WO2020066541A1 - Composition polymérisable à base de cristaux liquides et film de contraste de phase - Google Patents

Composition polymérisable à base de cristaux liquides et film de contraste de phase Download PDF

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WO2020066541A1
WO2020066541A1 PCT/JP2019/035092 JP2019035092W WO2020066541A1 WO 2020066541 A1 WO2020066541 A1 WO 2020066541A1 JP 2019035092 W JP2019035092 W JP 2019035092W WO 2020066541 A1 WO2020066541 A1 WO 2020066541A1
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group
carbon atoms
liquid crystal
ring
polymerizable liquid
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PCT/JP2019/035092
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Japanese (ja)
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伊藤　学
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日本ゼオン株式会社
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Definitions

  • the present invention relates to a polymerizable liquid crystal composition and a retardation film.
  • a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound is coated on a suitable substrate such as a resin film to form a layer, and the polymerizable liquid crystal compound is oriented in the polymerizable liquid crystal composition layer to form a polymerizable liquid crystal compound.
  • the layer is cured while maintaining the orientation of the liquid crystal compound to form a cured liquid crystal layer, thereby producing a retardation film (see Patent Document 1).
  • the molecular orientation is maintained in the liquid crystal cured layer.
  • devices such as an image display device to which the retardation film is applied have become thinner, and accordingly, a retardation film having a large birefringence ⁇ n has been required.
  • the retardation film may be used in a place where the temperature becomes high, such as in an automobile. Therefore, it is preferable that the retardation film has thermal durability, in which the optical properties are hardly changed even when exposed to a high temperature, and that the reduction rate of the in-plane retardation Re is particularly small. Is preferred.
  • a retardation film having (1) good molecular orientation, (2) large birefringence ⁇ n, and (3) thermal durability in a well-balanced manner; and a polymerizable liquid crystal composition capable of producing such a retardation film Things are required.
  • the inventors of the present invention have intensively studied to solve the above-mentioned problems. As a result, they have found that the above problem can be solved by a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, a specific crosslinking agent, and a polymerization initiator, and have completed the present invention. That is, the present invention provides the following.
  • a polymerizable liquid crystal composition including a polymerizable liquid crystal compound, a crosslinking agent having a cycloalkane structure, and a polymerization initiator.
  • the crosslinker contains a polymerizable group, and the polymerizable group equivalent of the crosslinker calculated by [crosslinker molecular weight] / [number of polymerizable groups per crosslinker molecule] is 10 or more and 1000 or less.
  • a retardation film having (1) good molecular orientation, (2) large birefringence ⁇ n, and (3) thermal durability in a well-balanced manner; and such a retardation film can be produced.
  • a polymerizable liquid crystal composition can be provided.
  • the “long” film refers to a film having a length of 5 times or more with respect to the width, preferably having a length of 10 times or more, and specifically, a roll.
  • the upper limit of the length of the film is not particularly limited, and may be, for example, 100,000 times or less the width.
  • the slow axis of the film or layer means the in-plane slow axis of the film or layer unless otherwise specified.
  • the oblique direction of a long film refers to an in-plane direction of the film and a direction that is neither parallel nor perpendicular to the longitudinal direction of the film, unless otherwise specified.
  • a material having a positive intrinsic birefringence means a material whose refractive index in the stretching direction is larger than that in the direction perpendicular thereto unless otherwise specified.
  • a material having a negative intrinsic birefringence means a material whose refractive index in a stretching direction is smaller than a refractive index in a direction perpendicular thereto unless otherwise specified.
  • the value of the intrinsic birefringence can be calculated from the permittivity distribution.
  • nx represents the refractive index in the direction (in-plane direction) perpendicular to the thickness direction of the layer and in the direction giving the maximum refractive index.
  • ny represents the refractive index in the in-plane direction of the layer and in a direction perpendicular to the direction of nx.
  • nz represents the refractive index in the thickness direction of the layer.
  • d represents the thickness of the layer.
  • the measurement wavelength is 590 nm unless otherwise specified.
  • the birefringence ⁇ n is usually a value (Re / d) obtained by dividing the in-plane retardation Re by d.
  • inverse wavelength dispersion characteristics refer to in-plane retardation Re (450) at a wavelength of 450 nm, in-plane retardation Re (550) at a wavelength of 550 nm, and in-plane retardation at a wavelength of 650 nm unless otherwise specified.
  • the retardation Re (650) refers to a property satisfying the following formulas (1) and (2). Re (450) / Re (550) ⁇ 1.00 (1) Re (650) / Re (550)> 1.00 (2)
  • the directions of the elements are “parallel”, “vertical” and “orthogonal”, unless otherwise specified, within a range that does not impair the effects of the present invention, for example, ⁇ 3 °, ⁇ 2 ° or ⁇ 1 °. May be included.
  • (meth) acryloyl includes methacryloyl, acryloyl, and combinations thereof
  • (meth) acryloyloxy includes methacryloyloxy, acryloyloxy, and combinations thereof. I do.
  • the polymerizable liquid crystal composition of the present embodiment includes a polymerizable liquid crystal compound, a crosslinking agent having a cycloalkane structure, and a polymerization initiator.
  • the polymerizable liquid crystal composition may contain a compound that does not itself undergo a polymerization reaction (eg, a surfactant).
  • a liquid crystal compound is a compound that can exhibit a liquid crystal phase when blended and aligned in a composition.
  • the polymerizable liquid crystal compound is a liquid crystal compound which can be polymerized in a composition in a state of exhibiting such a liquid crystal phase and become a polymer while maintaining the orientation of molecules in the liquid crystal phase.
  • the polymerizable liquid crystal compound usually contains a polymerizable group and a mesogen structure.
  • the polymerizable group (also referred to as a polymerizable functional group) means a group that can be polymerized under polymerization conditions such as radical polymerization and ionic polymerization (anionic polymerization and cationic polymerization).
  • the polymerizable group is preferably a monovalent group.
  • Examples of the polymerizable group that may be included in the polymerizable liquid crystal compound include a radical polymerizable group that can be polymerized under radical polymerization conditions, such as a vinyl group, an isocyanate group, a (meth) acryloyl group, and a (meth) acryloyloxy group;
  • Examples include an ionic polymerizable group such as a group that can be polymerized under ionic polymerization conditions, preferably a radical polymerizable group, and more preferably a (meth) acryloyloxy group.
  • the number of such polymerizable groups in one molecule of the polymerizable liquid crystal compound is generally 2 or more, preferably 2 or more, 6 or less, more preferably 2 or more and 4 or less, and further preferably 2 or more.
  • the polymerizable group may be directly bonded to a ring structure that can be included in the polymerizable liquid crystal compound, or may be bonded to the ring structure via a linking group.
  • the ring structure that can be included in the polymerizable liquid crystal compound will be described later.
  • a mesogenic structure is a rigid structure that imparts liquid crystallinity and orientation to a compound having the structure, and usually includes two or more independent ring structures, and the ring structure is a single bond or an sp1 hybrid orbital or an sp2 hybrid orbital. Is a structure linked by a linking group having The group having the sp1 hybrid orbital and the group having the sp2 hybrid orbital are preferably divalent groups.
  • the independent ring structure of the mesogen structure may have a substituent.
  • the ring structure include an alicyclic (also referred to as cycloaliphatic) structure which may have a substituent, an aromatic hydrocarbon structure which may have a substituent, and a substituent. And an aromatic heterocyclic structure which may have a substituent.
  • Examples of the alicyclic structure include monocyclic alicyclic structures having 5 to 20 carbon atoms (eg, cyclopentane ring structure, cyclohexane ring structure, cycloheptane ring structure, cyclooctane ring structure); A bicyclic alicyclic structure (eg, decahydronaphthalene, adamantane) represented by Formulas 5 to 20; and a polycyclic alicyclic structure having three or more rings.
  • the alicyclic structure may be a saturated alicyclic structure or an alicyclic structure containing an unsaturated bond, but a saturated alicyclic structure is preferred.
  • alicyclic structure a cyclohexane ring structure is more preferred, and a cyclohexane-1,4-diyl group is still more preferred.
  • the alicyclic structure may be contained in the mesogen structure as a trans form, may be contained in the mesogen structure as a cis form, or may be contained in the mesogen structure as a mixture of the cis form and the trans form. . Among them, it is preferable that the trans-form is included in the mesogen structure.
  • the aromatic hydrocarbon structure examples include an aromatic hydrocarbon structure having 6 to 20 carbon atoms, such as a benzene ring structure and a naphthalene ring structure.
  • a benzene ring structure is preferable, and a 1,4-phenylene group is more preferable.
  • the aromatic hydrocarbon structure means a hydrocarbon structure in which at least one ring constituting the aromatic hydrocarbon structure has aromaticity, and all the rings constituting the aromatic hydrocarbon structure are aromatic. It does not have to have a family.
  • non-aromatic heterocyclic structure examples include a piperidine ring structure, a piperazine ring structure, a morpholine ring structure, a tetrahydrofuran ring structure, a tetrahydropyran ring structure, a dioxane ring structure, a 1,3-dithiolane ring structure, a pyrrolidine ring structure, and the like.
  • examples thereof include a non-aromatic heterocyclic structure having 2 to 20 carbon atoms.
