WO2020175620A1 - Photoalignment film composition, photoalignment film, and laminate - Google Patents

Photoalignment film composition, photoalignment film, and laminate Download PDF

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Publication number
WO2020175620A1
WO2020175620A1 PCT/JP2020/008033 JP2020008033W WO2020175620A1 WO 2020175620 A1 WO2020175620 A1 WO 2020175620A1 JP 2020008033 W JP2020008033 W JP 2020008033W WO 2020175620 A1 WO2020175620 A1 WO 2020175620A1
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group
photo
composition
alignment film
repeating unit
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PCT/JP2020/008033
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French (fr)
Japanese (ja)
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一茂 中川
賢謙 前田
太朗 橋爪
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富士フイルム株式会社
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Priority to KR1020217025661A priority Critical patent/KR102525275B1/en
Priority to JP2021502365A priority patent/JP7212136B2/en
Publication of WO2020175620A1 publication Critical patent/WO2020175620A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • 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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

Definitions

  • the present invention relates to a composition for photo-alignment film, a photo-alignment film, and a laminate.
  • Optically anisotropic layers formed using liquid crystal compounds are used in various applications such as optical compensation sheets and retardation films.
  • An optical alignment film is known as an alignment film for forming such an optically anisotropic layer.
  • Patent Document 1 discloses a composition for a photo-alignment film containing a polymer 8 having a structural unit 3 1 containing a photocinnamate group, a low molecular weight compound having a cinnamate group and having a smaller molecular weight than the polymer 8. Is disclosed.
  • Patent Document 1 International Publication No. 2 0 1 7/0 6 9 2 5 2
  • the present inventors have a structural unit 3 1 having a photoalignable group-containing structural unit 3 1 and a crosslinkable group-containing structural unit 3 2 described in Patent Document 1, and a crosslinkable group-containing structural unit 3
  • the characteristics of the composition for a photo-alignment film containing a copolymer having a high ratio of 2 and an acid generator were measured.
  • a photo-alignment film formed using the composition for photo-alignment film stored for several days (for example, about 1 week) after preparation and a photo-alignment film formed using the composition for photo-alignment film immediately after preparation An alignment film was prepared, and an optically anisotropic layer was formed on both of them using a composition containing a liquid crystal compound, and the alignment property of the liquid crystal compound was evaluated. As a result, it was found that the orientation of the liquid crystal compound was deteriorated when the composition for photoalignment film stored for several days after preparation was used.
  • the excellent alignment of the liquid crystal compound in the optically anisotropic layer is also referred to as “excellent liquid crystal alignment”.
  • An object of the present invention is to provide a composition for a photo-alignment film capable of forming a photo-alignment film in which an optically anisotropic layer formed thereon has excellent liquid crystal alignment even after storage for a predetermined period.
  • this invention also makes it a subject to provide a photo-alignment film and a laminated body. Means for solving the problem
  • a composition for a photo-alignment film which comprises an amine compound having a boiling point of 50 to 230 ° and having no proton on a nitrogen atom.
  • composition for a photo-alignment film according to (1) or (2) wherein the content of the amine compound is 5 to 400 mol% with respect to the content molar amount of the acid generator.
  • the repeating unit containing a photoalignable group contains a repeating unit represented by the formula () described below,
  • composition for a photo-alignment film according to any one of (1) to (3), wherein the repeating unit containing a crosslinkable group contains a repeating unit represented by the following formula (Mi).
  • the repeating unit including a crosslinkable group contains a crosslinkable group represented by any of the formulas (XI) to (3) described below, and the repeating unit according to any one of (1) to (4) Composition for photo-alignment film.
  • An optical anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound, and a laminate.
  • composition for a photo-alignment film which can form a photo-alignment film having excellent liquid crystal alignment of the optically anisotropic layer formed thereon even after storage for a predetermined period.
  • a photo-alignment film and a laminated body can be provided.
  • 6 (s) and [3 ⁇ 4 1: (s) represent in-plane retardation and thickness-direction retardation at wavelengths, respectively. Unless otherwise specified, the wavelength is 550 nm.
  • ⁇ ⁇ (s) and The value in (s) is the value measured by the wavelength value in Yachibu 0380 1/1/1 (manufactured by Optoscience). Average refractive index ( / 3) and film thickness ( ⁇ 1 )) by typing
  • [3 ⁇ 4 ⁇ (s) is displayed as the value calculated by Yachibu ⁇ 03 ⁇ ⁇ 1 ⁇ /1-1 and means (s ).
  • — 1 ⁇ /1 2 manufactured by ATAGO Co., Ltd.
  • — 1 ⁇ /1 2 manufactured by ATAGO Co., Ltd.
  • Cycloolefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), polystyrene (1.59).
  • the (meth)acryloyl group is a concept including both an acryloyl group and a methacryloyl group.
  • a feature of the composition for a photo-alignment film of the present invention is that it contains a predetermined amine compound.
  • the inventors of the present invention used the composition for photoalignment film after storage for a predetermined period of time to perform the It has been found that when an alignment film is formed and an optically anisotropic layer is formed thereon, the liquid crystal alignment property of the obtained optically anisotropic layer is inferior.
  • the reaction of the crosslinkable group by the acid generated from the acid generator during the storage of the composition for photoalignment film when the content of the repeating unit containing a crosslinkable group is large, the reaction of the crosslinkable group by the acid generated from the acid generator during the storage of the composition for photoalignment film. It has been found that the liquid crystal progresses, and as a result, the liquid crystal alignment is affected. Then, they have found that the use of a predetermined amine compound in order to suppress the reaction of such a crosslinkable group can reduce the influence of the acid generator and obtain a desired effect.
  • optically anisotropic layer formed on the photo-alignment film is also excellent in durability evaluated in the Example section described later.
  • composition for a photo-alignment film of the present invention comprises a repeating unit containing a photo-alignable group and a repeating unit containing a cross-linkable group, a predetermined photo-alignable copolymer, an acid generator, and a predetermined And an amine compound.
  • composition for photo-alignment film has a boiling point of 50 to 230 ° and an amine compound having no proton on the nitrogen atom (hereinafter, also referred to as “specific amine compound”).
  • the boiling point of the specific amine compound is 50 to 230 ° ⁇ , and the liquid crystal alignment property of the optically anisotropic layer formed on the photo-alignment film is more excellent (hereinafter, simply “the effect of the present invention It is also referred to as "excellent point.”), 80 to 225 ° is preferable, and 100 to 220 ° is more preferable.
  • excellent point means the boiling point at 1 atm.
  • composition for photo-alignment film contains an amine compound having a partial structure represented by >1 ⁇ ]_!!, the liquid crystal alignment property is not improved, and the composition for photo-alignment film may gel. is there.
  • the specific amine is not particularly limited as long as it satisfies the above characteristics, and examples thereof include secondary amines and tertiary amines.
  • the specific amine may be linear or cyclic.
  • Examples of the case where the specific amine is cyclic include the case where the specific amine has a heterocycle.
  • the heterocycle may be an aromatic heterocycle or an aliphatic heterocycle. Examples of the heterocycle include a pyridine ring.
  • the heterocycle may have a substituent.
  • substituents include an alkyl group and an alkoxy group.
  • the compound represented by the formula (2) is preferable because the effect of the present invention is more excellent.
  • R 1 , R 2 and R 3 each independently represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • the alkyl group has 1 to 20 carbon atoms, and from the viewpoint that the effect of the present invention is more excellent, 1 to 10 is preferable, and 2 to 5 is more preferable.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group (for example, an n_propyl group and an isopropyl group), a butyl group, and a pentyl group.
  • Examples of the specific amine include diisopropylethylamine and triptylamine.
  • composition for photo-alignment film contains a photo-alignable copolymer having a predetermined repeating unit.
  • the photoalignable copolymer has a repeating unit A containing a photoalignable group.
  • the “photoalignable group” refers to a group having a photoalignment function in which rearrangement or an anisotropic chemical reaction is induced by irradiation with light having anisotropy (for example, plane polarized light).
  • a photo-alignment group capable of undergoing at least one of dimerization and isomerization under the action of light is preferable because it has excellent alignment uniformity and also has favorable thermal stability or chemical stability.
  • Examples of the photo-orienting group that dimerizes by the action of light include cinnamic acid derivatives (M. Schadt et a 1., J. App 1. Phys., vo l. 31, No. 7, page 2155 (1992)), coumarin derivative (M. Schadt et a 1., Nature., vo l. 381, page 212 (1996) ), chalcone derivative (Toshihiro Ogawa et al., Proceedings of the Liquid Crystal Conference, 2AB03 (1997)), maleimide derivative, and benzophenone derivative (YK Jang et al., SI D Int. Symposium Digest, P-53 (1997))
  • examples of the photo-orienting group that is isomerized by the action of light include an azobenzene compound (K. Ichimura et al., Mol. Cryst. Liq. Cryst 298, 221 (1997)) and a stilbene compound (G. Victor and B. M. Torke Ison, Macromolecules, 20, 2241 (1987)), Spiropyran compounds (K. Ichimura et a 1., Chemistry Letters, page 1063 (1992); K. Ichimura et al., Thin Solid Films, vol. 23 5, page 101 (1993)), cinnamic acid compound (K.
  • the photo-alignment group is at least one selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, azobenzene compounds, stilbene compounds, and spiropyran compounds.
  • a group having a derivative skeleton is preferable, and a group having a cinnamic acid derivative skeleton or a coumarin derivative skeleton is more preferable.
  • repeating unit A a repeating unit represented by the following formula (A) is preferable because the effect of the present invention is more excellent.
  • [3 ⁇ 4 5 represents a hydrogen atom or a methyl group.
  • 1_ 1 represents a divalent linking group containing a nitrogen atom and a cycloalkane ring, and some of the carbon atoms constituting the cycloalkane ring are selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. It may be substituted with a carbon atom.
  • 8 6 , 8 7 , 8 8 Each independently represents a hydrogen atom or a substituent, and two adjacent groups of [3 ⁇ 4 6 , [3 ⁇ 4 7 , [3 ⁇ 4 8 , [3 ⁇ 4 9 and [3 ⁇ 4 10] are bonded to each other to form a ring. May be.
  • represented 1_ 1 have One divalent linking group will be described that includes a nitrogen atom and a cycloalkane ring.
  • some of the carbon atoms constituting the cycloalkane ring may be substituted with a hetero atom selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom.
  • the nitrogen atom may not be present separately from the cycloalkane ring.
  • the cycloalkane ring is preferably a cycloalkane ring having 6 or more carbon atoms, and examples thereof include a cyclohexane ring, a cyclopeptane ring, a cyclooctane ring, a cyclododecane ring, and a cyclodocosane ring.
  • the divalent linking group represented by any one of 1) to (10) is preferable.
  • *1 represents the bonding position with the carbon atom constituting the main chain in the above formula (8)
  • *2 represents the above formula (). Represents the bonding position with the carbon atom constituting the carbonyl group.
  • the solubility in the solvent used for forming the light-alignment film and the photo-alignment film obtained are
  • the divalent linking group represented by any one of the above formulas (2), (3), (7) and (8) is preferable from the viewpoint of achieving a good balance with the solvent resistance.
  • substitution group will be described.
  • the above equation (8) As described above, and 10 may be hydrogen atoms instead of substituents.
  • the substituents represented by one embodiment are, independently of each other, a halogen atom and a straight chain having 1 to 20 carbon atoms in that the photo-alignment group easily interacts with the liquid crystal compound and the effect of the present invention is more excellent.
  • Kill group alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, cyano group, amino group or represented by the following formula (11) It is preferable that the group is
  • ⁇ represents a bonding position with the benzene ring in the formula (8)
  • [3 ⁇ 4 12 represents a monovalent organic group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
  • the linear alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • the branched alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 3 to 6 carbon atoms, and examples thereof include an isopropyl group and I 6 A butyl group may be mentioned.
  • the cyclic alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
  • the linear halogenated alkyl group having 1 to 20 carbon atoms is preferably a fluoroalkyl group having 1 to 4 carbon atoms, and examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and And a perfluorobutyl group. Of these, a trifluoromethyl group is preferable.
  • the alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 6 to 18 carbon atoms, and an alkoxy group having 6 to 14 carbon atoms. More preferable.
  • Radecyloxy group hexyloxy group, door-octyloxy group, decyloxy group, dodecyloxy group, or A tetradecyloxy group is preferred.
  • the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a ⁇ -methylphenyl group, and a naphthyl group. preferable.
  • the aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group, and a phenyloxy group is preferable.
  • amino group for example, primary amino group (an 1 ⁇ 1 11 2); a secondary amino group such as methylamino group, dimethylamino group, diethylamino group, dibenzyl amino group, and a A tertiary amino group such as a group having a nitrogen atom as a bond of a nitrogen-containing heterocyclic compound (eg, pyrrolidine, piperidine, piperazine, etc.).
  • a nitrogen-containing heterocyclic compound eg, pyrrolidine, piperidine, piperazine, etc.
  • the monovalent organic group represented by [3 ⁇ 4 12 in the above formula (11) is, for example, a straight chain having 1 to 20 carbon atoms. Alternatively, a cyclic alkyl group may be mentioned.
  • an alkyl group having 1 to 6 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, and a propyl group, and a methyl group or an ethyl group is preferable.
  • cyclic alkyl group an alkyl group having 3 to 6 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, and a cyclohexyl group is preferable.
  • the photo-alignment group easily interacts with the liquid crystal compound, and the effect of the present invention is more excellent. And out of ⁇ 0 2020/175 620 12 ((17 2020/008033
  • 8 in the above formula (8) is an electron-donating substituent because the reaction efficiency is improved when irradiated with light.
  • the electron-donating substituent is the Hammett value.
  • ⁇ et 1 A substituent having a substituent constant ⁇ 7) of 0 or less, and examples thereof include an alkyl group, a halogenated alkyl group, and an alkoxy group.
  • an alkoxy group is preferable, and an alkoxy group having 6 to 16 carbon atoms is more preferable because the effect of the present invention is more excellent, and a carbon number of 7 to
  • repeating unit 8 containing a photo-alignable group examples include repeating units 81 1 to 81 5 shown below.
  • IV! 6 represents a methyl group
  • M represents an ethyl group.
  • the “1,4-cyclohexyl group” contained in the divalent linking group of repeating units 8 — 1 to 8 — 10 may be either a cis isomer or a trans isomer. , Preferably in trans form.
  • the photoalignable copolymer has a repeating unit including a crosslinkable group.
  • the crosslinkable group include an epoxy group, an epoxycyclohexyl group, a xenonyl group, and a functional group having an ethylenically unsaturated double bond, and a cationically polymerizable group is preferable, and the following formula (XI) More preferred is at least one crosslinkable group selected from the group consisting of (3).
  • Ai represents a bond
  • repeating unit a repeating unit represented by the following formula (M) is preferable because the effect of the present invention is more excellent.
  • Examples of the divalent linking group 2 represented in terms the effect of the present invention is more excellent, linear optionally carbon atoms, which may 1-1 8 have a substituent, branched or cyclic An alkylene group, an optionally substituted arylene group having 6 to 12 carbon atoms, an ether group (101), a carbonyl group (10 ( ⁇ ) 1), and a substituent An imino group which may have a group A divalent linking group combining at least two groups selected from the group consisting of (for example, O-alkylene group 1) is preferred.
  • examples of the substituent that the alkylene group, the arylene group and the imino group may have include, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group and a carboxy group. Group, an alkoxycarbonyl group, and a hydroxyl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
  • alkyl group for example, a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group Base, _Butyl group, isoptyl group, 360-butyl group, 1_butyl group, and cyclohexyl group) are more preferable, an alkyl group having 1 to 4 carbon atoms is further preferable, and a methyl group or ethyl group. ⁇ 2020/175 620 17 ⁇ (:171? 2020/008033
  • Ru groups are particularly preferred.
  • an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, and methoxetoxy group) Is more preferable, an alkoxy group having 1 to 4 carbon atoms is further preferable, and a methoxy group or an ethoxy group is particularly preferable.
  • aryl group examples include an aryl group having 6 to 12 carbon atoms, examples of which include a phenyl group, ⁇ -methylphenyl group, and naphthyl group, with a phenyl group being preferred.
  • aryloxy group examples include phenoxy, naphthoxy, imidazoyloxy, benzimidazoyloxy, pyridin-4-yloxy, pyrimidinyloxy, quinazolinyloxy, purinyloxy, and thiophen-3-yloxy.
  • alkoxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl.
  • Examples of the linear alkylene group having 1 to 18 carbon atoms include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a decylene group, an undecylene group, a dodecylene group, and a tridecylene group.
  • Examples of the branched chain alkylene group having 1 to 18 carbon atoms include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-methylpropylene group.
  • Examples of the cyclic alkylene group having 1 to 18 carbon atoms include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, a norbornane-diyl group, And a 6 X O -tetrahydrodicyclopentadienyl group, and a cyclohexylene group is preferable.
  • Examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, and a 2,2′-methylenebisphenyl group, and a phenylene group is preferable.
  • Examples of the crosslinkable group represented by X in the above formula (M) include the above-mentioned crosslinkable groups.
  • repeating unit that includes a crosslinkable group examples include the following repeating units: Miichi 1 to Miichi 17.
  • repeating unit including a crosslinkable group examples include the following repeating units: Michi 18 to Michi 47.
  • the photoalignable copolymer may have other repeating units in addition to the above-described repeating unit and repeating unit, as long as the effects of the present invention are not impaired.
