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• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
• • 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
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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  • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
  • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
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  • 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
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  • C09K19/3857—Poly(meth)acrylate derivatives containing at least one asymmetric carbon 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
  • C09K19/38—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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3016—Polarising elements involving passive liquid crystal elements
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/13363—Birefringent elements, e.g. for optical compensation
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details

Definitions

• the present invention relates to a polymerizable liquid crystal mixed composition, a retardation plate containing a liquid crystal cured film which is a cured product of the polymerizable liquid crystal mixed composition, an elliptical polarizing plate including the retardation plate, and an organic EL display device.
• an optical film such as a retardation plate used in a flat panel display device (FPD), for example, a coating liquid obtained by dissolving a polymerizable liquid crystal compound in a solvent is applied to a supporting base material and then polymerized.
• a polymerizable liquid crystal compound for example, a nematic liquid crystal compound having a rod-like structure in which 2 to 4 6-membered rings are connected is known.
• the retardation plate is required to be capable of polarization conversion in the entire wavelength region as one of its characteristics, and for example, the inverse wavelength dispersibility of [Re (450) / Re (550)] ⁇ 1. It is known that uniform polarization conversion is theoretically possible in the indicated wavelength range.
• a polymerizable compound capable of forming such a retardation plate is disclosed in, for example, Patent Document 1.
• a coating liquid obtained by dissolving a polymerizable liquid crystal compound as disclosed in Patent Document 1 in a solvent is applied to a supporting base material to form a coating film, and then the polymerizable liquid crystal compound contained in the coating film is nematic.
• An optical film such as a retardation plate can be obtained by a method of transferring to a liquid crystal phase state of equality, drying the coating film, and distilling off the solvent.
• its solubility in a solvent may be low due to its molecular structure. It has been found that such a polymerizable liquid crystal compound having low solubility has a problem that orientation defects are likely to occur in the obtained optical film.
• Such a compound may be precipitated in the coating liquid, which not only deteriorates the film-forming property but also causes an orientation defect in the obtained optical film.
• a polymerizable liquid crystal compound containing an aromatic ring can be a suitable material for obtaining a retardation plate having anti-wavelength dispersibility and excellent optical characteristics, while having a highly symmetric molecular structure. It was found that there is a problem that the solubility is further inferior due to such a molecular structure.
• the present invention is a polymerizable liquid crystal mixed composition having excellent solubility in a solvent and film-forming property, preferably a polymerizable liquid crystal mixed composition showing reverse wavelength dispersibility and suitable for producing a retardation plate having high optical characteristics.
• the purpose is to provide.
• M 1 represents a divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocycle.
• B 1 and B 2 are independently single-bonded, alkylene groups having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2- , -R a3 COOR a4- , -R a5 OCOR a6.
• R a1 to R a8 are independently single bonds or alkylene groups having 1 to 4 carbon atoms
• R b is an alkylene group having 1 to 4 carbon atoms
• R c and R d are 1 to 4 carbon atoms.
• L 1 and L 2 are independently single-bonded, alkylene groups having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2- , -R a3 COOR a4- , -R a5 OCOR a6.
• R a1 to R a8 are independently single bonds or alkylene groups having 1 to 4 carbon atoms
• R b is an alkylene group having 1 to 4 carbon atoms
• R c and R d are 1 to 4 carbon atoms.
• E a and E b each independently represent an alkanediyl group having 1 to 20 carbon atoms, wherein the hydrogen atom contained in the alkanediyl group is replaced with an alkyl group or a halogen atom having 1 to 4 carbon atoms.
• -CH 2- contained in the alkanediyl group may be substituted with -O- or -S- (provided that a plurality of -O- and / or -S- are present.
• the polymerizable liquid crystal compound includes a polymerizable liquid crystal compound in which E a and E b in the formula (I) are the same as each other.
• E 1 is defined in the same way as E a and E b in the above formula (I), and the two E 1s are the same]
• the polymerizable liquid crystal compound (I-1) represented by, at least 1 defined based on the structure of the polymerizable liquid crystal compound (I-1) and the polymerizable liquid crystal compound (I-1).
• L 1, L 2 , E 1, P, n1 and n2 are each identical
• E 2 represents an alkanediyl group having 1 to 20 carbon atoms, which is different from E 1 in the formula (I-1), and here, the hydrogen atom contained in the alkanediyl group has 1 to 4 carbon atoms. It may be substituted with an alkyl group or a halogen atom, and -CH 2- contained in the alkanediyl group may be substituted with -O- or -S- (however, -O- and / or-.
• E 2 the formula (I-2) is the same as the E 2 in, and have the same two E 2 in formula (I-3)]
• M 1 is a divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocycle having a total number of ⁇ electrons contained in N ⁇ of 16 or more and less than 36.
• formula (I-1) and each E 1 in formula (I-2), formula (I-2) and formula (I-3) in each E 2 are both a carbon number of 4 to 20 It is an alkanediyl group and Table formula (I-1) and the formula and the number of carbon atoms of the alkane-diyl group represented by each of E 1 of (I-2) in the formula (I-2) and formula (I-3) each E 2 in The polymerizable liquid crystal mixed composition according to any one of [1] to [5] above, wherein the difference from the number of carbon atoms of the alkanediyl group is 2 or more.
• M 1 , B 1 , B 2 , G 1 , G 2 , L 1 , L 2 , P, n1 and n 2 are the same as each other.
• the polymerizable liquid crystal mixed composition according to any one of [1] to [6] above, each containing 10 mol% or more of the polymerizable liquid crystal compound represented by the formula (I-3).
• Nx represents the main refractive index at a wavelength of ⁇ nm in the direction parallel to the plane of the liquid crystal cured film in the refractive index ellipse formed by the liquid crystal cured film
• ny represents the refractive index ellipse formed by the liquid crystal cured film.
• the retardation plate according to the above [9] which has the optical characteristics represented by.
• nx represents the refractive index at the wavelength ⁇ nm in the direction parallel to the plane of the liquid crystal cured film in the refractive index ellipse formed by the liquid crystal cured film
• ny represents the refractive index formed by the liquid crystal cured film.
• the refractive index elliptical body it represents the refractive index at a wavelength of ⁇ nm which is parallel to the plane of the liquid crystal cured film and perpendicular to the direction of nx
• nz is the refractive index formed by the liquid crystal cured film.
• the retardation plate according to the above [9] which has the optical characteristics represented by.
• An organic EL display device including the elliptical polarizing plate according to the above [12].
• R 1 and R 2 represent reactive groups independently of each other.
• M 1, L 1, L 2 , G 1, G 2, P, n1 and n2 M 1 in the formula (I-1), L 1 , L 2, G 1, G 2, P, n1 and n2 Represents the same meaning as E 1 represents the same meaning as E 1 in formula (I-1), E 2 represents the same meaning as E 2 in formula (I-2).
• E 1 represents the same meaning as E 1 in formula (I-1)
• E 2 represents the same meaning as E 2 in formula (I-2).
• a polymerizable liquid crystal mixed composition having excellent solubility in a solvent and film forming property, preferably a polymerizable liquid crystal mixture suitable for producing a retardation plate exhibiting anti-wavelength dispersibility and having high optical characteristics.
• the composition can be provided.
• the polymerizable liquid crystal mixed composition of the present invention contains at least three kinds of polymerizable liquid crystal compounds having different molecular structures from each other and represented by the formula (I). High solubility in a solvent can be ensured by containing at least three kinds of polymerizable liquid crystal compounds having different molecular structures from each other but having similar molecular structures represented by the formula (I).
• M 1 represents a divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocycle.
• B 1 and B 2 are independently single-bonded, alkylene groups having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2- , -R a3 COOR a4- , -R a5 OCOR a6.
• R a1 to R a8 are independently single bonds or alkylene groups having 1 to 4 carbon atoms
• R b is an alkyl group having 1 to 4 carbon atoms
• R c and R d are 1 to 4 carbon atoms.
• L 1 and L 2 are independently single-bonded, alkylene groups having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2- , -R a3 COOR a4- , -R a5 OCOR a6.
• R a1 to R a8 are independently single bonds or alkylene groups having 1 to 4 carbon atoms
• R b is an alkylene group having 1 to 4 carbon atoms
• R c and R d are 1 to 4 carbon atoms.
• E a and E b each independently represent an alkanediyl group having 1 to 20 carbon atoms, wherein the hydrogen atom contained in the alkanediyl group is replaced with an alkyl group or a halogen atom having 1 to 4 carbon atoms.
• -CH 2- contained in the alkanediyl group may be substituted with -O- or -S- (provided that a plurality of -O- and / or -S- are present. , These are not adjacent to each other),
• P is an acryloyl oxyl group or a methacryloyl oxyl group, n1 and n2 are 1 or 2 independently, respectively].
• the polymerizable liquid crystal mixed composition of the present invention contains, as the at least three kinds of polymerizable liquid crystal compounds, a polymerizable liquid crystal compound in which E a and E b in the formula (I) are the same as each other, and the polymerizable liquid crystal compound.
• the polymerizable liquid crystal compound having the smallest number of carbon atoms in the alcandiyl group represented by E a and E b is represented by the formula (I-1): [In formula (I-1), M 1 , B 1 , B 2 , G 1 , G 2 , L 1 , L 2 , P, n 1 and n 2 are M 1 , B 1 , B 2 , G 1 , G 2 in the above formula (I).
• E 1 is defined in the same way as E a and E b in the above formula (I), and the two E 1s are the same]
• the polymerizable liquid crystal compound (I-1) represented by (hereinafter, also referred to as “polymerizable liquid crystal compound (I-1)”) the polymerizable liquid crystal compound (I-1) and the polymerizable liquid crystal compound (I-1) are said to be polymerizable.
