Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/12—Esters of phenols or saturated alcohols
  • C08F222/24—Esters containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
  • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
  • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
  • C09K19/3497—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom the heterocyclic ring containing sulfur and nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
  • C09K19/3833—Polymers with mesogenic groups in the side chain
  • C09K19/3842—Polyvinyl derivatives
  • C09K19/3852—Poly(meth)acrylate derivatives
  • C09K19/3861—Poly(meth)acrylate derivatives containing condensed ring systems
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
  • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Definitions

• the present invention relates to a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, an image display device, and a method for producing a polymerizable liquid crystal composition.
• Polymerizable liquid crystal compounds that exhibit reverse wavelength dispersion have been actively researched because they have features such as enabling accurate conversion of light wavelengths over a wide wavelength range and allowing retardation films to be made thinner due to their high birefringence.
• a T-type molecular design guideline is generally adopted, and it is required to shorten the wavelength of the molecular long axis and to lengthen the wavelength of the short axis located at the center of the molecule.
• JP 2010-031223 A International Publication No. 2014/010325 JP 2016-081035 A
• Patent Documents 1 to 3 The inventors have studied Patent Documents 1 to 3 and found that, depending on the type of polymerizable compound, the solubility of the polymerizable liquid crystal composition may be poor, and precipitates may form in the solution of the polymerizable liquid crystal composition.
• the present invention aims to provide a polymerizable liquid crystal composition that has excellent solubility and low precipitation from solution, an optically anisotropic film, an optical film, a polarizing plate, an image display device, and a method for producing the polymerizable liquid crystal composition.
• the present inventors conducted intensive research to achieve the above object, and as a result, discovered that a polymerizable liquid crystal composition containing four specific polymerizable liquid crystal compounds, each having a different structure in at least one of the core portion and the side chain portion, has excellent solubility and low precipitation tendency from a solution, and thus completed the present invention. That is, the present inventors have found that the above problems can be solved by the following configuration.
• the polymerizable liquid crystal composition according to [1] further comprising polymerizable liquid crystal compounds P3 and P6 represented by formulas (3) and (6) described later.
• [4] The polymerizable liquid crystal composition according to any one of [1] to [3], which has smectic liquid crystal properties.
• [5] An optically anisotropic film obtained by fixing the alignment state of the polymerizable liquid crystal composition according to any one of [1] to [4].
• [6] The optically anisotropic film according to [5], which satisfies formula (F) described below.
• [7] An optical film having the optically anisotropic film according to [5] or [6].
• [8] A polarizing plate comprising the optical film according to [7] and a polarizer.
• An image display device comprising the optical film according to [7] or the polarizing plate according to [8].
• a method for producing a polymerizable liquid crystal composition comprising dissolving polymerizable liquid crystal compounds P1 and P3 represented by formulas (1) and (3) described later in a solvent and reacting the compounds to obtain a polymerizable liquid crystal composition containing polymerizable liquid crystal compounds P1 to P3 represented by formulas (1) to (3) described later and a solvent.
• a method for producing a polymerizable liquid crystal composition comprising dissolving polymerizable liquid crystal compounds P1 and P4 represented by formulas (1) and (4) described later in a solvent and reacting the compounds to obtain a polymerizable liquid crystal composition containing polymerizable liquid crystal compounds P1, P2, P4, and P5 represented by formulas (1), (2), (4), and (5) described later and a solvent.
• the method for producing a polymerizable liquid crystal composition according to [11] wherein the polymerizable liquid crystal composition contains polymerizable liquid crystal compounds P3 and P6 represented by the following formulas (3) and (6) described later.
• the present invention can provide a polymerizable liquid crystal composition that has excellent solubility and low precipitation from a solution, an optically anisotropic film, an optical film, a polarizing plate, an image display device, and a method for producing the polymerizable liquid crystal composition.
• FIG. 1 is a schematic cross-sectional view showing an example of an optical film.
• 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 limit or lower limit of a certain numerical range described in a stepwise manner may be replaced with the upper limit or lower limit of another stepwise described numerical range.
• the upper limit or lower limit of a certain 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)acrylic is a notation representing "acrylic” or “methacrylic”.
• the bonding direction of a divalent group is not particularly limited unless the bonding position is clearly stated.
• L2 is -O-CO- in the bond of " L1 - L2 - L3 "
• 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 550 nm unless otherwise specified.
• the polymerizable liquid crystal composition of the present invention contains polymerizable liquid crystal compounds P1, P2, P4 and P5 represented by the following formulas (1), (2), (4) and (5):
• the polymerizable liquid crystal composition is preferably a polymerizable liquid crystal composition containing polymerizable liquid crystal compounds P1 to P6 represented by the following formulas (1) to (6).
• W1 represents a monovalent group represented by formula (7) described below, all of which have the same ClogP value
• W2 represents a monovalent group represented by formula (8) described below, all of which have the same ClogP value, provided that the ClogP value of W1 is different from the ClogP value of W2.
• Ar1 represents a divalent aromatic ring having the same ClogP value
• Ar2 represents a divalent aromatic ring having the same ClogP value
• at least one of Ar1 and Ar2 represents an aromatic ring selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-7) described below, with the proviso that the ClogP value of Ar1 is greater than the ClogP value of Ar2.
• the ClogP value is the value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water. Any known method or software can be used to calculate the ClogP value, but unless otherwise specified, the present invention uses the ClogP program built into ChemDraw 20.1 by PerkinElmer.
• the ClogP value of Ar1 is greater than the ClogP value of Ar2
• Ar1 and Ar2 are structures having different ClogP values, and the structure having the greater ClogP value is Ar1.
• the polymerizable liquid crystal composition containing the polymerizable liquid crystal compounds P1, P2, P4 and P5 represented by the above formulas (1), (2), (4) and (5) has excellent solubility and low precipitation tendency from a solution.
• the reason why this effect is manifested is not clear in detail, but the present inventors speculate as follows. That is, since the polymerizable liquid crystal compounds P1, P2, P4 and P5 represented by the above formulas (1), (2), (4) and (5) have different structures in at least one of the core portion and the side chain portion, it is presumed that the packing of the molecules is inhibited, and as a result, the solubility of the polymerizable liquid crystal compounds in organic solvents is improved.
• Each component of the polymerizable liquid crystal composition of the present invention will be described in detail below.
• the polymerizable liquid crystal composition of the present invention contains the polymerizable liquid crystal compounds P1, P2, P4, and P5 represented by the following formulas (1), (2), (4), and (5), It is preferable that the liquid crystal composition contains polymerizable liquid crystal compounds P1 to P6 represented by the following formulas (1) to (6).
• W1 represents a monovalent group represented by the following formula (7) having the same ClogP value
• W2 represents a monovalent group represented by the following formula (8) having the same ClogP value, provided that the ClogP value of W1 is different from the ClogP value of W2.