  • aromatic heterocyclic structure examples include a pyrrole ring structure, a diazole ring structure, a triazole ring structure, an oxazole ring structure, a pyridine ring structure, a pyrazine ring structure, a pyrimidine ring structure, a quinoline ring structure, a furan ring structure, a thiophene ring structure, Benzothiazole ring structure, Benzoisoxazole ring structure, Benzoisothiazole ring structure, Benzimidazole ring structure, Benzoxadiazole ring structure, Benzoxazole ring structure, Benzothiadiazole ring structure, Benzothiophene ring structure, Benzotriazine ring structure, Benzo Examples include an aromatic heterocyclic structure having 2 to 20 carbon atoms such as a triazole ring structure, a benzopyrazole ring structure, and a benzopyranone ring structure,
  • Examples of the substituent which the ring structure may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a cyano group.
  • the number of these substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • the number of such independent ring structures in the mesogenic structure is usually 2 to 20, preferably 3 to 15, more preferably 5 to 9.
  • ⁇ ⁇ In the polymerizable liquid crystal compound used in the present embodiment, two or more such independent ring structures are linked by a single bond or a linking group having an sp1 hybrid orbital or an sp2 hybrid orbital. Therefore, a structure in which a plurality of benzene rings such as biphenyl and terphenyl are connected by a single bond, and a structure in which a benzene ring and an alicyclic structure such as a cyclohexane ring are connected by a single bond can be a mesogenic structure.
  • the aromatic ring structure may be an aromatic hydrocarbon structure or an aromatic heterocyclic structure, but is preferably an aromatic hydrocarbon structure.
  • Examples of the group having a psp1 hybrid orbital include a group represented by —C ⁇ C—.
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R ′′ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms which may have a substituent.
  • Examples of the alkyl group having 1 to 20 carbon atoms in R ′′ and the substituent that the alkyl group (he) may have include monovalent groups having 6 to 20 carbon atoms such as phenyl, naphthyl, and fluorenyl.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • the polymerizable liquid crystal compound used in the present embodiment is not particularly limited as long as it has the polymerizable group and the mesogen structure, but preferably has a plurality of terminal polymerizable groups and the plurality of terminal polymerizable groups. A region between the groups (hereinafter, referred to as “main chain”) has a mesogen structure.
  • the polymerizable liquid crystal compound of the present embodiment may have a group whose terminal is not a polymerizable group (hereinafter, referred to as “side chain”) bonded to the main chain, and the mesogen structure is included in the side chain. You may go out.
  • the polymerizable liquid crystal compound has a main chain and a side chain bonded to the ring structure of the main chain, preferably, a ring structure contained in one main chain around the ring structure to which the side chain is bonded, and the other Have the same number of ring structures in the main chain. That is, the polymerizable liquid crystal compound has a structure in which the main chain has (2n + 1) ring structures, and the side chain is bonded to the (n + 1) th ring structure counted from one end of the main chain.
  • n is an integer of 1 or more.
  • n is preferably an integer of 1 or more and 10 or less, more preferably an integer of 2 or more and 4 or less, and particularly preferably 2.
  • the (n + 1) th ring structure counted from one end of the main chain includes an alicyclic structure, an aromatic hydrocarbon structure, a non-aromatic heterocyclic structure, an aromatic heterocyclic structure, and the like, and is preferable.
  • an alicyclic structure, an aromatic hydrocarbon structure, or an aromatic heterocyclic structure more preferably an aromatic ring structure such as an aromatic hydrocarbon structure or an aromatic heterocyclic structure, and particularly preferably.
  • a benzene ring structure and most preferably a 1,4-phenylene group.
  • n-th and (n + 2) -th ring structures counted from one end of the main chain are preferably both alicyclic structures, more preferably both cyclohexane structures, and both cyclohexane- Particularly preferred is a 1,4-diyl group.
  • the plurality of independent ring structures of the main chain are usually connected by a single bond, a group having an sp1 hybrid orbital, or a group having an sp2 hybrid orbital.
  • the linking group is preferably a divalent group.
  • the side chain bonded to the main chain may or may not include an independent ring structure, but preferably includes an independent ring structure.
  • the side chain ring structure is not particularly limited, but includes an alicyclic structure, an aromatic hydrocarbon structure, a non-aromatic heterocyclic structure, and an aromatic heterocyclic structure, and is preferably an aromatic hydrocarbon ring.
  • An aromatic ring structure such as a structure or an aromatic heterocyclic structure.
  • aromatic ring structure examples include a fluorene ring structure, a naphthalene ring structure, a benzoxazole ring structure, a benzothiazole ring structure, a naphtho [1,2-d] thiazole ring structure, and a naphtho [2,1-d] thiazole ring structure.
  • the ring structure of the side chain is usually linked to one of the ring structures of the main chain by a single bond or a linking group.
  • the linking group that bonds the ring structure of the side chain (preferably the aromatic ring structure) to one of the ring structures of the main chain may be any of sp1 hybrid orbital, sp2 hybrid orbital, and sp3 hybrid orbital linking group.
  • R ′′ is as defined above.
  • R hc represents an organic group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms; It is preferably a group represented by Rh described below, and more preferably a benzothiazol-2-yl group which may have a substituent.
  • R ′′ is as defined above.
  • R ′′ is preferably a group represented by R g described below, and may be an alkyl group having 1 to 20 carbon atoms which may have a substituent; or an alkyl group having a substituent (he) And more preferably an alkyl group having a substituent (he).
  • the substituent of the alkyl group (he) is preferably one or more selected from the group consisting of a phenyl group, a naphthyl group, a fluorenyl group, and a xanthenyl group, and more preferably a naphthyl group.
  • the substituent is preferably bonded to a terminal carbon atom of an alkyl group having 1 to 20 carbon atoms; or a terminal carbon atom, terminal oxygen atom or terminal sulfur atom of the alkyl group (he).
  • the liquid crystallinity and orientation of the polymerizable liquid crystal compound used in the present embodiment may be, for example, a coating substrate (for example, A coating liquid containing a compound is applied to a rubbed surface of a polyimide film for a horizontal alignment film) to form a coating film.
  • a coating substrate for example, A coating liquid containing a compound is applied to a rubbed surface of a polyimide film for a horizontal alignment film
  • the coating film (1) flows It can be confirmed by having a temperature region that simultaneously exhibits the properties and (2) birefringence.
  • a sample plate was prepared by sandwiching a compound between two glass plates provided with a rubbed polyimide horizontal alignment film, and the sample plate was heated from room temperature to 200 ° C. using a hot stage (10 ° C.). / Min) and then cooling from 200 ° C. to room temperature (10 ° C./min), it was confirmed that the compound film had a temperature region that simultaneously exhibited (1) fluidity and (2) birefringence. I do.
  • phase difference and the film thickness in the in-plane direction of the sample plate are measured while changing the temperature, and the value at each temperature can be calculated from the obtained phase difference and the film thickness.
  • the phase difference can be measured by a phase difference measuring device (for example, AXOMETRICS “Axo @ Scan”).
  • the film thickness can be measured by a light interference type film thickness meter (for example, manufactured by Filmetrics).
  • the molecular weight of the polymerizable liquid crystal compound is preferably 300 or more, more preferably 500 or more, particularly preferably 800 or more, preferably 2000 or less, more preferably 1700 or less, and particularly preferably 1500 or less.
  • the polymerizable liquid crystal composition may contain one kind of the polymerizable liquid crystal compound alone, or may contain two or more kinds of the compound in an arbitrary ratio.
  • the polymerizable liquid crystal compound used in the present embodiment may be a reverse wavelength dispersive polymerizable liquid crystal compound, and is preferably a reverse wavelength dispersive polymerizable liquid crystal compound.
  • the reverse wavelength dispersive polymerizable liquid crystal compound refers to a polymerizable liquid crystal compound in which, when a polymer is obtained by homogenous alignment, the obtained polymer exhibits reverse wavelength dispersion characteristics.
  • the fact that the polymerizable liquid crystal compound has reverse wavelength dispersion can be confirmed by the following method.
  • a liquid crystal composition containing a polymerizable liquid crystal compound, a surfactant, and a solvent is prepared.
  • a liquid crystal composition is applied to a coating base material having an alignment control force applied to the surface to form a coating film, and the coating film is dried to form a polymerizable liquid crystal compound layer.
  • In-plane retardation Re (450), Re (550), and Re (650) were measured, and Re (450) / Re (550) ⁇ 1.00, and Re (650) / Re (550)> 1. Check that it is .00.
  • the polymerizable liquid crystal compound is preferably a compound represented by the following formula (I).
  • the compound represented by the formula (I) can exhibit reverse wavelength dispersion characteristics.
  • Ar is 1H-isoindole-1,3 (2H) -dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, imidazole ring, indole ring, oxadiazole ring, oxazole ring, oxazolopyrazine ring, Oxazolopyridin ring, oxazolopyridazyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, thiazolopyrazine ring, thiazolopyridine ring, thiazolopyridazine ring, Thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthyridine ring, pyra
  • Ar represents a divalent organic group having 6 to 67 carbon atoms.
  • Preferred examples of Ar include groups represented by any of the following formulas (II-1) to (II-7).
  • * represents a bonding position to Z 1 or Z 2 .
  • E 1 and E 2 are each independently —CR 11 R 12 —, —S—, —NR 11 —, —CO— and —.
  • R 11 and R 12 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • E 1 and E 2 are preferably each independently —S—.
  • D 1 to D 3 each independently represent an aromatic hydrocarbon ring group which may have a substituent or a substituent. Represents an aromatic heterocyclic group which may be possessed.
  • the number of carbon atoms of the group represented by D 1 to D 3 is, independently of each other, usually 2 to 100.
  • the number of carbon atoms of the aromatic hydrocarbon ring group in D 1 to D 3 is preferably 6 to 30.