• a polymerizable liquid crystal compound represented by (hereinafter, also referred to as “polymerizable liquid crystal compound (I-2)”) and at least one formula defined based on the structure of the polymerizable liquid crystal compound (I-1).
• (I-3) [In formula (I-3), M 1 , B 1 , B 2 , G 1 , G 2 , L 1 , L 2 , P, n 1 and n 2 are M 1 , B 1 , B 2 , G 1 , G in the above formula (I-1). 2 , L 1 , L 2 , P, n1 and n2, respectively.
• E 2 the formula (I-2) is the same as the E 2 in, and have the same two E 2 in formula (I-3)] Includes a polymerizable liquid crystal compound represented by (hereinafter, also referred to as “polymerizable liquid crystal compound (I-3)”).
• the polymerizable liquid crystal mixed composition contains a plurality of compounds corresponding to the above formula (I-1), E a and E b among the compounds corresponding to the compounds represented by the formula (I-1).
• the polymerizable liquid crystal compound having the smallest number of carbon atoms in the alkanediyl group represented by is referred to as "polymerizable liquid crystal compound (I-1)".
• the alkanediyl group represented by E a and E b has a substituent
• the "carbon number of the alkane diyl group represented by E a and E b " is the formula among the alkane diyl groups represented by E a and E b. It means the number of carbon atoms of the portion constituting the main chain of the compound represented by (I-1).
• the above-mentioned three kinds of polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) constituting the polymerizable liquid crystal mixed composition of the present invention are molecules of the polymerizable liquid crystal compound (I-1).
• the parts other than M 1 in each formula (I-1), (I-2) and (I-3) hereinafter, the M 1 part is referred to as the "core part” and the parts other than M 1).
• the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) are similar to each other, the polymerizable liquid crystal compounds are easily mixed with each other and dissolved in a solvent as a mixed composition. Can enhance sex. Therefore, more for the same amount or less amount of solvent than when the polymerizable liquid crystal compound (I-1), (I-2) or (I-3) is dissolved in the solvent alone.
• the polymerizable liquid crystal compound of (I-1), (I-2) or (I-3) can be easily dissolved, and the solvent cannot be dissolved by the polymerizable liquid crystal compound (I-1), (I-2) or (I-3) alone. It may be possible to dissolve it as a composition.
• the amount of solvent required to prepare the coating liquid can be reduced, and as the types of solvents that can be selected increase, the choices regarding the base material, alignment film, manufacturing conditions, etc. to be used increase. It is also advantageous in. Further, by improving the solubility of the polymerizable liquid crystal compound in the solvent, precipitation and stacking of the polymerizable liquid crystal compound in the coating solution can be suppressed.
• the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) are each represented by the formula (I): It is a polymerizable liquid crystal compound represented by.
• the compound having the structure represented by the formula (I) is usually a polymerizable liquid crystal compound that exhibits birefringence with anti-wavelength dispersibility when polymerized in a unidirectionally oriented state, and is uniform over a wide wavelength range. Polarization conversion is possible. Therefore, by using the polymerizable liquid crystal compound represented by the formula (I), it is possible to obtain a polymerizable liquid crystal composition that can impart good display characteristics when used in a display device.
• R a1 to R a8 are independently single bonds or alkylene groups having 1 to 4 carbon atoms
• R b is an alkylene group having 1 to 4 carbon atoms
• R c and R d are 1 to 4 carbon atoms. It is an alkyl group of 4 or a hydrogen atom.
• B 1 and B 2 are each independently preferably a single bond, -OR a2-1 -, - CH 2 -, - CH 2 CH 2 -, - COOR a4-1 -, or -OCOR a6-1 - a .
• R a2-1 , R a4-1 , and R a6-1 independently represent either single bond, -CH 2- , or -CH 2 CH 2- .
• B 1 and B 2 are independent, more preferably single bond, -O-, -CH 2 CH 2- , -COO-, -COOCH 2 CH 2- , or -OCO-, respectively.
• B 1 and B 2 may be the same or different from each other.
• B 1 and B 2 are the same as each other means that the structures of B 1 and B 2 are the same when viewed with M 1 as the center.
• G 1 and G 2 , L 1 and L 2 , and E a and E b are independent, more preferably single bond, -O-, -CH 2 CH 2- , -COO-, -COOCH 2 CH 2- , or -OCO-, respectively.
• B 1 and B 2 may be the same or different from each other.
• B 1 and B 2 are the same as each other means that the structures of B 1 and B 2 are the same when viewed with M 1 as the center.
• G 1 and G 2 independently represent a divalent alicyclic hydrocarbon group or an aromatic group, and the hydrogen atom contained in the divalent alicyclic hydrocarbon group or an aromatic group is a halogen atom. , It may be substituted with an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group.
• the carbon atoms constituting the divalent alicyclic hydrocarbon group or aromatic group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and when n1 and / or n2 is 2, two.
• G 1 and / or two G 2s may be the same or different, respectively.
• G 1 and G 2 are each independently substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, preferably a 1,4-phenylenediyl group.
• a 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1 substituted with a methyl group.
• G 1 and G 2 may be the same or different from each other. When two G 1 and two G 2 are present, it is preferable that at least one of them is a divalent alicyclic hydrocarbon group.
• G 1 and G 2 bonded to B 1 or B 2 is a divalent alicyclic hydrocarbon group, and in particular, since it exhibits good liquidity, B It is more preferred that both G 1 and G 2 attached to 1 or B 2 are 1,4-trans-cyclohexanediyl groups, and both G 1 and G 2 attached to B 1 or B 2 are 1 , 4-trans-cyclohexanediyl groups, and none of G 1 and G 2 adjacent to B 1 or B 2 are 1,4-phenylenediyl groups.
• L 1 and L 2 are independently single-bonded, alkylene groups having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2- , -R a3 COOR a4- , -R a5 OCOR a6.
• R a1 to R a8 are independent single bonds or alkylene groups having 1 to 4 carbon atoms
• R b is an alkylene group having 1 to 4 carbon atoms
• R c and R d are 1 to 4 carbon atoms.
• L 1 and L 2 are each independently preferably a single bond, -OR a2-1 -, - CH 2 -, - CH 2 CH 2 -, - COOR a4-1 - or OCOR a6-1 - a.
• R a2-1 , R a4-1 , and R a6-1 independently represent either single bond, -CH 2- , or -CH 2 CH 2- .
• L 1 and L 2 are each independently, more preferably a single bond, -O -, - CH 2 CH 2 -, - COO -, - COOCH 2 CH 2 -, - OCO- or -OCOCH 2 CH 2 - is ..
• L 1 and L 2 may be the same or different from each other.
• E a and E b each independently represent an alkanediyl group having 1 to 20 carbon atoms.
• the hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group or a halogen atom having 1 to 4 carbon atoms
• -CH 2- contained in the alkanediyl group is -O- or. It may be replaced with -S- (however, if there are a plurality of -O- and / or -S-, they are not adjacent to each other).
• Each of E a and E b is independently, preferably an alkanediyl group having 4 to 20 carbon atoms, and more preferably an alkanediyl group having 4 to 11 carbon atoms.
• Three of the polymerizable liquid crystal compound constituting the polymerizable liquid crystal mixture composition of the present invention (I-1), (I -2) and (I-3) is, E a and / or E in formula (I)
• the structure of the group corresponding to the structure represented by b is different from each other.
• P is an acryloyl oxyl group or a methacryloyl oxyl group.
• the two Ps are the same.
• M 1 is a divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocycle.
• the aromatic hydrocarbon ring and the aromatic heterocycle referred to here are those in which the number of ⁇ electrons of the ring structure is [4n + 2] (n represents an integer) according to Hückel's law (in the case of an aromatic heterocycle, the aromatic heterocycle).
• -N and -S- like meet Hückel's rule, including a non-covalent electron pair on the heteroatom) refers to, as exemplified by example below (M 1 -1) ⁇ (M 1 -23) It may have two or more such groups via a divalent linking group.
• the divalent linking group M 1 may contain one aromatic hydrocarbon ring or an aromatic heterocycle, or may contain two or more aromatic hydrocarbon rings.
• the divalent linking group M 1 may be a divalent aromatic hydrocarbon group which may have a substituent, and the substituent may be used. It may be a divalent aromatic heterocyclic group which may have.
• two or more aromatic hydrocarbon rings or aromatic heterocycles are contained, only the aromatic hydrocarbon ring or only a plurality of aromatic heterocycles may be contained, and the aromatic hydrocarbon ring and the aromatic heterocycle may be contained. May contain one or more of each. Two or more aromatic hydrocarbon rings and / or aromatic heterocycles may be bonded to each other by a single bond or a divalent bonding group such as —CO—O—, —O—.
• Examples of the aromatic hydrocarbon ring that can be contained in M 1 include a benzene ring, a naphthalene ring, an anthracene ring and the like, and a benzene ring and a naphthalene ring are preferable.
• aromatic heterocycle examples include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrrolin ring, an imidazole ring, and a pyrazole ring.
• M 1 contains a nitrogen atom
• the nitrogen atom preferably has ⁇ electrons.
• M 1 preferably has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and has a thiazole ring, a benzothiazole ring or a benzofuran ring. Is more preferable, and it is further preferable to have a benzothiazole ring.
• M 1 has an aromatic hetero ring containing at least two hetero atoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom
• the aromatic hetero ring is B 1 in the formula (I).
• B 2 may be directly bonded to form a divalent linking group, or may be contained as a substituent of a divalent linking group directly bonded to B 1 and B 2 , but the above aromatics. it is preferred that the entire M 1 group containing a heterocyclic ring is sterically arranged substantially perpendicular direction to the molecular orientation direction.