• Ar1 represents a divalent aromatic ring having the same ClogP value
• Ar2 represents a divalent aromatic ring having the same ClogP value
• at least one of Ar1 and Ar2 represents an aromatic ring selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-7) described below, with the proviso that the ClogP value of Ar1 is greater than the ClogP value of Ar2.
• m and n each independently represent an integer of 1 or more.
• D 1 , D 2 , E 1 and E 2 each independently represent a single bond, -CO-, -O-, -S-, -C( ⁇ S)-, -CR 1 R 2 -, -CR 3 ⁇ CR 4 -, -NR 5 -, or a divalent linking group consisting of a combination of two or more of these, and R 1 to R 5 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
• multiple E 1 's may be the same or different, and when n is an integer of 2 or more, multiple E 2 's may be the same or different.
• A1 and A2 each independently represent an aromatic ring having 6 or more carbon atoms which may have a substituent, or a cycloalkane ring having 6 or more carbon atoms which may have a substituent.
• the multiple A1 's may be the same or different, and when n is an integer of 2 or more, the multiple A2 's may be the same or different.
• SP 1 and SP 2 each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, or a divalent linking group in which one or more of -CH 2 - constituting the alkylene group, alkenylene group, or alkynylene group are replaced with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q represents a substituent.
• L1 and L2 each independently represent a monovalent organic group, and at least one of L1 and L2 represents a polymerizable group.
• Ar1 or Ar2 in the above formulas (1), (2), (4) and (5) is an aromatic ring represented by formula (Ar-3) described later, at least one of L1 and L2 and L3 and L4 in formula (Ar-3) described later represents a polymerizable group.
• n and n each independently represent an integer of 1 or greater, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2.
• examples of the divalent linking group represented by one embodiment of D 1 , D 2 , E 1 and E 2 include, for example, -CO-O-, -C( ⁇ S)O-, -CR 1 R 2 -, -CR 1 R 2 -CR 1 R 2 -, -O-CR 1 R 2 -, -CR 1 R 2 -O-CR 1 R 2 -, -CO-O-CR 1 R 2 -, -O-CO-CR 1 R 2 -, -CR 1 R 2 -O-CO-CR 1 R 2 -, -CR 1 R 2 -O-CO-CR 1 R 2 -, -CR 1 R 2 -CO-O-CR 1 R 2 -, -NR 5 -CR 1 R 2 - and -CO-NR 5 -.
• R 1 , R 2 and R 5 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
• D1 and D2 are preferably a single bond.
• E 1 and E 2 are preferably —O—, —CO—O— or —CO—NR 5 —, and more preferably —CO—O—.
• examples of the aromatic ring having 6 or more carbon atoms represented by one embodiment of A1 and A2 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthroline ring, etc., and aromatic heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, a benzothiazole ring, etc.
• aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthroline ring, etc.
• aromatic heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, a benzothiazole ring, etc.
• examples of the cycloalkane ring having 6 or more carbon atoms represented by one embodiment of A1 and A2 include a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclododecane ring, a cyclodocosane ring, etc.
• a cyclohexane ring e.g., a 1,4-cyclohexylene group, etc.
• a trans-1,4-cyclohexylene group is more preferable.
• examples of the substituent that the aromatic ring having 6 or more carbon atoms or the cycloalkane ring having 6 or more carbon atoms may have include, for example, an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylamino group, a dialkylamino group, an alkylamide group, an alkenyl group, an alkynyl group, a halogen atom, a cyano group, a nitro group, an alkylthiol group, and an N-alkylcarbamate group.
• an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferable.
• the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a cyclohexyl group, etc.), still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
• the alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.), still more preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.
• Examples of the alkoxycarbonyl group include groups in which an oxycarbonyl group (—O—CO— group) is bonded to the above-mentioned alkyl group.
• a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group or an isopropoxycarbonyl group is preferred, and a methoxycarbonyl group is more preferred.
• the alkylcarbonyloxy group include groups in which a carbonyloxy group (—CO—O— group) is bonded to the above-mentioned alkyl groups. Among these, a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group or an isopropylcarbonyloxy group is preferable, and a methylcarbonyloxy group is more preferable.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
• the alkylene group having 1 to 20 carbon atoms represented by one embodiment of SP 1 and SP 2 may be either linear or branched, and is preferably an alkylene group having 1 to 12 carbon atoms.
• Suitable examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, and a heptylene group.
• the alkenylene group having 2 to 20 carbon atoms represented by one embodiment of SP 1 and SP 2 may be either linear or branched, and is preferably an alkenylene group having 2 to 20 carbon atoms, such as an ethenylene group, a propenylene group, or a butenylene group.
• the alkynylene group having 2 to 20 carbon atoms represented by one embodiment of SP 1 and SP 2 may be either linear or branched, and a suitable example is an ethynylene group.
• SP 1 and SP 2 may be a divalent linking group in which one or more of the -CH 2 - constituting the alkylene group, alkenylene group, or alkynylene group are replaced with -O-, -S-, -NH-, -N(Q)-, or -CO-, and examples of the substituent represented by Q include the same substituents as those explained for A 1 and A 2 in the above formulas (7) and (8).
• examples of the monovalent organic group represented by L 1 and L 2 include an alkyl group, an aryl group, and a heteroaryl group.
• the alkyl group may be linear, branched, or cyclic, but is preferably linear.
• the number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.
• the aryl group may be monocyclic or polycyclic, but is preferably monocyclic.
• the number of carbon atoms in the aryl group is preferably 6 to 25, and more preferably 6 to 10.
• the heteroaryl group may be monocyclic or polycyclic.
• the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3.
• the heteroatoms constituting the heteroaryl group are preferably nitrogen atoms, sulfur atoms, and oxygen atoms.
• the number of carbon atoms in the heteroaryl group is preferably 6 to 18, and more preferably 6 to 12.
• the alkyl group, aryl group, and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same as those described for A 1 and A 2 in the above formulas (7) and (8).
• the polymerizable group represented by at least one of L 1 and L 2 is not particularly limited, but is preferably a polymerizable group capable of radical polymerization or cation polymerization.
• a known radical polymerizable group can be used, and a suitable one can be an acryloyloxy group or a methacryloyloxy group.
• the polymerization rate of the acryloyloxy group is generally fast, and from the viewpoint of improving productivity, the acryloyloxy group is preferred, but the methacryloyloxy group can also be used as the polymerizable group.
• a known cationic polymerizable group can be used, and specific examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group.
• an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
• Particularly preferred examples of the polymerizable group include those represented by any of the following formulas (P-1) to (P-20).
• examples of the divalent aromatic ring represented by Ar1 and Ar2 include aromatic rings having 6 or more carbon atoms, and specific examples thereof include the same as those explained for A1 and A2 in the above formulas (7) and (8).