  • Examples of the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D 1 to D 3 include a phenyl group and a naphthyl group. Among them, a phenyl group is more preferred as the aromatic hydrocarbon ring group.
  • Examples of the substituent which the aromatic hydrocarbon ring group represented by D 1 to D 3 may have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; and a carbon atom number such as a methyl group, an ethyl group and a propyl group.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • Ra is an alkyl group having 1 to 6 carbon atoms; and an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, which may have a substituent.
  • aromatic hydrocarbon ring groups To 20 aromatic hydrocarbon ring groups;
  • R b is an alkyl group having 1 to 20 carbon atoms which may have a substituent; an alkenyl group having 2 to 20 carbon atoms which may have a substituent; A cycloalkyl group having 3 to 12 carbon atoms; and an aromatic hydrocarbon ring group having 6 to 12 carbon atoms which may have a substituent.
  • the number of carbon atoms of the alkyl group having 1 to 20 carbon atoms in R b is preferably 1 to 12, more preferably 4 to 10.
  • Examples of the alkyl group having 1 to 20 carbon atoms for R b include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a 1-methylpentyl group, and a 1-ethylpentyl group.
  • Examples of the substituent which the alkyl group having 1 to 20 carbon atoms in R b may have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a dimethylamino group and the like having 2 to 12 carbon atoms.
  • N, N-dialkylamino group C1-C20 alkoxy group such as methoxy group, ethoxy group, isopropoxy group, butoxy group; C1-C12 alkoxy group such as methoxymethoxy group, methoxyethoxy group An alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; a triazolyl group, a pyrrolyl group, a furanyl group; An aromatic heterocyclic group having 2 to 20 carbon atoms such as a thienyl group, a thiazolyl group, a benzothiazol-2-ylthio group; a cyclopropyl group, a cyclopentyl group, A cycloalkyl group having 3 to 8 carbon atoms such as a cyclohexyl group; a
  • the number of carbon atoms of the alkenyl group having 2 to 20 carbon atoms in R b is preferably 2 to 12.
  • Examples of the alkenyl group having 2 to 20 carbon atoms for R b include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, undecenyl and the like.
  • Dodecenyl tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, and icosenyl groups.
  • Examples of the substituent which may have an alkenyl group having 2 to 20 carbon atoms in R b include the same examples as the substituent group which may have an alkyl group having 1 to 20 carbon atoms in R b.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms for R b include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like. Especially, as a cycloalkyl group, a cyclopentyl group and a cyclohexyl group are preferable.
  • Examples of the substituent which the cycloalkyl group having 3 to 12 carbon atoms in R b may have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a carbon atom having 2 to 12 carbon atoms such as a dimethylamino group.
  • substituent of the cycloalkyl group include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; a methoxy group and an ethoxy group.
  • a C1-C6 alkoxy group such as a group or isopropoxy group; a nitro group; and a C6-C20 aromatic hydrocarbon ring group such as a phenyl group or a naphthyl group.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • Examples of the aromatic hydrocarbon ring group having 6 to 12 carbon atoms for R b include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Among them, a phenyl group is preferred as the aromatic hydrocarbon ring group.
  • Examples of the substituent which the aromatic hydrocarbon ring group having 6 to 12 carbon atoms in R b may have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a carbon atom such as a dimethylamino group.
  • the substituent of the aromatic hydrocarbon ring group includes a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a carbon atom having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group and a butoxy group.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • the aromatic heterocyclic group in D 1 to D 3 preferably has 2 to 30 carbon atoms.
  • Examples of the aromatic heterocyclic group having 2 to 30 carbon atoms for D 1 to D 3 include a 1-benzofuranyl group, a 2-benzofuranyl group, an imidazolyl group, an indolinyl group, a flazanyl group, an oxazolyl group, a quinolyl group, and a thiadiazolyl group.
  • examples of the aromatic heterocyclic group include monocyclic aromatic heterocyclic groups such as a furanyl group, a pyranyl group, a thienyl group, an oxazolyl group, a furazanyl group, a thiazolyl group, and a thiadiazolyl group; Zolyl group, quinolyl group, 1-benzofuranyl group, 2-benzofuranyl group, phthalimide group, benzo [c] thienyl group, benzo [b] thienyl group, thiazolopyridyl group, thiazolopyrazinyl group, benzoisoxazolyl And an aromatic heterocyclic group having a condensed ring, such as a benzyl group, a benzooxadiazolyl group, or a benzothiadiazolyl group.
  • monocyclic aromatic heterocyclic groups such as a furanyl group, a pyranyl group, a thienyl group, an
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • D 4 to D 5 each independently represent an acyclic group which may have a substituent. D 4 and D 5 may form a ring together with the carbon atom to which they are attached.
  • the number of carbon atoms of the group represented by D 4 to D 5 is, independently of each other, usually 1 to 100.
  • the number of carbon atoms of the acyclic group in D 4 to D 5 is preferably 1 to 13.
  • Examples of the acyclic group for D 4 to D 5 include an alkyl group having 1 to 6 carbon atoms; a cyano group; a carboxyl group; a fluoroalkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms.
  • Rx represents an organic group having 1 to 12 carbon atoms. Specific examples of R x include an alkoxy group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxyl group.
  • Examples of the substituent which the non-cyclic group represented by D 4 to D 5 may have include, for example, the same examples as the substituents which the aromatic hydrocarbon ring group represented by D 1 to D 3 may have.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • D 4 and D 5 When D 4 and D 5 together with the carbon atom to which they are attached form a ring, D 4 and D 5 form an organic group containing a ring.
  • the organic group include a group represented by the following formula. In the following formula, * represents the position of the carbon to which D 4 and D 5 are bonded.
  • R * represents an alkyl group having 1 to 3 carbon atoms.
  • R ** represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a phenyl group which may have a substituent.
  • R ** represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a phenyl group which may have a substituent.
  • R **** is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, hydroxyl group, and represents a group selected from the group consisting of -COOR 13.
  • R 13 represents an alkyl group having 1 to 3 carbon atoms.
  • substituents which the phenyl group may have include, for example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a cyano group and an amino group Is mentioned.
  • a halogen atom, an alkyl group, a cyano group and an alkoxy group are preferred as the substituent.
  • the number of substituents in the phenyl group may be one or more. Further, the plurality of substituents may be the same or different.
  • the number of carbon atoms of the group represented by D 6 (including the number of carbon atoms of the substituent) is usually from 3 to 100.
  • R f represents a group selected from the group consisting of a hydrogen atom; and an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • R g represents a group selected from the group consisting of a hydrogen atom; and an organic group having 1 to 30 carbon atoms which may have a substituent.
  • the preferred range of the number of carbon atoms of the alkyl group having 1 to 20 carbon atoms in R g and examples thereof are the same as the alkyl group having 1 to 20 carbon atoms in R b .
  • Examples of the substituent that the alkyl group having 1 to 20 carbon atoms in R g may have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a dimethylamino group and the like having 2 to 12 carbon atoms.
  • N, N-dialkylamino group C1-C20 alkoxy group such as methoxy group, ethoxy group, isopropoxy group, butoxy group; C1-C12 alkoxy group such as methoxymethoxy group, methoxyethoxy group An alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; a triazolyl group, a pyrrolyl group, a furanyl group; An aromatic heterocyclic group having 2 to 20 carbon atoms such as a thiophenyl group; a cycloalkyl having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group; Alkyl group; cycloalkyloxy group having 3 to 8 carbon atoms such as cycl
  • the preferred range of the number of carbon atoms of the alkenyl group having 2 to 20 carbon atoms in R g and examples thereof are the same as the alkenyl group having 2 to 20 carbon atoms in R b .
  • Examples of the substituent which may have an alkenyl group having 2 to 20 carbon atoms in R g include the same examples as the substituent group which may have an alkyl group having 1 to 20 carbon atoms in R g.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • the alkynyl group having 2 to 20 carbon atoms in R g includes, for example, ethynyl group, propynyl group, 2-propynyl group (propargyl group), butynyl group, 2-butynyl group, 3-butynyl group, pentynyl group, 2- Examples include a pentynyl group, a hexynyl group, a 5-hexynyl group, a heptynyl group, an octynyl group, a 2-octynyl group, a nonanyl group, a decanyl group, and a 7-decanyl group.
  • Examples of the substituent which may have an alkynyl group having 2 to 20 carbon atoms in R g include the same examples as the substituent group which may have an alkyl group having 1 to 20 carbon atoms in R g.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms in R g include the same examples as the cycloalkyl group having 3 to 12 carbon atoms in R b .
  • Examples of the substituent which may have a cycloalkyl group having 3 to 12 carbon atoms in R g include the same examples as the substituent group which may have an alkyl group having 1 to 20 carbon atoms in R g.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • Examples of the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R g include the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D 1 to D 3 .
  • Examples of the substituent which the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R g may have include the same examples as the substituents which the aromatic hydrocarbon ring group having D 1 to D 3 may have.
  • Examples of the aromatic heterocyclic group having 2 to 30 carbon atoms in R g include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in D 1 to D 3 .
  • Examples of the substituent that the aromatic heterocyclic group having 2 to 30 carbon atoms in R g may have include, for example, the same examples as the substituents that the aromatic hydrocarbon ring group of D 1 to D 3 may have. .
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • G x is a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; and a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent.
  • R 14 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the “divalent aliphatic hydrocarbon group” is preferably a divalent chain aliphatic hydro
  • F x represents an organic group having at least one aromatic hydrocarbon ring and aromatic heterocyclic ring.