  • the content 3 of the repeating unit and the content of the repeating unit M in the photoalignable copolymer satisfy the following formula (1) in mass ratio.
  • the relationship of the formula (1) represents the ratio of the content 13 to the total of the content 3 of the repeating unit and the content 13 of the repeating unit.
  • the range / (3 + 13) is preferably 0.75 to 0.95, more preferably 0.80 to 0.993.
  • the content of the repeating unit is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferably 3 to 30 mass% with respect to all repeating units in the photoalignable copolymer, and 5 to 25% by mass is more preferable.
  • the content of the repeating unit is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferably 70 to 97% by mass, and 75 to 95% by mass with respect to all repeating units in the photoalignable copolymer. % Is more preferable.
  • Weight average molecular weight of photoalignable copolymer Is preferably from 100,000 to 500,000, more preferably from 30,000 to 30,000, from the viewpoint that the effect of the present invention is more excellent.
  • the weight average molecular weight and the number average molecular weight in the present invention are values measured by the gel permeation chromatography ( ⁇ ) method under the following conditions.
  • the composition for photo-alignment film contains an acid generator.
  • the acid generator has a function of initiating the polymerization of the above-mentioned crosslinkable group.
  • the acid generator is not particularly limited, and examples thereof include a thermal acid generator and a photoacid generator.
  • the thermal acid generator is not particularly limited in its structure as long as it is a compound capable of decomposing by heat to generate a specific acid. Usually, it is composed of an anion obtained by removing hydrogen ion from a predetermined acid and a cation. Composed.
  • Examples of the acid include compounds represented by the formulas (8) to (M), and ⁇ .
  • the number of carbon atoms in the perfluoroalkyl group is not particularly limited, but is preferably 1 to 10 and more preferably 1 to 5.
  • the number of carbon atoms in the perfluoroalkylene group is not particularly limited, but is preferably 2 to 10 and more preferably 3 to 5.
  • the number of carbon atoms in the perfluoroalkyl group is not particularly limited, but 1 to 10 is preferable.
  • aryl group which may have a substituent.
  • the aryl group include a phenyl group and a naphthyl group.
  • the type of the substituent is not particularly limited, but examples thereof include an alkyl group and a halogen atom (preferably a fluorine atom).
  • the number of carbon atoms in the perfluoroalkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 5 is more preferable.
  • n represents an integer of 1 to 6. Among them, n is preferably an integer of 3 to 6,
  • Examples of the anion include the following.
  • the cation a known cation that is decomposed by heat can be used.
  • the cation preferably has a skeleton in which thermal decomposition starts at 30 to 200°, and more preferably has a skeleton in which thermal decomposition starts at 40 to 150°.
  • the sulfonium cation represented by the formula () or the iodonium cation represented by the formula ( ⁇ ) is preferable from the viewpoint of handleability.
  • [0078] and [3 ⁇ 4 9 1 and [3 ⁇ 4 9 2 each independently represent a hydrocarbon group which may have a substituent.
  • a hydrocarbon group an alkyl group (for example, a methyl group, an ethyl group) or an aryl group (for example, a phenyl group) is preferable.
  • the kind of the substituent is not particularly limited, and examples thereof include an alkyl group, an aryl group, a hydroxy group, an amino group, a carboxy group, a sulfone amide group, a 1 ⁇ 1-sulfonyl amide group, an acyl group, an acyloxy group, an alkoxy group. , An alkyl group, a halogen atom, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an ester carbonate group, and a cyano group.
  • Examples of the cation include the following.
  • the photo-acid generator is a compound that decomposes by light to generate a specific acid. ⁇ 2020/175 620 24 ⁇ (:171? 2020 /008033
  • the structure is not particularly limited, but a compound that reacts with an actinic ray having a wavelength of 300 n or more, preferably 300 0 to 450 n and generates an acid is preferable.
  • the wavelength 300 The above photoacid generators that are not directly sensitive to actinic rays can also be used in combination with sensitizers to generate wavelengths of 300 Any compound capable of reacting with the above-mentioned actinic rays and generating an acid can be preferably used in combination with a sensitizer.
  • Examples of the photoacid generator include onium salt compounds, trichloromethyl-3-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imidsulfonate compounds, and oximesulphonate compounds. Is mentioned.
  • composition for photo-alignment film may contain components other than the components described above.
  • Other components include solvents.
  • Solvents include water and organic solvents.
  • organic solvent examples include ketones (eg, acetone, 2-butanone, methylisoeptylketone, and cyclohexanone), ethers (eg, dioxane and tetrahydrofuran), aliphatic hydrocarbons (eg, For example, hexane), alicyclic hydrocarbons (eg, cyclohexane), aromatic hydrocarbons (eg, toluene, xylene, and trimethylbenzene)
  • ketones eg, acetone, 2-butanone, methylisoeptylketone, and cyclohexanone
  • ethers eg, dioxane and tetrahydrofuran
  • aliphatic hydrocarbons eg, For example, hexane
  • alicyclic hydrocarbons eg, cyclohexane
  • aromatic hydrocarbons eg, toluene, xylene, and trimethylbenzene
  • Halogenated carbons eg dichloromethane, dichloroethane, dichlorobenzene and chlorotoluene
  • esters eg methyl acetate, ethyl acetate and butyl acetate
  • water alcohols
  • alcohols eg ethanol, isopropanol, Butanol and cyclohexanol
  • cellosolves eg, methylcellosolve and ethylcellosolve
  • cellosolve acetates eg, methylcellosolve and ethylcellosolve
  • sulfoxides eg, dimethylsulfoxide
  • amides eg, dimethylformamid
  • the solvent may be used alone or in combination of two or more. ⁇ 2020/175 620 25 ⁇ (: 171? 2020 /008033
  • composition for photo-alignment film may contain components other than the above, and examples thereof include a crosslinking catalyst, an adhesion improver, a leveling agent, a surfactant, and a plasticizer.
  • composition for photo-alignment film contains the above-mentioned photo-alignable copolymer, an acid generator, and a specific amine compound.
  • the method for preparing the composition for a photo-alignment film is not particularly limited, and the above components may be mixed at once or may be mixed stepwise.
  • the content of the photoalignable copolymer in the composition for photoalignment film is not particularly limited, but when the composition for photoalignment film contains a solvent, relative to 100 parts by mass of the solvent, O.1 to 50 parts by mass is preferable, and 0.5 to 20 parts by mass is more preferable.
  • the content of the acid generator in the composition for the photo-alignment film is not particularly limited, but in terms of the effect of the present invention being more excellent, with respect to the total mass of the photo-alignment copolymer, 0.1 to 30 mass% Is preferable, and 0.5 to 2.0 mass% is more preferable.
  • the content of the specific amine in the composition for a photo-alignment film is not particularly limited, but it is often 1 to 100 mol% with respect to the content molar amount of the acid generator (total molar amount). From the viewpoint that the above effect is more excellent, 5 to 400 mol% is preferable, and 10 to 300 mol% is more preferable.
  • a photo-alignment film can be formed using the composition for photo-alignment film.
  • the photo-alignment film can be produced by a conventionally known production method except that the composition for photo-alignment film described above is used.
  • a step of forming a precursor film using the composition for photo-alignment film described above can be produced by a manufacturing method including a polarized light or a precursor film and a light irradiation step of irradiating the surface of the precursor film with non-polarized light from an oblique direction.
  • the precursor film forming step is a step of forming a precursor film using the composition for photo-alignment film.
  • the precursor film means a film that is subjected to photo-alignment treatment. ⁇ 0 2020/175 620 26 ⁇ (: 17 2020 /008033
  • the procedure of the above steps is not limited as long as the precursor film can be formed.
  • the composition for a light directing film is applied onto a support to form a coating film, and the coating film is subjected to a curing treatment (heat treatment and Light irradiation treatment) to form a precursor film.
  • the support to which the composition for a photo-alignment film is applied is not particularly limited, and examples thereof include a glass substrate and a polymer film.
  • Materials for the polymer film include cellulose-based polymers; acrylic-based polymers having acrylic acid ester polymers such as polymethylmethacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalate and polyethylene naphthalate.
  • Polyester polymers polystyrene, acrylonitrile styrene copolymers and other styrene polymers; polyethylene, polypropylene and ethylene-propylene copolymers and other polyolefin polymers; vinyl chloride polymers; nylon and aromatic polyamides Polymers; Imide polymers; Sulfone polymers; Polyethersulfone polymers; Polyetheretherketone polymers; Polyphenylene sulfide polymers; Vinylidene chloride polymers; Vinyl alcohol polymers; Vinyl ptillal polymers; Examples thereof include arylate-based polymers; polyoxymethylen-based polymers; epoxy-based polymers; and polymers obtained by mixing these polymers.
  • the thickness of the support is not particularly limited, but is preferably 5 to 200, and 10 to
  • the method for applying the composition for a photo-alignment film is not particularly limited, but for example, spin coating, die coating, gravure coating, flexo printing! ⁇ , and inkjet printing.
  • the method of curing the coating film of the composition for a photo-alignment film is not particularly limited, and examples thereof include heat treatment and light irradiation treatment.
  • the acid generator is a thermal acid generator, ⁇ 2020/175 620 27 ⁇ (:171? 2020 /008033
  • heat treatment is preferable as the curing treatment
  • the acid generator is a photoacid generator
  • light irradiation treatment is preferable as the curing treatment.
  • the conditions for heat treatment are not particularly limited, and optimal conditions are selected as appropriate depending on the material used, but the heating temperature is preferably 50 to 150 ° ⁇ , and 80 to 140° O is more preferable.
  • the heating time is preferably 0.1 to 60 minutes, more preferably 0.5 to 30 minutes.
  • the conditions of the light irradiation treatment are not particularly limited, and it is preferable to use ultraviolet rays.
  • the procedure for separately performing the coating film forming treatment and the curing treatment has been described above, they may be performed simultaneously. That is, the curing treatment may be carried out at the time of forming the coating film. Specifically, a method of heating (or irradiating with light) while applying the composition for a photo-alignment film on a support can be mentioned.
  • the light irradiation treatment is a step of irradiating the surface of the polarized film or the precursor film with non-polarized light from an oblique direction.
  • the polarized light with which the precursor film of the composition for a photo-alignment film is irradiated is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, and elliptically polarized light, and linearly polarized light is preferable.
  • the “oblique direction” for irradiating non-polarized light is not particularly limited as long as it is a direction inclined by a polar angle 0 ( ⁇ ⁇ 0 ⁇ 90 ° ) with respect to the normal direction of the precursor film surface.
  • the polar angle 0 is preferably 20 to 80 ° .
  • the wavelength of polarized light or non-polarized light is not particularly limited as long as it can impart the orientation control ability to the liquid crystal compound in the precursor film, and examples thereof include ultraviolet rays, near ultraviolet rays, and visible rays. Rays can be mentioned. Of these, near-ultraviolet rays of 250 to 450 are preferable.
  • a light source for irradiating polarized light or non-polarized light for example, a xenon lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a metal halide ⁇ 2020/175 620 28 ⁇ (:171? 2020 /008033
  • the wavelength range for irradiation can be limited.
  • linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources.
  • the cumulative amount of polarized or unpolarized light is not particularly limited,
  • the illuminance of polarized light or non-polarized light is not particularly limited.
  • the film thickness of the photo-alignment film is not particularly limited, and is preferably 10 to 100 nm, more preferably 10 to 700 nm.
  • the laminate of the present invention has the above-mentioned photo-alignment film and an optically anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound.
  • the laminate of the present invention preferably further has a support, and specifically, it preferably has a support, a photo-alignment film and an optically anisotropic layer in this order. ..
  • the support and the photo-alignment film are as described above.
  • optically anisotropic layer will be described in detail.
  • the optically anisotropic layer of the laminate may be an optically anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound (hereinafter, also referred to as “composition for optically anisotropic layer”).
  • composition for optically anisotropic layer a liquid crystal compound
  • examples include conventionally known optically anisotropic layers.
  • the optically anisotropic layer is preferably a layer obtained by curing a liquid crystal composition containing a liquid crystal compound having a polymerizable group.
  • the optically anisotropic layer may have a single-layer structure or a structure in which a plurality of layers are laminated (laminate).
  • liquid crystal compound and optional additives will be described below.
  • the liquid crystal compound can be classified into a rod-shaped type and a disc-shaped type according to its shape. ⁇ 2020/175 620 29 ⁇ (:171? 2020 /008033
  • Polymers generally refer to polymers with a degree of polymerization of 100 or more (Polymer physics/Phase transition dynamics, Masao Doi,
  • any liquid crystal compound can be used, but it is preferable to use a rod-shaped liquid crystal compound or a discotic liquid crystal compound, and it is more preferable to use a rod-shaped liquid crystal compound.
  • the liquid crystal compound preferably has a polymerizable group.
  • the liquid crystal compound preferably has two or more polymerizable groups in one molecule. Incidentally, after the liquid crystal compound is fixed by polymerization, it is no longer necessary to exhibit liquid crystallinity.
  • the type of the polymerizable group is not particularly limited, a functional group capable of addition polymerization reaction is preferable, a polymerizable ethylenically unsaturated group or a ring polymerizable group is preferable, and a (meth)acryloyl group, vinyl Group, styryl group, or allyl group is more preferable, and (meth)acryloyl group is further preferable.
  • Examples of the rod-shaped liquid crystal compound are those described in claim 1 of Japanese Patent Publication No. 11-513109 or in paragraphs [0026] to [098] of Japanese Patent Laid-Open No. 2005-289980.
  • As the discotic liquid crystal compound for example, paragraphs [00 20] to [0067] of JP 2007 _ 1 08732 or paragraph [0000 1 of JP 2010-244038 A can be used.
  • ] To [01 08] can be preferably used.
  • liquid crystal compound a reverse wavelength dispersion liquid crystal compound can be used.
  • the “reverse wavelength dispersion” liquid crystal compound means an in-plane retardation ([3 ⁇ 4 6) value at a specific wavelength (visible light range) of a retardation film produced by using the liquid crystal compound. In this case, the 6 value becomes equal or higher as the measurement wavelength increases.
  • the liquid crystal compound is preferably a liquid crystal compound represented by the formula (3).
  • ⁇ ⁇ ⁇ 2, eight 1 and eight 2 each independently may have a substituent, a divalent aromatic hydrocarbon group having the number 6-1 2 carbons, or a 5-8 carbon atoms represents a divalent alicyclic hydrocarbon group, ⁇ _ ⁇ _1 constituting the alicyclic hydrocarbon group 1 2 - of one or more on the one hundred and one, May be substituted with.
  • 3 1 and 3 2 are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbons, or a linear or branched chain having 1 to 12 carbons. At least one of _ 01 to 1 2 — constituting the alkylene group of
  • a plurality of Snake 3 are the same - or different and a plurality of eight 1 may each become different, even the same.
  • ⁇ represents an integer of ⁇ _ ⁇ 2, when n is 2, a plurality of snake 4 are the same - or different and a plurality of eight 2 can be the respective same different It may be.
  • Eight represents an organic group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, which may have a substituent.
  • 1 1 and 1_ 2 each independently represents a monovalent organic group.
  • 1,2-phenylene group 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, and
  • 2,6-naphthylene group is mentioned, and among them, 1,4-phenylene group is preferred.
  • 1,4-phenylene group is preferred.
  • trans-1,4-phenylene group is more preferable.
  • the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by 0 1 , 0 2 % 1 and 2 is preferably a 5-membered ring group or a 6-membered ring group.
  • the alicyclic hydrocarbon group may be saturated or unsaturated, but a saturated alicyclic hydrocarbon group is preferable. Examples of the divalent alicyclic hydrocarbon group include those described in JP-A No. 20 1 2 _ 210 6 8
  • 3 1 and 3 2 are shown a linear or branched alkylene group of from 1 to 1 2 carbon atoms, for example, methylene group, ethylene group, propylene group, Puchire down, pentylene, hexylene Group, a methylhexylene group, and a heptylene group.
  • 3 1 and 3 2 are as described above, constitute a straight chain or branched chain alkylene group having 1 to 2 carbon atoms
  • the top is 101, 13-, It may be a monovalent (0) — or a divalent linking group substituted with 1001, and a substituent represented by 0 is a group in the formula (8 “1 1) described later. Examples of the substituent which 1 may have include
  • Examples of the monovalent organic group represented by !_ 1 and !_ 2 include an alkyl group, an aryl group, and a heteroaryl group.
  • the alkyl group may be linear, branched or cyclic, but linear is preferred.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms.
  • the aryl group may be monocyclic or polycyclic, but monocyclic is preferred.
  • the carbon number of the aryl group is preferably 6 to 25, more preferably 6 to 10 ⁇ 2020/175 620 32 units (: 171-1? 2020 /008033
  • the heteroaryl group may be monocyclic or polycyclic.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3.
  • the hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom.
  • the heteroaryl group preferably has 4 to 18 carbon atoms, and more preferably 4 to 12 carbon atoms.
  • the alkyl group, aryl group and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents as the substituent that may be possessed by Ogura 1 in the formula (8 "-1 1") to be described later.
  • At least one of !_ 1 and 1_ 2 is preferably a polymerizable group.
  • the polymerizable group is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
  • radically polymerizable group a generally known radically polymerizable group can be used, and an acryloyl group or a methacryloyl group is preferable.
  • an acryloyl group is generally known to have a higher polymerization rate, and an acryloyl group is preferable from the viewpoint of improving productivity, but a methacryloyl group can be used as a polymerizable group in the same manner.