• the total number of ⁇ electrons contained in the divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocycle represented by M 1 N ⁇ is preferably 16 or more, more preferably. Is 18 or more, particularly preferably 20 or more. Further, it is preferably less than 36, more preferably 30 or less, still more preferably 26 or less, and particularly preferably 24 or less.
• Examples of the divalent linking group represented by M 1 include the following groups.
• * mark represents a linking unit
• Z 0, Z 1 and Z 2 each independently represent a hydrogen atom, a halogen atom, C 1-12 Alkyl group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms.
• alkylthio group with 1 to 12 carbon atoms N-alkylamino group with 1 to 12 carbon atoms
• N, N-dialkylamino group with 2 to 12 carbon atoms N-alkylsulfamoyl group with 1 to 12 carbon atoms
• Z 0 , Z 1 and Z 2 may contain a polymerizable group.
• Q 1 and Q 2 each independently, -CR 2 'R 3' - , - S -, - NH -, - NR 2 '-, - CO- or O- to represent, R 2' and R 3 ' Independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• J 1 and J 2 independently represent a carbon atom or a nitrogen atom.
• Y 1 , Y 2 and Y 3 each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.
• W 1 and W 2 independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.
• Examples of the aromatic hydrocarbon group in Y 1 , Y 2 and Y 3 include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, and a phenyl group.
• a naphthyl group is preferable, and a phenyl group is more preferable.
• the aromatic heterocyclic group has 4 to 20 carbon atoms containing at least one heteroatom such as a nitrogen atom such as a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group or a benzothiazolyl group, an oxygen atom and a sulfur atom.
• Aromatic heterocyclic groups are mentioned, and a frill group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.
• Y 1 , Y 2 and Y 3 may be independently substituted polycyclic aromatic hydrocarbon groups or polycyclic aromatic heterocyclic groups, respectively.
• the polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly.
• the polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.
• Z 0 , Z 1 and Z 2 are preferably hydrogen atoms, halogen atoms, alkyl groups having 1 to 12 carbon atoms, cyano groups, nitro groups, and alkoxy groups having 1 to 12 carbon atoms, respectively.
• 0 is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group
• Z 1 and Z 2 are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, and a cyano group.
• Z 0 , Z 1 and Z 2 may contain a polymerizable group.
• Q 1 and Q 2 -NH -, - S -, - NR 2 '-, - O- are preferable, R 2' is preferably a hydrogen atom. Of these, -S-, -O-, and -NH- are particularly preferable.
• Y 1 together with the nitrogen atom and Z 0 which is attached, may form an aromatic heterocyclic group.
• the aromatic heterocyclic groups include those described above as aromatic heterocycle M 1 optionally has, for example, a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, Examples thereof include an indol ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring.
• This aromatic heterocyclic group may have a substituent.
• Y 1 may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted as described above, together with the nitrogen atom to which the Y 1 is bonded and Z 0 .
• a benzofuran ring, a benzothiazole ring, a benzoxazole ring and the like can be mentioned.
• the polymerizable liquid crystal compound constituting the polymerizable liquid crystal mixture composition of the present invention (I-1), (I -2) and (I-3) is, E a and the structure represented by the above formula (I) / Or they differ from each other only in the structure of the arcandyl group represented by E b .
• the polymerizable liquid crystal compound (I-2) constitutes a mesogen portion with the polymerizable liquid crystal compound (I-1). It differs only in the structure of either one of the alkandyl groups corresponding to E a and E b of the formula (I) [E 2 in the formula (I-2)].
• the polymerizable liquid crystal compound (I-3) is composed of the polymerizable liquid crystal compound (I-1) and two alkanediyl groups [formula (I)) corresponding to E a and E b of the formula (I) constituting the mesogen portion. -3) It differs only in the structure of E 2 ] in.
• the polymerizable liquid crystal compound (I-3) differs only in the structure of the alkanediyl group represented by E 1 in the formula (I-2) constituting the mesogen portion from the polymerizable liquid crystal compound (I-2). ..
• the polymerizable liquid crystal compounds can be easily mixed with each other, and the solubility in a solvent as a mixed composition can be enhanced.
• a polymerizable liquid crystal mixed composition having excellent film-forming properties can be obtained.
• M 1 , B 1 , B 2 in the formula (I-1) G 1 , G 2 , L 1 , L 2 , P, n 1 and n 2 are M 1 , B 1 , B 2 , G 1 , G 2 , L 1 , L 2 , P, n 1 in the formula (I).
• the E 1 in formula (I-1) include the same ones as exemplified as E a and E b in the formula (I), E 1 in formula (I-1) is identical to each other is there.
• n1 and n2 are the same in the formula (I-1).
• the ring structures of the mesogen portions having a symmetrical relationship with the core portion as the center are the same.
• n1 and n2 are each 1, more preferably the G 1 and G 2 are identical to each other, If n1 and n2 are each 2, and G 2 which binds to G 1 and B 2 which binds to B 1 is the same with each other, and, (not adjacent to B 1 or B 2) the other in G 1 And G 2 are more preferably the same as each other.
• the molecular structures of the mesogen portions, which are symmetrical with respect to the core portion are the same as each other.
• n1 and n2 are each 1, more preferably the L 1 and L 2 are identical to each other, If n1 and n2 are each 2, the same each and L 1 and L 2 which binds to E 1 each other, and it is more preferable and the other of L 1 and L 2 are identical to each other.
• B 1 and B 2 are the same, G 1 and G 2 are the same, L 1 and L 2 are the same, and n 1 and n 2 are the same.
• B 1 and B 2 are the same, G 1 and G 2 are the same, L 1 and L 2 are the same, and n 1 and n 2 are both 2.
• a liquid crystal compound having a molecular structure with high symmetry tends to be inferior in solubility, but in the present invention, the liquid crystal compound having such a molecular structure with high symmetry is a mixture of liquid crystal compounds having a structure similar to each other. Therefore, the solubility in a solvent is improved. Therefore, the present invention is suitable for the use of a polymerizable liquid crystal compound having a highly symmetric molecular structure, which has not been sufficiently soluble in a solvent by itself.
• B 1 and B 2 are the same as each other means that the structures of B 1 and B 2 are the same when viewed with M 1 as the center.
• B 1 is -O-CO- *.
• B 2 which is the same as B 1 is * 2-CO-O- (* 1 and * 2 each independently represent a bond with M 1 ).
• G 1 and G 2 and L 1 and L 2 .
• examples of the polymerizable liquid crystal compound (I-1) include compounds described in JP-A-2019-0031777 and the like.
• n1 and n2 are M 1 , B 1 , B 2 , G 1 , G 2 , L in the formula (I-1) in the polymerizable liquid crystal compound (I-1) contained together in the polymerizable liquid crystal mixed composition. It is the same as 1 , L 2 , E 1 , P, n1 and n2.
• E 2 in the formula (I-2) is an alkanediyl group having 1 to 20 carbon atoms different from E 1 in the formula (I-1), and is exemplified as E a and E b in the formula (I). Something similar to the one.
• the polymerizable liquid crystal compound (I-2) since E 1 and E 2 constituting the mesogen portion have different structures from each other, the polymerizable liquid crystal compound (I-2) has an asymmetric structure centered on M 1 which is the core portion. Has a part.
• Polymerizable liquid crystal compound (I-2), about a divalent linking group represented by M 1 (core portion) has a molecular structure in which the mesogenic portions other than M 1 is asymmetric, the center core portion
• M 1 core portion
• the ring structures of the mesogen portions having a symmetrical relationship with each other are the same, and it is further preferable that the ring structures of E 1 and E 2 in the formula (I-2) are asymmetrical. Therefore, it is preferable that n1 and n2 are the same in the formula (I-2). It is more preferable that G 1 and G 2 are the same as each other when n1 and n2 are 1 respectively.
• n1 and n2 are each 2, are identical to each other and a G 2 which binds to G 1 and B 2 which binds to B 1, and that the other in G 1 and G 2 are identical to each other More preferred.
• n1 and n2 are each 1, more preferably the L 1 and L 2 are identical to each other, If n1 and n2 are each 2, the same as L 1 and L 2 which are bound to E 1 each other, and, more preferably the other of L 1 and L 2 are identical to each other, It is particularly preferred that B 1 and B 2 are the same, G 1 and G 2 are the same, L 1 and L 2 are the same, and n 1 and n 2 are the same.
• the structure of the polymerizable liquid crystal compound (I-2) is specified in relation to the polymerizable liquid crystal compound (I-1) contained together in the polymerizable liquid crystal mixed composition, and the polymerizable liquid crystal compound (I-) is specified. It differs from 1) only in the structure corresponding to one of -E 1- [-E 2- in the formula (I-2)] in the formula (I-1) constituting the mesogen portion.
• the polymerizable liquid crystal compound (I-2) contained in the polymerizable liquid crystal mixed composition of the present invention may be only one type or two or more types.
• the polymerizable liquid crystal compound (I-2) is a compound represented by the formula (I-2a). And the compound represented by the formula (I-2b).
• E 2 in the formula (I-3) is the same as E 2 in the formula (I-2) in the polymerizable liquid crystal compound (I-2) contained together in the polymerizable liquid crystal mixed composition, and is the same as E 2 in the formula (I-2).
• two E 2 of I-3) in are identical to each other.
• the polymerizable liquid crystal compound (I-3) has the same ring structure of the mesogen portion, which has a symmetrical relationship with the core portion as the center, with the divalent linking group (core portion) represented by M 1 as the center. Is more preferable, and it is more preferable to have a molecular structure in which the mesogen moiety other than M 1 is symmetrical. Therefore, it is preferable that n1 and n2 are the same in the formula (I-3). It is more preferable that G 1 and G 2 are the same as each other when n1 and n2 are 1 respectively.