  • the number of carbon atoms of this organic group is preferably 2 or more, more preferably 7 or more, still more preferably 8 or more, particularly preferably 10 or more, and preferably 30 or less.
  • the number of carbon atoms of the organic group does not include the carbon atom of the substituent.
  • Examples of the aromatic hydrocarbon ring in F x e.g., a benzene ring, a naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, a fluorene ring, an aromatic hydrocarbon ring having 6 to 30 carbon atoms.
  • Fx has a plurality of aromatic hydrocarbon rings
  • the plurality of aromatic hydrocarbon rings may be the same as or different from each other.
  • Aromatic hydrocarbon ring in F x may have a substituent.
  • substituent which may have an aromatic hydrocarbon ring in F x e.g., fluorine atom, such as chlorine atom, a halogen atom; a cyano group; a methyl group, an ethyl group, and propyl group, C 1 -C 1-6
  • An alkyl group having 2 to 6 carbon atoms such as a vinyl group and an allyl group; a halogenated alkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group and a pentafluoroethyl group; a dimethylamino group and the like
  • An N, N-dialkylamino group having 2 to 12 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group; a nitro group; -OCF 3 ; -C ( O)
  • Examples of the aromatic heterocyclic ring in F x include 1H-isoindole-1,3 (2H) -dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, imidazole ring, indole ring, oxa ring Diazole ring, oxazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyridazyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, thiazolopyrazine Ring, thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring,
  • the aromatic heterocyclic ring in F x may have a substituent.
  • substituents that the aromatic heterocyclic ring in F x may have include, for example, the same examples as the substituents that the aromatic hydrocarbon ring in F x may have.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • F x include “a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic hetero ring and having 2 to 20 carbon atoms, which may have a substituent”.
  • this cyclic group may be appropriately referred to as “cyclic group (a)”.
  • Examples of the substituent which the cyclic group (a) may have include the same examples as the substituent an aromatic hydrocarbon ring in F x may have.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • cyclic group (a) include an optionally substituted hydrocarbon ring group having 6 to 20 carbon atoms and having at least one aromatic hydrocarbon ring having 6 to 18 carbon atoms. No. Hereinafter, this hydrocarbon ring group may be appropriately referred to as “hydrocarbon ring group (a1)”.
  • hydrocarbon ring group (a1) examples include a phenyl group (C6), a naphthyl group (C10), an anthracenyl group (C14), a phenanthrenyl group (C14), and a pyrenyl group.
  • C16 fluorenyl (C13), indanyl (C9), 1,2,3,4-tetrahydronaphthyl (C10), 1,4-dihydronaphthyl
  • hydrocarbon ring group (a1) examples include groups represented by the following formulas (1-1) to (1-21). Further, these groups may have a substituent.
  • "-" means, extending from an arbitrary position of the ring, represents a bond to Y x.
  • cyclic group (a) has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring having 6 to 18 carbon atoms and an aromatic heterocyclic ring having 2 to 18 carbon atoms. And a heterocyclic group having 2 to 20 carbon atoms which may have a substituent.
  • this heterocyclic group may be appropriately referred to as “heterocyclic group (a2)”.
  • heterocyclic group (a2) examples include a phthalimide group, a 1-benzofuranyl group, a 2-benzofuranyl group, an acridinyl group, an isoquinolinyl group, an imidazolyl group, an indolinyl group, a furazanyl group, an oxazolyl group, an oxazolopyrazinyl group, Zolopyridinyl group, oxazolopyridazinyl group, oxazolopyrimidinyl group, quinazolinyl group, quinoxalinyl group, quinolyl group, cinnolinyl group, thiadiazolyl group, thiazolyl group, thiazolopyrazinyl group, thiazolopyridinyl group , Thiazolopyridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naph
  • heterocyclic group (a2) examples include groups represented by the following formulas (2-1) to (2-51). Further, these groups may have a substituent.
  • "-" means, extending from an arbitrary position of the ring, represents a bond to Y x.
  • X represents -CH 2- , -NR c- , an oxygen atom, a sulfur atom, -SO- or -SO 2- .
  • Y and Z each independently represent -NR c- , an oxygen atom, a sulfur atom, -SO- or -SO 2- .
  • E represents -NR c- , an oxygen atom or a sulfur atom.
  • R c represents a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group (provided that an oxygen atom, a sulfur atom, -SO- , —SO 2 — are not adjacent to each other.)
  • F x “a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring and having 2 to 20 carbon atoms, which may have a substituent, and at least one of An alkyl group having 1 to 18 carbon atoms, which is substituted by a hydrogen atom and may have a substituent other than the cyclic group.
  • this substituted alkyl group may be appropriately referred to as “substituted alkyl group (b)”.
  • alkyl group having 1 to 18 carbon atoms in the substituted alkyl group (b) examples include a methyl group, an ethyl group, a propyl group and an isopropyl group.
  • the “cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring and having 2 to 20 carbon atoms which may have a substituent” includes, for example, a cyclic group
  • the groups in the range described as the group (a) are exemplified.
  • the “optionally substituted cyclic group having 2 to 20 carbon atoms having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring” in the substituted alkyl group (b) includes a fluorenyl group A group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring such as a benzothiazolyl group; an optionally substituted aromatic hydrocarbon ring group; an optionally substituted aromatic heterocyclic group; And a group consisting of an optionally substituted aromatic heterocycle having a linking group.
  • Preferred examples of the aromatic hydrocarbon ring group in the substituted alkyl group (b) include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a fluorenyl group. And a hydrogen ring group.
  • the aromatic hydrocarbon ring group in the substituted alkyl group (b) may have a substituent.
  • substituents include the same examples as the substituent an aromatic hydrocarbon ring in F x may have.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • Preferred examples of the aromatic heterocyclic group in the substituted alkyl group (b) include a phthalimido group, a 1-benzofuranyl group, a 2-benzofuranyl group, an acridinyl group, an isoquinolinyl group, an imidazolyl group, an indolinyl group, a furazanyl group, an oxazolyl group, Zolopyrazinyl, oxazolopyridinyl, oxazolopyridazinyl, oxazolopyrimidinyl, quinazolinyl, quinoxalinyl, quinolyl, cinnolinyl, thiadiazolyl, thiazolyl, thiazolopyrazinyl , Thiazolopyridyl, thiazolopyridazinyl, thiazolopyrimidinyl, thienyl, triazinyl, triazolyl, naphthyridinyl
  • the aromatic heterocyclic group in the substituted alkyl group (b) may have a substituent.
  • substituents include the same examples as the substituent an aromatic hydrocarbon ring in F x may have.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • Examples of the “group consisting of an aromatic hydrocarbon ring having a linking group” and the “group consisting of an aromatic heterocycle having a linking group” in the substituted alkyl group (b) include, for example, a phenylthio group, a naphthylthio group, an anthracenylthio group Phenanthrenylthio group, pyrenylthio group, fluorenylthio group, phenyloxy group, naphthyloxy group, anthracenyloxy group, phenanthrenyloxy group, pyrenyloxy group, fluorenyloxy group, benzoisoxazolylthio group, Benzoisothiazolylthio, benzooxadiazolylthio, benzoxazolylthio, benzothiadiazolylthio, benzothiazolylthio, benzothienylthio, benzoisoxazolyloxy, benzoisothiazolyl Oxy group
  • the “group consisting of an aromatic hydrocarbon ring having a linking group” and the “group consisting of an aromatic heterocycle having a linking group” in the substituted alkyl group (b) may each have a substituent.
  • substituents include the same examples as the substituent an aromatic hydrocarbon ring in F x may have.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • substituted alkyl group (b) examples include groups represented by the following formulas (3-1) to (3-11). Further, these groups may have a substituent.
  • "-" means, extending from an arbitrary position of the ring, represents a bond to Y x.
  • * represents a bonding position.
  • F x is preferably a group represented by any of the following formulas (i-1) to (i-9).
  • F x is a group represented by any of the following formulas (i-1) to (i-13). It is preferred that The groups represented by the following formulas (i-1) to (i-13) may have a substituent. In the following formula, * represents a bonding position.
  • F x is particularly preferably a group represented by any one of the following formulas (ii-1) ⁇ (ii -18).
  • F x is a group represented by any of the following formulas (ii-1) to (ii-24) Is particularly preferred.
  • the groups represented by the following formulas (ii-1) to (ii-24) may have a substituent.
  • the meaning of Y is as described above.
  • * represents a bonding position.
  • the total number of ⁇ electrons contained in the ring structure in F x is preferably 8 or more, more preferably 10 or more, and 20 or less. And more preferably 18 or less.
  • the total number of ⁇ electrons contained in the ring structure in F x is preferably 4 or more, and more preferably 6 or more. More preferably, it is preferably 20 or less, more preferably 18 or less.
  • R h is, having one or more aromatic rings selected from the group consisting of aromatic heterocyclic aromatic hydrocarbon ring and 2 to 30 carbon atoms of 6 to 30 carbon atoms, represents an organic group.
  • R h has an aromatic hydrocarbon ring (1) one or more carbon atoms 6-30, hydrocarbon ring group having 6 to 40 carbon atoms, and the like.
  • the hydrocarbon ring group having an aromatic hydrocarbon ring may be appropriately referred to as “(1) hydrocarbon ring group”.
  • (1) specific examples of the hydrocarbon ring group include the following groups.
  • the hydrocarbon ring group may have a substituent.
  • substituents which the hydrocarbon ring group may have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a C1 to C6 group such as a methyl group, an ethyl group and a propyl group.
  • the meanings of Ra and Rb are as described above.