  • cationically polymerizable groups As the cationically polymerizable group, generally known cationically polymerizable groups can be used. Examples thereof include alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, and vinyloxy group. Is mentioned. Of these, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is more preferable.
  • Examples of preferable polymerizable groups include the following.
  • Both !_ 1 and 1_ 2 are preferably a polymerizable group, and more preferably an acryloyl group or a methacryloyl group.
  • [0111] represents an organic group having at least one aromatic ring which may have a substituent and is selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle.
  • the aromatic hydrocarbon ring may be a monocyclic ring or a polycyclic ring.
  • the carbon number of the aromatic hydrocarbon ring is preferably 6 to 25, more preferably 6 to 10.
  • the aromatic heterocycle may be a monocycle or a polycycle.
  • the hetero atom forming the aromatic compound ring is preferably a nitrogen atom, a sulfur atom or an oxygen atom.
  • the aromatic heterocycle preferably has 4 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.
  • substituents examples include known substituents.
  • the above-mentioned " 1 " is preferably any aromatic ring selected from the group consisting of groups represented by the following formulas (8"-1" to (8"-15).
  • ⁇ represents the bonding position with 0 1 or 0 2 .
  • 0 1 represents 1 ⁇ 1 or 0 1 to 1.
  • 0 2 represents 1-, 101, or 1 ([3 ⁇ 4 5 )-, Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Reference 1 represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms.
  • Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by 1 include a heteroaryl group such as a cenyl group, a thiazolyl group, a furyl group, a pyridyl group, and a benzofuryl group.
  • the aromatic heterocyclic group also includes a group in which a benzene ring and an aromatic heterocycle are condensed.
  • substituent which may be possessed ⁇ 1, for example, an alkyl group, alkoxy group, a nitro group, an alkylsulfonyl group, an alkyloxycarbonyl group, a cyano group, and, a halogen atom.
  • alkyl group for example, a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group Base, _Butyl group, isoptyl group, 360-butyl group, 1_butyl group, and cyclohexyl group) are more preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is Particularly preferred.
  • an alkyl group having 1 to 8 carbon atoms for example, methyl group, ethyl group, propyl group, isopropyl group Base, _Butyl group, isoptyl group, 360-butyl group, 1_butyl group, and cyclohexyl group
  • an alkyl group having 1 to 4 carbon atoms is more preferable
  • an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, and methoxetoxy group) Is more preferable, an alkoxy group having 1 to 4 carbon atoms is further preferable, and a methoxy group or an ethoxy group is particularly preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
  • 1 , 2, and 3 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent alicyclic carbon group having 3 to 20 carbon atoms.
  • an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group ⁇ 2020/175 620 36 ⁇ (: 171-1? 2020 /008033
  • Ethyl group isopropyl group, 6 "-pentyl group (1, 1-dimethylpropyl group), I 6 "I-butyl group, or 1, 1-dimethyl-3,3-dimethylbutyl group is more preferable, methyl group, Ethyl group, or 1 6 ”
  • the I-butyl group is particularly preferred.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group, and , A monocyclic saturated hydrocarbon group such as an ethyl cyclohexyl group; a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclodecenyl group, a cyclopentenyl group, a cyclohexagenyl group, a cyclooctagenenyl group Group and monocyclic unsaturated hydrocarbon group such as cyclodecadiene group; bicyclo [2.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-ditylphenyl group, a naphthyl group, and a biphenyl group, and an aryl group having 6 to 12 carbon atoms.
  • a group (particularly a phenyl group) is preferred.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom or a bromine atom is preferable.
  • alkyl group having 1 to 6 carbon atoms examples include, for example, methyl group, ethyl group, propyl group, isopropyl group, _Butyl group, isoptyl group, 360-butyl group, ⁇ “-butyl group, And 11-hexyl groups.
  • eighty three and eighty four are, independently, 101 and ([3 ⁇ 4 10 )-, -3 —, and, Represents a group selected from the group consisting of ⁇ 2020/175 620 37 ⁇ (:171? 2020/008033
  • Examples thereof include the same substituents as the substituent 1 may have in the above formula (8 “_ 1 ).
  • X is a hydrogen atom or a Group 14 to Group 1 to which a substituent may be bonded.
  • examples of the non-metal atom of Groups 14 to 16 represented by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent.
  • the group, the formula (eight "one 1) those in ⁇ 1 is similar to the substituent which may have the like.
  • 0 3 and 0 4 are, independently of each other, a single bond, a 10101, a 10 (
  • 3 3 and 3 4 are each independently a single bond, a linear or branched alkylene group of number 1-1 2 carbons or straight-chain carbon number of 1-1 2 or ⁇ _ 01 constituting the branched chain alkylene group having 1 2 - of one or more one hundred and one,
  • [0122] represents an organic group having 2 to 30 carbon atoms, which has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle.
  • the aromatic ring in X and V may have a substituent, and 8X and 8so may be bonded to each other to form a ring.
  • 0 3 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
  • composition for the optically anisotropic layer may contain a component other than the above-mentioned liquid crystal compound.
  • the composition for the optically anisotropic layer may contain a polymerization initiator.
  • the polymerization initiator used is selected according to the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
  • examples of the photopolymerization initiator include ⁇ -carbonyl compound, acyloin ether, Examples include a hydrocarbon-substituted aromatic acylloin compound, a polynuclear quinone compound, and a combination of a triarylimidazole dimer and an aminophenyl ketone.
  • the amount of the polymerization initiator used is preferably 0.01 to 20% by mass, and more preferably 0.5 to 5% by mass, based on the total solid content of the composition.
  • the composition for the optically anisotropic layer may contain a polymerizable monomer.
  • the polymerizable monomer include radically polymerizable or cationically polymerizable compounds.
  • a polyfunctional radically polymerizable monomer is preferable, and one that is copolymerizable with the above-mentioned polymerizable group-containing liquid crystal compound is preferable.
  • those described in paragraphs [0 0 1 8] to [0 0 2 0] of JP-A-2000-2296423 can be mentioned.
  • the content of the polymerizable monomer is preferably 1 to 50 mass% and more preferably 2 to 30 mass% with respect to the total mass of the liquid crystal compound.
  • composition for the optically anisotropic layer may contain a surfactant from the viewpoint of the uniformity of the coating film and the strength of the film.
  • a fluorine compound is particularly preferable.
  • composition for an optically anisotropic layer may contain a dichroic substance from the viewpoint of causing the optically anisotropic layer to function as a polarizer.
  • the above-mentioned dichroic substance is not particularly limited, and visible light absorbing substance (dichroic dye), light emitting substance (fluorescent substance, phosphorescent substance), ultraviolet ray absorbing substance, infrared absorbing substance, non-linear optical substance, carbon nanotube,
  • inorganic substances for example, quantum rods
  • dichroic substances dichroic dyes
  • composition for the optically anisotropic layer may contain an organic solvent.
  • organic solvent include the same ones as described in the above-mentioned composition for photoalignment film of the present invention.
  • the composition for the optically anisotropic layer includes a vertical alignment promoter such as a polarizer interface side vertical aligning agent and an air interface side vertical aligning agent, and a polarizer interface side horizontal aligning agent and an air interface.
  • a vertical alignment promoter such as a polarizer interface side vertical aligning agent and an air interface side vertical aligning agent
  • a polarizer interface side horizontal aligning agent and an air interface include aligning agents such as a horizontal alignment promoting agent such as a side horizontal aligning agent.
  • composition for an optically anisotropic layer may contain an adhesion improver, a plasticizer, a polymer and the like in addition to the above components.
  • the method for forming the optically anisotropic layer using the composition for optically anisotropic layer is not particularly limited.
  • the composition for optically anisotropic layer may be applied onto the above-mentioned photo-alignment film.
  • Examples include a method of forming a coating film and subjecting the obtained coating film to a curing treatment (irradiation with ultraviolet rays (light irradiation treatment) or heat treatment) to form an optically anisotropic layer.
  • composition for the optically anisotropic layer can be applied by a known method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).
  • a known method eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method.
  • the film thickness of the optically anisotropic layer is not particularly limited, and is preferably 0.1 to 10 and more preferably 0.5 to 5.
  • the in-plane retardation of the optically anisotropic layer at a wavelength of 550 n is not particularly limited, but 110 to 160 is preferable. ⁇ 2020/175 620 40 ⁇ (: 171? 2020 /008033
  • the laminated body can be applied to various uses.
  • an image display device including a display element and a laminated body can be mentioned.
  • the display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter, abbreviated as “M!”) display panel, and a plasma display panel. Liquid crystal cells or organic display panels are preferred. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, and an organic date display device using an organic semiconductor display panel as a display element.
  • An organic semiconductor display device which is an example of the image display device of the present invention includes, for example, a polarizer, the laminate of the present invention, and an organic solar display panel in this order from the viewing side. Aspects are preferred.
  • the above-mentioned polarizer is not particularly limited as long as it is a member having a function of converting light into a specific linearly polarized light, and as an absorption-type polarizer that can utilize a conventionally known absorption-type polarizer and reflection-type polarizer, An iodine-based polarizer, a dye-based polarizer using a dichroic dye, and a polyene-based polarizer are used.
  • the iodine-based polarizer and the dye-based polarizer include a coating-type polarizer and a stretch-type polarizer, both of which are applicable.
  • Patent No. 50481 2 0 Publication Patent 5 1 439 18 Publication
  • Patent No. 469 1 205 Japanese Patent No. 475 1 481 and Japanese Patent No. 475 1 486 can be mentioned.
  • ⁇ 2020/175 620 41 Japanese Patent No. 475 620 41 ⁇ (:171? 2020/008033
  • Examples of reflective polarizers include a polarizer in which thin films having different birefringence are laminated, a wire-grid polarizer, and a polarizer in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wavelength plate are combined. Is mentioned.
  • polyvinyl alcohol resin In particular, a polarizer containing at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymer is preferable.
  • the thickness of the polarizer is not particularly limited and is preferably 3 to 60, more preferably 5 to 30.
  • An organic semiconductor display panel is a member in which a light emitting layer or a plurality of organic compound thin films including the light emitting layer are formed between a pair of electrodes of an anode and a cathode.
  • the organic display panel may have a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a protective layer, and the like, and each of these layers is different. It may have the function of.
  • reaction solution was cooled to room temperature (23 ° C)
  • the reaction solution was suction filtered to remove the precipitated salt.
  • the obtained organic layer was stirred with a stirring blade, a thermometer, a dropping port and a reflux tube. It was transferred to a 2 1_3 flask equipped with it and stirred under water cooling.
  • the following monomer 8_1 corresponds to the monomer forming the above-mentioned repeating unit 8_1.
  • the following monomer, which forms the repeating unit, Minichi 1, is used as (Manufactured by Daicel) was used.
  • Polymer 1 having a photoalignable group was obtained by drying with air blowing for a period of time.
  • Composition 1 for photo-alignment film was prepared as follows. Composition for photo-alignment film 1 Polymer _ 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Part by mass Thermal acid generator port _ 1 3.0 0 parts by mass Diisopropylethylamine 0.60 parts by mass Putyl acetate 9 5 3.1 2 parts by mass ⁇ 2020/175 620 44 ⁇ (:171? 2020 /008033
  • the prepared composition for photo-alignment film 1 was sealed in a glass bottle and stored in a sealed state at normal temperature for 7 days.
  • the cellulose acylate film As the cellulose acylate film, the same film as that used in Example 6 of Japanese Patent Laid-Open No. 20 1 2-2 15 6 8 9 was used. On one surface of this film, the composition for photo-alignment film 1 stored for 7 days was applied by a bar coater. Then, the film coated with the composition for photo-alignment film 1 was dried on a hot plate at 125° for 2 minutes to remove the solvent, and a precursor film having a thickness of 0.3 was formed. Irradiation of the obtained precursor film with polarized ultraviolet light By using an ultra-high pressure mercury lamp), a photo-alignment film was formed.
  • the following coating solution 1 for optically anisotropic layer was coated on the photo-alignment film using a bar coater.
  • the coating film formed on the photo-alignment film is heated to 120 ° ⁇ with warm air and then cooled to 60 ° ⁇ , and then a high-pressure mercury lamp is used in a nitrogen atmosphere for a wavelength of 1 20 ° ⁇
  • a high-pressure mercury lamp is used in a nitrogen atmosphere for a wavelength of 1 20 ° ⁇
  • a laminate was produced in the same manner as in Example 1 except that the composition 2 for a photo-alignment film was changed to the composition 2 for a photo-alignment film.
  • Composition for photo-alignment film 2 Polymer _ 1 1 00.00 parts by weight The above thermal acid generator port _ 1 3.00 parts by weight Diisopropylethylamine 0.011 3 parts by weight Putyl acetate 953.1.2 parts by weight Methyl Tyrketone 238. 28 parts by mass
  • a laminate was produced in the same manner as in Example 1 except that the composition 3 for a photo-alignment film was changed to the composition 3 for a photo-alignment film.
  • Polymer _ 1 10.00 0.00 parts by mass
  • Thermal acid generator port _ 1 3.00 parts by mass Diisopropylethylamine 2.03 parts by mass Putyl acetate 953.
  • An optical layered body was produced in the same manner as in Example 1 except that the composition 4 for the photo-alignment film was changed to the composition 4 for the photo-alignment film.
  • This optical laminate was used as the optical laminate of Example 4.
  • Composition for photo-alignment film 4 Polymer _ 1 1 00.00 parts by mass Thermal acid generator mouth _ 1 3.00 parts by mass Triptylamine ⁇ .86 parts by mass Putyl acetate 953.1.2 parts by mass Methyl ethyl ketone 238. 28 parts by mass
  • optically anisotropic layer coating liquid 2 instead of the optically anisotropic layer coating liquid 1 used in Example 1, the following optically anisotropic layer coating liquid 2 was used, and following the same procedure as in Example 1, using a bar coater, Coating solution 2 for optically anisotropic layer was applied.
  • the coating film formed on the alignment film was heated to 1 0_Rei ° ⁇ with warm air, then, using a high pressure mercury lamp under a nitrogen atmosphere was cooled to 90 ° ⁇ ,
  • Coating liquid for optically anisotropic layer 2 Polymerizable liquid crystal compound 1-_ 4 40.00 parts by mass Polymerizable liquid crystal compound 1-_ 5 40.00 part by mass Polymerizable liquid crystal compound-1-20.00 part by mass Above Polymerization initiator 3 _ 1 ⁇ .60 parts by mass Polymerizable compound below _ 1 7.00 parts by mass Leveling agent (above compound _ 1) ⁇ .1 ⁇ parts by mass Methyl ethyl ketone 200.00 parts by mass Cyclopentanone 200.00 parts by mass
  • a laminate was produced in the same manner as in Example 1 except that the composition for photoalignment film 1 was changed to the following composition for photoalignment film 5.
  • Composition for photo-alignment film 5 Polymer _ 1 1 00.00 parts by mass The above thermal acid generator mouth _ 1 3.00 parts by mass Putyl acetate 953. 1 2 parts by mass Methyl ethyl ketone 238. 28 parts by mass
  • a laminate was produced in the same manner as in Example 1 except that the composition for photoalignment film 1 was changed to the composition for photoalignment film 6 below.
  • Composition for photo-alignment film 6 Polymer _ 1 1 00.00 parts by mass The above thermal acid generator mouth _ 1 3.00 parts by mass — Butylamine ⁇ .34 parts by mass Putyl acetate 953.1.2 parts by mass ⁇ 2020/175 620 50 ⁇ (: 171? 2020 /008033
  • Minami There is very little light leakage in the observation field of view.
  • a pressure-sensitive adhesive was attached to the laminate obtained in each of the examples and comparative examples, the adhesive surface was attached to glass, and the laminate and the glass were attached to each other at a temperature of 85 ° C and a humidity of 85%. 6 (550) of the laminate after holding for 72 hours in the above environment was evaluated based on the following criteria.
  • Min When the ratio of 8 ⁇ (550) after holding is less than 98% under 6 (550) before holding in an environment of temperature 85 ° and humidity 85%.
  • the "addition amount” column of "acid generator” represents the content (% by mass) of the acid generator with respect to the total mass of the photoalignable copolymer.
  • the "addition amount” column of "amine compound” represents the content (molar amount) of the amine compound with respect to the total moles of the acid generator.
  • Liquid crystal 1 means that the coating liquid 1 for optically anisotropic layer was used, ⁇ 2020/175 620 51 ⁇ (: 171? 2020/008033
  • Liquid crystal 2 means that the coating liquid 2 for optically anisotropic layer was used.
  • composition for photo-alignment film 1 was applied to the cellulose acylate film 1 with a slit die coater so as to have a coating width of 1310. Then photo-alignment ⁇ 2020/175 620 52 ⁇ (:171? 2020 /008033
  • the film coated with the film composition 1 was blown with hot air at 125 ° to dry for 2 minutes to remove the solvent and form a precursor film having a thickness of 0.3. Irradiation of the obtained precursor film with polarized ultraviolet light By using an ultra-high pressure mercury lamp), a long photo-alignment film was formed.
  • a slit die coater was used to apply the coating liquid 2 for optically anisotropic layer with a coating width of 1320 so as to completely cover both sides of the photo-alignment film.
  • a coating film with hot air heated to 1 0_Rei ° ⁇ , then using a high-pressure mercury lamp under a nitrogen atmosphere and the mixture was cooled to 9 0 ° ⁇ at wavelength 3 6 5 nm
  • the coating film was irradiated with UV of 50,000"/ ⁇ 2 while heating it to 125°.