• n1 and n2 are each 2, are identical to each other and a G 2 which binds to G 1 and B 2 which binds to B 1, and that the other in G 1 and G 2 are identical to each other More preferred.
• n1 and n2 are each 1, more preferably the L 1 and L 2 are identical to each other, If n1 and n2 are each 2, the same as L 1 and L 2 which are bound to E 1 each other, and, more preferably the other of L 1 and L 2 are identical to each other, It is particularly preferred that B 1 and B 2 are the same, G 1 and G 2 are the same, L 1 and L 2 are the same, and n 1 and n 2 are the same.
• the structure of the polymerizable liquid crystal compound (I-3) is specified in relation to the polymerizable liquid crystal compounds (I-1) and (I-2) both contained in the polymerizable liquid crystal mixed composition, and is polymerized. It differs from the sex liquid crystal compound (I-1) only in the structure corresponding to -E 1- [-E 2- in the formula (I-3)] in the formula (I-1) constituting the mesogen portion, and ,
• the polymerizable liquid crystal compound (I-2) has a structure corresponding to -E 1- [one of -E 2- in the formula (I-3)] in the formula (I-2) constituting the mesogen portion. Only different.
• the polymerizable liquid crystal compound (I-3) contained in the polymerizable liquid crystal mixed composition of the present invention may be only one type or two or more types.
• the polymerizable liquid crystal compounds (I-1) and (I-3) constituting the polymerizable liquid crystal mixed composition of the present invention are represented by M 1 in the formula (I-1) or the formula (I-3). It is preferable to have a molecular structure in which a portion (mesogen portion) other than M 1 is symmetrical about a divalent linking group (core portion).
• the polymerizable liquid crystal compound (I-2) has a divalent linking group (core portion) represented by M 1 in the formula (I-2) as a center, and a portion (mesogen portion) other than M 1. It has an asymmetric molecular structure.
• the polymerizable liquid crystal mixed composition of the present invention is a polymerizable liquid crystal compound (I-1) which is at least three kinds of polymerizable liquid crystal compounds whose structures are similar to each other and has a mesogen portion having a symmetrical structure centered on a core portion.
• (I-3) and the polymerizable liquid crystal compound (I-2) having a mesogen portion having an asymmetric structure centered on the core portion are contained, the polymerizable liquid crystal compounds are easily mixed with each other, and the mixture with respect to the solvent as the mixed composition.
• the solubility can be further increased. Therefore, more for the same amount or less amount of solvent than when the polymerizable liquid crystal compound (I-1), (I-2) or (I-3) is dissolved in the solvent alone.
• the polymerizable liquid crystal compound of it becomes possible to easily dissolve the polymerizable liquid crystal compound of.
• undissolved polymerizable liquid crystal compound is unlikely to remain in the coating liquid, high coatability at the time of film formation can be ensured, and the polymerizable liquid crystal mixed composition having excellent film formation property is obtained.
• the amount of solvent required to prepare the coating liquid can be reduced, and as the types of solvents that can be selected increase, the choices such as the base material, alignment film, and manufacturing conditions to be used increase. It is also advantageous in.
• each E 1 in formula (I-1) and formula (I-2), formula (I-2) and each E 2 in formula (I-3) is All of them are preferably alkanediyl groups having 4 to 20 carbon atoms.
• Formula (I-1) and formula each E 1 of (I-2) in the formula (I-2) and formula (I-3) alkanediyl group for each E also 2 are both carbon atoms 4-20 in , and the and the formula (I-1) and the formula and the number of carbon atoms of the alkane-diyl group represented by each of E 1 of (I-2) in the formula (I-2) and formula (I-3) in the It is more preferable that the difference from the carbon number of the alkanediyl group represented by each E 2 is 2 or more.
• the difference in the number of carbon atoms of the alcandiyl group is 2 or more, the solubility of each polymerizable liquid crystal compound in the solvent as a liquid crystal mixed composition can be effectively enhanced, and thus the coating property and the film forming property are improved. It is possible to obtain a polymerizable liquid crystal mixed composition which is excellent and suitable for producing an optical film with high production efficiency.
• the upper limit of the difference between the number of carbon atoms of the alkanediyl group is usually 20 or less, preferably 9 or less, and more preferably 7 or less.
• the difference in the number of carbon atoms is "all 2 or more”
• a plurality of kinds of polymerizable liquid crystal compounds (I-2) and / or (I-3) are present, all the polymerizable liquid crystal compounds (I-) are present.
• the carbon number of the alkanediyl group represented by E 2 in 2) and / or (I-3) is the alkanediyl group represented by each E 1 in the formulas (I-1) and (I-2). It means that it differs from the number of carbon atoms of.
• Examples of the combination of the polymerizable liquid crystal compounds represented by the formula (I) constituting the polymerizable liquid crystal mixed composition of the present invention include the combinations illustrated in Tables 1 to 4 below.
• Polymerizable liquid crystal mixture compositions described in each table comprises a E a and / or E b of different three or more only in the polymerizable liquid crystal compound in the structure described as the basic structure.
• the polymerizable liquid crystal mixed composition of the present invention has M 1 , B 1 , B 2 , G 1 , G 2 , L 1 , L 2 , P, and n1 among the polymerizable liquid crystal compounds represented by the formula (I). And n2 are the same as each other [that is, the molecular structures other than the structure corresponding to the structure represented by Ea and / or Eb in the formula (I) are the same as each other] represented by the formula (I).
• the polymerizable liquid crystal compound represented by the formula (I-1), the polymerizable liquid crystal compound represented by the formula (I-2), and the formula (I-3) ) Is preferably contained in an amount of 10 mol% or more of each of the polymerizable liquid crystal compounds.
• the polymerizable liquid crystal mixed composition of the present invention may have a higher content of the polymerizable liquid crystal compound (I-2) than the content of the polymerizable liquid crystal compound (I-1).
• the content ratio [molar ratio, (I-1) :( I: 2)] of the polymerizable liquid crystal compounds (I-1) and (I-2) in the polymerizable liquid crystal mixed composition is preferably 1: 1. It is ⁇ 1: 5, more preferably 1: 1 ⁇ 1: 2.
• the content of the polymerizable liquid crystal compound (I-2) is larger than the content of the polymerizable liquid crystal compound (I-3), and the polymerizable liquid crystal compound (I-) in the polymerizable liquid crystal mixed composition.
• the content ratio [molar ratio, (I-2) :( I: 3)] of 2) and (I-3) is preferably 1: 8 to 8: 1, and more preferably 1: 4 to 4: 1. It is 1.
• the polymerizable liquid crystal mixed composition contains a plurality of types of polymerizable liquid crystal compounds (I-1), (I-2) and / or (I-3), the content ratio corresponds to each polymerizable liquid crystal compound. It is calculated as the total amount of compounds to be produced.
• a method for producing a polymerizable liquid crystal compound represented by the formula (I) such as the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) constituting the polymerizable liquid crystal mixed composition of the present invention.
• Is not particularly limited, and known organic synthetic reactions eg, condensation reactions, condensation reactions, condensation reactions, condensation reactions, condensation reactions, condensation reactions, condensation reactions, condensation reactions, condensation reactions, condensation reactions, Reaction, Wittich reaction, Schiff base formation reaction, benzylation reaction, Sonoh reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Heartwig reaction, Friedelcraft reaction, Heck reaction, Aldor reaction, etc.
• esterification of an alcohol compound and a carboxylic acid compound having a structure corresponding to the desired structure of the polymerizable liquid crystal compound can be prepared by reaction.
• the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) constituting the polymerizable liquid crystal mixed composition of the present invention are prepared separately and then three kinds are mixed. It can be a liquid crystal mixture. Further, with the reactive group R 2 of the compound represented by the following formula (III-1), with the reactive group R 2 of the compound represented by (III-2), compounds represented by (III-3) It can also be prepared as a liquid crystal mixture containing the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) by a method including reacting with R 1 of the above. [In the formula, R 1 and R 2 represent reactive groups independently of each other.
• M 1, L 1, L 2 , G 1, G 2, P, n1 and n2 M 1 in the formula (I-1), L 1 , L 2, G 1, G 2, P, n1 and n2 Represents the same meaning as E 1 represents the same meaning as E 1 in formula (I-1), E 2 represents the same meaning as E 2 in formula (I-2).
• the latter method is preferable.
• R 1 in the formula (III-3), formula (III-1) and the (III-2) R 2 in the polymerizable liquid crystal compound react together (I-1) ⁇ (I -3)
• Any structure can form the structures represented by B 1 and B 2 in the formulas (I-1) to (I-3).
• the reactive group represented by R 1 and / or R 2 include a hydroxyl group, a carboxyl group, an amino group and the like, and R 1 and R 2 depending on the reaction used in the production of the polymerizable liquid crystal compound.
• the reactive groups represented by may be selected respectively.
• R 1 in formula (III-3) is a hydroxyl group as a compound represented by formula (III-3).
• a certain alcohol compound, a compound represented by the formula (III-1), and R 2 in the formulas (III-1) and (III-2) as compounds represented by the formula (III-2) are carboxyl groups, respectively.
• the polymerizable liquid crystal mixture of the present invention can be produced by carrying out an esterification reaction with a certain carboxylic acid compound.
• the esterification reaction can be carried out according to the same method as the esterification reaction that can be used for producing the polymerizable liquid crystal compound represented by the formula (I), for example, JP-A-2019-0031777 described above.
• the methods and conditions described in 1 can be adopted.
• the contents of -2) and (I-3) can be controlled.
• a large number of compounds can be synthesized at the same time. Assuming that the mole fractions of the carboxylic acid compounds are An, Bn, and Cn when the total of the carboxylic acid compounds is 1, the total of the polymerizable liquid crystal compounds (I-1) and (I-2) is 1.