  • a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • R h has one or more aromatic ring selected from the group consisting of (2) of carbon atoms 6-30 aromatic hydrocarbon ring and aromatic heterocyclic ring having 2 to 30 carbon atoms And a heterocyclic group having 2 to 40 carbon atoms.
  • the heterocyclic group having an aromatic ring may be appropriately referred to as “(2) heterocyclic group”.
  • (2) Specific examples of the heterocyclic group include the following groups.
  • R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the heterocyclic group may have a substituent.
  • substituents that the (2) heterocyclic group may have include, for example, the same examples as the substituents that the (1) hydrocarbon ring group may have.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • R h is (3) one or more groups selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group having 2 to 30 carbon atoms of 6 to 30 carbon atoms And an alkyl group having 1 to 12 carbon atoms.
  • this substituted alkyl group may be appropriately referred to as “(3) substituted alkyl group”.
  • Examples of the “alkyl group having 1 to 12 carbon atoms” in the substituted alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • Examples of the “aromatic hydrocarbon ring group having 6 to 30 carbon atoms” in the substituted alkyl group include, for example, the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D 1 to D 3 .
  • No. (3) Examples of the “aromatic heterocyclic group having 2 to 30 carbon atoms” in the substituted alkyl group include, for example, the same examples as the aromatic heterocyclic groups having 2 to 30 carbon atoms in D 1 to D 3 . .
  • the substituted alkyl group may further have a substituent.
  • substituents that the (3) substituted alkyl group may have include, for example, the same examples as the substituents that the (1) hydrocarbon ring group may have.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • R h is (4) one or more groups selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group having 2 to 30 carbon atoms of 6 to 30 carbon atoms And an alkenyl group having 2 to 12 carbon atoms.
  • this substituted alkenyl group may be referred to as “(4) substituted alkenyl group” as appropriate.
  • Examples of the “alkenyl group having 2 to 12 carbon atoms” in the substituted alkenyl group include a vinyl group and an allyl group.
  • Examples of the “aromatic hydrocarbon ring group having 6 to 30 carbon atoms” in the substituted alkenyl group include, for example, the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D 1 to D 3 .
  • No. (4) Examples of the “aromatic heterocyclic group having 2 to 30 carbon atoms” in the substituted alkenyl group include, for example, the same examples as the aromatic heterocyclic groups having 2 to 30 carbon atoms in D 1 to D 3 . .
  • the substituted alkenyl group may further have a substituent.
  • substituents that the substituted alkenyl group may have include, for example, the same examples as the substituents that the (1) hydrocarbon ring group may have.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • R h is (5) one or more groups selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group having 2 to 30 carbon atoms of 6 to 30 carbon atoms And alkynyl groups having 2 to 12 carbon atoms.
  • This substituted alkynyl group may be appropriately referred to as “(5) substituted alkynyl group” hereinafter.
  • Examples of the “alkynyl group having 2 to 12 carbon atoms” in the substituted alkynyl group include an ethynyl group and a propynyl group.
  • Examples of the “aromatic hydrocarbon ring group having 6 to 30 carbon atoms” in the substituted alkynyl group include, for example, the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D 1 to D 3 .
  • Examples of the “aromatic heterocyclic group having 2 to 30 carbon atoms” in the substituted alkynyl group include, for example, the same examples as the aromatic heterocyclic groups having 2 to 30 carbon atoms in D 1 to D 3 . .
  • the substituted alkynyl group may further have a substituent.
  • substituents that the substituted alkynyl group may have include, for example, the same examples as the substituents that the (1) hydrocarbon ring group may have.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • R h examples include the following groups.
  • R h More preferred examples of R h include the following groups.
  • R h include the following groups.
  • Rh described above may further have a substituent.
  • substituents include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; a vinyl group and an allyl group.
  • the meanings of Ra and Rb are as described above.
  • a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • R i represents an organic group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms.
  • R i include a hydrocarbon ring group having 6 to 40 carbon atoms and having at least one aromatic hydrocarbon ring having 6 to 30 carbon atoms.
  • Another preferred example of R i has one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms. Heterocyclic groups having 2 to 40 carbon atoms are exemplified.
  • R i include the following groups.
  • the meaning of R is as described above.
  • the group represented by any of formulas (II-1) to (II-7) may further have a substituent other than D 1 to D 6 .
  • substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, and an N-alkylamino having 1 to 6 carbon atoms.
  • N N-dialkylamino group having 2 to 12 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylsulfinyl group having 1 to 6 carbon atoms, carboxyl group, thioalkyl group having 1 to 6 carbon atoms And N-alkylsulfamoyl groups having 1 to 6 carbon atoms, and N, N-dialkylsulfamoyl groups having 2 to 12 carbon atoms.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • Ar in the formula (I) include groups represented by the following formulas (III-1) to (III-10). Further, the groups represented by the formulas (III-1) to (III-10) may have an alkyl group having 1 to 6 carbon atoms as a substituent. In the following formula, * represents a bonding position.
  • R 21 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • a 1 , A 2 , B 1 and B 2 each independently represent a cyclic aliphatic group which may have a substituent, and an aromatic which may have a substituent.
  • a 1 , A 2 , B 1 and B 2 each independently represent a cycloaliphatic group having 5 to 20 carbon atoms which may have a substituent or a substituent.
  • Examples of the cyclic aliphatic group for A 1 , A 2 , B 1 and B 2 include, for example, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, 1,4-cycloheptane-1,4 A cycloalkanediyl group having 5 to 20 carbon atoms, such as -diyl group, cyclooctane-1,5-diyl group; decahydronaphthalene-1,5-diyl group, decahydronaphthalene-2,6-diyl group; And a bicycloalkanediyl group having 5 to 20 carbon atoms.
  • an optionally substituted cycloalkanediyl group having 5 to 20 carbon atoms is preferable, a cyclohexanediyl group is more preferable, and a cyclohexane-1,4-diyl group is particularly preferable.
  • the cyclic aliphatic group may be a trans form, a cis form, or a mixture of a cis form and a trans form. Among them, the trans form is more preferable.
  • Examples of the substituent which the cyclic aliphatic group in A 1 , A 2 , B 1 and B 2 may have include, for example, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, Examples include a nitro group and a cyano group.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • Examples of the aromatic group in A 1 , A 2 , B 1 and B 2 include, for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, Aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as 5-naphthylene group, 2,6-naphthylene group, 4,4′-biphenylene group; furan-2,5-diyl group, thiophene-2,5
  • An aromatic heterocyclic group having 2 to 20 carbon atoms such as -diyl group, pyridine-2,5-diyl group, pyrazine-2,5-diyl group and the like; Among them, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms is preferable, a phenylene group is more preferable, and a 1,4-phenylene group is particularly preferable.
  • the substituent which the aromatic group in A 1 , A 2 , B 1 and B 2 may have is, for example, the same as the substituent which the cyclic aliphatic group in A 1 , A 2 , B 1 and B 2 may have Examples are given.
  • the number of substituents may be one or more. Further, the plurality of substituents may be the same or different.
  • R 22 and R 23 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Y 3 and Y 4 are preferably each independently —O—.
  • G 1 and G 2 each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and a methylene group contained in an aliphatic hydrocarbon group having 3 to 20 carbon atoms.
  • a group in which one or more of (—CH 2 —) is substituted with —O— or —C ( O) —;
  • a hydrogen atom contained in the organic group of G 1 and G 2 may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.
  • Specific examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in G 1 and G 2 include an alkylene group having 1 to 20 carbon atoms.
  • Specific examples of the aliphatic hydrocarbon group having 3 to 20 carbon atoms in G 1 and G 2 include an alkylene group having 3 to 20 carbon atoms.
  • P 1 and P 2 each independently represent a polymerizable functional group.
  • Compound (I) can be produced, for example, by reacting a hydrazine compound with a carbonyl compound described in WO2012 / 147904.
  • polymerizable liquid crystal compound examples include, for example, a compound represented by the following formula.
  • a compound represented by the formula (A-1) and a compound represented by the formula (A-2) are preferable, and a compound represented by the formula (A-2) is more preferable.
  • the amount of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition is preferably 1% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, and preferably 85% by weight or less, more preferably Is at most 80% by weight, more preferably at most 60% by weight.
  • the cross-linking agent used in the present embodiment is a compound having no mesogenic structure and capable of forming a bridge bond with the polymerizable liquid crystal compound, and is a compound having a cycloalkane structure.
  • the crosslinking agent having a cycloalkane structure is also referred to as a cycloalkane structure-containing crosslinking agent.
  • Preferred examples of the cycloalkane structure-containing crosslinking agent include a compound having a polymerizable group and one independent cycloalkane structure, or a polymerizable group and a plurality of independent cycloalkane structures linked by a linking group having an sp3 hybrid orbital.
  • a compound having a polymerizable group and one independent cycloalkane structure is particularly preferable.
  • polymerizable group examples include the same groups as the polymerizable group that can be contained in the polymerizable liquid crystal compound, preferably a radical polymerizable group or an ionic polymerizable group, more preferably a radical polymerizable group. And more preferably a (meth) acryloyloxy group.
  • the crosslinking agent generally contains two or more polymerizable groups per molecule, preferably 2 to 6, more preferably 2 only.
  • the cycloalkane structure may be a single ring structure or a structure of two or more rings.
  • the number of carbon atoms in the cycloalkane structure is usually 5 to 50, preferably 5 to 20, and more preferably 5 to 15.
  • Examples of the monocyclic cycloalkane structure include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure.