• At least one of Ar1 and Ar2 represents an aromatic ring selected from the group consisting of groups represented by the following formulae (Ar-1) to (Ar-7), in which * represents the bonding position with an oxygen atom.
• Q1 represents N or CH
• Q2 represents -S-, -O-, or -N( R6 )-
• R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• Y1 represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent.
• alkyl group having 1 to 6 carbon atoms represented by one embodiment of R 6 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.
• aromatic hydrocarbon group having 6 to 12 carbon atoms represented by one embodiment of Y1 include aryl groups such as a phenyl group, a 2,6-diethylphenyl group, and a naphthyl group.
• Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by one embodiment of Y 1 include heteroaryl groups such as a thienyl group, a thiazolyl group, a furyl group, and a pyridyl group.
• examples of the substituent that Y 1 may have include the same substituents as those explained for A 1 and A 2 in the above formulas (7) and (8).
• Z 1 , Z 2 and Z 3 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent aromatic heterocyclic group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR 7 , -NR 8 R 9 or -SR 10 , R 7 to R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z 1 and Z 2 may be bonded to each other to form an aromatic ring.
• an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, specifically, a methyl group, an ethyl group, an isopropyl group, a tert-pentyl group (1,1-dimethylpropyl group), a tert-butyl group, or a 1,1-dimethyl-3,3-dimethyl-butyl group is further preferable, and a methyl group, an ethyl group, or a tert-butyl group is particularly preferable.
• Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group, and an ethylcyclohexyl group; monocyclic unsaturated hydrocarbon groups such as a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclodecenyl group, a cyclopentadienyl group, a cyclohexadienyl group, a cyclooctadienyl group,
• the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, and a biphenyl group, and an aryl group having 6 to 12 carbon atoms (particularly a phenyl group) is preferred.
• Specific examples of the monovalent aromatic heterocyclic group having 6 to 20 carbon atoms include a 4-pyridyl group, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.
• halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom, a chlorine atom, and a bromine atom are preferred.
• specific examples of the alkyl group having 1 to 6 carbon atoms represented by one embodiment of R 7 to R 10 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.
• Z1 and Z2 may be bonded to each other to form an aromatic ring
• an example of a structure in which Z1 and Z2 in the above formula (Ar-1) are bonded to each other to form an aromatic ring is a group represented by the following formula (Ar-1a):
• * represents the bonding position with the oxygen atom in the above formulas (1) to (6).
• Q 1 , Q 2 and Y 1 are the same as those explained in the above formula (Ar-1).
• A3 and A4 each independently represent a group selected from the group consisting of -O-, -N( R11 )-, -S-, and -CO-, and R11 represents a hydrogen atom or a substituent.
• R11 represents a hydrogen atom or a substituent.
• substituent represented by R 11 include the same substituents as those explained for A 1 and A 2 in the above formulae (7) and (8).
• X represents a nonmetallic atom of Groups 14 to 16.
• the nonmetallic atom may have a hydrogen atom or a substituent bonded thereto.
• examples of the non-metallic atom of Groups 14 to 16 represented by X include an oxygen atom, a sulfur atom, a nitrogen atom bonded to a hydrogen atom or a substituent [ ⁇ N—R N1 , R N1 represents a hydrogen atom or a substituent], and a carbon atom bonded to a hydrogen atom or a substituent [ ⁇ C—(R C1 ) 2 , R C1 represents a hydrogen atom or a substituent].
• substituents include an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (e.g., a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, and a hydroxyl group.
• examples of the divalent linking group include the same groups as those explained in relation to D 1 , D 2 , E 1 and E 2 in the above formulae (7) and (8).
• SP 3 and SP 4 each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, or a divalent linking group in which one or more of -CH 2 - constituting the alkylene group, alkenylene group, or alkynylene group are replaced with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q represents a substituent.
• examples of the alkylene group, alkenylene group and alkynylene group include those similar to those explained in relation to SP 1 and SP 2 in the above formulas (7) and (8).
• examples of the substituent include the same substituents as those explained for A 1 and A 2 in the above formulas (7) and (8).
• L 3 and L 4 each independently represent a monovalent organic group, and at least one of L 3 and L 4 and L 1 and L 2 in the above formulas (7) and (8) represents a polymerizable group.
• the monovalent organic group include the same ones as those explained in relation to L 1 and L 2 in the above formulas (7) and (8).
• the polymerizable group include the same groups as those explained in relation to L 1 and L 2 in the above formulas (7) and (8).
• Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles.
• Ay represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles.
• the aromatic rings in Ax and Ay may have a substituent, and Ax and Ay may be bonded to form a ring.
• Q3 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
• Ax and Ay include those described in paragraphs [0039] to [0095] of WO 2014/010325.
• Specific examples of the alkyl group having 1 to 20 carbon atoms represented by Q3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group, and examples of the substituent include the same as the substituents that may be possessed by G1 and G2 in the above formula (5).
• examples of the compounds represented by the above formulas (1), (3), (4) and (6) include the compounds represented by general formula (1) described in JP-A-2010-084032 (particularly, the compounds described in paragraphs [0067] to [0073]), the compounds represented by general formula (II) described in JP-A-2016-053709 (particularly, the compounds described in paragraphs [0036] to [0043]), and the compounds represented by general formula (1) described in JP-A-2016-081035 (particularly, the compounds described in paragraphs [0043] to [0055]).
• the compounds represented by the above formulas (1), (3), (4) and (6) are preferably compounds represented by the following formulas (1) to (22), and specifically, the compounds having the side chain structures shown in Tables 1 to 3 below as K (side chain structure) in the following formulas (1) to (22) are respectively exemplified.
• the polymerizable liquid crystal compounds P1 to P6 represented by the above formulas (1) to (6) the polymerizable liquid crystal compounds P2 and P5 represented by the above formulas (2) and (5) are exemplified by compounds having different side chain structures shown in Tables 1 to 3 below as two K (side chain structures) in the following formulas (1) to (22).
• the "*" shown in the side chain structure of K indicates the bonding position with the aromatic ring.
• the groups adjacent to the acryloyloxy group and the methacryloyl group, respectively represent a propylene group (a group in which a methyl group is substituted with an ethylene group), and the structure represents a mixture of positional isomers in which the position of the methyl group is different.
• the following formulae (A), (B), (C), (D), and (E) are satisfied when the area percentages of the polymerizable liquid crystal compounds P1 to P6 are measured at a measurement wavelength of 254 nm using a high performance liquid chromatograph (HPLC), the larger of the area percentages of the polymerizable liquid crystal compounds P1 and P3 is designated as C1 and the smaller is designated as C3, the larger of the area percentages of the polymerizable liquid crystal compounds P4 and P6 is designated as C4 and the smaller is designated as C6, and the area percentages of the polymerizable liquid crystal compounds P2 and P5 are designated as C2 and C5, respectively.