• the theoretical mole fraction of the polymerizable compound (I-2) is similarly represented by 1-Sn.
• the polymerizable liquid crystal mixed composition of the present invention is a polymerizable liquid crystal compound other than the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) as long as it does not affect the effects of the present invention. May include.
• Polymerizable liquid crystal compounds Other than the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3), the polymerizable liquid crystal compounds have, for example, a molecular structure represented by the formula (I), and have a molecular structure represented by the formula (I).
• polymerizable liquid crystal compound which does not correspond to any of the polymerizable liquid crystal compounds (I-2) and (I-3) in relation to the polymerizable liquid crystal compound represented by I-1), it generally has a positive wavelength dispersibility.
• the following polymerizable liquid crystal compounds for example, "3.8.6 Network (completely bridged type)", "6.5” of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000).
• 1.1 Liquid crystal material b.
• Polymerizable nematic liquid crystal material a compound having a polymerizable group and the like can be mentioned.
• the content thereof is the polymerizable liquid crystal compound. It is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and 50 parts by mass or less with respect to a total of 100 parts by mass of (I-1), (I-2) and (I-3). Is more preferable. In particular, if the content of the liquid crystal compounds having significantly different molecular structures is too large, phase separation may occur and the appearance may be significantly impaired. Therefore, the polymerizable liquid crystal compound constituting the polymerizable liquid crystal mixed composition of the present invention is used.
• N1 and n2 are substantially identical to the polymerizable liquid crystal compounds M 1 , B 1 , B 2 , G 1 , G 2 , L 1 , L 2 , P, n 1 and n 2 in formula (I-1). It is more preferable to be configured.
• the said "substantially composed" is the total of the polymerizable liquid crystal compounds whose content of the polymerizable liquid crystal compound represented by the formula (I) is contained in the polymerizable liquid crystal mixed composition of the present invention. It means that it is 90% by mass or more with respect to the mass.
• the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal mixed composition is, for example, 70 to 99.5% by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal mixed composition. It is a part, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and further preferably 90 to 95 parts by mass.
• the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film.
• the solid content of the polymerizable liquid crystal mixed composition means all the components excluding volatile components such as organic solvents from the polymerizable liquid crystal mixed composition.
• the polymerizable liquid crystal mixed composition of the present invention contains an organic solvent, a photopolymerization initiator, a polymerization inhibitor, and a photosensitizer. It may further contain additives such as a sensitive agent and a leveling agent. As each of these components, only one kind may be used, or two or more kinds may be used in combination.
• the polymerizable liquid crystal mixed composition is usually applied to a base material or the like in a state of being dissolved in a solvent, and therefore preferably contains a solvent.
• a solvent capable of dissolving the polymerizable liquid crystal compound constituting the polymerizable liquid crystal mixed composition such as the polymerizable liquid crystal compounds (I-1) to (I-3) is preferable, and the polymerization of the polymerizable liquid crystal compound is preferable. It is preferably a solvent inert to the reaction.
• solvent examples include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol and alcohols such as propylene glycol monomethyl ether.
• Solvents Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone.
• Ketone solvent aliphatic hydrocarbon solvent such as pentane, hexane and heptane; alicyclic hydrocarbon solvent such as ethylcyclohexane; aromatic hydrocarbon solvent such as toluene and xylene; nitrile solvent such as acetonitrile; tetrahydrofuran and dimethoxyethane and the like Ether solvent; chlorine-containing solvent such as chloroform and chlorobenzene; amide-based solvent such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, etc. Be done.
• organic solvents are preferable, and alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide-based solvents and aromatic hydrocarbon solvents are more preferable.
• the content of the solvent in the polymerizable liquid crystal mixed composition is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal mixed composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal mixed composition is preferably 2 to 50 parts by mass, and more preferably 5 to 30 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal mixed composition is low, so that the thickness of the film becomes substantially uniform, and unevenness tends to be less likely to occur. The solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.
• the polymerizable liquid crystal mixed composition of the present invention preferably contains a polymerization initiator.
• the polymerization initiator is a compound that can generate a reactive species by the contribution of heat or light and initiate a polymerization reaction of a polymerizable liquid crystal or the like.
• the reactive active species include active species such as radicals, cations and anions.
• a photopolymerization initiator that generates radicals by light irradiation is preferable from the viewpoint of easy reaction control.
• photopolymerization initiator examples include benzoin compounds, benzophenone compounds, benzyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, triazine compounds, iodonium salts and sulfonium salts.
• Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above, BASF Japan Co., Ltd.) (Made), Sakeol BZ, Sakeall Z, Sakeall BEE (manufactured by Seiko Kagaku Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), ADEKA PUTMER SP- 152, ADEKA OPTMER SP-170, ADEKA OPTMER N-1717, ADEKA OPTMER N-1919, ADEKA ARCULDS NCI-831,
• the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and above all, the ⁇ -acetophenone type.
• a polymerization initiator and an oxime-based photopolymerization initiator are preferable.
• Examples of the ⁇ -acetophenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1.
• 2-methyl-2-morpholino-1- Included are 4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one.
• Examples of commercially available ⁇ -acetophenone compounds include Irgacure 369, 379EG, 907 (all manufactured by BASF Japan Ltd.) and Sequol BEE (manufactured by Seiko Kagaku Co., Ltd.).
• the oxime-based photopolymerization initiator generates methyl radicals when irradiated with light. With this methyl radical, the polymerization of the polymerizable liquid crystal compound in the deep part of the formed liquid crystal cured film proceeds suitably. Further, from the viewpoint of more efficiently advancing the polymerization reaction in the deep part of the formed liquid crystal cured film, it is preferable to use a photopolymerization initiator capable of efficiently utilizing ultraviolet rays having a wavelength of 350 nm or more.
• a triazine compound and an oxime ester type carbazole compound are preferable, and an oxime ester type carbazole compound is more preferable from the viewpoint of sensitivity.
• the oxime ester type carbazole compound include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl)]. ) -9H-Carbazole-3-yl] -1- (O-acetyloxime) and the like.
• oxime ester-type carbazole compound Commercially available products of the oxime ester-type carbazole compound include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Japan Ltd.), ADEKA OPTMER N-1919, and ADEKA ARCLUS NCI-831 (above). , ADEKA CORPORATION) and the like.
• the amount of the photopolymerization initiator added is usually 0.1 part by mass to 30 parts by mass, preferably 1 part by mass to 20 parts by mass, and more preferably 1 part by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is a mass part to 15 parts by mass. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation of the polymerizable liquid crystal compound is not easily disturbed.
• Polymerization inhibitors include hydroquinones having substituents such as hydroquinone and alkyl ethers; catechols having substituents such as alkyl ethers such as butyl catechol; pyrogallols, 2,2,6,6-tetramethyl-1-. Radical trapping agents such as piperidinyloxy radicals; thiophenols; ⁇ -naphthylamines and ⁇ -naphthols.
• the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound, and is preferably 0. It is 1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.
• the photopolymerization initiator can be made highly sensitive.
• the photosensitizer include xanthones such as xanthones and thioxanthones; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; rubrenes.
• the photosensitizer include xanthones such as xanthones and thioxanthones; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; rubrenes.
• the content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.
• the polymerizable liquid crystal mixed composition of the present invention may contain a leveling agent.
• the leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal mixed composition and flattening the film obtained by applying the leveling agent, for example, silicone-based, polyacrylate-based and perfluoroalkyl.
• a system leveling agent can be mentioned.
• DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all momentary performance materials Japan GK) (Manufactured by), Florinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) R-08 , R-30, R-90, F-410, F-411, F-443, F-445, F-470, F
• F-483 (all manufactured by DIC Co., Ltd.), Ftop (trade name) EF301, EF303, EF351, EF352 (all manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Surflon (registered) Trademarks) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.) , Product name E1830, E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names: manufactured by BM Chemie), etc. Can be mentioned. Of these, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferable.
• the content of the leveling agent in the polymerizable liquid crystal mixed composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound.
• the content of the leveling agent is within the above range, it is easy to orient the polymerizable liquid crystal compound, and the obtained liquid crystal cured film tends to be smoother, which is preferable.
• the polymerizable liquid crystal mixed composition may contain two or more kinds of leveling agents.
• the polymerizable liquid crystal mixed composition of the present invention is prepared by adding a solvent, a polymerization initiator, a polymerization inhibitor, and light to the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3), if necessary. It can be prepared by adding an additive such as a sensitizer or a leveling agent and stirring and mixing at a predetermined temperature.
• the polymerizable liquid crystal mixed composition of the present invention has high solubility in a solvent of the polymerizable liquid crystal compound, and is excellent in coating property and film forming property. The occurrence of orientation defects can be suppressed. Therefore, by using the polymerizable liquid crystal mixed composition of the present invention, it is possible to form a film without deteriorating the optical characteristics that the polymerizable liquid crystal compound can originally express, and the liquid crystal having excellent optical characteristics. A cured film can be obtained. Therefore, the present invention is a cured product of the polymerizable liquid crystal mixed composition of the present invention, and the polymerizable liquid crystal compound in the polymerizable liquid crystal mixed composition is a cured product of the polymerizable liquid crystal mixed composition.
• the retardation plate containing a liquid crystal cured film that is cured in an oriented state.
• the retardation plate made of the liquid crystal cured film can sufficiently exhibit the optical characteristics that the polymerizable liquid crystal compound used can originally exhibit, and can be a retardation plate having high optical performance.
• the liquid crystal cured film constituting the retardation plate of the present invention includes a homopolymer of a polymerizable liquid crystal compound (I-1) in an oriented state, a homopolymer of a polymerizable liquid crystal compound (I-2), and a polymerizable liquid crystal compound ( It may be composed of the homopolymer of I-3), or may be composed of the copolymer in the oriented state of the mixture of the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3). It may have been.