  • bicyclic or higher polycyclic cycloalkane structure examples include a bicycloheptane structure, a tricyclodecane structure (eg, tricyclo [3.3.1.1 3,7 ] decane structure (adamantane structure), and tricyclo [5. 2.1.0 2,6 ] decane structure), and a bicyclodecane structure.
  • Examples of the linking group having an sp3 hybrid orbital linking a plurality of cycloalkane structures include —O—, —O—CH 2 —, —O—CH 2 —CH 2 —, —CF 2 —O—, and —CF. 2 -CF 2 -, - O- CH 2 -CH 2 -O-, and the like, such as an alkylene group, preferably an alkylene group.
  • Specific examples of alkylene groups, -CH 2 -, - CH 2 -CH 2 -, - C (CH 3) 2 - is like, preferably -CH 2 is - (methylene group).
  • the cycloalkane structure-containing crosslinking agent may contain only one cycloalkane structure per molecule or may contain two or more cycloalkane structures.
  • the polymerizable group contained in the crosslinking agent may be directly bonded to the cycloalkane structure, or may be bonded via a linking group.
  • Examples of the linking group capable of bonding the polymerizable group to the cycloalkane structure include an alkylene group having 1 to 5 carbon atoms, and a methylene group is preferable.
  • the polymerizable group equivalent of the cycloalkane structure-containing crosslinking agent used in the present embodiment is calculated by [molecular weight of crosslinking agent] / [number of polymerizable groups per molecule of crosslinking agent].
  • the polymerizable group equivalent of the cycloalkane structure-containing crosslinking agent used in the present embodiment is preferably 10 or more, more preferably 50 or more, still more preferably 100 or more, particularly preferably 120 or more, and most preferably 145 or more.
  • the group contained as a polymerizable group is a (meth) acryloyloxy group
  • the polymerizable group equivalent is referred to as “acryl equivalent”.
  • the number of carbon atoms of the cycloalkane structure contained in the cycloalkane structure-containing cross-linking agent used in the present embodiment is defined as the number of carbon atoms C
  • the number of carbon atoms of the structural portion other than the cycloalkane structure is defined as the number of carbon atoms S. I do.
  • the ratio (C / S) of the number of carbon atoms C to the number of carbon atoms S (C / S) is preferably 0.01 or more, more preferably 0.1 or more, further preferably 0.5 or more, particularly preferably 1 or more, and most preferably.
  • 1.2 or more preferably 20 or less, more preferably 10 or less, further preferably 5 or less, particularly preferably 3 or less, most preferably 2.5 or less, preferably 0.01 to 20, more preferably Is 0.1 to 10, more preferably 0.5 to 5, particularly preferably 1 to 3, and most preferably 1.2 to 2.5.
  • the solubility parameter (SP value) of the cycloalkane structure-containing crosslinking agent is preferably 10 or more, more preferably 15 or more, preferably 30 or less, more preferably 25 or less, further preferably 20 or less, preferably It is 10 to 30, more preferably 15 to 25, even more preferably 15 to 20.
  • the SP value means a Hildebrand solubility parameter (Hildebrand ⁇ solubility ⁇ parameter). This SP value can be calculated by SP value calculation software “HSPiP@ver.4.1.7” (available from http://www.hansen-solubility.com/index.php).
  • cycloalkane structure-containing crosslinking agent examples include a compound represented by the following formula (C-1) and a compound represented by the following formula (C-2).
  • the compound represented by the formula (C-1) is commercially available, for example, as “NK Ester A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the compound represented by the formula (C-2) is commercially available, for example, as "Adamantane derivative Diapurest” manufactured by Mitsubishi Gas Chemical Company.
  • the cycloalkane structure-containing cross-linking agent may be used alone or in a combination of two or more in any ratio.
  • the amount of the cycloalkane structure-containing crosslinking agent is preferably at least 0.1 part by weight, more preferably at least 1 part by weight, still more preferably at least 5 parts by weight, particularly preferably at least 8 parts by weight, per 100 parts by weight of the polymerizable liquid crystal compound. At least 100 parts by weight, preferably at most 100 parts by weight, more preferably at most 50 parts by weight, further preferably at most 25 parts by weight, particularly preferably at most 17 parts by weight, preferably at 0.1-100 parts by weight, It is preferably 1 to 50 parts by weight, more preferably 5 to 25 parts by weight, particularly preferably 8 to 17 parts by weight.
  • the polymerization initiator refers to an agent exhibiting a polymerization initiating action for initiating polymerization of a polymerizable compound.
  • the polymerization initiator include a radical polymerization initiator for starting radical polymerization and an ionic polymerization initiator for starting ionic polymerization.
  • a polymerization initiator capable of polymerizing a polymerizable group contained in the polymerizable liquid crystal compound and the crosslinking agent may be used.
  • the polymerization initiator is preferably a radical polymerization initiator.
  • radical polymerization initiator examples include thermal radical generators that generate active species capable of initiating polymerization of a polymerizable liquid crystal compound by heating; visible light, ultraviolet light (such as i-ray), far ultraviolet light, electron beam, and X-ray. And the like, a photo-radical generator that is a compound that generates an active species capable of initiating polymerization of a polymerizable liquid crystal compound by exposure to an active energy ray.
  • a photo radical generator is preferable.
  • Examples of the photoradical polymerization initiator include acetophenone compounds, biimidazole compounds, triazine compounds, oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, ⁇ -diketone compounds, polynuclear quinone compounds. , A xanthone-based compound, a diazo-based compound, and an imidosulfonate-based compound, preferably an acetophenone-based compound or an oxime-based compound, and more preferably an oxime-based compound.
  • O-acyl oxime compounds are preferred. These compounds can generate an active radical, an active acid, or both an active radical and an active acid upon exposure.
  • the acetophenone-based compound is a compound having an acetophenone structure.
  • Specific examples of the acetophenone-based compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, and 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1- ON.
  • a commercially available product may be used as the acetophenone-based compound.
  • Examples of commercially available products include "Irgacure 379" (manufactured by BASF).
  • the oxime compound is preferably a compound having an O-acyloxime structure, for example, 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime), 1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- ⁇ 2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy] Benzoyl ⁇ -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [4- [3- [4-[[2- (
  • a commercially available product may be used as the oxime compound.
  • Examples of commercially available products include: “NCI-700”, “NCI-730”, “NCI-831”, “NCI-930” (manufactured by ADEKA); “DFI-020”, “DFI-091” (Dai-Tomix) And “IrgacureOXE03” and “IrgacureOXE04” (manufactured by BASF).
  • the ionic polymerization initiator examples include an anionic polymerization initiator and a cationic polymerization initiator.
  • Specific examples of the anionic polymerization initiator include alkyl lithium compounds; monolithium salts or monosodium salts such as biphenyl, naphthalene and pyrene; and polyfunctional polymerization initiators such as dilithium salts and trilithium salts.
  • cationic polymerization initiator examples include protic acids such as sulfuric acid, phosphoric acid, perchloric acid, and trifluoromethanesulfonic acid; Lewis acids such as boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride; Onium salts; concomitant agents of aromatic onium salts and reducing agents;
  • polymerization initiators may be used alone or in a combination of two or more in any ratio.
  • the amount of the polymerization initiator is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, based on the total amount of the polymerizable liquid crystal compound and the crosslinking agent. It is particularly preferably at least 3% by weight, preferably at most 20% by weight, more preferably at most 15% by weight, further preferably at most 10% by weight, particularly preferably at most 5% by weight, preferably at most 0.1 to 20% by weight. % By weight, more preferably 0.5 to 15% by weight, still more preferably 1 to 10% by weight, and particularly preferably 3 to 5% by weight.
  • the polymerizable liquid crystal composition may contain a surfactant as an optional component in addition to the polymerizable liquid crystal compound, the cycloalkane structure-containing crosslinking agent, and the polymerization initiator.
  • the surfactant may be any of an ionic surfactant and a nonionic surfactant. Ionic surfactants are further classified into anionic surfactants, cationic surfactants, and amphoteric surfactants.
  • anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali metal salts of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate Monoethanolamine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer monoethanolamine, and polyoxyethylene alkyl ether phosphate
  • cationic surfactants include alkyl quaternary ammonium salts and their ethylene oxide adducts.
  • amphoteric surfactants include alkyl betaines such as alkyl dimethyl amino acetate betaine; and alkyl imidazolines.
  • nonionic surfactant examples include polyoxyethylene oleyl ether; polyoxyethylene lauryl ether; polyoxyethylene nonyl phenyl ether; polyoxyethylene alkyl ether phosphate; polyoxyethylene sorbitan monostearate; Rates; dimethyl silicone, diphenyl silicone, modified polysiloxane, and other silicone-based surfactants; and fluorine-based surfactants containing a fluoroalkyl group.
  • a nonionic surfactant is preferable.
  • a silicone-based surfactant and a fluorine-based surfactant are preferred, and a fluorine-based surfactant is more preferred.
  • fluorine-based surfactants examples include “Megafac” series manufactured by DIC Corporation and “Surflon” series manufactured by AGC Seimi Chemical Co., Ltd.
  • One surfactant may be used alone, or two or more surfactants may be used in combination at an arbitrary ratio.
  • the amount of the surfactant is preferably at least 0.01% by weight, more preferably at least 0.05% by weight, further preferably at least 0.1% by weight, based on the total amount of the polymerizable liquid crystal compound and the crosslinking agent. , Preferably 5% by weight or less, more preferably 2% by weight or less, still more preferably 1% by weight or less, particularly preferably 0.5% by weight or less, preferably 0.01 to 5% by weight, more preferably Is 0.05 to 2% by weight, more preferably 0.1 to 1% by weight, particularly preferably 0.1 to 0.5% by weight.