• HPLC high performance liquid chromatograph
• C1+C2+C3+C4+C5+C6 100% (A) C1+C4 ⁇ 25% (B) 50% ⁇ C2+C5 ⁇ 1% (C) 25% ⁇ C3+C6 ⁇ 0% (D) 5% ⁇
• the area % measured by HPLC is the area % measured under the following conditions.
• Apparatus High-performance liquid chromatograph measuring device Prominence 20 (manufactured by Shimadzu Corporation) Column: TSK-GEL ODS-100Z (manufactured by TOSOH Corporation) Eluent: acetonitrile/water Buffer: 0.1% phosphoric acid Measurement solution: 30 ⁇ L of the sample to be measured is diluted with 10 mL of tetrahydrofuran. Measurement wavelength: 254 nm
• the contents of the polymerizable liquid crystal compounds P1 to P6 are preferably the amounts shown below, respectively, relative to the total mass of the polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition.
• the compound contained in a larger amount is referred to as polymerizable liquid crystal compound P1
• the compound contained in a smaller amount is referred to as polymerizable liquid crystal compound P3.
• polymerizable liquid crystal compound P4 70 to 20% by mass
• polymerizable liquid crystal compound P6 the compound contained in a smaller amount
• Polymerizable liquid crystal compound P1 70 to 20% by mass
• Polymerizable liquid crystal compound P2 30 to 0.1% by mass
• Polymerizable liquid crystal compound P3 5 to 0% by mass
• Polymerizable liquid crystal compound P4 70 to 20% by mass
• Polymerizable liquid crystal compound P5 30 to 0.1% by mass
• Polymerizable liquid crystal compound P6 5 to 0% by mass
• the polymerizable liquid crystal composition of the present invention exhibits nematic or smectic liquid crystal properties in an arbitrary temperature range, and the behavior exhibited may be either enantiotropic or monotropic.
• the film it is preferable that the film has smectic liquid crystallinity, because this makes it possible to obtain a retardation film with higher contrast.
• the polymerizable liquid crystal composition of the present invention may contain, in addition to the above-mentioned polymerizable liquid crystal compounds P1 to P6, other polymerizable compounds having one or more polymerizable groups.
• the polymerizable group of the other polymerizable compound is not particularly limited, and examples thereof include an acryloyloxy group, a methacryloyloxy group, a vinyl group, a styryl group, an allyl group, etc.
• the other polymerizable compound has an acryloyloxy group or a methacryloyloxy group.
• the other polymerizable compound is preferably another polymerizable compound having 1 to 4 polymerizable groups, and more preferably another polymerizable compound having 2 polymerizable groups, because this improves the durability of the optically anisotropic film that is formed.
• polymerizable compounds include those represented by the above formulas (1), (3), (4), and (6), but having different Ar1 and Ar2 structures from the polymerizable liquid crystal compounds P1, P3, P4, and P6. Further, other polymerizable compounds include the compounds described in paragraphs [0073] to [0074] of JP2016-053709A. Further, other polymerizable compounds include the compounds represented by formulae (M1), (M2), and (M3) described in paragraphs [0030] to [0033] of JP2014-077068A, and more specifically, specific examples thereof are described in paragraphs [0046] to [0055] of the same publication.
• the content is preferably less than 50% by mass based on the total mass including the above-mentioned polymerizable liquid crystal compounds P1 to P6.
• the polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.
• the polymerization initiator used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet light.
• Examples of the photopolymerization initiator include ⁇ -carbonyl compounds (described in U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in U.S. Pat. No. 2,448,828), ⁇ -hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Pat. No.
• the polymerization initiator is also preferably an oxime-type polymerization initiator, and specific examples thereof include the initiators described in paragraphs [0049] to [0052] of WO 2017/170443.
• the polymerizable liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability in forming an optically anisotropic film.
• the solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., toluene, xylene, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl ket
• the polymerizable liquid crystal composition of the invention preferably contains a leveling agent from the viewpoint of maintaining the surface of the optically anisotropic film smooth and facilitating alignment control.
• a leveling agent a fluorine-based leveling agent or a silicon-based leveling agent is preferable because it has a high leveling effect relative to the amount added, and a fluorine-based leveling agent is more preferable because it is less likely to cause bleeding (bloom, bleed).
• leveling agent examples include compounds described in JP-A-2007-069471, paragraphs [0079] to [0102], compounds represented by general formula (I) described in JP-A-2013-047204 (particularly, compounds described in paragraphs [0020] to [0032]), and compounds represented by general formula (I) described in JP-A-2012-211306 (particularly, compounds represented by paragraphs [0022] to [0029]).
• Examples of the compound include compounds described in the paragraphs 2002-129162, liquid crystal alignment promoters represented by general formula (I) described in JP-A-2002-129162 (particularly compounds described in paragraphs [0076] to [0078] and [0082] to [0084]), and compounds represented by general formulas (I), (II) and (III) described in JP-A-2005-099248 (particularly compounds described in paragraphs [0092] to [0096]).
• the compound may also function as an alignment control agent, which will be described later.
• the polymerizable liquid crystal composition of the present invention may contain an alignment control agent, if necessary.
• the alignment control agent can form various alignment states, such as homogeneous alignment, homeotropic alignment (vertical alignment), tilted alignment, hybrid alignment, and cholesteric alignment, and can also realize specific alignment states more uniformly and with more precise control.
• a low molecular weight alignment control agent or a polymeric alignment control agent can be used.
• low molecular weight orientation control agents reference can be made to, for example, paragraphs [0009] to [0083] of JP 2002-20363 A, paragraphs [0111] to [0120] of JP 2006-106662 A, and paragraphs [0021] to [0029] of JP 2012-211306 A, the contents of which are incorporated herein by reference.
• the compounds described in JP2008-225281A, paragraphs [0023] to [0032], JP2012-208397A, paragraphs [0052] to [0058], JP2008-026730A, paragraphs [0024] to [0055], and JP2016-193869A, paragraphs [0043] to [0055], etc. can be referred to, the contents of which are incorporated herein by reference.
• cholesteric alignment can be achieved by adding a chiral agent to the polymerizable composition of the present invention, and the direction of rotation of the cholesteric alignment can be controlled by the direction of the chirality.
• the pitch of the cholesteric alignment can be controlled according to the alignment control force of the chiral agent.
• the content is preferably 0.01 to 10 mass % and more preferably 0.05 to 5 mass % based on the total solid content mass in the polymerizable liquid crystal composition.
• the content is within this range, a desired alignment state can be achieved, and a uniform and highly transparent optically anisotropic film can be obtained without precipitation, phase separation, alignment defects, etc.
• These alignment control agents can further impart a polymerizable functional group, in particular a polymerizable functional group polymerizable with the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition of the present invention.
• the polymerizable liquid crystal composition of the invention may contain a polymerization inhibitor, if necessary, from the viewpoint of storing it as a solution.