• the liquid crystal cured film constituting the retardation plate of the present invention is a polymerizable liquid crystal compound (I-1), (I-2) and (I-). It is preferably composed of the copolymer in the oriented state of the mixture of 3).
• the retardation plate of the present invention is a cured product of the polymerizable liquid crystal mixed composition of the present invention, and has optical properties represented by the following formulas (1), (2) and (3).
• the liquid crystal cured film is usually a cured product obtained by curing a polymerizable liquid crystal compound in a state of being horizontally oriented with respect to the plane of the liquid crystal cured film (hereinafter, also referred to as "horizontally oriented liquid crystal cured film").
• Re ( ⁇ ) represents the in-plane retardation value of the cured liquid crystal film at a wavelength of ⁇ nm
• Re (nx ( ⁇ ) ⁇ ny ( ⁇ )) ⁇ d (d is the thickness of the cured liquid crystal film).
• Nx represents the main refractive index at a wavelength of ⁇ nm in the direction parallel to the plane of the liquid crystal cured film in the refractive index ellipse formed by the liquid crystal cured film
• ny represents the refractive index ellipse formed by the liquid crystal cured film. Represents the refractive index at a wavelength of ⁇ nm in a direction parallel to the plane of the liquid crystal cured film and orthogonal to the nx direction).
• the in-plane retardation value at a short wavelength of the horizontally oriented liquid crystal cured film is smaller than the in-plane retardation value at a long wavelength. It shows so-called reverse wavelength dispersibility.
• Re (450) / Re (550) is preferably 0.70 or more, more preferably 0.78 or more, and therefore, because the inverse wavelength dispersibility is improved and the optical characteristics of the retardation plate are further improved. It is preferably 0.92 or less, more preferably 0.90 or less, still more preferably 0.87 or less, particularly preferably 0.86 or less, and even more preferably 0.85 or less.
• Re (650) / Re (550) is preferably 1.00 or more, more preferably 1.01 or more, and further preferably 1.02 or more.
• the effect of improving the specular hue (coloring) when an elliptical polarizing plate including a retardation plate including the horizontally oriented liquid crystal cured film is applied to an organic EL display device.
• a more preferable range of the in-plane retardation value is 120 nm ⁇ Re (550) ⁇ 170 nm, and a more preferable range is 130 nm ⁇ Re (550) ⁇ 150 nm.
• the retardation plate of the present invention is a cured product of the polymerizable liquid crystal mixed composition of the present invention, and has optical properties represented by the following formulas (4), (5) and (6).
• the liquid crystal cured film is usually a cured product obtained by curing a polymerizable liquid crystal compound in a state of being oriented in a direction perpendicular to the plane of the liquid crystal cured film (hereinafter, also referred to as "vertically oriented liquid crystal cured film").
• Rth ( ⁇ ) represents the phase difference value in the thickness direction of the cured liquid crystal film at the wavelength ⁇ nm
• Rth ((nx ( ⁇ ) + ny ( ⁇ )) / 2-nz) ⁇ d (d is).
• nx represents the main refractive index at the wavelength ⁇ nm in the direction parallel to the plane of the cured liquid crystal film in the refractive index ellipse formed by the cured liquid crystal film
• ny represents the cured liquid crystal film.
• the refractive index of the elliptical body is parallel to the plane of the cured liquid crystal film and represents the refractive index at a wavelength of ⁇ nm in the direction orthogonal to the direction of nx, where nz is the refractive index formed by the cured liquid crystal film. In a rate elliptical body, it represents the refractive index at a wavelength of ⁇ nm in the direction perpendicular to the plane of the liquid crystal cured film).
• the value of Rth (450) / Rth (550) in the vertically oriented liquid crystal cured film is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0.92 or less, more preferably 0. It is 90 or less, more preferably 0.87 or less, particularly preferably 0.86 or less, and even more preferably 0.85 or less.
• Rth (650) / Rth (550) is preferably 1.0 or more, more preferably 1.01 or more, and further preferably 1.02 or more.
• the oblique reflection hue when an elliptical polarizing plate including a retardation plate including the vertically oriented liquid crystal cured film is applied to an organic EL display device is to be improved.
• the retardation value Rth (550) in the film thickness direction of the vertically oriented liquid crystal cured film is more preferably ⁇ 90 nm or more, further preferably ⁇ 80 nm or more, and more preferably ⁇ 50 nm or less.
• the retardation plate of the present invention is, for example, A step of forming a coating film of the polymerizable liquid crystal mixed composition of the present invention, drying the coating film, and orienting the polymerizable liquid crystal compound in the polymerizable liquid crystal mixed composition, and It can be produced by a method including a step of polymerizing a polymerizable liquid crystal compound by light irradiation while maintaining an oriented state to form a liquid crystal cured film.
• the coating film of the polymerizable liquid crystal mixed composition can be formed by applying the polymerizable liquid crystal composition on a substrate or an alignment film described later.
• the base material include a glass base material and a film base material, and a resin film base material is preferable from the viewpoint of processability.
• Resins constituting the film substrate include, for example, polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohols; polyethylene terephthalates; polymethacrylic acid esters; polyacrylic acid esters; triacetylcellulose, Examples include diacetyl cellulose and cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyether ketones; polyphenylene sulfide and plastics such as polyphenylene oxide.
• polyolefins such as polyethylene, polypropylene, and norbornene-based polymers
• cyclic olefin-based resins include polyvinyl alcohols; polyethylene terephthalates; polymethacrylic acid esters; polyacrylic acid esters; triacetylcellulose, Examples include diacetyl cellulose
• Such a resin can be formed into a film by a known means such as a solvent casting method and a melt extrusion method to form a base material.
• the surface of the base material may have a protective layer formed of acrylic resin, methacrylic resin, epoxy resin, oxetane resin, urethane resin, melamine resin, etc., and may be subjected to a mold release treatment such as silicone treatment, a corona treatment, etc. Surface treatment such as plasma treatment may be applied.
• a commercially available product may be used as the base material.
• examples of commercially available cellulose ester base materials include cellulose ester base materials manufactured by Fuji Photo Film Co., Ltd. such as Fujitac Film; manufactured by Konica Minolta Opto Co., Ltd. such as "KC8UX2M”, “KC8UY”, and “KC4UY”. Cellulose ester base material and the like.
• Commercially available cyclic olefin resins include, for example, cyclic olefin resins manufactured by Ticona (Germany) such as “Topas (registered trademark)"; cyclic olefins manufactured by JSR Co., Ltd. such as "Arton (registered trademark)".
• Cyclic olefin resins manufactured by Nippon Zeon Co., Ltd. such as “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)”; Mitsui such as "Apel” (registered trademark) Cyclic olefin resin manufactured by Chemical Co., Ltd. can be mentioned.
• a commercially available cyclic olefin resin base material can also be used.
• As commercially available cyclic olefin resin base materials cyclic olefin resin base materials manufactured by Sekisui Chemical Industry Co., Ltd.
• the thickness of the base material is usually 5 to 300 ⁇ m, preferably 10 to 150 ⁇ m.
• Examples of the method for applying the polymerizable liquid crystal mixed composition to a substrate or the like include a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method and other coating methods, and a flexographic printing method.
• Known methods such as a method can be mentioned.
• a dry coating film is formed by removing the solvent by drying or the like.
• the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
• the heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used and the material of the base material or the like forming the coating film, but is usually used in order to phase-transfer the polymerizable liquid crystal compound to the liquid crystal phase state.
• the temperature is equal to or higher than the liquid crystal phase transition temperature.
• the liquid crystal phase transition temperature (smetic) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal mixed composition can be heated to a temperature of about (phase transition temperature or nematic phase transition temperature) or higher.
• the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like.
• the phase transition temperature in the polymerizable liquid crystal mixed composition of the present invention containing at least three kinds of polymerizable liquid crystal compounds is the same ratio as the composition of the fully polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition in the polymerizable liquid crystal composition. Means the temperature measured using a mixture of polymerizable liquid crystal compounds mixed in.
• the polymerizable liquid crystal mixed composition of the present invention contains at least three types of polymerizable liquid crystal compounds (I-1), (I-2) and (I-3), and usually each of them is a single polymerizable liquid crystal compound.
• the liquid crystal phase can be transferred at a temperature lower than the temperature at which (I-1), (I-2) or (I-3) is transferred to the liquid crystal phase. Therefore, in the production of the retardation plate using the polymerizable liquid crystal mixed composition of the present invention, excessive consumption of thermal energy can be suppressed and production efficiency can be improved. Further, since the liquid crystal phase transition can be performed by heating at a relatively low temperature, there is an advantage that the choice of the supporting base material to which the polymerizable liquid crystal mixed composition is applied is expanded.
• the heating time can be appropriately determined depending on the heating temperature, the type of the polymerizable liquid crystal compound used, the type of the solvent, its boiling point and its amount, etc., but is usually 15 seconds to 10 minutes, preferably 0.5 to 0.5 minutes. 5 minutes.
• the solvent may be removed from the coating film at the same time as heating the polymerizable liquid crystal compound to the liquid crystal phase transition temperature or higher, or separately, but it is preferable to remove the solvent at the same time from the viewpoint of improving productivity.
• an appropriate amount of solvent in the coating film is applied under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal mixed composition does not polymerize.
• a pre-drying step may be provided to remove the liquid crystal.
• drying method in the pre-drying step examples include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method, and the drying temperature (heating temperature) in the drying step is the type of polymerizable liquid crystal compound used and the solvent. It can be appropriately determined according to the type of the above, its boiling point, its amount and the like.
• the polymerizable liquid crystal compound is polymerized by light irradiation while maintaining the orientation state of the polymerizable liquid crystal compound, whereby the polymer of the polymerizable liquid crystal compound existing in the desired orientation state is used.