  • the orientation of the liquid crystal compound was fixed, and the laminate (long film) of Example 6 was produced.
  • the thickness of the 140 optically anisotropic layer was 2.5 ⁇ Ji rr ⁇ s (meth)acryloyl reaction rate was 85 %.
  • Example 7 was applied so as to completely cover both sides of the photo-alignment film. While the coating liquid was in an undried state, a scraper was pressed against both ends of the film as a scraping member to thin the coating liquid 2 for the optically anisotropic layer. In addition, in the present Example 7, from one end of the substrate to 10 ⁇ 3 The range is lightly coated. Subsequently, the coating film was dried and the orientation was fixed in the same manner as in Example 6 to produce the laminate of Example 7. Of the obtained laminate (5 5 0) 1 4 0 n m, 2 is the center thickness of the optical anisotropic layer. 5 "1, part of the thickness 1 interest thin coating in the manner described above at the end of the optically anisotropic layer, (Meth) acryloyl reaction rate was 85%
  • the coating liquid 2 for optically anisotropic layer was applied to the photo-alignment film in the same manner as in Example 6. After that, the coating film formed on the orientation film is heated to 100 ° with hot air and cooled to 90 ° , and then the web edge part to 30 To the left and right Using a high-pressure mercury lamp equipped with a shading plate, irradiate the coating film with 100 mJ / cm 2 of ultraviolet light at a wavelength of 365 nm, and then do not heat it to 125 °C for the second irradiation. The entire surface of the coating film was irradiated with ultraviolet rays of 500 m J / cm 2 without providing a light shielding plate.
  • the alignment of the liquid crystal compound was fixed, and the laminate of Example 8 was produced.
  • the R e (550) of the obtained laminate was 140 nm, the thickness was 2.5 ⁇ m, and the (meth)acryloyl reaction rate was 85%.
  • the coating liquid 2 for optically anisotropic layer was applied to the photo-alignment film.
  • the coating film formed on the alignment film was heated to 100 ° C with warm air, cooled to 90 ° C, and then, under a nitrogen atmosphere, a high pressure mercury lamp was used to set a wavelength of 100 nm. Irradiate the entire surface of the coating with mJ/cm 2 of UV light, and then heat it to 125°C while using a high pressure mercury lamp equipped with a light shield plate at a position of 3 Omm from the edge of the web to 50 OmJ/cm 2 .
  • the coating film was irradiated with ultraviolet rays.
  • Example 9 the orientation of the liquid crystal compound was fixed, and the laminate of Example 9 was produced.
  • the region where the second layer was not irradiated with UV light from the light-shielding plate of the obtained laminate had a Re (550) of 140 nm, an optically anisotropic layer thickness of 2.5 Mm, and a (meth)acryloyl reaction. The rate was 60%.
  • the edge of the support during transportation was visually evaluated.
  • Mami The unsupported area between the transport ports, where the web edge is
  • Example 6 in the long film coated with the composition for a photo-alignment film of the present invention, a force is likely to be generated at the end portion, but as shown in Examples 7 to 9, It can be improved by partial processing.

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Abstract

The present invention provides: a photoalignment film composition capable of, even after being preserved for a predetermined period of time, forming a photoalignment film having excellent liquid crystal aligning ability with respect an optical anisotropic layer formed thereon; a photoalignment film; and a laminate. This photoalignment film composition contains: a photoalignment copolymer which has a repeating unit A including a photoalignment group and a repeating unit B including a cross-linking group and in which content a of the repeating unit A and content b of the repeating unit B satisfy formula (1) in mass ratio; an acid generator; and an amine compound having a boiling point of 50-230°C and not having a proton on a nitrogen atom. (1): 0.70≤b/(a+b)≤0.97

Description

\¥0 2020/175620 1 卩（：17 2020 /008033 明 細 書 \¥0 2020/175 620 1 ((17 2020/008033 Clarification
発明の名称 ： 光配向膜用組成物、 光配向膜、 積層体 Title of invention: Composition for photo-alignment film, photo-alignment film, laminate
技術分野 Technical field
[0001 ] 本発明は、 光配向膜用組成物、 光配向膜、 および、 積層体に関する。 The present invention relates to a composition for photo-alignment film, a photo-alignment film, and a laminate.
背景技術 Background technology
[0002] 液晶化合物を用いて形成される光学異方性層は、 光学補償シートおよび位 相差フィルムなどとして種々の用途に用いられている。 このような光学異方 性層を形成するための配向膜として、 光配向膜が知られている。 [0002] Optically anisotropic layers formed using liquid crystal compounds are used in various applications such as optical compensation sheets and retardation films. An optical alignment film is known as an alignment film for forming such an optically anisotropic layer.
特許文献 1 には、 光シンナメート基を含む構成単位 3 1 を有する重合体八 と、 シンナメート基を有し、 重合体八よりも分子量が小さい低分子化合物巳 と、 を含む光配向膜用組成物が開示されている。 Patent Document 1 discloses a composition for a photo-alignment film containing a polymer 8 having a structural unit 3 1 containing a photocinnamate group, a low molecular weight compound having a cinnamate group and having a smaller molecular weight than the polymer 8. Is disclosed.
先行技術文献 Prior art documents
特許文献 Patent literature
[0003] 特許文献 1 :国際公開第 2 0 1 7 / 0 6 9 2 5 2号 [0003] Patent Document 1: International Publication No. 2 0 1 7/0 6 9 2 5 2
発明の概要 Summary of the invention
発明が解決しようとする課題 Problems to be Solved by the Invention
[0004] 本発明者らは、 特許文献 1 に記載された、 光配向性基を含む構成単位 3 1 と架橋性基を含む構成単位 3 2とを有し、 架橋性基を含む構成単位 3 2の比 率が高い共重合体と、 酸発生剤とを含む光配向膜用組成物の特性について検 言寸した。 The present inventors have a structural unit 3 1 having a photoalignable group-containing structural unit 3 1 and a crosslinkable group-containing structural unit 3 2 described in Patent Document 1, and a crosslinkable group-containing structural unit 3 The characteristics of the composition for a photo-alignment film containing a copolymer having a high ratio of 2 and an acid generator were measured.
具体的には、 調製後から数日間 （例えば、 1週間程度） 保存した光配向膜 用組成物を用いて形成した光配向膜と、 調製直後の光配向膜用組成物を用い て形成した光配向膜とを用意し、 両者の上に液晶化合物を含む組成物を用い て光学異方性層を形成して、 液晶化合物の配向性を評価した。 その結果、 調 製後から数日間保存した光配向膜用組成物を用いた場合に、 液晶化合物の配 向性が劣化することが知見された。 以後、 光学異方性層において液晶化合物 の配向性が優れることを、 「液晶配向性に優れる」 ともいう。 〇 2020/175620 2 卩（：171? 2020 /008033 Specifically, a photo-alignment film formed using the composition for photo-alignment film stored for several days (for example, about 1 week) after preparation and a photo-alignment film formed using the composition for photo-alignment film immediately after preparation An alignment film was prepared, and an optically anisotropic layer was formed on both of them using a composition containing a liquid crystal compound, and the alignment property of the liquid crystal compound was evaluated. As a result, it was found that the orientation of the liquid crystal compound was deteriorated when the composition for photoalignment film stored for several days after preparation was used. Hereinafter, the excellent alignment of the liquid crystal compound in the optically anisotropic layer is also referred to as “excellent liquid crystal alignment”. 〇 2020/175 620 2 卩 (: 171-1? 2020 /008033
本発明は、 所定期間保存した後でも、 その上に形成された光学異方性層の 液晶配向性が優れる光配向膜を形成できる光配向膜用組成物を提供すること を課題とする。 An object of the present invention is to provide a composition for a photo-alignment film capable of forming a photo-alignment film in which an optically anisotropic layer formed thereon has excellent liquid crystal alignment even after storage for a predetermined period.
また、 本発明は、 光配向膜および積層体を提供することも課題とする。 課題を解決するための手段 Moreover, this invention also makes it a subject to provide a photo-alignment film and a laminated body. Means for solving the problem
[0005] 本発明者は、 従来技術の問題点について鋭意検討した結果、 以下の構成に より上記課題を解決できることを見出した。 [0005] As a result of earnest studies on the problems of the prior art, the present inventor has found that the above problems can be solved by the following configurations.
[0006] （1） 光配向性基を含む繰り返し単位 と、 架橋性基を含む繰り返し単位 巳とを有し、 (1) having a repeating unit containing a photoalignable group and a repeating unit containing a crosslinkable group
繰り返し単位 の含有量 3と、 繰り返し単位巳の含有量 とが、 質量比で 下記式 （1） を満たす光配向性共重合体と、 A photo-alignable copolymer in which the content of the repeating unit 3 and the content of the repeating unit satisfy the following formula (1) in a mass ratio:
〇. 7 0 £匕/ （3 + 13） £〇. 9 7 · · · （1） ○ 0.70 匕 / (3 + 13) £ ○. 9 7 ··· (1)
酸発生剤と、 An acid generator,
沸点が 5 0〜 2 3 0 °〇であり、 窒素原子上にプロトンを有さないアミン化 合物と、 を含む光配向膜用組成物。 A composition for a photo-alignment film, which comprises an amine compound having a boiling point of 50 to 230 ° and having no proton on a nitrogen atom.
（2） アミン化合物が後述する式 （2） で表される化合物を含む、 （1） に記載の光配向膜用組成物。 (2) The composition for a photo-alignment film according to (1), wherein the amine compound contains a compound represented by the formula (2) described below.
（3） アミン化合物の含有量が、 酸発生剤の含有モル量に対して、 5〜 4 0 0モル％である、 （1） または （2） に記載の光配向膜用組成物。 (3) The composition for a photo-alignment film according to (1) or (2), wherein the content of the amine compound is 5 to 400 mol% with respect to the content molar amount of the acid generator.
（4） 光配向性基を含む繰り返し単位 が、 後述する式 （ ） で表される 繰り返し単位を含み、 (4) The repeating unit containing a photoalignable group contains a repeating unit represented by the formula () described below,
架橋性基を含む繰り返し単位巳が、 後述する式 （巳） で表される繰り返し 単位を含む、 （1） 〜 （3） のいずれかに記載の光配向膜用組成物。 The composition for a photo-alignment film according to any one of (1) to (3), wherein the repeating unit containing a crosslinkable group contains a repeating unit represented by the following formula (Mi).
（5） 架橋性基を含む繰り返し単位巳が、 後述する式 （X I） 〜 （乂3） のいずれかで表される架橋性基を含む、 （1） 〜 （4） のいずれかに記載の 光配向膜用組成物。 (5) The repeating unit including a crosslinkable group contains a crosslinkable group represented by any of the formulas (XI) to (3) described below, and the repeating unit according to any one of (1) to (4) Composition for photo-alignment film.
（6） （1） 〜 （5） のいずれかに記載の光配向膜用組成物を用いて形成 した、 光配向膜。 〇 2020/175620 3 卩（：171? 2020 /008033 (6) An optical alignment film formed by using the composition for an optical alignment film according to any one of (1) to (5). 〇 2020/175 620 3 卩 (：171? 2020 /008033
（7） （6） に記載の光配向膜と、 (7) The photo-alignment film according to (6),
液晶化合物を含む液晶組成物を用いて形成される光学異方性層と、 を有す る、 積層体。 An optical anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound, and a laminate.
発明の効果 Effect of the invention
[0007] 本発明によれば、 所定期間保存した後でも、 その上に形成された光学異方 性層の液晶配向性に優れる光配向膜を形成できる光配向膜用組成物を提供で きる。 According to the present invention, it is possible to provide a composition for a photo-alignment film, which can form a photo-alignment film having excellent liquid crystal alignment of the optically anisotropic layer formed thereon even after storage for a predetermined period.
また、 本発明によれば、 光配向膜および積層体を提供できる。 発明を実施するための形態 Moreover, according to this invention, a photo-alignment film and a laminated body can be provided. MODE FOR CARRYING OUT THE INVENTION
[0008] 以下、 本発明について詳細に説明する。 なお、 本明細書において 「〜」 を 用いて表される数値範囲は、 「〜」 の前後に記載される数値を下限値および 上限値として含む範囲を意味する。 まず、 本明細書で用いられる用語につい て説明する。 Hereinafter, the present invention will be described in detail. In addition, in this specification, the numerical range represented by using "-" means the range which includes the numerical values described before and after "-" as a lower limit and an upper limit. First, the terms used in this specification will be explained.
[0009] 本発明において、
Figure imgf000004_0001
6 （ス） および [¾ 1: （ス） は、 それぞれ波長スにお ける面内のレタデーシヨンおよび厚み方向のレタデーシヨンを表す。 特に記 載がないときは、 波長スは、 5 5 0 n mとする。 [0009] In the present invention,
Figure imgf000004_0001
6 (s) and [¾ 1: (s) represent in-plane retardation and thickness-direction retardation at wavelengths, respectively. Unless otherwise specified, the wavelength is 550 nm.
本発明において、 ^㊀ （ス） および
Figure imgf000004_0002
（ス） は八父〇 3〇 8门 0 9 1\/1 ー 1 （オプトサイエンス社製） において、 波長スで測定した値である。 八 X〇 3〇 8 にて平均屈折率 （
Figure imgf000004_0004
/ 3） と膜厚 （¢1
Figure imgf000004_0003
） ） を入力することにより、 In the present invention, ^ ㊀ (s) and
Figure imgf000004_0002
The value in (s) is the value measured by the wavelength value in Yachibu 0380 1/1/1 (manufactured by Optoscience). Average refractive index (
Figure imgf000004_0004
/ 3) and film thickness (¢1
Figure imgf000004_0003
)) by typing
遅相軸方向 （° ） Slow axis direction ( ° )
（ス） = [¾ 0 （ス） (S) = [¾ 0 (s)
（ス） = （ （1^十％） / " 2—〇 ^ X ¢1 (S) = ((1^10%) / "2—〇^X¢1
が算出される。 Is calculated.
なお、 [¾〇 （ス） は、 八父〇 3〇 3门 〇 1\/1 ー 1で算出される数値と して表示されるものであるが、 （ス） を意味している。 In addition, [¾ 〇 (s) is displayed as the value calculated by Yachibu 〇 03 门 〇 1\/1-1 and means (s ).
[0010] 八 X〇 3〇 8 にて用いられる平均屈折率は、 アッベ屈折計
Figure imgf000004_0005
— 4 丁、 アタゴ （株） 製） を使用し、 光源にナトリウムランプ （ス = 5 8 9 n 〇 2020/175620 4 卩（：171? 2020 /008033 [0010] The average refraction index used in 8 X 0 30 8 is the Abbe refractometer.
Figure imgf000004_0005
— 4 units, manufactured by Atago Co., Ltd., and used a sodium lamp (s = 5 8 9 n ) as the light source. 〇 2020/175 620 4 卩 (：171? 2020 /008033
） を用いて測定する。 また、 波長依存性を測定する場合は、 多波長アッベ屈 折計
Figure imgf000005_0001
— 1\/1 2 （アタゴ （株） 製） にて、 干渉フィルターとの組み合わせで 測定できる。 ) Is used for measurement. In addition, when measuring the wavelength dependence,
Figure imgf000005_0001
— 1\/1 2 (manufactured by ATAGO Co., Ltd.) can be used in combination with an interference filter.
また、 ポリマーハンドブック （」〇1~1 \^丨 1_巳丫& 3〇 3 , I N 0） 、 および、 各種光学フィルムのカタログの値を使用できる。 主な光学フィル ムの平均屈折率の値を以下に例示する ：セルロースアシレート （1 . 4 8）Also, the values in the Polymer Handbook (“○ 1 to 1 \^ 丨 1_ 跳丫 & 30,000, IN 0) and catalogs of various optical films can be used. Examples of the average refractive index values of major optical films are given below: Cellulose acylate (1.48)
、 シクロオレフィンポリマー （1 . 5 2） 、 ポリカーボネート （1 . 5 9） 、 ポリメチルメタクリレート （ 1 . 4 9） 、 ポリスチレン （ 1 . 5 9） 。 , Cycloolefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), polystyrene (1.59).
[001 1 ] また、 （メタ） アクリロイル基は、 アクリロイル基およびメタクリロイル 基の両方を含む概念である。 [001 1] Further, the (meth)acryloyl group is a concept including both an acryloyl group and a methacryloyl group.
[0012] 本発明の光配向膜用組成物の特徴点としては、 所定のアミン化合物を含む 点が挙げられる。 A feature of the composition for a photo-alignment film of the present invention is that it contains a predetermined amine compound.
上述したように、 本発明者らは、 光配向性共重合体中において架橋性基を 含む繰り返し単位の含有量が多い場合、 所定期間保存した後の光配向膜用組 成物を用いて光配向膜を形成して、 その上に光学異方性層を形成すると、 得 られる光学異方性層の液晶配向性が劣ることを知見している。 その原因につ いて検討したところ、 架橋性基を含む繰り返し単位の含有量が多い場合、 光 配向膜用組成物を保存している間に、 酸発生剤から発生した酸によって架橋 性基の反応が進行してしまい、 その結果、 液晶配向性に影響を与えることを 知見した。 そして、 そのような架橋性基の反応を抑制するために、 所定のア ミン化合物を用いると、 酸発生剤の影響が軽減でき、 所望の効果が得られる ことを見出している。 As described above, when the content of the repeating unit containing a crosslinkable group in the photoalignable copolymer is high, the inventors of the present invention used the composition for photoalignment film after storage for a predetermined period of time to perform the It has been found that when an alignment film is formed and an optically anisotropic layer is formed thereon, the liquid crystal alignment property of the obtained optically anisotropic layer is inferior. As a result of examining the cause, when the content of the repeating unit containing a crosslinkable group is large, the reaction of the crosslinkable group by the acid generated from the acid generator during the storage of the composition for photoalignment film. It has been found that the liquid crystal progresses, and as a result, the liquid crystal alignment is affected. Then, they have found that the use of a predetermined amine compound in order to suppress the reaction of such a crosslinkable group can reduce the influence of the acid generator and obtain a desired effect.