• a polymerization inhibitor hydroquinone-based, benzoquinone-based, hindered phenol-based, hindered amine-based, stable radical-based, etc. can be used.
• polymerization becomes more likely to occur as the oxygen concentration in the solution decreases, polymerization can be suppressed by, for example, ensuring that the free space volume of the storage container is sufficiently large and supplying oxygen (air) to the solution during storage (ventilating the solution).
• an increase in storage temperature makes polymerization more likely to occur, it is preferable to keep the storage temperature at room temperature or lower, and it is preferable to store the product in a refrigerator at 10° C. or lower.
• the polymerizable liquid crystal composition of the present invention may contain components other than the above-mentioned components, such as a liquid crystal compound other than the above-mentioned polymerizable liquid crystal compound, a surfactant, a tilt angle control agent, an alignment aid, a plasticizer, and a crosslinking agent.
• a liquid crystal compound other than the above-mentioned polymerizable liquid crystal compound such as a surfactant, a tilt angle control agent, an alignment aid, a plasticizer, and a crosslinking agent.
• the optically anisotropic film of the present invention is an optically anisotropic film obtained by fixing the alignment state of the above-mentioned polymerizable liquid crystal composition of the present invention.
• a method for forming an optically anisotropic film for example, a method in which the above-mentioned polymerizable liquid crystal composition of the present invention is used to obtain a desired alignment state, and then the liquid crystal composition is fixed by polymerization, can be mentioned.
• the polymerization conditions are not particularly limited, but in the polymerization by light irradiation, it is preferable to use ultraviolet light.
• 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 , further preferably 30 mJ/cm 2 to 3 J/cm 2 , and particularly preferably 50 to 1000 mJ/cm 2.
• the polymerization may be carried out under heating conditions.
• the optically anisotropic film can be formed on any support in the optical film of the present invention described below, or on a polarizer in the polarizing plate of the present invention described below.
• optically anisotropic film of the present invention preferably satisfies the following formula (F). 0.50 ⁇ Re(450)/Re(550) ⁇ 1.00 (F)
• the optically anisotropic film of the present invention is preferably a positive A plate or a positive C plate, and more preferably a positive A plate.
• the positive A plate and the positive C plate are defined as follows.
• the refractive index in the slow axis direction the direction in which the in-plane refractive index is maximum
• the refractive index in the direction perpendicular to the in-plane slow axis is ny
• the refractive index in the thickness direction is nz
• the positive A plate satisfies the relationship of formula (A1)
• the positive C plate satisfies the relationship of formula (C1).
• the positive A plate has a positive Rth value
• the positive C plate has a negative Rth value.
• ny ⁇ nz includes a case where (ny-nz) ⁇ d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm
• nx ⁇ nz includes a case where (nx-nz) ⁇ d is -10 to 10 nm, preferably -5 to 5 nm.
• nx ⁇ ny includes a case where (nx-ny) ⁇ d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm.
• Re(550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, even more preferably 130 to 150 nm, and particularly preferably 130 to 140 nm.
• ⁇ /4 plate refers to a plate having a ⁇ /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).
• the optical film of the present invention is an optical film having the optically anisotropic film of the present invention.
• the structure of the optical film will be described with reference to Fig. 1.
• Fig. 1 is a schematic cross-sectional view showing an example of the optical film. It should be noted that FIG. 1 is a schematic diagram, and the thickness and positional relationships of the layers do not necessarily correspond to the actual ones, and the support and alignment film shown in FIG. 1 are both optional components.
• An optical film 10 shown in FIG. 1 comprises, in this order, a support 16, an alignment film 14, and an optically anisotropic film 12 obtained by processing the alignment state of the polymerizable liquid crystal composition of the present invention.
• Various members used in the optical film will be described in detail below.
• optically anisotropic film in the optical film of the present invention is the optically anisotropic film of the present invention described above.
• the thickness of the optically anisotropic film is not particularly limited, but is preferably 0.1 to 10 ⁇ m, and more preferably 0.5 to 5 ⁇ m.
• the optical film of the present invention may have a support as a substrate for forming an optically anisotropic film.
• a support is preferably transparent, and specifically, preferably has a light transmittance of 80% or more.
• Such supports include glass substrates and polymer films, and examples of materials for the polymer film include cellulose-based polymers; acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers (AS resins); polyolefin-based polymers such as polyethylene, polypropylene and ethylene-propylene copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamides; imide-based polymers; sulfone-based polymers; polyethersulfone-based polymers; polyetheretherketone-based polymers; polyphenylene sulfide-based polymers; vinylidene chloride-based polymers;
• the thickness of the support is not particularly limited, but is preferably 5 to 60 ⁇ m, and more preferably 5 to 30 ⁇ m.
• the optical film of the present invention has any of the above-mentioned supports, it is preferable that the optical film has an alignment layer between the support and the optically anisotropic film.
• the above-mentioned support may also serve as the alignment layer.
• Alignment films are generally made mainly of polymers. Polymer materials for alignment films are described in many publications, and many commercial products are available.
• the polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof, particularly modified or unmodified polyvinyl alcohol.
• Examples of the alignment film that can be used in the present invention include the alignment film described in WO 01/88574, page 43, line 24 to page 49, line 8; the modified polyvinyl alcohol described in Japanese Patent No. 3907735, paragraphs [0071] to [0095]; and the liquid crystal alignment film formed by the liquid crystal alignment agent described in JP 2012-155308 A.
• a photo-alignment film as the alignment film, since it is possible to prevent deterioration of the surface condition by not contacting the alignment film surface during formation of the alignment film.
• the photo-alignment film is not particularly limited, but examples thereof include polymer materials such as polyamide compounds and polyimide compounds described in paragraphs [0024] to [0043] of International Publication No. 2005/096041; a liquid crystal alignment film formed from a liquid crystal alignment agent having a photo-alignment group described in JP-A-2012-155308; and a product name LPP-JP265CP manufactured by Rolic Technologies.
• the thickness of the alignment film is not particularly limited, but from the viewpoint of mitigating surface irregularities that may exist on the support and forming an optically anisotropic film with a uniform thickness, the thickness is preferably 0.01 to 10 ⁇ m, more preferably 0.01 to 1 ⁇ m, and even more preferably 0.01 to 0.5 ⁇ m.
• the optical film of the present invention may have another optically anisotropic film in addition to the optically anisotropic film of the present invention. That is, the optical film of the present invention may have a laminate structure of the optically anisotropic film of the present invention and another optically anisotropic film.
• Such other optically anisotropic films are not particularly limited as long as they are optically anisotropic films obtained by using the other polymerizable compounds (particularly, liquid crystal compounds) described above without blending either one of the polymerizable liquid crystal compounds (I) and the polymerizable compound (II) described above.
• liquid crystal compounds can be classified into rod-shaped and disc-shaped types based on their shape.