• a certain liquid crystal cured film is formed. Since the polymerizable liquid crystal composition of the present invention can be highly polymerized by irradiation with light such as high-intensity ultraviolet rays while suppressing damage to the polymerizable liquid crystal compound, the polymerization method is usually a photopolymerization method. Is used.
• the light to be applied to the dry coating film is appropriately selected according to the type of the polymerization initiator, the type of the polymerizable liquid crystal compound, and the amount thereof contained in the dry coating film.
• Specific examples thereof include one or more types of light and active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, ⁇ -rays, ⁇ -rays and ⁇ -rays.
• ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use a photopolymerization apparatus widely used in the art, so that photopolymerization can be performed by ultraviolet light.
• the polymerization temperature can be controlled by irradiating light while cooling the dry coating film by an appropriate cooling means.
• a cooling means By adopting such a cooling means, if the polymerizable liquid crystal compound is polymerized at a lower temperature, a liquid crystal cured film can be appropriately formed even if a base material having a relatively low heat resistance is used. It is also possible to promote the polymerization reaction by raising the polymerization temperature within a range in which defects due to heat during light irradiation (deformation due to heat of the base material, etc.) do not occur.
• a patterned cured film can also be obtained by masking or developing during photopolymerization.
• Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excima laser, and a wavelength range.
• Examples thereof include an LED light source that emits 380 to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.
• the ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm 2 .
• the ultraviolet irradiation intensity is preferably the intensity in the wavelength region effective for activating the photopolymerization initiator.
• the time for irradiating light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, still more preferably 0.1 seconds to 1 minute. is there.
• the integrated light intensity is 10 to 3,000 mJ / cm 2 , preferably 50 to 2,000 mJ / cm 2 , and more preferably 100 to 1,000 mJ / cm. It is 2 .
• the thickness of the liquid crystal cured film can be appropriately selected depending on the display device to be applied, and is preferably 0.2 to 3 ⁇ m, more preferably 0.2 to 2 ⁇ m.
• the coating film of the polymerizable liquid crystal mixed composition may be formed on the alignment film.
• the alignment film has an orientation-regulating force that aligns the polymerizable liquid crystal compound in a desired direction.
• an alignment film having an orientation restricting force for horizontally aligning a polymerizable liquid crystal compound may be referred to as a horizontal alignment film
• an alignment film having an orientation regulating force for vertically aligning a polymerizable liquid crystal compound may be referred to as a vertical alignment film.
• the orientation regulating force can be arbitrarily adjusted according to the type of alignment film, surface condition, rubbing conditions, etc., and when the alignment film is formed of a photoalignable polymer, it can be arbitrarily adjusted according to polarization irradiation conditions, etc. It is possible to do.
• the alignment film preferably has solvent resistance that does not dissolve when the polymerizable liquid crystal mixed composition is applied, and also has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound described later. ..
• the alignment film include an alignment film containing an orientation polymer, a photoalignment film, a grub alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the orientation direction, and the like, and the accuracy of the orientation angle and A photoalignment film is preferable from the viewpoint of quality.
• the oriented polymer examples include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule and polyamic acid, which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and poly. Examples thereof include oxazol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Of these, polyvinyl alcohol is preferable.
• the oriented polymer can be used alone or in combination of two or more.
• the alignment film containing the orientation polymer is usually obtained by applying a composition in which the orientation polymer is dissolved in a solvent (hereinafter, may be referred to as "orientation polymer composition") to a substrate to remove the solvent or. It is obtained by applying an oriented polymer composition to a substrate, removing a solvent, and rubbing (rubbing method).
• the solvent include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal mixed composition.
• the concentration of the oriented polymer in the oriented polymer composition may be within the range in which the oriented polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solid content with respect to the solution, and is 0. .1 to 10% is more preferable.
• a commercially available alignment film material may be used as it is as the orientation polymer composition.
• Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).
• Examples of the method of applying the oriented polymer composition to the base material include the same methods as those exemplified as the method of applying the polymerizable liquid crystal mixed composition to the base material.
• Examples of the method for removing the solvent contained in the oriented polymer composition include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
• a rubbing treatment can be performed as needed to impart orientation regulating force to the alignment film (rubbing method).
• a method of imparting orientation-regulating force by the rubbing method a rubbing cloth is wrapped around a rotating rubbing roll, and an orientation polymer composition is applied to the substrate and annealed to form the surface of the substrate. Examples thereof include a method of contacting a film of an oriented polymer. If masking is performed during the rubbing treatment, a plurality of regions (patterns) having different orientation directions can be formed on the alignment film.
• the photo-alignment film is usually formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as “composition for forming a photo-alignment film”) to a substrate, removing the solvent, and then polarized light. It is obtained by irradiating (preferably polarized UV).
• composition for forming a photo-alignment film a composition containing a polymer or monomer having a photoreactive group and a solvent
• polarized light preferably polarized UV
• the photoalignment film is also advantageous in that the direction of the orientation regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.
• a photoreactive group is a group that produces a liquid crystal alignment ability when irradiated with light.
• Specific examples thereof include groups involved in photoreactions that are the origin of liquid crystal orientation ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction generated by light irradiation. Of these, groups involved in the dimerization reaction or photocrosslinking reaction are preferable because they are excellent in orientation.
• a photoreactive group involved in a photodimerization reaction is preferable, and a photoalignment film having a relatively small amount of polarized light required for photoalignment and excellent thermal stability and stability over time can be easily obtained. Cinnamoyle groups and chalcone groups are preferred.
• the polymer having a photoreactive group a polymer having a cinnamoyl group such that the terminal portion of the side chain of the polymer has a cinnamic acid structure is particularly preferable.
• a photoalignment-inducing layer By applying the composition for forming a photoalignment film on a base material, a photoalignment-inducing layer can be formed on the base material.
• the solvent contained in the composition include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal mixed composition, and are appropriately used depending on the solubility of the polymer or monomer having a photoreactive group. You can choose.
• the content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the target photo-alignment film, but the composition for forming a photo-alignment film. It is preferably at least 0.2% by mass, more preferably in the range of 0.3 to 10% by mass, based on the mass of the above.
• the composition for forming a photoalignment film may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer as long as the characteristics of the photoalignment film are not significantly impaired.
• Examples of the method of applying the composition for forming a photoalignment film to the base material include the same method as the method of applying the orientation polymer composition to the base material.
• Examples of the method for removing the solvent from the applied composition for forming a photoalignment film include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
• the polarized light is irradiated from the base material side to obtain polarized light. It may be in the form of transmitting and irradiating. Further, it is particularly preferable that the polarized light is substantially parallel light.
• the wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable.
• Examples of the light source used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet light lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps and metal halide lamps. preferable.
• a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because they have a high emission intensity of ultraviolet rays having a wavelength of 313 nm.
• Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizer.
• a polarizer a polarizing filter, a polarizing prism such as Gran Thomson or Gran Tailor, or a wire grid type polarizer can be used.
• the groove alignment film is a film having an uneven pattern or a plurality of grooves on the surface of the film.
• the polymerizable liquid crystal compound is applied to a film having a plurality of linear grubs arranged at equal intervals, the liquid crystal molecules are oriented in the direction along the groove.
• a method of forming an uneven pattern by performing exposure and rinsing treatment after exposure through an exposure mask having a pattern-shaped slit on the surface of the photosensitive polyimide film, and a plate having grooves on the surface A method of forming a layer of UV-curable resin before curing on a shaped master, transferring the formed resin layer to a substrate and then curing, and a film of UV-curable resin before curing formed on the substrate. Examples thereof include a method in which a roll-shaped master having a plurality of grooves is pressed to form irregularities and then cured.
• a fluoropolymer such as perfluoroalkyl and a silane compound, and silane compounds thereof, and the like are used.
• a polysiloxane compound obtained by the condensation reaction of the above may be used.
• the constituent elements include Si element and C element from the viewpoint that the surface tension can be easily lowered and the adhesion to the layer adjacent to the alignment film can be easily improved.
• the compound is preferable, and the silane compound can be preferably used.
• the silane compound a silane-containing ionic compound or the like can be used, and by using such a silane compound, the vertical orientation regulating force can be enhanced.
• the silane compound one type may be used alone, two or more types may be used in combination, or may be mixed with other materials.
• silane compound is a nonionic silane compound
• a silane compound having an alkyl group at the molecular terminal is preferable, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferable from the viewpoint of easily increasing the vertical orientation restricting force. ..
• the thickness of the alignment film is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm, more preferably 10 to 500 nm or less, and further preferably. Is in the range of 10 to 300 nm, particularly preferably 50 to 250 nm.
• the present invention includes an elliptical polarizing plate including the retardation plate and the polarizing film of the present invention.
• the polarizing film is a film having a polarizing function, and examples thereof include a stretched film having a dye having absorption anisotropy adsorbed and a film containing a film coated with a dye having absorption anisotropy as a polarizer. Examples of the dye having absorption anisotropy include a dichroic dye.
• a film containing a stretched film having a dye having absorption anisotropy adsorbed as a polarizer is usually obtained by uniaxially stretching a polyvinyl alcohol-based resin film and dyeing the polyvinyl alcohol-based resin film with a bicolor dye.
• the polyvinyl alcohol-based resin is obtained by saponifying the polyvinyl acetate-based resin.
• the polyvinyl acetate-based resin in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith is used.
• examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
• the degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more.
• the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used.
• the degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably in the range of 1,500 to 5,000.
• a film formed of such a polyvinyl alcohol-based resin is used as a raw film for a polarizing film.
• the method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method.
• the film thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 ⁇ m.
• the uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, at the same time as dyeing, or after dyeing.
• the uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. It is also possible to perform uniaxial stretching at these multiple stages.