  • optional ingredients include, for example, a solvent.
  • a solvent those capable of dissolving the polymerizable liquid crystal compound are preferable.
  • an organic solvent is usually used.
  • organic solvent examples include ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone and methyl isobutyl ketone; acetate solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as chloroform, dichloromethane and dichloroethane; Ether solvents such as 1,4-dioxane, cyclopentylmethyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolan, and 1,2-dimethoxyethane; and aromatic hydrocarbon solvents such as toluene, xylene and mesitylene.
  • ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone and methyl isobutyl ketone
  • acetate solvents such as butyl acetate and
  • the boiling point of the solvent is preferably from 60 ° C to 250 ° C, more preferably from 60 ° C to 150 ° C, from the viewpoint of excellent handleability.
  • the amount of the solvent is preferably at least 200 parts by weight, more preferably at least 250 parts by weight, particularly preferably at least 300 parts by weight, and preferably at least 650 parts by weight, based on 100 parts by weight of the total of the polymerizable liquid crystal compound and the crosslinking agent. Parts by weight, more preferably 550 parts by weight or less, particularly preferably 450 parts by weight or less.
  • the amount of the solvent is equal to or more than the lower limit of the above range, generation of foreign substances can be suppressed, and when the amount of the solvent is equal to or less than the upper limit of the above range, the drying load can be reduced.
  • an optional component that can be included in the polymerizable liquid crystal composition is a polymerizable compound other than the polymerizable liquid crystal compound and the cycloalkane structure-containing crosslinking agent; a metal; a metal complex; a metal oxide such as titanium oxide; , A coloring agent such as a pigment; a luminescent material such as a fluorescent material and a phosphorescent material; a leveling agent; a thixo agent; a gelling agent; a polysaccharide; an ultraviolet absorber; an infrared absorber; an antioxidant; .
  • the amount of each of these components may be from 0.1 to 20 parts by weight based on 100 parts by weight of the total of the dispersible polymerizable liquid crystal compound and the crosslinking agent.
  • the retardation film of the present embodiment is obtained by polymerizing a polymerizable liquid crystal composition. That is, the retardation film of the present embodiment includes a cured layer obtained by polymerizing a compound (eg, a polymerizable liquid crystal compound, a crosslinking agent) included in the polymerizable liquid crystal composition and capable of participating in a polymerization reaction.
  • a compound eg, a polymerizable liquid crystal compound, a crosslinking agent
  • Examples and preferable examples of the polymerizable liquid crystal composition are described in [1. Polymerizable liquid crystal composition], and the same as the examples and preferred examples of the polymerizable liquid crystal composition.
  • a retardation film By forming a retardation film using the polymerizable liquid crystal composition, a retardation film having good balance of molecular orientation, large birefringence ⁇ n, and heat durability can be obtained.
  • the orientation of the retardation film can be evaluated, for example, by visual observation of the retardation film and observation by a polarizing optical microscope.
  • the thermal durability can be evaluated by measuring the degree to which the in-plane retardation Re of the retardation film has decreased after the thermal durability test of the retardation film before the thermal durability test.
  • the condition of the heat durability test may be 85 ° C. for 100 hours.
  • the retardation film may have optical characteristics according to the alignment state of the polymerizable liquid crystal compound.
  • the retardation film may have reverse wavelength dispersive birefringence ⁇ n. Therefore, the retardation film may have in-plane retardation Re of reverse wavelength dispersion.
  • the retardation film has a large birefringence ⁇ n.
  • the birefringence ⁇ n of the retardation film is preferably at least 0.040, more preferably at least 0.050, and is preferably as large as possible, but is usually at most 0.20.
  • the thickness of the retardation film can be appropriately set so that characteristics such as retardation can be set in a desired range.
  • the thickness of the retardation film is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 7 ⁇ m or less.
  • the cured layer which is a retardation film, can be manufactured by, for example, a manufacturing method including the following steps (i) to (iii). (I) forming a layer of the polymerizable liquid crystal composition on the support surface; (Ii) a step of aligning the polymerizable liquid crystal compound contained in the layer of the polymerizable liquid crystal composition. (Iii) a step of polymerizing and curing the layer of the polymerizable liquid crystal composition.
  • any surface capable of supporting the layer of the polymerizable liquid crystal composition can be used as the support surface.
  • a flat surface without concave portions and convex portions is usually used as the support surface.
  • a resin film is usually used as the substrate.
  • a thermoplastic resin is used as the resin.
  • a resin having a positive intrinsic birefringence value is preferable as the resin from the viewpoints of high alignment regulating force, high mechanical strength, and low cost.
  • a resin containing an alicyclic structure-containing polymer such as a norbornene-based resin, because it is excellent in transparency, low moisture absorption, dimensional stability, and lightness.
  • a suitable example of the resin contained in the base material is given by a trade name, as the norbornene resin, a product of Zeonor series manufactured by Zeon Corporation can be mentioned.
  • the surface of the substrate as the support surface is preferably subjected to a treatment for imparting an alignment regulating force in order to promote the alignment of the polymerizable liquid crystal compound in the layer of the polymerizable liquid crystal composition.
  • the alignment regulating force refers to a property of a support surface capable of aligning a polymerizable liquid crystal compound in a polymerizable liquid crystal composition.
  • the treatment for imparting the alignment regulating force to the support surface include a photo-alignment treatment, a rubbing treatment, an alignment film forming treatment, an ion beam orientation treatment, and a stretching treatment. Among them, a stretching treatment is preferable.
  • a step of forming a layer of the polymerizable liquid crystal composition on a support surface such as the surface of the base material is performed.
  • a layer of the polymerizable liquid crystal composition is formed by coating the polymerizable liquid crystal composition on the support surface.
  • a method of applying the polymerizable liquid crystal composition for example, curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, A gravure coating method, a die coating method, a gap coating method, and a dipping method are mentioned.
  • a step of aligning the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition layer is performed.
  • the layer of the polymerizable liquid crystal composition is usually subjected to an alignment treatment, whereby the polymerizable liquid crystal compound is aligned in a direction corresponding to the alignment regulating force of the support surface.
  • the alignment treatment is usually performed by adjusting the temperature of the layer of the polymerizable liquid crystal composition to a predetermined alignment temperature.
  • the alignment temperature may be a temperature equal to or higher than the liquid crystalization temperature of the polymerizable liquid crystal composition.
  • the orientation temperature is preferably a temperature lower than the glass transition temperature of the resin contained in the base material. Thereby, generation of distortion of the base material due to the alignment treatment can be suppressed.
  • the treatment may be performed at a temperature of 50 ° C. to 160 ° C. for 30 seconds to 5 minutes.
  • the orientation of the polymerizable liquid crystal compound may be immediately achieved by applying the polymerizable liquid crystal composition. Therefore, the alignment treatment for aligning the polymerizable liquid crystal compound does not necessarily need to be performed on the layer of the polymerizable liquid crystal composition.
  • a step of curing the layer of the polymerizable liquid crystal composition to obtain a cured layer is performed.
  • the polymerizable liquid crystal compound is polymerized, and the layer of the polymerizable liquid crystal composition is cured.
  • the step of curing the layer of the polymerizable liquid crystal composition as described above not only the polymerization reaction of the polymerizable liquid crystal compound but also the crosslinking reaction of the crosslinking agent can proceed.
  • a method suitable for the properties of the components contained in the polymerizable liquid crystal composition can be selected.
  • the polymerization method include a method of irradiating active energy rays and a thermal polymerization method. Among them, a method of irradiating with an active energy ray is preferable because heating is unnecessary and the polymerization reaction can proceed at room temperature.
  • the irradiated active energy rays may include light such as visible light, ultraviolet light, and infrared light, and arbitrary energy rays such as an electron beam. Above all, a method of irradiating light such as ultraviolet light is preferable because of easy operation.
  • the method for producing a cured layer may further include an optional step in addition to the above steps.
  • the method for producing the cured layer may include a step of drying the layer of the polymerizable liquid crystal composition before the step of polymerizing the polymerizable liquid crystal compound. Such drying can be achieved by a drying method such as natural drying, heat drying, reduced pressure drying, and reduced pressure heating drying. By such drying, the solvent can be removed from the layer of the polymerizable liquid crystal composition.
  • the method for producing a cured layer may include a step of peeling the produced cured layer from the support surface.
  • the retardation film of the present embodiment may be used as an optical film in combination with another film.
  • a multilayer film including the substrate and the cured layer can be used as the retardation film.
  • the retardation film of the present embodiment may be used as a circularly polarizing plate in combination with a linear polarizer.
  • the thickness of the film was determined by a film thickness measuring device (“Filmetrics” manufactured by Filmetrics).
  • Thermal durability of the retardation film was evaluated according to the following.
  • the retardation film formed on the substrate was bonded to a slide glass with an adhesive (adhesive: “CS9621T” manufactured by Nitto Denko Corporation). Thereafter, the substrate was peeled off to prepare a test piece, and the in-plane retardation Re (0 hr) of the retardation film of the test piece was measured.
  • ⁇ Re (%) (Re (100 hr) ⁇ Re (0 hr)) / Re (0 hr) ⁇ 100
  • ⁇ Re (%) (Re (100 hr) ⁇ Re (0 hr)) / Re (0 hr) ⁇ 100
  • the thermal durability of the retardation film was evaluated according to the following criteria. Excellent: 1.7% ⁇
  • the retardation film was set on a polarizing optical microscope (“ECLIPSE LV100POL” manufactured by Nikon Corporation), and the polarizer and analyzer of the polarizing optical microscope were set to cross Nicol and observed. The observation was performed by adjusting the position of the optical film to the extinction position. The degree of the observed alignment defect was evaluated.