• High molecular weight generally refers to a compound with a degree of polymerization of 100 or more (Polymer Physics, Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).
• any liquid crystal compound can be used, but rod-shaped or discotic liquid crystal compounds (discotic liquid crystal compounds) are preferably used. Two or more rod-shaped liquid crystal compounds, two or more discotic liquid crystal compounds, or a mixture of rod-shaped and discotic liquid crystal compounds may be used.
• liquid crystal compound In order to fix the above liquid crystal compound, it is more preferable to form the liquid crystal compound using a rod-shaped or discotic liquid crystal compound having a polymerizable group, and it is even more preferable that the liquid crystal compound has two or more polymerizable groups in one molecule. In the case of a mixture of two or more liquid crystal compounds, it is preferable that at least one liquid crystal compound has two or more polymerizable groups in one molecule.
• rod-shaped liquid crystal compound for example, those described in claim 1 of JP-T-11-513019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used, and as the discotic liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038 can be preferably used, but are not limited thereto.
• the optical film of the present invention preferably contains an ultraviolet (UV) absorbing agent.
• the ultraviolet absorbing agent may be contained in the optically anisotropic film of the present invention, or may be contained in a member other than the optically anisotropic film constituting the optical film of the present invention.
• a support is preferably mentioned. Any conventionally known ultraviolet absorbing agent capable of expressing ultraviolet absorbing properties can be used as the ultraviolet absorbing agent.
• a benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorbing agent which has high ultraviolet absorbing properties and has ultraviolet absorbing ability (ultraviolet ray blocking ability) for use in an image display device.
• ultraviolet absorbing ability ultraviolet ray blocking ability
• two or more ultraviolet absorbents having different maximum absorption wavelengths can be used in combination.
• Specific examples of the ultraviolet absorber include the compounds described in JP-A-2012-18395, paragraphs [0258] to [0259] and the compounds described in JP-A-2007-72163, paragraphs [0055] to [0105].
• Commercially available products that can be used include Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, and Tinuvin 1577 (all manufactured by BASF).
• the polarizing plate of the present invention comprises the above-mentioned optical film of the present invention and a polarizer. Furthermore, when the above-mentioned optically anisotropic film of the present invention is a ⁇ /4 plate (positive A plate), the polarizing plate of the present invention can be used as a circular polarizing plate. Furthermore, in the polarizing plate of the present invention, when the optically anisotropic film of the present invention described above is a ⁇ /4 plate (positive A plate), the angle between the slow axis of the ⁇ /4 plate and the absorption axis of the polarizer described below is preferably 30 to 60°, more preferably 40 to 50°, even more preferably 42 to 48°, and particularly preferably 45°.
• the "slow axis" of the ⁇ /4 plate means the direction in the plane of the ⁇ /4 plate in which the refractive index is maximum
• the "absorption axis" of the polarizer means the direction in which the absorbance is highest.
• the polarizer in the polarizing plate of the present invention is not particularly limited as long as it is a member having a function of converting light into a specific linearly polarized light, and a conventionally known absorptive polarizer and reflective polarizer can be used.
• the absorption polarizer include iodine-based polarizers, dye-based polarizers using a dichroic dye, and polyene-based polarizers.
• Iodine-based polarizers and dye-based polarizers include coating-type polarizers and stretching-type polarizers, and either can be used, but a polarizer made by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching it is preferable.
• a polarizer made by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching it is preferable a polarizer made by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching it is preferable.
• methods of obtaining a polarizer by stretching and dyeing a laminated film in which a polyvinyl alcohol layer is formed on a substrate can be described in Japanese Patent No. 5,048,120, Japanese Patent No. 5,143,918, Japanese Patent No. 4,691,205, Japanese Patent No. 4,751,481, and Japanese Patent No. 4,751,486. These known techniques related to polarizers can also be
• a polarizer in which thin films with different birefringence are laminated a wire grid type polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region is combined with a quarter-wave plate, or the like is used.
• a polarizer containing a polyvinyl alcohol resin a polymer containing --CH 2 --CHOH-- as a repeating unit, in particular at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer is preferred in terms of superior adhesion.
• the thickness of the polarizer is not particularly limited, but is preferably 3 ⁇ m to 60 ⁇ m, more preferably 5 ⁇ m to 30 ⁇ m, and even more preferably 5 ⁇ m to 15 ⁇ m.
• the polarizing plate of the present invention may have a pressure-sensitive adhesive layer disposed between the optically anisotropic film in the optical film of the present invention and the polarizer.
• Pressure-sensitive adhesives that can be used in the present invention include, but are not limited to, polyvinyl alcohol-based pressure-sensitive adhesives.
• the image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention.
• 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 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 polarizing plate of the present invention and a liquid crystal cell.
• the polarizing plate of the present invention it is preferable to use the polarizing plate of the present invention as the front side polarizing plate among the polarizing plates provided on both sides of the liquid crystal cell, and it is more preferable to use the polarizing plate of the present invention as the front side and rear side polarizing plates.
• 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, but not limited to, a VA (Vertical Alignment) mode, an OCB (Opticaly Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode.
• a TN mode liquid crystal cell 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 liquid crystal display devices, and are described in many publications.
• a 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 (MVA mode) liquid crystal cell in which the VA mode is multi-domained to widen the viewing angle (described in SID97, Digest of tech.
• 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 JP-A-2006-215326 and JP-A-2008-538819.
• An organic EL display device which is one example of the image display device of the present invention, may include, from the viewing side, a polarizer, a ⁇ /4 plate (positive A plate) made of the optically anisotropic film of the present invention, and an organic EL A preferred embodiment has the display panel 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.
• the method for producing a polymerizable liquid crystal composition according to the first aspect of the present invention is a method for producing a polymerizable liquid crystal composition, which comprises dissolving the polymerizable liquid crystal compounds P1 and P3 represented by the above formulas (1) and (3) in a solvent and reacting them (hereinafter, also abbreviated as "side chain exchange reaction") to obtain a polymerizable liquid crystal composition containing the polymerizable liquid crystal compounds P1 to P3 represented by the above formulas (1) to (3) and a solvent.
• the method for producing a polymerizable liquid crystal composition according to the second aspect of the present invention is a method for producing a polymerizable liquid crystal composition, which comprises dissolving the polymerizable liquid crystal compounds P1 and P4 represented by the above formulas (1) and (4) in a solvent and reacting them (side chain exchange reaction) to obtain a polymerizable liquid crystal composition containing the polymerizable liquid crystal compounds P1, P2, P4, and P5 represented by the above formulas (1), (2), (4), and (5) and a solvent, and is preferably a method for producing a polymerizable liquid crystal composition, which comprises obtaining a polymerizable liquid crystal composition containing the polymerizable liquid crystal compounds P1 to P6 represented by the above formulas (1) to (6) and a solvent.