なお、 上記光配向膜上に形成される光学異方性層は、 後述する実施例欄で 評価する耐久性にも優れる。 The optically anisotropic layer formed on the photo-alignment film is also excellent in durability evaluated in the Example section described later.
[0013] 本発明の光配向膜用組成物は、 光配向性基を含む繰り返し単位 と架橋性 基を含む繰り返し単位巳とを所定の光配向性共重合体と、 酸発生剤と、 所定 のアミン化合物とを含む。 The composition for a photo-alignment film of the present invention comprises a repeating unit containing a photo-alignable group and a repeating unit containing a cross-linkable group, a predetermined photo-alignable copolymer, an acid generator, and a predetermined And an amine compound.
以下、 まず、 光配向膜用組成物に含まれる各成分について詳述する。 なお 〇 2020/175620 5 卩（：171? 2020 /008033 Hereinafter, first, each component contained in the composition for a photo-alignment film will be described in detail. Note that 〇 2020/175 620 5 卩 (: 171? 2020 /008033
、 以下では、 本発明の特徴点の一つであるアミン化合物について先に詳述す る。 The amine compound, which is one of the features of the present invention, will be described in detail below.
[0014] ＜アミン化合物＞ [Amine Compound]
光配向膜用組成物は、 沸点が 5 0〜 2 3 0 °〇であり、 窒素原子上にプロト ンを有さないアミン化合物 （以下、 「特定アミン化合物」 ともいう。 ） を含 む。 The composition for photo-alignment film has a boiling point of 50 to 230 ° and an amine compound having no proton on the nitrogen atom (hereinafter, also referred to as “specific amine compound”).
特定アミン化合物の沸点は、 5 0〜2 3 0 °〇であり、 光配向膜上に形成さ れる光学異方性層の液晶配向性がより優れる点 （以下、 単に 「本発明の効果 がより優れる点」 ともいう。 ） で、 8 0〜 2 2 5 °〇が好ましく、 1 0 0〜 2 2 0 °〇がより好ましい。 なお、 上記沸点は、 1気圧下における沸点を意味す る。 The boiling point of the specific amine compound is 50 to 230 ° 〇, and the liquid crystal alignment property of the optically anisotropic layer formed on the photo-alignment film is more excellent (hereinafter, simply “the effect of the present invention It is also referred to as "excellent point."), 80 to 225 ° is preferable, and 100 to 220 ° is more preferable. The above boiling point means the boiling point at 1 atm.
特定アミン化合物は、 窒素原子上にプロトンを有さない。 つまり、 ＞1\1 _ 1~1で表される部分構造を有さない。 光配向膜用組成物が＞ 1\] _ ! !で表される 部分構造を有するアミン化合物を含む場合、 液晶配向性の改善がみられず、 光配向膜用組成物がゲル化する恐れがある。 Certain amine compounds do not have a proton on the nitrogen atom. That is, it does not have a partial structure represented by >1\1 _ 1 ~ 1. When the composition for photo-alignment film contains an amine compound having a partial structure represented by >1\]_!!, the liquid crystal alignment property is not improved, and the composition for photo-alignment film may gel. is there.
[0015] 特定アミンは、 上記特性を満たせば特に制限されず、 2級アミンおよび 3 級アミンが挙げられる。 [0015] The specific amine is not particularly limited as long as it satisfies the above characteristics, and examples thereof include secondary amines and tertiary amines.
また、 特定アミンは、 鎖状であっても、 環状であってもよい。 特定アミン が環状である場合としては、 特定アミンが複素環を有する場合が挙げられる 。 複素環としては、 芳香族複素環であっても、 脂肪族複素環であってもよい 。 複素環としては、 ピリジン環が挙げられる。 Further, the specific amine may be linear or cyclic. Examples of the case where the specific amine is cyclic include the case where the specific amine has a heterocycle. The heterocycle may be an aromatic heterocycle or an aliphatic heterocycle. Examples of the heterocycle include a pyridine ring.
なお、 特定アミンが複素環を有する場合、 複素環は置換基を有していても よい。 置換基としては、 例えば、 アルキル基、 および、 アルコキシ基が挙げ られる。 When the specific amine has a heterocycle, the heterocycle may have a substituent. Examples of the substituent include an alkyl group and an alkoxy group.
[0016] 特定アミンとしては、 本発明の効果がより優れる点で、 式 （2） で表され る化合物が好ましい。 [0016] As the specific amine, the compound represented by the formula (2) is preferable because the effect of the present invention is more excellent.
[0017] [化 1 ] [0017] [Chemical 1]
Figure imgf000007_0001
Figure imgf000007_0001
[0018] 式 （2） 中、 R 1、 R 2、 および、 R 3は、 それぞれ独立に、 炭素数 1〜 2 0 の直鎖状、 分岐鎖状または環状のアルキル基を表す。 In the formula (2), R 1 , R 2 and R 3 each independently represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
上記アルキル基の炭素数は 1〜 2 0であり、 本発明の効果がより優れる点 で、 1〜 1 0が好ましく、 2〜 5がより好ましい。 The alkyl group has 1 to 20 carbon atoms, and from the viewpoint that the effect of the present invention is more excellent, 1 to 10 is preferable, and 2 to 5 is more preferable.
上記アルキル基としては、 例えば、 メチル基、 エチル基、 プロピル基 （例 えば、 n _プロピル基、 および、 イソプロピル基） 、 プチル基、 および、 ぺ ンチル基が挙げられる。 Examples of the alkyl group include a methyl group, an ethyl group, a propyl group (for example, an n_propyl group and an isopropyl group), a butyl group, and a pentyl group.
[0019] 上記特定アミンとしては、 例えば、 ジイソプロピルエチルアミン、 および 、 トリプチルアミンが挙げられる。 [0019] Examples of the specific amine include diisopropylethylamine and triptylamine.
[0020] ＜光配向性共重合体＞ [0020] <Photo-alignable copolymer>
光配向膜用組成物は、 所定の繰り返し単位を有する光配向性共重合体を含 む。 The composition for photo-alignment film contains a photo-alignable copolymer having a predetermined repeating unit.
[0021 ] （光配向性基を含む繰り返し単位 A） [0021] (Repeating unit A containing a photoalignable group)
光配向性共重合体は、 光配向性基を含む繰り返し単位 Aを有する。 ここで、 「光配向性基」 とは、 異方性を有する光 （例えば、 平面偏光など ） の照射により、 再配列または異方的な化学反応が誘起される光配向機能を 有する基をいい、 配向の均一性に優れ、 熱的安定性または化学的安定性も良 好となる点から、 光の作用により二量化および異性化の少なくとも一方が生 じる光配向性基が好ましい。 The photoalignable copolymer has a repeating unit A containing a photoalignable group. Here, the “photoalignable group” refers to a group having a photoalignment function in which rearrangement or an anisotropic chemical reaction is induced by irradiation with light having anisotropy (for example, plane polarized light). A photo-alignment group capable of undergoing at least one of dimerization and isomerization under the action of light is preferable because it has excellent alignment uniformity and also has favorable thermal stability or chemical stability.
[0022] 光の作用により二量化する光配向性基としては、 例えば、 桂皮酸誘導体 （M . Schadt et a 1. , J. App 1. Phys. , vo l. 31 , No. 7, page 2155 （1992）） 、 クマリン誘導体 （M. Schadt et a 1. , Nature. , vo l. 381 , page 212 （1996） ） 、 カルコン誘導体 （小川俊博他、 液晶討論会講演予稿集， 2AB03（1997）） 、 マレイミ ド誘導体、 および、 ベンゾフエノン誘導体 （Y. K. Jang et al., SI D Int. Symposium Digest, P-53（1997）） からなる群から選択される少なくと も 1種の誘導体の骨格を有する基が挙げられる。 [0022] Examples of the photo-orienting group that dimerizes by the action of light include cinnamic acid derivatives (M. Schadt et a 1., J. App 1. Phys., vo l. 31, No. 7, page 2155 (1992)), coumarin derivative (M. Schadt et a 1., Nature., vo l. 381, page 212 (1996) ), chalcone derivative (Toshihiro Ogawa et al., Proceedings of the Liquid Crystal Conference, 2AB03 (1997)), maleimide derivative, and benzophenone derivative (YK Jang et al., SI D Int. Symposium Digest, P-53 (1997)) A group having a skeleton of at least one derivative selected from the group consisting of
一方、 光の作用により異性化する光配向性基としては、 例えば、 アゾベン ゼン化合物 （K. Ichimura et al. , Mol. Cryst. Liq. Cryst 298, 221 （1997） ） 、 スチルベン化合物 （丄 G. Victor and 丄 M.Torke Ison, Macromolecules, 20 , 2241 （1987）） 、 スピロピラン化合物 （K. Ichimura et a 1. , Chemistry Le tters, page 1063 （1992） ; K. Ichimura et al·, Thin Solid Films, vol. 23 5, page 101 （1993）） 、 桂皮酸化合物 （K. Ichimura et a 1. , Macromo lecu les, 30, 903 （1997）） 、 および、 ヒドラゾノー /S—ケトエステル化合物 （S. Yam amura et a 1. , Liquid Crystals, vol. 13, No. 2, page 189 （1993）） から なる群から選択される少なくとも 1種の化合物の骨格を有する基が挙げられ る。 On the other hand, examples of the photo-orienting group that is isomerized by the action of light include an azobenzene compound (K. Ichimura et al., Mol. Cryst. Liq. Cryst 298, 221 (1997)) and a stilbene compound (G. Victor and B. M. Torke Ison, Macromolecules, 20, 2241 (1987)), Spiropyran compounds (K. Ichimura et a 1., Chemistry Letters, page 1063 (1992); K. Ichimura et al., Thin Solid Films, vol. 23 5, page 101 (1993)), cinnamic acid compound (K. Ichimura et a 1., Macromo lecu les, 30, 903 (1997)), and hydrazono/S-keto ester compound (S. Yam amura et. a 1., Liquid Crystals, vol. 13, No. 2, page 189 (1993)), and a group having a skeleton of at least one compound selected from the group consisting of:
[0023] これらのうち、 光配向性基が、 桂皮酸誘導体、 クマリン誘導体、 カルコン 誘導体、 マレイミ ド誘導体、 アゾベンゼン化合物、 スチルベン化合物、 およ び、 スピロピラン化合物からなる群から選択される少なくとも 1種の誘導体 の骨格を有する基であることが好ましく、 桂皮酸誘導体骨格またはクマリン 誘導体骨格を有する基であることがより好ましい。 [0023] Among these, the photo-alignment group is at least one selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, azobenzene compounds, stilbene compounds, and spiropyran compounds. A group having a derivative skeleton is preferable, and a group having a cinnamic acid derivative skeleton or a coumarin derivative skeleton is more preferable.
[0024] 繰り返し単位 Aとしては、 本発明の効果がより優れる点で、 下記式 （A） で表される繰り返し単位が好ましい。 As the repeating unit A, a repeating unit represented by the following formula (A) is preferable because the effect of the present invention is more excellent.
[0025] 〇 2020/175620 8 2020 /008033 [0025] 〇 2020/175 620 8 2020/008033
［化 2］ [Chemical 2]
Figure imgf000009_0001
Figure imgf000009_0001
［0026］ ［¾ 5は、 水素原子またはメチル基を表す。 1_ 1は、 窒素原子とシクロアルカ ン環とを含む 2価の連結基を表し、 シクロアルカン環を構成する炭素原子の 一部が、 窒素原子、 酸素原子および硫黄原子からなる群から選択されるへテ 口原子で置換されていてもよい。 8 6、 8 7、 8 8、
Figure imgf000009_0002
それぞ れ独立に、 水素原子または置換基を表し、 ［¾ 6、 ［¾ 7、 ［¾ 8、 ［¾ 9および［¾ 1 0の うち、 隣接する 2つの基が結合して環を形成していてもよい。 [0026] [¾ 5 represents a hydrogen atom or a methyl group. 1_ 1 represents a divalent linking group containing a nitrogen atom and a cycloalkane ring, and some of the carbon atoms constituting the cycloalkane ring are selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. It may be substituted with a carbon atom. 8 6 , 8 7 , 8 8 ,
Figure imgf000009_0002
Each independently represents a hydrogen atom or a substituent, and two adjacent groups of [¾ 6 , [¾ 7 , [¾ 8 , [¾ 9 and [¾ 10] are bonded to each other to form a ring. May be.
［0027］ 次に、 1_ 1が表す、 窒素原子とシクロアルカン環とを含む 2価の連結基につ いて説明する。 なお、 上述した通り、 シクロアルカン環を構成する炭素原子 の一部は、 窒素原子、 酸素原子および硫黄原子からなる群から選択されるへ テロ原子で置換されていてもよい。 また、 シクロアルカン環を構成する炭素 原子の一部が窒素原子で置換されている場合は、 シクロアルカン環とは別に 窒素原子を有していなくてもよい。 [0027] Next, represented 1_ 1, have One divalent linking group will be described that includes a nitrogen atom and a cycloalkane ring. As described above, some of the carbon atoms constituting the cycloalkane ring may be substituted with a hetero atom selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom. In addition, when a part of carbon atoms constituting the cycloalkane ring is substituted with a nitrogen atom, the nitrogen atom may not be present separately from the cycloalkane ring.
［0028］ また、 上記シクロアルカン環としては、 炭素数 6以上のシクロアルカン環 が好ましく、 例えば、 シクロヘキサン環、 シクロぺプタン環、 シクロオクタ ン環、 シクロドデカン環、 および、 シクロドコサン環が挙げられる。 [0028] Further, the cycloalkane ring is preferably a cycloalkane ring having 6 or more carbon atoms, and examples thereof include a cyclohexane ring, a cyclopeptane ring, a cyclooctane ring, a cyclododecane ring, and a cyclodocosane ring.
［0029］ 本発明の効果がより優れる点で、 上記式 （ ） 中の 1_ 1としては、 下記式 （ [0029] In the point that the effect of the present invention is more excellent, the following formula ( 1 ) is used as 1_1 in the above formula ().
1） 〜 （1 0） のいずれかで表される 2価の連結基が好ましい。 The divalent linking group represented by any one of 1) to (10) is preferable.
[0030] \¥0 2020/175620 9 20201008033 [0030] \\0 2020/175 620 9 20201008033
[化 3] [Chemical 3]
Figure imgf000010_0001
Figure imgf000010_0001
［0031］ 上記式 （1） 〜 （1 〇） 中、 * 1は、 上記式 （八） 中の主鎖を構成する炭 素原子との結合位置を表し、 * 2は、 上記式 （ ） 中のカルボニル基を構成 する炭素原子との結合位置を表す。 [0031] In the above formulas (1) to (10), *1 represents the bonding position with the carbon atom constituting the main chain in the above formula (8), and *2 represents the above formula (). Represents the bonding position with the carbon atom constituting the carbonyl group.
［0032］ 上記式 （1） 〜 （1 0） のいずれかで表される 2価の連結基のうち、 光配 向膜を形成する際に用いる溶媒に対する溶解性と、 得られる光配向膜の耐溶 剤性とのバランスが良好となる点から、 上記式 （2） 、 式 （3） 、 式 （7） および式 （8） のいずれかで表される 2価の連結基が好ましい。 [0032] Of the divalent linking groups represented by any of the above formulas (1) to (10), the solubility in the solvent used for forming the light-alignment film and the photo-alignment film obtained are The divalent linking group represented by any one of the above formulas (2), (3), (7) and (8) is preferable from the viewpoint of achieving a good balance with the solvent resistance.
［0033］ 次に、 上記式 （八）
Figure imgf000010_0002
および
Figure imgf000010_0003
[0033] Next, the above formula (8)
Figure imgf000010_0002
and
Figure imgf000010_0003
換基について説明する。 なお、 上記式 （八）
Figure imgf000010_0004
および 1〇が、 置換基ではなく水素原子であってもよいことは上述した通りであるThe substitution group will be described. The above equation (8)
Figure imgf000010_0004
As described above, and 10 may be hydrogen atoms instead of substituents.
〇 〇
［0034］ 上記式 （八）
Figure imgf000010_0005
の一態様が表す置換基は 、 光配向性基が液晶化合物と相互作用しやすくなり、 本発明の効果がより優 れる点で、 それぞれ独立に、 ハロゲン原子、 炭素数 1〜 2 0の直鎖状、 分岐 鎖状もしくは環状のアルキル基、 炭素数 1〜 2 0の直鎖状のハロゲン化アル 〇 2020/175620 10 卩（：171? 2020 /008033 [0034] Expression (8)
Figure imgf000010_0005
The substituents represented by one embodiment are, independently of each other, a halogen atom and a straight chain having 1 to 20 carbon atoms in that the photo-alignment group easily interacts with the liquid crystal compound and the effect of the present invention is more excellent. , Branched or cyclic alkyl groups, straight-chain halogenated alkyl groups with 1 to 20 carbon atoms 〇 2020/175 620 10 boxes (: 171-1? 2020 /008033
キル基、 炭素数 1〜 2 0のアルコキシ基、 炭素数 6〜 2 0のアリール基、 炭 素数 6〜 2 0のアリールオキシ基、 シアノ基、 アミノ基、 または、 下記式 （ 1 1） で表される基であることが好ましい。 Kill group, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, cyano group, amino group or represented by the following formula (11) It is preferable that the group is
[0035] [化 4]
Figure imgf000011_0001
[0035] [Chemical 4]
Figure imgf000011_0001
[0036] ここで、 上記式 （1 1） 中、 氺は、 上記式 （八） 中のベンゼン環との結合 位置を表し、 [¾ 1 2は、 1価の有機基を表す。 [0036] Here, in the formula (11), 蔚 represents a bonding position with the benzene ring in the formula (8), and [¾ 12 represents a monovalent organic group.