  • ECLIPSE LV100POL polarizing optical microscope
  • the orientation of the retardation film was comprehensively evaluated on the basis of the following criteria from the visual observation and the observation result by the polarizing optical microscope. Excellent: The retardation film is transparent, and no alignment defect is observed. OK: The retardation film is transparent, but slight alignment defects are observed. Poor: The retardation film is cloudy and alignment defects are clearly seen.
  • Reference Example 1 Evaluation of wavelength dispersibility of polymerizable liquid crystal compound (A-1) 100.0 parts of a reverse wavelength dispersible polymerizable liquid crystal compound represented by the following formula (A-1), 0.3 parts of Megafac F562 (manufactured by DIC) as a surfactant, and 1,3-dioxolane as a solvent (Manufactured by Toho Chemical Co., Ltd.) to obtain a liquid crystal composition.
  • A-1 a reverse wavelength dispersible polymerizable liquid crystal compound represented by the following formula (A-1)
  • Megafac F562 manufactured by DIC
  • 1,3-dioxolane as a solvent
  • a glass substrate (manufactured by EHC) having a rubbed polyimide horizontal alignment film cut into a 2.5 cm square was prepared.
  • the liquid crystal composition was applied on the alignment film of the glass substrate by spin coating using a spin coater (“A-200” manufactured by Mikasa Corporation) to form a layer of the liquid crystal composition.
  • the application conditions at this time were a rotation speed of 1100 rpm and an application time of 5 sec. Thereafter, the solvent was removed from the liquid crystal composition layer by air drying to obtain a sample plate provided with a glass substrate and a liquid crystal compound layer.
  • the sample plate was heated using a hot stage (“FP-80” manufactured by Mettler) to align the polymerizable liquid crystal compound (A-1) in the liquid crystal composition layer. Then, in the state where the polymerizable liquid crystal compound (A-1) was oriented as described above, the in-plane retardation Re of the liquid crystal compound layer was measured. The in-plane retardation Re was measured at measurement wavelengths of 450 nm, 550 nm, and 650 nm, and Re (450) / Re (550) and Re (650) / Re (550) were determined.
  • FP-80 manufactured by Mettler
  • a sample plate was prepared by sandwiching the polymerizable liquid crystal compound between two glass plates provided with a rubbed polyimide horizontal alignment film. The following test was performed on the sample plate.
  • the sample plate was heated from room temperature to 200 ° C (10 ° C / min), and then cooled from 200 ° C to room temperature (10 ° C / min).
  • the in-plane phase difference of the sample plate at a wavelength of 590 nm was measured by a phase difference measuring device (AXOMETRICS “Axo Scan”).
  • the film thickness of the sample plate was measured under the same temperature conditions as in the phase difference measurement using an optical interference type film thickness meter (manufactured by Filmetrics). From the obtained phase difference and film thickness, ⁇ n at each temperature was calculated. When ⁇ n> 0.001, it was determined that the compound film had birefringence.
  • the film of the polymerizable liquid crystal compound (A-1) had ⁇ n> 0.001 and had fluidity in a certain temperature range. That is, it was confirmed that the film of the polymerizable liquid crystal compound (A-1) had a temperature region where (1) fluidity and (2) birefringence were simultaneously exhibited. Was confirmed to have a mesogenic structure.
  • a polymerizable liquid crystal compound (A-2) represented by the formula (A-2) was used in place of the polymerizable liquid crystal compound (A-1) in the same manner as in Reference Example 1 to obtain a polymerizable compound. It was confirmed whether or not the liquid crystal compound (A-2) had a mesogenic structure. As a result, it was confirmed that the film of the polymerizable liquid crystal compound (A-2) had ⁇ n> 0.001 and had fluidity in a certain temperature range. That is, it has been confirmed that the film of the polymerizable liquid crystal compound (A-2) has a temperature range in which (1) fluidity and (2) birefringence are simultaneously exhibited. Was confirmed to have a mesogenic structure.
  • Example 1 (1-1. Preparation of composition) 19.18 parts of the compound represented by the formula (A-2) as a polymerizable liquid crystal compound, a crosslinking agent (trade name “NK Ester A-DCP”, manufactured by Shin-Nakamura Chemical Co., Ltd., SP value 18.7) 1.92 parts (10 parts based on 100 parts of polymerizable liquid crystal compound), surfactant (trade name “MegaFac F-562”, manufactured by DIC, fluorine-based surfactant) 0.06 parts (polymerizable liquid crystal) 0.31 part based on 100 parts of the compound, 0.28% by weight based on the total of the polymerizable liquid crystal compound and the crosslinking agent), a photopolymerization initiator (trade name "ADEKA ARKULS NCI-730", manufactured by ADEKA) 0.84 parts (4 parts based on 100 parts of the polymerizable liquid crystal compound, 3.9% by weight based on the total of the polymerizable liquid crystal compound and the crosslinking agent), and a mixed
  • thermoplastic norbornene resin manufactured by Nippon Zeon Co., Ltd., Tg: 126 ° C.
  • Tg 126 ° C.
  • the dried pellets are supplied to an extruder, melted in the extruder, passed through a polymer pipe and a polymer filter, extruded in a sheet form from a T-die onto a casting drum, cooled, and masked film ("FF1025" manufactured by Tretegar Co., Ltd.)
  • the substrate was rolled up while being protected by the above to obtain a roll of a base material before stretching having a thickness of 80 ⁇ m and a width of 1490 mm.
  • composition (X1) obtained in (1-1) was applied to one surface of the conveyed substrate (the surface to which the masking film was bonded) using a die coater. The composition was directly applied to form a layer of the composition (X1).
  • a cured layer formed of a cured product of the homogeneously oriented composition having a dry film thickness of 2.4 ⁇ m was obtained, and a multilayer film having a (base) / (cured layer) layer structure was obtained.
  • the above-mentioned evaluation was performed about the obtained cured layer as a retardation film. The results are shown in the table below.
  • Example 2 A cured layer (retardation film) was obtained and evaluated in the same manner as in Example 1 except that the following items were changed. The results are shown in the table below.
  • the crosslinking agent was 0.96 parts (5 parts based on 100 parts of the polymerizable liquid crystal compound).
  • Example 3 A cured layer (retardation film) was obtained and evaluated in the same manner as in Example 1 except that the following items were changed. The results are shown in the table below.
  • the crosslinking agent was 2.88 parts (15 parts based on 100 parts of the polymerizable liquid crystal compound).
  • Example 4 A cured layer (retardation film) was obtained and evaluated in the same manner as in Example 1 except that the following items were changed. The results are shown in the table below.
  • the crosslinking agent was 3.84 parts (20 parts based on 100 parts of the polymerizable liquid crystal compound).
  • Example 5 A cured layer (retardation film) was obtained and evaluated in the same manner as in Example 1 except that the following items were changed. The results are shown in the table below.
  • the compound represented by the formula (A-1) was used as the polymerizable liquid crystal compound instead of the compound represented by the formula (A-2).
  • the crosslinking agent was 0.96 parts (5 parts based on 100 parts of the polymerizable liquid crystal compound).
  • Example 6 A cured layer (retardation film) was obtained and evaluated in the same manner as in Example 1 except that the following items were changed. The results are shown in the table below.
  • the compound represented by the formula (A-1) was used as the polymerizable liquid crystal compound instead of the compound represented by the formula (A-2).
  • the crosslinking agent was 0.96 parts (5 parts based on 100 parts of the polymerizable liquid crystal compound).
  • "Irgacure 379" manufactured by BASF
  • A-1 Polymerizable liquid crystal compound represented by the formula (A-1)
  • A-2 Polymerizable liquid crystal compound A-DCP represented by the formula (A-2): “NK ester A-DCP” ( (Shin-Nakamura Chemical Co., Ltd.)
  • A-DPH “A-DPH” (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • UA-306I "UA-306I” (manufactured by Kyoeisha Chemical Co., Ltd.)
  • NCI-730 "ADEKA ARKLES NCI-730” (made by ADEKA)
  • Irg379 "Irgacure379” (manufactured by BASF)
  • the retardation film composed of a cured layer obtained by polymerizing and curing the polymerizable liquid crystal compositions according to Examples 1 to 6 has a sufficiently large birefringence ⁇ n of 0.040 or more and has good heat durability. And the orientation is good.
  • the retardation film composed of a cured layer obtained by polymerizing and curing the polymerizable liquid crystal compositions according to Comparative Examples 1 and 2 in which the crosslinking agent does not contain a cycloalkane structure has poor orientation.
  • the retardation film composed of a cured layer obtained by polymerizing and curing the polymerizable liquid crystal composition according to Comparative Example 3 containing no crosslinking agent has poor heat durability and orientation.

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Abstract

Cette composition polymérisable à base de cristaux liquides contient un composé cristallin liquide polymérisable, un agent de réticulation contenant une structure cycloalcane, et un initiateur de polymérisation. Le film de contraste de phase est formé par polymérisation de la composition polymérisable à base de cristaux liquides.
PCT/JP2019/035092 2018-09-28 2019-09-05 Composition polymérisable à base de cristaux liquides et film de contraste de phase WO2020066541A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP7405036B2 (ja) 2020-07-29 2023-12-26 日本ゼオン株式会社 液晶組成物、光学異方性層及び製造方法

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