• examples of the polymerizable liquid crystal compounds P1 and P3 and the solvent used in the first embodiment include those similar to those explained in the polymerizable liquid crystal composition of the present invention.
• the polymerizable liquid crystal compounds P1 and P4 and the solvent used in the second embodiment the same ones as those explained in the polymerizable liquid crystal composition of the present invention can be used.
• the ratio of the polymerizable liquid crystal compounds P1 and P3 in the side chain exchange reaction is not particularly limited, but from the viewpoint of reaction rate, it is preferable that the molar ratio is 1:1.
• the ratio of the polymerizable liquid crystal compounds P1 and P4 in the side chain exchange reaction is not particularly limited, but from the viewpoint of reaction rate, it is preferable that the molar ratio is 1:1.
• the reaction substrate concentration of the side chain exchange reaction in the first and second embodiments is preferably high from the viewpoint of improving the reaction rate.
• the reaction substrate concentration is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more.
• the solid content concentration may be diluted by adding a solvent after the reaction, and in that case, a solvent different from the solvent used in the reaction may be added.
• a catalyst before the side chain exchange reaction in order to rapidly proceed with the side chain exchange reaction.
• an acidic compound, a basic compound, or the like can be used, and among these, it is preferable to use a basic compound.
• the acidic compound that can be used include Bronsted acids such as hydrochloric acid and sulfuric acid; organic acids such as carboxylic acids, sulfonic acids and phosphoric acids; and Lewis acids such as aluminum oxide and titanium oxide. From the viewpoint of catalyst removal, those that can be handled as solid acids are preferred.
• the basic compound for example, organic amines such as triethylamine and N,N-diisopropylethylamine (hereinafter, DIPEA) are preferable.
• the method for producing a polymerizable liquid crystal composition when a catalyst (particularly, a basic compound) is added before the side chain exchange reaction, it is preferable to remove the catalyst after the side chain exchange reaction, from the viewpoints of suppressing fluctuations in the composition ratio and imparting storage stability.
• the method for removing the catalyst is not particularly limited, but examples thereof include removal by filtration, removal using an adsorbent, and removal by a liquid separation operation or a distillation operation.
• examples of adsorbents that adsorb the above-mentioned basic compounds include ion exchange resins, inorganic oxide adsorbents, activated carbon, etc.
• examples of the ion exchange resin that can be used include Amberlyst (manufactured by DuPont), Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd.), and Granular Shirasagi (manufactured by Osaka Gas Chemicals Co., Ltd.) can be used as the inorganic oxide adsorbent.
• the catalyst remaining rate is preferably as low as possible, but may remain within a range that does not affect storage stability. Specifically, the catalyst remaining rate is preferably 10 ppm or less, more preferably 1 ppm or less, and even more preferably 0.2 ppm or less, relative to the composition solution.
• the side chain exchange reaction is preferably in an equilibrium state since the composition ratio is stabilized when the reaction is close to equilibrium. That is, when the polymerizable liquid crystal compounds P1 and P3 are mixed in a molar ratio of 1:1 and reacted, the total content of P2 in the equilibrium state is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more. Similarly, when polymerizable liquid crystal compounds P1 and P4 are mixed in a molar ratio of 1:1 and reacted, the total content of P2 and P5 in the equilibrium state is preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more.
• the above-mentioned polymerizable liquid crystal composition of the present invention may be a polymerizable liquid crystal composition prepared by the method for producing a polymerizable liquid crystal composition according to the second aspect of the present invention, or may be a composition obtained by adding any compound to the polymerizable liquid crystal composition prepared by the method for producing a polymerizable liquid crystal composition according to the second aspect of the present invention.
• the compound that can be added include a polymerizable compound, a polymerization initiator, and an alignment control agent.
• these compounds may be added to the polymerized liquid crystal composition during the side chain exchange reaction, and for example, a catalyst such as a basic compound may be added to the composition for preparing an optically anisotropic film to cause the reaction. From the viewpoint of reaction control and removal of the catalyst after the reaction, it is preferable to carry out the reaction using only the polymerizable liquid crystal involved in the reaction, and then prepare the composition for preparing an optically anisotropic film.
• Reaction solution 1 having the following composition was prepared, heated to 60°C, dissolved uniformly, and then cooled to 40°C.
• Reaction solution 1 ⁇ - 55.9 parts by mass of the polymerizable liquid crystal AXA shown below - 44.1 parts by mass of the polymerizable liquid crystal BYB shown below - 300 parts by mass of cyclopentanone
• the group adjacent to the acryloyloxy group in the polymerizable liquid crystal AXA represents a propylene group (a group in which a methyl group is substituted with an ethylene group), and represents a mixture of positional isomers in which the position of the methyl group is different.
• Cyclopentanone was used as a washing liquid during filtration, and the final solid content concentration was adjusted to 20 mass %.
• the composition ratio of polymerizable liquid crystal composition 1 was confirmed by HPLC to be the following ratio.
• P3 0.2% of the following polymerizable liquid crystal
• BXB P4 34.5% of the following polymerizable liquid crystal
• BYB P5 9.1% of the following polymerizable liquid crystal AYB P6: 0.7% of the following polymerizable liquid crystal AYA ⁇
• the core aromatic ring in the polymerizable liquid crystal AXB has one methyl substituent, and represents a mixture of positional isomers in which the position of the methyl group is different.
• the amount of DIPEA remaining in the polymerizable liquid crystal composition 1 was below the detection limit (0.1 ppm).
• the polymerizable liquid crystal composition 1 was dropped onto a glass plate and the solvent was dried and removed, the solid content was observed under a polarizing microscope while adjusting the temperature using a heating stage (manufactured by Mettler Toledo), and it was confirmed that the composition exhibited smectic properties.
• Example 2 A polymerizable liquid crystal composition 2 was obtained in the same manner as in Example 1, except that a reaction solution 1 having the same composition as in Example 1 was used and the reaction temperature was set to 50° C.
• the composition ratio of the polymerizable liquid crystal composition 2 was confirmed by HPLC to be the following ratio.
• P2 Polymerizable liquid crystal AXB 25.2%
• P3 Polymerizable liquid crystal BXB 1.3%
• P4 Polymerizable liquid crystal BYB 22.5%
• P5 Polymerizable liquid crystal AYB 19.4%
• P6 Polymerizable liquid crystal AYA 3.6% ⁇
• the amount of DIPEA remaining in the polymerizable liquid crystal composition 2 was below the detection limit (0.1 ppm).
• the polymerizable liquid crystal composition 1 was dropped onto a glass plate and the solvent was dried and removed, the solid content was observed under a polarizing microscope while adjusting the temperature using a heating stage (manufactured by Mettler Toledo), and it was confirmed that the composition exhibited smectic properties.
• Reaction solution 3 having the following composition was prepared, heated to 60°C, dissolved uniformly, and then cooled to 50°C.