[0037] ハロゲン原子としては、 例えば、 フッ素原子、 塩素原子、 臭素原子、 およ び、 ヨウ素原子が挙げられ、 フッ素原子、 または、 塩素原子が好ましい。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
[0038] 炭素数 1〜 2 0の直鎖状のアルキル基としては、 炭素数 1〜 6のアルキル 基が好ましく、 例えば、 メチル基、 エチル基、 および、 门ープロピル基が挙 げられる。 [0038] The linear alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
炭素数 1〜 2 0の分岐鎖状のアルキル基としては、 炭素数 3〜 6のアルキ ル基が好ましく、 例えば、 イソプロピル基、 および、 I 6
Figure imgf000011_0002
プチル基が 挙げられる。 The branched alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 3 to 6 carbon atoms, and examples thereof include an isopropyl group and I 6
Figure imgf000011_0002
A butyl group may be mentioned.
炭素数 1〜 2 0の環状のアルキル基としては、 炭素数 3〜 6のアルキル基 が好ましく、 例えば、 シクロプロピル基、 シクロペンチル基、 および、 シク ロヘキシル基が挙げられる。 The cyclic alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
[0039] 炭素数 1〜 2 0の直鎖状のハロゲン化アルキル基としては、 炭素数 1〜 4 のフルオロアルキル基が好ましく、 例えば、 トリフルオロメチル基、 パーフ ルオロエチル基、 パーフルオロプロピル基、 および、 パーフルオロブチル基 が挙げられる。 なかでも、 トリフルオロメチル基が好ましい。 [0039] The linear halogenated alkyl group having 1 to 20 carbon atoms is preferably a fluoroalkyl group having 1 to 4 carbon atoms, and examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and And a perfluorobutyl group. Of these, a trifluoromethyl group is preferable.
[0040] 炭素数 1〜 2 0のアルコキシ基としては、 炭素数 1〜 1 8のアルコキシ基 が好ましく、 炭素数 6〜 1 8のアルコキシ基がより好ましく、 炭素数 6〜 1 4のアルコキシ基がさらに好ましい。 例えば、 メ トキシ基、 エトキシ基、 n —ブトキシ基、 メ トキシエトキシ基、 门ーヘキシルオキシ基、 门ーオクチル オキシ基、
Figure imgf000011_0003
デシルオキシ基、 ドデシルオキシ基、 および、 テト 〇 2020/175620 1 1 卩（：171? 2020 /008033 [0040] The alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 6 to 18 carbon atoms, and an alkoxy group having 6 to 14 carbon atoms. More preferable. For example, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, door-hexyloxy group, door-octyloxy group,
Figure imgf000011_0003
Decyloxy group, dodecyloxy group, and tet 〇 2020/175 620 1 1 卩(: 171? 2020/008033
ラデシルオキシ基が挙げられ、 ヘキシルオキシ基、 门ーオクチルオキシ 基、 デシルオキシ基、 ドデシルオキシ基、 または、
Figure imgf000012_0001
テトラデシ ルオキシ基が好ましい。 Radecyloxy group, hexyloxy group, door-octyloxy group, decyloxy group, dodecyloxy group, or
Figure imgf000012_0001
A tetradecyloxy group is preferred.
［0041］ 炭素数 6〜 2 0のアリール基としては、 炭素数 6〜 1 2のアリール基が好 ましく、 例えば、 フエニル基、 《—メチルフエニル基、 および、 ナフチル基 が挙げられ、 フエニル基が好ましい。 [0041] The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a <<-methylphenyl group, and a naphthyl group. preferable.
［0042］ 炭素数 6〜 2 0のアリールオキシ基としては、 炭素数 6〜 1 2のアリール オキシ基が好ましく、 例えば、 フエニルオキシ基、 および、 2 -ナフチルオ キシ基が挙げられ、 フエニルオキシ基が好ましい。 [0042] The aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group, and a phenyloxy group is preferable.
［0043］ アミノ基としては、 例えば、 第 1級アミノ基 （一 1\1 1~1 2） ; メチルアミノ基 などの第 2級アミノ基；ジメチルアミノ基、 ジエチルアミノ基、 ジベンジル アミノ基、 および、 含窒素複素環化合物 （例えば、 ピロリジン、 ピぺリジン 、 ピぺラジンなど） の窒素原子を結合手とした基などの第 3級アミノ基；が 挙げられる。 [0043] Examples of the amino group, for example, primary amino group (an 1 \ 1 11 2); a secondary amino group such as methylamino group, dimethylamino group, diethylamino group, dibenzyl amino group, and a A tertiary amino group such as a group having a nitrogen atom as a bond of a nitrogen-containing heterocyclic compound (eg, pyrrolidine, piperidine, piperazine, etc.).
［0044］ 上記式 （1 1） で表される基について、 上記式 （1 1） 中の［¾ 1 2が表す 1 価の有機基としては、 例えば、 炭素数 1〜 2 0の直鎖状または環状のアルキ ル基が挙げられる。 [0044] Regarding the group represented by the above formula (11), the monovalent organic group represented by [¾ 12 in the above formula (11) is, for example, a straight chain having 1 to 20 carbon atoms. Alternatively, a cyclic alkyl group may be mentioned.
直鎖状のアルキル基としては、 炭素数 1〜 6のアルキル基が好ましく、 例 えば、 メチル基、 エチル基、 および、 门ープロピル基が挙げられ、 メチル基 またはエチル基が好ましい。 As the linear alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, and a propyl group, and a methyl group or an ethyl group is preferable.
環状のアルキル基としては、 炭素数 3〜 6のアルキル基が好ましく、 例え ば、 シクロプロピル基、 シクロペンチル基、 および、 シクロヘキシル基が挙 げられ、 シクロヘキシル基が好ましい。 As the cyclic alkyl group, an alkyl group having 3 to 6 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, and a cyclohexyl group is preferable.
なお、 上記式 （1 1）
Figure imgf000012_0002
しては、 上述した直 鎖状のアルキル基および環状のアルキル基を複数組み合わせたものであって もよい。 Note that the above formula (1 1)
Figure imgf000012_0002
Alternatively, a combination of a plurality of the above-mentioned straight chain alkyl groups and cyclic alkyl groups may be used.
［0045］ 光配向性基が液晶化合物と相互作用しやすくなり、 本発明の効果がより優 れる点で、 上記式 （八） 中の
Figure imgf000012_0003
および のうち、 少なく \¥0 2020/175620 12 卩（：17 2020 /008033
Figure imgf000013_0001
[0045] In the above-mentioned formula (8), the photo-alignment group easily interacts with the liquid crystal compound, and the effect of the present invention is more excellent.
Figure imgf000012_0003
And out of \\0 2020/175 620 12 ((17 2020/008033
Figure imgf000013_0001
がいずれも水素原子であることがより好ましい。 Is more preferably a hydrogen atom.
［0046］ 光照射した際に反応効率が向上する点から、 上記式 （八） 中の 8が電子供 与性の置換基であることが好ましい。 [0046] It is preferable that 8 in the above formula (8) is an electron-donating substituent because the reaction efficiency is improved when irradiated with light.
ここで、 電子供与性の置換基 （電子供与性基） とは、 ハメッ ト値
Figure imgf000013_0002
^ e t 1:置換基定数 <7 ） が 0以下の置換基のことをいい、 例えば、 上述し た置換基のうち、 アルキル基、 ハロゲン化アルキル基、 および、 アルコキシ 基が挙げられる。 Here, the electron-donating substituent (electron-donating group) is the Hammett value.
Figure imgf000013_0002
^ et 1: A substituent having a substituent constant <7) of 0 or less, and examples thereof include an alkyl group, a halogenated alkyl group, and an alkoxy group.
これらのうち、 アルコキシ基であることが好ましく、 本発明の効果がより 優れる点で、 炭素数が 6〜 1 6のアルコキシ基がより好ましく、 炭素数 7〜 Of these, an alkoxy group is preferable, and an alkoxy group having 6 to 16 carbon atoms is more preferable because the effect of the present invention is more excellent, and a carbon number of 7 to
1 0のアルコキシ基がさらに好ましい。 More preferred is an alkoxy group of 10.
［0047］ 光配向性基を含む繰り返し単位八としては、 例えば、 以下に示す繰り返し 単位八一 1 ~八一 5 6が挙げられる。 なお、 下記式中、 IV! 6はメチル基を表 し、 巳 はエチル基を表す。 なお、 以下の具体例中、 繰り返し単位八_ 1〜 八_ 1 0の 2価の連結基に含まれる 「1 , 4—シクロヘキシル基」 は、 シス 体およびトランス体のいずれであつてもよいが、 トランス体であることが好 ましい。 [0047] Examples of the repeating unit 8 containing a photo-alignable group include repeating units 81 1 to 81 5 shown below. In the formula below, IV! 6 represents a methyl group, and M represents an ethyl group. In the following specific examples, the “1,4-cyclohexyl group” contained in the divalent linking group of repeating units 8 — 1 to 8 — 10 may be either a cis isomer or a trans isomer. , Preferably in trans form.
［0048］ ［化 5］ [0048] [Chemical 5]
Figure imgf000013_0003
Figure imgf000014_0002
Figure imgf000013_0003
Figure imgf000014_0002
A-16 A-17 A- 18 A- 19 A-16 A-17 A- 18 A- 19
[0049] Hb6] [0049] Hb6]
Figure imgf000014_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000015_0001
A-42 A^43 A-44 〇 2020/175620 15 卩（：171? 2020 /008033 A-42 A^43 A-44 〇 2020/175 620 15 卩 (：171? 2020 /008033
[0050] [化 7] [0050] [Chemical 7]
Figure imgf000016_0001
Figure imgf000016_0001
典-51 - 52 -53 *-54 -55 *-56 Code-51-52 -53 *-54 -55 *-56
[0051 ] （架橋性基を含む繰り返し単位巳） (Repeating unit containing a crosslinkable group)
光配向性共重合体は、 架橋性基を含む繰り返し単位巳を有する。 架橋性基としては、 例えば、 エポキシ基、 エポキシシクロヘキシル基、 才 キセタニル基、 および、 エチレン性不飽和二重結合を有する官能基が挙げら れ、 カチオン重合性基が好ましく、 下記式 （X I） 〜 （乂3） からなる群か ら選択される少なくとも 1種の架橋性基がより好ましい。 The photoalignable copolymer has a repeating unit including a crosslinkable group. Examples of the crosslinkable group include an epoxy group, an epoxycyclohexyl group, a xenonyl group, and a functional group having an ethylenically unsaturated double bond, and a cationically polymerizable group is preferable, and the following formula (XI) More preferred is at least one crosslinkable group selected from the group consisting of (3).
[0052] [化 8] [0052] [Chemical 8]
Figure imgf000016_0002
Figure imgf000016_0002
_ （ 2） （ 3） _ ( twenty three)
[0053] 上記式 （X I） 〜 （乂3） 中、 氺は結合手を表し、
Figure imgf000016_0003
水素原子、 メチ ル基またはエチル基を表す。 [0053] In the above formulas (XI) to (3), Ai represents a bond,
Figure imgf000016_0003
Represents a hydrogen atom, a methyl group or an ethyl group.
[0054] 繰り返し単位巳としては、 本発明の効果がより優れる点で、 下記式 （巳） で表される繰り返し単位が好ましい。 [0054] As the repeating unit, a repeating unit represented by the following formula (M) is preferable because the effect of the present invention is more excellent.
[0055] 〇 2020/175620 16 卩（：171? 2020 /008033 [0055] 〇 2020/175 620 16 卩 (：171? 2020 /008033
[化 9] [Chemical 9]
Figure imgf000017_0001
Figure imgf000017_0001
綱 Rope
[0056] 上記式 （巳） 中、
Figure imgf000017_0002
は、 水素原子またはメチル基を表し、 1_ 2は、 2価の 連結基を表し、 Xは、 架橋性基を表す。 [0056] In the above formula (M),
Figure imgf000017_0002
Represents a hydrogen atom or a methyl group, 1_ 2 represents a divalent connecting group, X represents a crosslinkable group.
[0057] 上記式 （巳） 中の！- 2が表す 2価の連結基としては、 本発明の効果がより優 れる点で、 置換基を有していてもよい炭素数 1〜 1 8の直鎖状、 分岐鎖状ま たは環状のアルキレン基、 置換基を有していてもよい炭素数 6〜 1 2のアリ —レン基、 エーテル基 （一〇一） 、 カルボニル基 （一〇 （=〇） 一） 、 およ び、 置換基を有していてもよいイミノ基
Figure imgf000017_0003
からなる群から選択さ れる少なくとも 2以上の基を組み合わせた 2価の連結基 （例えば、
Figure imgf000017_0004
〇ーアルキレン基一） であることが好ましい。 [0057] In the above formula (Mimi)! - Examples of the divalent linking group 2 represented in terms the effect of the present invention is more excellent, linear optionally carbon atoms, which may 1-1 8 have a substituent, branched or cyclic An alkylene group, an optionally substituted arylene group having 6 to 12 carbon atoms, an ether group (101), a carbonyl group (10 (=○) 1), and a substituent An imino group which may have a group
Figure imgf000017_0003
A divalent linking group combining at least two groups selected from the group consisting of (for example,
Figure imgf000017_0004
O-alkylene group 1) is preferred.
[0058] ここで、 アルキレン基、 アリーレン基およびイミノ基が有していてもよい 置換基としては、 例えば、 ハロゲン原子、 アルキル基、 アルコキシ基、 アリ —ル基、 アリールオキシ基、 シアノ基、 カルボキシ基、 アルコキシカルボニ ル基、 および、 水酸基が挙げられる。 [0058] Here, examples of the substituent that the alkylene group, the arylene group and the imino group may have include, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group and a carboxy group. Group, an alkoxycarbonyl group, and a hydroxyl group.
ハロゲン原子としては、 例えば、 フッ素原子、 塩素原子、 臭素原子、 およ び、 ヨウ素原子が挙げられ、 フッ素原子、 または、 塩素原子が好ましい。 アルキル基としては、 例えば、 炭素数 1〜 1 8の直鎖状、 分岐鎖状または 環状のアルキル基が好ましく、 炭素数 1〜 8のアルキル基 （例えば、 メチル 基、 エチル基、 プロピル基、 イソプロピル基、
Figure imgf000017_0005
_ブチル基、 イソプチル基 、 3 6 0—ブチル基、 1 _ブチル基、 および、 シクロヘキシル基） がより好 ましく、 炭素数 1〜 4のアルキル基がさらに好ましく、 メチル基またはエチ 〇 2020/175620 17 卩（：171? 2020 /008033 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable. As the alkyl group, for example, a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group Base,
Figure imgf000017_0005
_Butyl group, isoptyl group, 360-butyl group, 1_butyl group, and cyclohexyl group) are more preferable, an alkyl group having 1 to 4 carbon atoms is further preferable, and a methyl group or ethyl group. 〇 2020/175 620 17 卩(：171? 2020/008033
ル基が特に好ましい。 Ru groups are particularly preferred.
アルコキシ基としては、 例えば、 炭素数 1〜 1 8のアルコキシ基が好まし く、 炭素数 1〜 8のアルコキシ基 （例えば、 メ トキシ基、 ェトキシ基、 n - ブトキシ基、 および、 メ トキシェトキシ基） がより好ましく、 炭素数 1〜 4 のアルコキシ基がさらに好ましく、 メ トキシ基またはェトキシ基が特に好ま しい。 As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, and methoxetoxy group) Is more preferable, an alkoxy group having 1 to 4 carbon atoms is further preferable, and a methoxy group or an ethoxy group is particularly preferable.
アリール基としては、 例えば、 炭素数 6〜 1 2のアリール基が挙げられ、 例えば、 フェニル基、 《 -メチルフェニル基、 および、 ナフチル基が挙げら れ、 フェニル基が好ましい。 Examples of the aryl group include an aryl group having 6 to 12 carbon atoms, examples of which include a phenyl group, <<-methylphenyl group, and naphthyl group, with a phenyl group being preferred.
アリールオキシ基としては、 例えば、 フェノキシ、 ナフトキシ、 イミダゾ イルオキシ、 ベンゾイミダゾイルオキシ、 ピリジンー 4—イルオキシ、 ピリ ミジニルオキシ、 キナゾリニルオキシ、 プリニルオキシ、 および、 チオフェ ンー 3 -イルオキシが挙げられる。 Examples of the aryloxy group include phenoxy, naphthoxy, imidazoyloxy, benzimidazoyloxy, pyridin-4-yloxy, pyrimidinyloxy, quinazolinyloxy, purinyloxy, and thiophen-3-yloxy.
アルコキシカルボニル基としては、 例えば、 メ トキシカルボニル、 および 、 ェトキシカルボニルが挙げられる。 Examples of alkoxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl.