• rolls having different peripheral speeds may be uniaxially stretched, or thermal rolls may be used to uniaxially stretch.
• the uniaxial stretching may be a dry stretching in which the stretching is performed in the atmosphere, or a wet stretching in which the polyvinyl alcohol-based resin film is swollen using a solvent.
• the draw ratio is usually about 3 to 8 times.
• Dyeing of a polyvinyl alcohol-based resin film with a dichroic dye is performed, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.
• iodine or a dichroic organic dye is used as the dichroic dye.
• the dichroic organic dye include C.I. I.
• examples thereof include a dichroic direct dye composed of a disazo compound such as DIRECT RED 39, and a dichroic direct dye composed of a compound such as trisazo and tetrakisazo.
• the polyvinyl alcohol-based resin film is preferably immersed in water before the dyeing treatment.
• iodine When iodine is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide and dyeing is usually adopted.
• the iodine content in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water.
• the content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water.
• the temperature of the aqueous solution used for dyeing is usually about 20 to 40 ° C.
• the immersion time (staining time) in this aqueous solution is usually about 20 to 1,800 seconds.
• a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing is usually adopted.
• the content of the dichroic organic dye in this aqueous solution is usually about 1 ⁇ 10 -4 to 10 parts by mass, preferably 1 ⁇ 10 -3 to 1 part by mass, more preferably 1 ⁇ 10 -3 to 1 part by mass, per 100 parts by mass of water. Is 1 ⁇ 10 -3 to 1 ⁇ 10 -2 parts by mass.
• This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid.
• the temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80 ° C.
• the immersion time (staining time) in this aqueous solution is usually about 10 to 1,800 seconds.
• the boric acid treatment after dyeing with a dichroic dye can usually be performed by immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution.
• the content of boric acid in this aqueous boric acid solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water.
• this boric acid aqueous solution preferably contains potassium iodide, and the content of potassium iodide in that case is usually 0.1 to 100 parts by mass per 100 parts by mass of water. It is about 15 parts by mass, preferably 5 to 12 parts by mass.
• the immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds.
• the temperature of the boric acid treatment is usually 50 ° C. or higher, preferably 50 to 85 ° C., and more preferably 60 to 80 ° C.
• the polyvinyl alcohol-based resin film after boric acid treatment is usually washed with water.
• the water washing treatment can be performed, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water.
• the temperature of water in the washing treatment is usually about 5 to 40 ° C.
• the immersion time is usually about 1 to 120 seconds.
• the drying process can be performed using, for example, a hot air dryer or a far-infrared heater.
• the temperature of the drying treatment is usually about 30 to 100 ° C, preferably 50 to 80 ° C.
• the drying treatment time is usually about 60 to 600 seconds, preferably 120 to 600 seconds.
• the moisture content of the polarizer is reduced to a practical level.
• the water content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. If the moisture content is less than 5% by weight, the polarizer loses its flexibility and the polarizer may be damaged or broken after its drying. Further, if the water content exceeds 20% by mass, the thermal stability of the polarizer may deteriorate.
• the thickness of the polarizer obtained by uniaxially stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying on the polyvinyl alcohol-based resin film is preferably 5 to 40 ⁇ m.
• Examples of the film coated with the dye having absorption anisotropy include a composition containing a dichroic dye having liquid crystal properties, a film obtained by applying a composition containing a dichroic dye and a polymerizable liquid crystal, and the like. Can be mentioned.
• the film preferably has a protective film on one or both sides thereof.
• Examples of the protective film include the same resin films as those exemplified above as the base material that can be used for producing the liquid crystal cured film.
• the film coated with the dye having absorption anisotropy is preferably thin, but if it is too thin, the strength is lowered and the processability tends to be inferior.
• the thickness of the film is usually 20 ⁇ m or less, preferably 5 ⁇ m or less, and more preferably 0.5 to 3 ⁇ m.
• film coated with the dye having absorption anisotropy include the films described in JP2012-33249A.
• a polarizing film can be obtained by laminating a transparent protective film on at least one surface of the polarizing element thus obtained via an adhesive.
• a transparent protective film a transparent film similar to the resin film exemplified above can be preferably used as a base material that can be used for producing a liquid crystal cured film.
• the elliptical polarizing plate of the present invention is configured to include the retardation plate and the polarizing film of the present invention.
• the retardation plate and the polarizing film of the present invention are combined with an adhesive layer or an adhesive layer.
• the elliptical polarizing plate of the present invention can be obtained by laminating through the polarizing plate.
• the retardation plate of the present invention including the horizontally oriented liquid crystal cured film and the polarizing film are laminated
• the slow axis (optical axis) of the horizontally oriented liquid crystal cured film constituting the retardation plate it is preferable to laminate the polarizing film so that the angle formed by the absorption shaft of the polarizing film is 45 ⁇ 5 °.
• the elliptical polarizing plate of the present invention may have a configuration provided by a conventional general elliptical polarizing plate, a polarizing film, and a retardation plate.
• a configuration for example, it is used for the purpose of protecting the surface of an adhesive layer (sheet) for bonding an elliptical polarizing plate to a display element such as an organic EL, a polarizing film or a retardation plate from scratches and stains.
• Protective film and the like may be used for the purpose of protecting the surface of an adhesive layer (sheet) for bonding an elliptical polarizing plate to a display element such as an organic EL, a polarizing film or a retardation plate from scratches and stains.
• the elliptical polarizing plate of the present invention can be used in various display devices.
• the display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source.
• Display devices include liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, electron emission display devices (for example, electric field emission display devices (FED), surface electric field emission display devices). (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection type display device (for example, grating light valve (GLV) display device, display device having a digital micromirror device (DMD)). ) And piezoelectric ceramic displays.
• EL organic electroluminescence
• EL inorganic electroluminescence
• touch panel display devices touch panel display devices
• electron emission display devices for example, electric field emission display devices (FED), surface electric field emission display devices).
• FED electric
• the liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, a projection type liquid crystal display device, and the like. These display devices may be display devices for displaying a two-dimensional image or may be a three-dimensional display device for displaying a three-dimensional image.
• the elliptical polarizing plate of the present invention may be an organic electroluminescence. It can be suitably used for an EL) display device and an inorganic electroluminescence (EL) display device, and the laminate of the present invention can be suitably used for a liquid crystal display device and a touch panel display device. These display devices have optical characteristics. By providing the elliptical polarizing plate of the present invention having excellent characteristics, good image display characteristics can be exhibited.
• Example 1 Production of liquid crystal mixture (A-1)
• a liquid crystal mixture represented by the following formula (A-1) (hereinafter referred to as "liquid crystal mixture (A-1)") was synthesized according to the following scheme.
• the obtained chloroform solution was added dropwise to heptane (manufactured by Wako Pure Chemical Industries, Ltd.) having a weight three times the weight of chloroform contained in the solution to precipitate a solid. Subsequently, the precipitated solid was removed by filtration, washed with 20 g of heptane three times, and then dried under reduced pressure at 40 ° C. to obtain 5.96 g of the liquid crystal mixture (A-1). The yield of the liquid crystal mixture (A-1) was 98% based on the compound (G-1).
• Example 2 Production of liquid crystal mixture (A-2)
• the compound represented by the following formula (E-3) is used, and the compound represented by the formula (E-1): the compound represented by the formula (E-1): formula (E-3)
• a liquid crystal mixture (A-2) was produced in the same manner as in Example 1 except that the molar ratio of the compound represented by (1) was 50:50.
• Example 3 Production of liquid crystal mixture (A-3)
• the compound represented by the following formula (E-3) is used, and the compound represented by the formula (E-2): the compound represented by the formula (E-2): formula (E-3).
• a liquid crystal mixture (A-3) was produced in the same manner as in Example 1 except that the molar ratio of the compound represented by (1) was 50:50.
• Example 4 Production of liquid crystal mixture (A-4)
• the compound represented by the formula (E-1) and the compound represented by the formula (E-2) the compound represented by the formula (E-3) shown below was used. Except that the molar ratios of the compound represented by the formula (E-1), the compound represented by the formula (E-2) and the compound represented by the formula (E-3) were equally divided, the same as in Example 1.
• a liquid crystal mixture (A-4) was produced in the same manner.
• Example 5 Production of liquid crystal mixture (A-5)
• a liquid crystal mixture (A-5) was produced in the same manner as in Example 1 except that the compound represented by the following formula (G-2) was used instead of the compound represented by the formula (G-1). did.
• Example 6 Production of liquid crystal mixture (A-6)
• a liquid crystal mixture (A-6) was produced in the same manner as in Example 2 except that the compound represented by the following formula (G-2) was used instead of the compound represented by the formula (G-1). did.
• Example 7 Production of liquid crystal mixture (A-7)
• a liquid crystal mixture (A-7) was produced in the same manner as in Example 3 except that the compound represented by the following formula (G-2) was used instead of the compound represented by the formula (G-1). did.
• Example 8 Production of liquid crystal mixture (A-8)
• a liquid crystal mixture (A-8) was produced in the same manner as in Example 4 except that the compound represented by the following formula (G-2) was used instead of the compound represented by the formula (G-1). did.
• Example 1 A polymerizable liquid crystal compound was synthesized in the same manner as in Example 1 except that 5.40 parts of the compound represented by the formula (E-1) was used without using the compound represented by the formula (E-2). did.
• Table 6 shows the obtained liquid crystal mixture and the polymerizable liquid crystal compound.
• the polymerizable liquid crystal compound contained in the liquid crystal mixture and the polymerizable liquid crystal compound synthesized in Comparative Examples 1 and 2 represent the compound represented by the following formula (I').
• (G1-1) and (G2-1) in Table 6 represent the following partial structures, respectively (* in the formula represents a bond with an oxygen atom).

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