• Reaction solution 3 ⁇ - 62.5 parts by mass of the above polymerizable liquid crystal AXA - 37.5 parts by mass of the below polymerizable liquid crystal CYC - 300 parts by mass of cyclopentanone
• Reaction solution 4 having the following composition was prepared, heated to 60°C, dissolved uniformly, and then cooled to 50°C.
• Reaction solution 4 ⁇ - 47.8 parts by mass of the polymerizable liquid crystal DZD shown below - 52.2 parts by mass of the polymerizable liquid crystal AXA shown above - 300 parts by mass of cyclopentanone
• Reaction solution 5 having the following composition was prepared, heated to 60°C, dissolved uniformly, and then cooled to 50°C.
• Reaction solution 5 ⁇ - 56.8 parts by mass of the above polymerizable liquid crystal BYB - 43.2 parts by mass of the above polymerizable liquid crystal CYC - 300 parts by mass of cyclopentanone
• Cyclopentanone was used as a washing liquid during filtration, and the final solid concentration was adjusted to 20 wt %.
• the composition ratio of polymerizable liquid crystal composition 5 was confirmed by HPLC to be the following ratio. ⁇ HPLC Area Percentage of Polymerizable Liquid Crystal Composition 5 ⁇ P1: the above polymerizable liquid crystal BYB 41.2% P2: 27.5% of the following polymerizable liquid crystal BYC P3: the above polymerizable liquid crystal CYC 31.3% ⁇
• Example 6 Using the polymerizable liquid crystal composition 1 prepared in Example 1, an optically anisotropic film-forming coating liquid 1 having the following composition was prepared.
• ⁇ Optically anisotropic film forming coating solution 1 ⁇ - 153.0 parts by mass of the above polymerizable liquid crystal composition 1 - 6.7 parts by mass of the above polymerizable liquid crystal
• AXA - 16.5 parts by mass of the above polymerizable liquid crystal BYB - 20.0 parts by mass of polymerizable liquid crystal 7 described below - 16.5 parts by mass of polymerizable liquid crystal 8 described below - 16.5 parts by mass of polymerizable liquid crystal 9 described below - 15.0 parts by mass of polymerizable liquid crystal 10 described below - 3.0 parts by mass of polymerizable compound M1 described below - 1.5 parts by mass of polymerization initiator S1 described below - 0.1 part by mass of leveling agent P1 described below -
• Example 7 instead of the polymerizable liquid crystal composition 1 contained in the coating liquid 1 for forming an optically anisotropic film, the polymerizable liquid crystal composition 2 prepared in Example 2 was used to prepare a coating liquid 2 for forming an optically anisotropic film having the following composition.
• the polymerizable liquid crystal composition 2 101.3 parts by mass the polymerizable liquid crystal AXA 21.3 parts by mass the polymerizable liquid crystal BYB 15.4 parts by mass the polymerizable liquid crystal 7 20.0 parts by mass the polymerizable liquid crystal 8 16.5 parts by mass the polymerizable liquid crystal 9 16.5 parts by mass the polymerizable liquid crystal 10 15.0 parts by mass the polymerizable compound M1 3.0 parts by mass the polymerization initiator S1 1.5 parts by mass the leveling agent P1 0.1 parts by mass cyclopentanone 133.9 parts by mass methyl ethyl ketone 64.2 parts by mass
• Example 8 instead of the polymerizable liquid crystal composition 1 contained in the coating liquid 1 for forming an optically anisotropic film, the polymerizable liquid crystal composition 3 prepared in Example 3 was used to prepare the coating liquid 3 for forming an optically anisotropic film having the following composition.
• Optically anisotropic film forming coating solution 3 the polymerizable liquid crystal composition 3 101.2 parts by mass the polymerizable liquid crystal AXA 24.5 parts by mass the polymerizable liquid crystal CYC 9.0 parts by mass the polymerizable liquid crystal 7 20.0 parts by mass the polymerizable liquid crystal 8 16.5 parts by mass the polymerizable liquid crystal 9 16.5 parts by mass the polymerizable liquid crystal 10 15.0 parts by mass the polymerizable compound M1 3.0 parts by mass the polymerization initiator S1 1.5 parts by mass the leveling agent P1 0.1 parts by mass cyclopentanone 133.9 parts by mass methyl ethyl ketone 64.2 parts by mass
• Example 9 instead of the polymerizable liquid crystal composition 1 contained in the coating liquid 1 for forming an optically anisotropic film, the polymerizable liquid crystal composition 4 prepared in Example 4 was used to prepare a coating liquid 4 for forming an optically anisotropic film having the following composition.
• a comparative coating liquid H1 for forming an optically anisotropic film having the following composition was prepared.
• ⁇ Optically anisotropic film forming coating solution H1 ⁇ the polymerizable liquid crystal AXA 20.0 parts by mass the polymerizable liquid crystal BYB 27.0 parts by mass the polymerizable liquid crystal 7 20.0 parts by mass the polymerizable liquid crystal 8 16.5 parts by mass the polymerizable liquid crystal 9 16.5 parts by mass the polymerizable liquid crystal 10 15.0 parts by mass the polymerizable compound M1 3.0 parts by mass the polymerization initiator S1 1.5 parts by mass the leveling agent P1 0.1 parts by mass cyclopentanone 214.9 parts by mass methyl ethyl ketone 64.2 parts by mass
• Precipitability 1 Whitening in areas between 75% and 100%
• Precipitation 2 Whitening in areas between 25% and less than 75%
• Precipitation 3 Whitening in areas between 0% and less than 25%
• Example 1 Polymerizable Liquid Crystal Composition 1): Precipitability 3
• Example 2 Polymerizable Liquid Crystal Composition 2): Precipitability 3
• Example 3 Polymerizable Liquid Crystal Composition 3): Precipitability 3
• Example 4 Polymerizable Liquid Crystal Composition 4): Precipitability 3
• Example 6 Optical anisotropic film forming coating solution 1): Precipitability 3
• Example 7 Optically anisotropic film-forming coating solution 2): Precipitability 3
• Example 8 Optical anisotropic film-forming coating solution 3
• Example 9 Optically anisotropic film-forming coating solution 4): Precipitability 3 Comparative Example 1 (Optically Anisotropic

Landscapes

• Chemical & Material Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=92501051

Family Applications (1)

Country Status (4)

Citations (8)

• 2024
  • 2024-02-09 JP JP2025502276A patent/JPWO2024176869A1/ja active Pending
  • 2024-02-09 WO PCT/JP2024/004484 patent/WO2024176869A1/ja not_active Ceased
  • 2024-02-09 CN CN202480010767.4A patent/CN120641796A/zh active Pending
• 2025
  • 2025-07-16 US US19/271,140 patent/US20250340781A1/en active Pending

Patent Citations (8)

Also Published As

Similar Documents

Legal Events