[0059] 炭素数 1〜 1 8の直鎖状のアルキレン基としては、 例えば、 メチレン基、 ェチレン基、 プロピレン基、 プチレン基、 ペンチレン基、 ヘキシレン基、 デ シレン基、 ウンデシレン基、 ドデシレン基、 トリデシレン基、 テトラデシレ ン基、 ペンタデシレン基、 へキサデシレン基、 ヘプタデシレン基、 および、 オクタデシレン基が挙げられる。 [0059] Examples of the linear alkylene group having 1 to 18 carbon atoms include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a decylene group, an undecylene group, a dodecylene group, and a tridecylene group. Group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, and octadecylene group.
炭素数 1〜 1 8の分岐鎖状のアルキレン基としては、 例えば、 ジメチルメ チレン基、 メチルェチレン基、 2 , 2 -ジメチルプロピレン基、 および、 2 —ェチルー 2—メチルプロピレン基が挙げられる。 Examples of the branched chain alkylene group having 1 to 18 carbon atoms include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-methylpropylene group.
炭素数 1〜 1 8の環状のアルキレン基としては、 例えば、 シクロプロピレ ン基、 シクロブチレン基、 シクロペンチレン基、 シクロヘキシレン基、 シク 口オクチレン基、 シクロデシレン基、 アダマンタンージイル基、 ノルボルナ ンージイル基、 および、 6 X〇 -テトラヒドロジシクロペンタジェンージイ ル基が挙げられ、 シクロヘキシレン基が好ましい。 〇 2020/175620 18 卩（：171? 2020 /008033 Examples of the cyclic alkylene group having 1 to 18 carbon atoms include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, a norbornane-diyl group, And a 6 X O -tetrahydrodicyclopentadienyl group, and a cyclohexylene group is preferable. 〇 2020/175 620 18 卩 (：171? 2020 /008033
[0060] 炭素数 6〜 1 2のアリーレン基としては、 例えば、 フエニレン基、 キシリ レン基、 ビフエニレン基、 ナフチレン基、 および、 2 , 2’ ーメチレンビス フエニル基が挙げられ、 フエニレン基が好ましい。 Examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, and a 2,2′-methylenebisphenyl group, and a phenylene group is preferable.
[0061 ] 上記式 （巳） 中の Xが表す架橋性基としては、 上述した架橋性基の例が挙 げられる。 [0061] Examples of the crosslinkable group represented by X in the above formula (M) include the above-mentioned crosslinkable groups.
[0062] 架橋性基を含む繰り返し単位巳としては、 例えば、 以下に示す繰り返し単 位巳一 1 ~巳一 1 7が挙げられる。 [0062] Examples of the repeating unit that includes a crosslinkable group include the following repeating units: Miichi 1 to Miichi 17.
[0063] [化 10] [0063] [Chemical 10]
Figure imgf000019_0001
Figure imgf000019_0001
[0064] また、 架橋性基を含む繰り返し単位巳としては、 例えば、 以下に示す繰り 返し単位巳一 1 8 ~巳一 4 7も挙げられる。 [0064] Further, examples of the repeating unit including a crosslinkable group include the following repeating units: Michi 18 to Michi 47.
[0065] \¥0 2020/175620 19 卩（：17 2020 /008033 [0065] \¥0 2020/175 620 19 卩(: 17 2020/008033
[化 1 1 ] [Chemical 1 1]
Figure imgf000020_0001
Figure imgf000020_0001
[0066] 光配向性共重合体は、 本発明の効果を阻害しない限り、 上述した繰り返し 単位 および繰り返し単位巳以外に、 他の繰り返し単位を有していてもよい 他の繰り返し単位としては、 例えば、 アクリル酸エステル化合物、 メタク リル酸エステル化合物、 マレイミ ド化合物、 アクリルアミ ド化合物、 アクリ ロニトリル、 マレイン酸無水物、 スチレン化合物、 および、 ビニル化合物か らなる群から選択される化合物由来の繰り返し単位が挙げられる。 〇 2020/175620 20 卩（：171? 2020 /008033 [0066] The photoalignable copolymer may have other repeating units in addition to the above-described repeating unit and repeating unit, as long as the effects of the present invention are not impaired. , An acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylic amide compound, an acrylonitrile, a maleic anhydride, a styrene compound, and a repeating unit derived from a compound selected from the group consisting of a vinyl compound. Can be mentioned. 〇 2020/175 620 20 boxes (: 171-1?2020/008033
[0067] 光配向性共重合体中における繰り返し単位 の含有量 3と、 繰り返し単位 巳の含有量匕とは、 質量比で下記式 （1） を満たす。 式 （1） の関係は、 繰 り返し単位 の含有量 3および繰り返し単位の含有量 13の合計に対する、 含 有量 13の比を表す。 [0067] The content 3 of the repeating unit and the content of the repeating unit M in the photoalignable copolymer satisfy the following formula (1) in mass ratio. The relationship of the formula (1) represents the ratio of the content 13 to the total of the content 3 of the repeating unit and the content 13 of the repeating unit.
〇. 70£匕/ （3 + 13） £〇. 97 · · · （1） 〇.70 £匕 / (3 + 13) £ 〇.97 ··· (1)
なかでも、 本発明の効果がより優れる点で、 匕/ （3 + 13） は〇. 75〜 〇. 95が好ましく、 〇. 80〜〇. 93がより好ましい。 Above all, from the viewpoint that the effect of the present invention is more excellent, the range / (3 + 13) is preferably 0.75 to 0.95, more preferably 0.80 to 0.993.
[0068] 繰り返し単位 の含有量は特に制限されないが、 本発明の効果がより優れ る点で、 光配向性共重合体中の全繰り返し単位に対して、 3〜 30質量％が 好ましく、 5〜 25質量％がより好ましい。 [0068] The content of the repeating unit is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferably 3 to 30 mass% with respect to all repeating units in the photoalignable copolymer, and 5 to 25% by mass is more preferable.
繰り返し単位巳の含有量は特に制限されないが、 本発明の効果がより優れ る点で、 光配向性共重合体中の全繰り返し単位に対して、 70〜 97質量％ が好ましく、 75〜 95質量％がより好ましい。 The content of the repeating unit is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferably 70 to 97% by mass, and 75 to 95% by mass with respect to all repeating units in the photoalignable copolymer. % Is more preferable.
[0069] 光配向性共重合体の重量平均分子量
Figure imgf000021_0001
は、 本発明の効果がより優れ る点から、 1 〇〇〇〇〜 500000が好ましく、 30000〜 30000 0がより好ましい。 [0069] Weight average molecular weight of photoalignable copolymer
Figure imgf000021_0001
Is preferably from 100,000 to 500,000, more preferably from 30,000 to 30,000, from the viewpoint that the effect of the present invention is more excellent.
ここで、 本発明における重量平均分子量および数平均分子量は、 以下に示 す条件でゲル浸透クロマトグラフ （〇 〇） 法により測定された値である。 Here, the weight average molecular weight and the number average molecular weight in the present invention are values measured by the gel permeation chromatography (○○) method under the following conditions.
-溶媒 （溶離液） ： 丁1~1 （テトラヒドロフラン） -Solvent (eluent): 1 to 1 (tetrahydrofuran)
装置名 ： 丁〇 3〇1~1 1~11_〇一8320〇 ?〇
Figure imgf000021_0002
Device name: D 〇 3 〇 1 ~ 1 1 ~ 11_ 〇 1 8320 〇 ?〇
Figure imgf000021_0002
-カラム温度： 40°〇 -Column temperature: 40°
-試料濃度： 〇. 1質量％ -Sample concentration: 0. 1% by mass
Figure imgf000021_0003
Figure imgf000021_0003
-校正曲線： 丁〇3〇1~1製丁3 <標準ポリスチレン 1\/1\«=280000 〇〜 1 050
Figure imgf000021_0004
03~ 1. 06） までの 7サンプルによる 校正曲線を使用 〇 2020/175620 21 卩（：171? 2020 /008033 -Calibration curve: 3 x 1 to 1 binding 3 <standard polystyrene 1\/1\ «=280000 〇 to 1 050
Figure imgf000021_0004
Calibration curve with 7 samples from 03 to 1.06) 〇 2020/175 620 21 卩 (: 171? 2020 /008033
[0070] ＜酸発生剤＞ [0070] <Acid generator>
光配向膜用組成物は、 酸発生剤を含む。 酸発生剤は、 上述した架橋性基の 重合を開始させる機能を有する。 The composition for photo-alignment film contains an acid generator. The acid generator has a function of initiating the polymerization of the above-mentioned crosslinkable group.
酸発生剤としては特に制限されないが、 例えば、 熱酸発生剤および光酸発 生剤が挙げられる。 The acid generator is not particularly limited, and examples thereof include a thermal acid generator and a photoacid generator.
[0071 ] 熱酸発生剤としては、 熱により分解して特定酸を発生する化合物であれば 特にその構造は制限されないが、 通常、 所定の酸より水素イオンを取り除い てなるアニオンと、 カチオンとから構成される。 [0071] The thermal acid generator is not particularly limited in its structure as long as it is a compound capable of decomposing by heat to generate a specific acid. Usually, it is composed of an anion obtained by removing hydrogen ion from a predetermined acid and a cation. Composed.
酸としては、 例えば、 式 （八） 〜 （巳） で表される化合物、 および、
Figure imgf000022_0001
匕 ^が挙げられる。 Examples of the acid include compounds represented by the formulas (8) to (M), and
Figure imgf000022_0001
匕^.
[0072] [化 12] [0072] [Chemical 12]
Figure imgf000022_0002
Figure imgf000022_0002
[0073] 式 （八） 中、
Figure imgf000022_0004
および
Figure imgf000022_0003
は、 それぞれ独立に、 パーフルオロアルキル基 を表す。 パーフルオロアルキル基中の炭素数は特に制限されないが、 1〜 1 〇が好ましく、 1〜 5がより好ましい。 [0073] In formula (8),
Figure imgf000022_0004
and
Figure imgf000022_0003
Each independently represents a perfluoroalkyl group. The number of carbon atoms in the perfluoroalkyl group is not particularly limited, but is preferably 1 to 10 and more preferably 1 to 5.
式 （巳） 中、
Figure imgf000022_0005
は、 パーフルオロアルキレン基を表す。 パーフルオロアル キレン基中の炭素数は特に制限されないが、 2〜 1 0が好ましく、 3〜 5が より好ましい。 During the ceremony (Mimi),
Figure imgf000022_0005
Represents a perfluoroalkylene group. The number of carbon atoms in the perfluoroalkylene group is not particularly limited, but is preferably 2 to 10 and more preferably 3 to 5.
式 （〇 中、
Figure imgf000022_0006
は、 それぞれ独立に、 パーフルオロアルキル基を表す。 パ —フルオロアルキル基中の炭素数は特に制限されないが、 1〜 1 0が好まし 〇 2020/175620 22 卩(：171? 2020 /008033 Expression (○,
Figure imgf000022_0006
Each independently represents a perfluoroalkyl group. The number of carbon atoms in the perfluoroalkyl group is not particularly limited, but 1 to 10 is preferable. 〇 2020/175 620 22 卩 (: 171? 2020 /008033
く、 2〜 5がより好ましい。 2-5 is more preferable.
式 （口） 中、
Figure imgf000023_0001
は、 それぞれ独立に、 フッ素原子、 または、 置換基を有し ていてもよいアリール基を表す。 アリール基としては、 フエニル基およびナ フチル基が挙げられる。 置換基の種類は特に制限されないが、 例えば、 アル キル基、 および、 ハロゲン原子 （好ましくは、 フッ素原子） が挙げられる。 式 （巳） 中、
Figure imgf000023_0002
は、 それぞれ独立に、 パーフルオロアルキル基を表す。 パ —フルオロアルキル基中の炭素数は特に制限されないが、 1〜 1 0が好まし く、 1〜 5がより好ましい。 Inside the formula (mouth),
Figure imgf000023_0001
Are each independently a fluorine atom or an aryl group which may have a substituent. Examples of the aryl group include a phenyl group and a naphthyl group. The type of the substituent is not particularly limited, but examples thereof include an alkyl group and a halogen atom (preferably a fluorine atom). During the ceremony (Mimi),
Figure imgf000023_0002
Each independently represents a perfluoroalkyl group. The number of carbon atoms in the perfluoroalkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 5 is more preferable.
nは、 1〜 6の整数を表す。 なかでも、 nは、 3〜 6の整数が好ましく、 n represents an integer of 1 to 6. Among them, n is preferably an integer of 3 to 6,
6がより好ましい。 6 is more preferable.
[0074] アニオンとしては、 以下が例示される。 [0074] Examples of the anion include the following.
[0075] [化 13] [0075] [Chemical 13]
Figure imgf000023_0003
Figure imgf000023_0003
[0076] カチオンとしては、 熱で分解する公知のカチオンを使用できる。 カチオン は、 3 0〜 2 0 0 °〇で熱分解が開始する骨格を有することが好ましく、 4 0 〜 1 5 0 °〇で熱分解が開始する骨格を有することがより好ましい。 なかでも 、 取り扱い性の点から、 式 （ ） で表されるスルホニウムカチオン、 または 、 式 （〇） で表されるヨードニウムカチオンが好ましい。 [0076] As the cation, a known cation that is decomposed by heat can be used. The cation preferably has a skeleton in which thermal decomposition starts at 30 to 200°, and more preferably has a skeleton in which thermal decomposition starts at 40 to 150°. Among them, the sulfonium cation represented by the formula () or the iodonium cation represented by the formula (◯) is preferable from the viewpoint of handleability.
[0077] 〇 2020/175620 23 2020 /008033 [0077] 〇 2020/175 620 23 2020/008033
[化 14] [Chemical 14]
Figure imgf000024_0001
Figure imgf000024_0001
[0078] および [¾ 9 1および [¾ 9 2は、 それぞれ独立に、 置換基を有してい てもよい炭化水素基を表す。 炭化水素基としては、 アルキル基 （例えば、 メ チル基、 ェチル基） 、 または、 アリール基 （例えば、 フエニル基） が好まし い。 [0078] and [¾ 9 1 and [¾ 9 2 each independently represent a hydrocarbon group which may have a substituent. As the hydrocarbon group, an alkyl group (for example, a methyl group, an ethyl group) or an aryl group (for example, a phenyl group) is preferable.
置換基の種類は特に制限されず、 例えば、 アルキル基、 アリール基、 ヒド ロキシ基、 アミノ基、 カルボキシ基、 スルホンアミ ド基、 1\1—スルホニルア ミ ド基、 アシル基、 アシルオキシ基、 アルコキシ基、 アルキル基、 ハロゲン 原子、 アルコキシカルボニル基、 アルコキシカルボニルオキシ基、 炭酸エス テル基、 および、 シアノ基が挙げられる。 The kind of the substituent is not particularly limited, and examples thereof include an alkyl group, an aryl group, a hydroxy group, an amino group, a carboxy group, a sulfone amide group, a 1\1-sulfonyl amide group, an acyl group, an acyloxy group, an alkoxy group. , An alkyl group, a halogen atom, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an ester carbonate group, and a cyano group.
カチオンとしては、 例えば、 以下が挙げられる。 Examples of the cation include the following.
[0079] [化 15] [0079] [Chemical 15]
Figure imgf000024_0002
Figure imgf000024_0002
[0080] 光酸発生剤としては、 光により分解して特定酸を発生する化合物であれば 〇 2020/175620 24 卩（：171? 2020 /008033 [0080] The photo-acid generator is a compound that decomposes by light to generate a specific acid. 〇 2020/175 620 24 卩 (：171? 2020 /008033
特にその構造は制限されないが、 波長 3 0 0 n 以上、 好ましくは波長 3 0 〇〜 4 5 0 n の活性光線に感応し、 酸を発生する化合物が好ましい。 また 、 波長 3 0 0
Figure imgf000025_0001
以上の活性光線に直接感応しない光酸発生剤についても、 増感剤と併用することによって波長 3 0 0
Figure imgf000025_0002
以上の活性光線に感応し、 酸 を発生する化合物であれば、 増感剤と組み合わせて好ましく用いることがで きる。 The structure is not particularly limited, but a compound that reacts with an actinic ray having a wavelength of 300 n or more, preferably 300 0 to 450 n and generates an acid is preferable. In addition, the wavelength 300
Figure imgf000025_0001
The above photoacid generators that are not directly sensitive to actinic rays can also be used in combination with sensitizers to generate wavelengths of 300
Figure imgf000025_0002
Any compound capable of reacting with the above-mentioned actinic rays and generating an acid can be preferably used in combination with a sensitizer.
[0081 ] 光酸発生剤としては、 例えば、 オニウム塩化合物、 トリクロロメチルー 3 —トリアジン類、 スルホニウム塩、 ヨードニウム塩、 第四級アンモニウム塩 類、 ジアゾメタン化合物、 イミ ドスルホネート化合物、 および、 オキシムス ルホネート化合物が挙げられる。 [0081] Examples of the photoacid generator include onium salt compounds, trichloromethyl-3-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imidsulfonate compounds, and oximesulphonate compounds. Is mentioned.
[0082] ＜その他成分＞ [0082] <Other ingredients>
光配向膜用組成物は、 上述した成分以外の他の成分を含んでいてもよい。 他の成分としては、 溶媒が挙げられる。 溶媒としては、 水および有機溶媒 が挙げられる。 The composition for photo-alignment film may contain components other than the components described above. Other components include solvents. Solvents include water and organic solvents.
