30 mL) were added, and the resulting solid was suction filtered to obtain dichroic substance B-5 (4.2 g).
• DMAc N,N-dimethylacetamide
• Example 1 The optical laminate of Example 1 was produced as follows.
• Cellulose acylate film 1 was prepared as follows.
• the film was further dried by conveying it between rolls of a heat treatment device to prepare an optical film having a thickness of 40 ⁇ m, which was used as cellulose acylate film 1.
• the in-plane retardation of the obtained cellulose acylate film 1 was 0 nm.
• optical laminate As described below, an optical laminate including the above-mentioned cellulose acylate film 1, the photo-alignment layer PA1, the light absorption anisotropic film P1, and the oxygen barrier layer B1, arranged adjacent to each other in this order, was prepared.
• a coating solution PA1 for forming an alignment layer having the following composition was continuously applied with a wire bar onto the cellulose acylate film 1.
• the support on which the coating film was formed was dried with hot air at 140° C. for 120 seconds, and then the coating film was irradiated with polarized ultraviolet light (10 mJ/cm 2 , using an ultra-high pressure mercury lamp) to form a photoalignment layer PA1, thereby obtaining a TAC film with a photoalignment layer.
• a liquid crystal composition P1 having the following composition was continuously applied by a wire bar onto the photo-alignment layer PA1 of the obtained TAC film with a photo-alignment layer to form a coating layer P1 (coating film forming step).
• the coating layer P1 was heated at 140° C. for 30 seconds, and then cooled to room temperature (23° C.) (cleavage step). Next, it was heated at 80° C. for 60 seconds and cooled again to room temperature (orientation step).
• an LED (Light Emitting Diode) lamp (center wavelength 365 nm) was used to irradiate the photo-alignment layer PA1 with an illuminance of 200 mW/ cm2 for 2 seconds to form an optically absorptive anisotropic film P1 on the photo-alignment layer PA1 (curing step).
• the optically absorptive anisotropic film P1 had a thickness of 2.0 ⁇ m.
• Liquid crystal composition P1 0.150 parts by mass of polymerizable boronic acid compound B1 described below; 2.680 parts by mass of polymer liquid crystal compound L1 described below; 1.201 parts by mass of low molecular weight liquid crystal compound LM1 described below; 1.081 parts by mass of dichroic material Y1 described below; 0.278 parts by mass of dichroic material M1 described below; 1.142 parts by mass of dichroic material C1 described below; 0.060 parts by mass of surfactant F1 described below; 0.054 parts by mass of acid generator San-Aid SI-B3A; and polymerization initiator I1.
• IRGACUREOXE-02 manufactured by BASF
• Dichroic substance Y1 (dichroic substance B-1)
• a composition B1 for forming an oxygen barrier layer having the following composition was continuously applied with a wire bar, and then the composition was dried for 2 minutes with hot air at 100° C. to form a polyvinyl alcohol (PVA) alignment layer (oxygen barrier layer B1) having a thickness of 1.1 ⁇ m on the optically absorptive anisotropic film P1.
• PVA polyvinyl alcohol
• ⁇ Composition B1 for forming oxygen barrier layer ⁇ - 3.80 parts by mass of the following modified polyvinyl alcohol - 0.20 parts by mass of Irgcure 2959 initiator - 70 parts by mass of water - 30 parts by mass of methanol
• Example 1 an optical laminate of Example 1 was obtained, which had a cellulose acylate film 1, a photo-alignment layer PA1, a light-absorbing anisotropic film P1, and an oxygen barrier layer B1 adjacent to each other in this order.
• Example 2 to 14 and Comparative Examples 1 to 3 An optical laminate was produced in the same manner as in Example 1, except that the dichroic material Y1 (dichroic material B-1) was replaced with a dichroic material shown in Table 1 below.
• Az0 represents the absorbance of the optically absorptive anisotropic film for polarized light in the absorption axis direction
• Ay0 represents the absorbance of the optically absorptive anisotropic film for polarized light in the transmission axis direction.
• AA Orientation degree is 0.95 or more
• B Orientation degree is 0.90 or more and less than 0.83
• C Orientation degree is less than 0.90
• Solubility concentration of dichroic substance in filtrate / concentration of dichroic substance in composition
• Solubility concentration of dichroic substance in filtrate / concentration of dichroic substance in composition
• a calibration curve was used, which was prepared by preparing dichroic substance solutions at concentrations of 10 mg/10 mL, 1.0 mg/10 mL, 0.10 mg/10 mL, and 0.010 mg/10 mL and measuring each solution by HPLC. The results were evaluated according to the following criteria. ⁇ Evaluation criteria> A: Solubility is 0.95 or more B: Solubility is 0.50 or more and less than 0.95 C: Solubility is less than 0.50
• a comparison of Examples 1 to 4 reveals that when n in the above formula (1) is an integer of 2 or more, the degree of orientation of the optically absorptive anisotropic film becomes higher. Furthermore, by comparing Example 10 with other Examples, it was found that when X in the above formula (1) is an acid-cleavable group represented by any one of the above formulas (A1) to (A5), the degree of orientation of the optically absorptive anisotropic film to be produced is higher. Furthermore, by comparing Example 5 with the other Examples, it was found that when the two R A2 in the above formula (A2) each independently represent a linear or branched monovalent aliphatic hydrocarbon group, the solubility of the liquid crystal composition becomes better. Moreover, by comparing Example 14 with the other Examples, it was found that when the molecular weight of R A2 in the above formula (A2) was 300 or less, the degree of orientation of the optically absorptive anisotropic film was further increased.
• Example 15 The optical laminate of Example 15 was produced as follows.
• the transmittance central axis angle ⁇ of the laminate produced in Example 15 was measured by the method described above and was found to be 0°.
• a polyvinyl alcohol (PVA) alignment layer (oxygen barrier layer B1) was formed in the same manner as in Example 1.
• PVA polyvinyl alcohol
• oxygen barrier layer B1 oxygen barrier layer
• the solubility of the liquid crystal composition P2 was evaluated in the same manner as in Example 1, and the result was an A rating.
• the degree of orientation of the optically absorptive anisotropic film in the optical laminate produced in Example 15 was calculated by the following method and evaluated according to the following criteria, resulting in an AA rating.
• the polar angle which is the angle with respect to the normal direction of the optically absorptive anisotropic film, was changed in 1° increments from -70° to 70° during measurement, and the Mueller matrix was measured at 400 nm to 700 nm at each polar angle to derive the minimum transmittance (Tmin).
• Tmin at the polar angle at which Tmin is highest is defined as Tm(0)
• Tmin in the direction 40° larger than the polar angle at which Tmin is highest is defined as Tm(40).
• the absorbance (A) was calculated from the obtained Tm(0) and Tm(40) according to the following formula, and A(0) and A(40) were calculated.
• A -log(Tm)
• Tm represents the transmittance
• A represents the absorbance.

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