有機溶媒としては、 例えば、 ケトン類 （例えば、 アセトン、 2—ブタノン 、 メチルイソプチルケトン、 および、 シクロへキサノン） 、 エーテル類 （例 えば、 ジオキサン、 および、 テトラヒドロフラン） 、 脂肪族炭化水素類 （例 えば、 ヘキサン） 、 脂環式炭化水素類 （例えば、 シクロヘキサン） 、 芳香族 炭化水素類 （例えば、 トルエン、 キシレン、 および、 トリメチルベンゼン） Examples of the organic solvent include ketones (eg, acetone, 2-butanone, methylisoeptylketone, and cyclohexanone), ethers (eg, dioxane and tetrahydrofuran), aliphatic hydrocarbons (eg, For example, hexane), alicyclic hydrocarbons (eg, cyclohexane), aromatic hydrocarbons (eg, toluene, xylene, and trimethylbenzene)
、 ハロゲン化炭素類 （例えば、 ジクロロメタン、 ジクロロエタン、 ジクロロ ベンゼン、 および、 クロロトルエン） 、 エステル類 （例えば、 酢酸メチル、 酢酸エチル、 および、 酢酸プチル） 、 水、 アルコール類 （例えば、 エタノー ル、 イソプロパノール、 ブタノール、 および、 シクロへキサノール） 、 セロ ソルブ類 （例えば、 メチルセロソルブ、 および、 エチルセロソルブ） 、 セロ ソルプアセテート類、 スルホキシド類 （例えば、 ジメチルスルホキシド） 、 ならびに、 アミ ド類 （例えば、 ジメチルホルムアミ ド、 および、 ジメチルア セトアミ ド） が挙げられる。 , Halogenated carbons (eg dichloromethane, dichloroethane, dichlorobenzene and chlorotoluene), esters (eg methyl acetate, ethyl acetate and butyl acetate), water, alcohols (eg ethanol, isopropanol, Butanol and cyclohexanol), cellosolves (eg, methylcellosolve and ethylcellosolve), cellosolve acetates, sulfoxides (eg, dimethylsulfoxide), and amides (eg, dimethylformamid) And dimethylacetamide).
溶媒は、 1種単独で用いてもよく、 2種以上を併用してもよい。 〇 2020/175620 25 卩（：171? 2020 /008033 The solvent may be used alone or in combination of two or more. 〇 2020/175 620 25 卩 (: 171? 2020 /008033
[0083] 光配向膜用組成物は、 上記以外の他の成分を含んでいてもよく、 例えば、 架橋触媒、 密着改良剤、 レべリング剤、 界面活性剤、 および、 可塑剤が挙げ られる。 [0083] The composition for photo-alignment film may contain components other than the above, and examples thereof include a crosslinking catalyst, an adhesion improver, a leveling agent, a surfactant, and a plasticizer.
[0084] ＜光配向膜用組成物＞ <Composition for photo-alignment film>
光配向膜用組成物は、 上述した光配向性共重合体、 酸発生剤、 および、 特 定アミン化合物を含む。 The composition for photo-alignment film contains the above-mentioned photo-alignable copolymer, an acid generator, and a specific amine compound.
光配向膜用組成物の調製方法は特に制限されず、 上記成分を一括して混合 してもよいし、 段階的に混合してもよい。 The method for preparing the composition for a photo-alignment film is not particularly limited, and the above components may be mixed at once or may be mixed stepwise.
[0085] 光配向膜用組成物中における光配向性共重合体の含有量は特に制限されな いが、 光配向膜用組成物が溶媒を含む場合、 溶媒 1 〇〇質量部に対して、 〇 . 1〜 5 0質量部が好ましく、 〇. 5〜 2 0質量部がより好ましい。 [0085] The content of the photoalignable copolymer in the composition for photoalignment film is not particularly limited, but when the composition for photoalignment film contains a solvent, relative to 100 parts by mass of the solvent, O.1 to 50 parts by mass is preferable, and 0.5 to 20 parts by mass is more preferable.
光配向膜用組成物中における酸発生剤の含有量は特に制限されないが、 本 発明の効果がより優れる点で、 光配向性共重合体全質量に対して、 〇 . 1〜 3 0質量％が好ましく、 〇. 5〜 2〇. 0質量％がより好ましい。 The content of the acid generator in the composition for the photo-alignment film is not particularly limited, but in terms of the effect of the present invention being more excellent, with respect to the total mass of the photo-alignment copolymer, 0.1 to 30 mass% Is preferable, and 0.5 to 2.0 mass% is more preferable.
光配向膜用組成物中における特定アミンの含有量は特に制限されないが、 酸発生剤の含有モル量 （全モル量） に対して、 1〜 1 0 0 0モル％の場合が 多く、 本発明の効果がより優れる点で、 5〜 4 0 0モル％が好ましく、 1 0 〜 3 0 0モル％がより好ましい。 The content of the specific amine in the composition for a photo-alignment film is not particularly limited, but it is often 1 to 100 mol% with respect to the content molar amount of the acid generator (total molar amount). From the viewpoint that the above effect is more excellent, 5 to 400 mol% is preferable, and 10 to 300 mol% is more preferable.
[0086] ＜光配向膜＞ [0086] <Photo-alignment film>
上記光配向膜用組成物を用いて、 光配向膜を形成できる。 A photo-alignment film can be formed using the composition for photo-alignment film.
光配向膜は、 上述した光配向膜用組成物を用いる以外は従来公知の製造方 法により製造でき、 例えば、 上述した光配向膜用組成物を用いて前駆体膜を 形成する工程と、 光配向膜用組成物の前駆体膜に対し、 偏光または前駆体膜 表面に対して斜め方向から非偏光を照射する光照射工程とを有する製造方法 により作製することができる。 The photo-alignment film can be produced by a conventionally known production method except that the composition for photo-alignment film described above is used. For example, a step of forming a precursor film using the composition for photo-alignment film described above, The precursor film of the composition for an alignment film can be produced by a manufacturing method including a polarized light or a precursor film and a light irradiation step of irradiating the surface of the precursor film with non-polarized light from an oblique direction.
[0087] （前駆体膜形成工程） (Precursor Film Forming Step)
前駆体膜形成工程は、 光配向膜用組成物を用いて前駆体膜を形成する工程 である。 なお、 前駆体膜とは、 光配向処理が施される膜を意味する。 \¥0 2020/175620 26 卩（：17 2020 /008033 The precursor film forming step is a step of forming a precursor film using the composition for photo-alignment film. The precursor film means a film that is subjected to photo-alignment treatment. \\0 2020/175 620 26 卩 (: 17 2020 /008033
上記工程の手順は前駆体膜を形成できれば制限されないが、 例えば、 光配 向膜用組成物を支持体上に塗布して塗膜を形成して、 塗膜に対して硬化処理 （加熱処理および光照射処理） を施して前駆体膜を形成する工程が挙げられ る。 The procedure of the above steps is not limited as long as the precursor film can be formed. For example, the composition for a light directing film is applied onto a support to form a coating film, and the coating film is subjected to a curing treatment (heat treatment and Light irradiation treatment) to form a precursor film.
以下、 この工程の手順について詳述する。 Hereinafter, the procedure of this step will be described in detail.
[0088] 光配向膜用組成物が塗布される支持体は特に制限されないが、 例えば、 ガ ラス基板およびポリマーフィルムが挙げられる。 [0088] The support to which the composition for a photo-alignment film is applied is not particularly limited, and examples thereof include a glass substrate and a polymer film.
ポリマーフィルムの材料としては、 セルロース系ポリマー；ポリメチルメ タクリレートおよびラクトン環含有重合体などのアクリル酸エステル重合体 を有するアクリル系ポリマー；熱可塑性ノルボルネン系ポリマー；ポリカー ボネート系ポリマー；ポリエチレンテレフタレートおよびポリエチレンナフ タレートなどのポリエステル系ポリマー；ポリスチレン、 アクリロニトリル スチレン共重合体などのスチレン系ポリマー；ポリエチレン、 ポリプロピ レンおよびエチレン · プロピレン共重合体などのポリオレフィン系ポリマー ;、 塩化ビニル系ポリマー；ナイロンおよび芳香族ポリアミ ドなどのアミ ド 系ポリマー；イミ ド系ポリマー；スルホン系ポリマー；ポリエーテルスルホ ン系ポリマー；ポリエーテルエーテルケトン系ポリマー；ポリフエニレンス ルフィ ド系ポリマー；塩化ビニリデン系ポリマー； ビニルアルコール系ポリ マー； ビニルプチラール系ポリマー； アリレート系ポリマー；ポリオキシメ チレン系ポリマー；エポキシ系ポリマー； またはこれらのポリマーを混合し たポリマーが挙げられる。 Materials for the polymer film include cellulose-based polymers; acrylic-based polymers having acrylic acid ester polymers such as polymethylmethacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalate and polyethylene naphthalate. Polyester polymers; polystyrene, acrylonitrile styrene copolymers and other styrene polymers; polyethylene, polypropylene and ethylene-propylene copolymers and other polyolefin polymers; vinyl chloride polymers; nylon and aromatic polyamides Polymers; Imide polymers; Sulfone polymers; Polyethersulfone polymers; Polyetheretherketone polymers; Polyphenylene sulfide polymers; Vinylidene chloride polymers; Vinyl alcohol polymers; Vinyl ptillal polymers; Examples thereof include arylate-based polymers; polyoxymethylen-based polymers; epoxy-based polymers; and polymers obtained by mixing these polymers.
[0089] 支持体の厚みは特に制限されないが、 5〜 2 0 0 が好ましく、 1 0〜 [0089] The thickness of the support is not particularly limited, but is preferably 5 to 200, and 10 to
1 0 0 がより好ましく、 2 0〜 9 0 がさらに好ましい。 100 is more preferable, and 20 to 90 is further preferable.
[0090] 光配向膜用組成物の塗布方法は特に制限されないが、 例えば、 スピンコー ティング、 ダイコーティング、 グラビアコーティング、 フレキソ印！^、 およ び、 インクジェッ ト印刷が挙げられる。 [0090] The method for applying the composition for a photo-alignment film is not particularly limited, but for example, spin coating, die coating, gravure coating, flexo printing! ^, and inkjet printing.
[0091 ] 光配向膜用組成物の塗膜に対する硬化処理の方法は特に制限されないが、 加熱処理および光照射処理が挙げられる。 例えば、 酸発生剤が熱酸発生剤で 〇 2020/175620 27 卩（：171? 2020 /008033 The method of curing the coating film of the composition for a photo-alignment film is not particularly limited, and examples thereof include heat treatment and light irradiation treatment. For example, if the acid generator is a thermal acid generator, 〇 2020/175 620 27 卩 (：171? 2020 /008033
ある場合、 硬化処理としては加熱処理が好ましく、 酸発生剤が光酸発生剤で ある場合、 硬化処理としては光照射処理が好ましい。 In some cases, heat treatment is preferable as the curing treatment, and when the acid generator is a photoacid generator, light irradiation treatment is preferable as the curing treatment.
加熱処理の条件は特に制限されず、 使用される材料に応じて適宜最適な条 件が選択されるが、 加熱温度としては 5 0〜 1 5 0 °〇が好ましく、 8 0〜 1 4 0 °〇がより好ましい。 加熱時間としては〇. 1〜 6 0分間が好ましく、 0 . 5〜 3 0分間がより好ましい。 The conditions for heat treatment are not particularly limited, and optimal conditions are selected as appropriate depending on the material used, but the heating temperature is preferably 50 to 150 ° 〇, and 80 to 140° O is more preferable. The heating time is preferably 0.1 to 60 minutes, more preferably 0.5 to 30 minutes.
光照射処理の条件は特に制限されず、 紫外線を用いることが好ましく、 照 The conditions of the light irradiation treatment are not particularly limited, and it is preferable to use ultraviolet rays.
2 0〇1」/〇 111 2〜 5
Figure imgf000028_0001
2 0 1'' / 0 111 2 to 5
Figure imgf000028_0001
[0092] なお、 上記では塗膜を形成する処理と硬化処理とが別途実施される手順に ついて述べたが、 両者は同時に実施してもよい。 つまり、 塗膜を形成する際 に合わせて硬化処理を実施してもよい。 具体的には、 光配向膜用組成物を支 持体上に塗布しつつ、 加熱する （または、 光照射する） 方法が挙げられる。 [0092] Although the procedure for separately performing the coating film forming treatment and the curing treatment has been described above, they may be performed simultaneously. That is, the curing treatment may be carried out at the time of forming the coating film. Specifically, a method of heating (or irradiating with light) while applying the composition for a photo-alignment film on a support can be mentioned.
[0093] （光照射処理） [0093] (Light irradiation treatment)
光照射処理は、 偏光または前駆体膜表面に対して斜め方向から非偏光を照 射する工程である。 The light irradiation treatment is a step of irradiating the surface of the polarized film or the precursor film with non-polarized light from an oblique direction.
光配向膜用組成物の前駆体膜に対して照射する偏光は特に制限はなく、 例 えば、 直線偏光、 円偏光、 および、 楕円偏光が挙げられ、 直線偏光が好まし い。 The polarized light with which the precursor film of the composition for a photo-alignment film is irradiated is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, and elliptically polarized light, and linearly polarized light is preferable.
また、 非偏光を照射する 「斜め方向」 とは、 前駆体膜表面の法線方向に対 して極角 0 （〇< 0 < 9〇° ） 傾けた方向である限り、 特に制限はなく、 極 角 0は 2 0〜 8 0 ° であることが好ましい。 The “oblique direction” for irradiating non-polarized light is not particularly limited as long as it is a direction inclined by a polar angle 0 (〇 <0 <90 ° ) with respect to the normal direction of the precursor film surface. The polar angle 0 is preferably 20 to 80 ° .
[0094] 偏光または非偏光における波長としては、 前駆体膜中の液晶化合物に対す る配向制御能を付与することができる限り、 特に制限はないが、 例えば、 紫 外線、 近紫外線、 および、 可視光線が挙げられる。 中でも、 2 5 0〜 4 5 0 门 の近紫外線が好ましい。 [0094] The wavelength of polarized light or non-polarized light is not particularly limited as long as it can impart the orientation control ability to the liquid crystal compound in the precursor film, and examples thereof include ultraviolet rays, near ultraviolet rays, and visible rays. Rays can be mentioned. Of these, near-ultraviolet rays of 250 to 450 are preferable.
また、 偏光または非偏光を照射するための光源としては、 例えば、 キセノ ンランプ、 高圧水銀ランプ、 超高圧水銀ランプ、 および、 メタルハライ ドラ 〇 2020/175620 28 卩（：171? 2020 /008033 As a light source for irradiating polarized light or non-polarized light, for example, a xenon lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a metal halide 〇 2020/175 620 28 卩 (：171? 2020 /008033
ンプが挙げられる。 このような光源から得た紫外線または可視光線に対して 、 干渉フィルタまたは色フィルタなどを用いることで、 照射する波長範囲を 制限できる。 また、 これらの光源からの光に対して、 偏光フィルタまたは偏 光プリズムを用いることで、 直線偏光を得ることができる。 Pump. By using an interference filter or a color filter for ultraviolet rays or visible rays obtained from such a light source, the wavelength range for irradiation can be limited. Further, linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources.
[0095] 偏光または非偏光の積算光量は特に制限されないが、 1〜 3
Figure imgf000029_0001
[0095] The cumulative amount of polarized or unpolarized light is not particularly limited,
Figure imgf000029_0001
2が好ましく、
Figure imgf000029_0002
しい。 2 is preferred,
Figure imgf000029_0002
Good
偏光または非偏光の照度は特に制限されないが、 〇. 1〜 3
Figure imgf000029_0003
The illuminance of polarized light or non-polarized light is not particularly limited.
Figure imgf000029_0003
が好ましく、 1〜 1 0 0〇1 \^//〇〇1 2がより好ましい。 Is preferred, and 1 to 10000 1 \^//○ 12 is more preferred.
[0096] 光配向膜の膜厚は特に制限されず、 1 0〜 1 0 0 0 n mが好ましく、 1 0 〜 7 0 0 n がより好ましい。 [0096] The film thickness of the photo-alignment film is not particularly limited, and is preferably 10 to 100 nm, more preferably 10 to 700 nm.
[0097] ＜積層体＞ [Laminate]
本発明の積層体は、 上記光配向膜と、 液晶化合物を含む液晶組成物を用い て形成される光学異方性層と、 を有する。 The laminate of the present invention has the above-mentioned photo-alignment film and an optically anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound.
また、 本発明の積層体は、 さらに支持体を有しているのが好ましく、 具体 的には、 支持体と光配向膜と光学異方性層とをこの順に有しているのが好ま しい。 The laminate of the present invention preferably further has a support, and specifically, it preferably has a support, a photo-alignment film and an optically anisotropic layer in this order. ..
支持体および光配向膜は、 上述した通りである。 The support and the photo-alignment film are as described above.
以下、 光学異方性層について詳述する。 Hereinafter, the optically anisotropic layer will be described in detail.
[0098] （光学異方性層） (Optically Anisotropic Layer)
積層体が有する光学異方性層は、 液晶化合物を含む液晶組成物 （以下、 「 光学異方性層用組成物」 ともいう。 ） を用いて形成された光学異方性層であ れば特に制限されず、 従来公知の光学異方性層が挙げられる。 The optically anisotropic layer of the laminate may be an optically anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound (hereinafter, also referred to as “composition for optically anisotropic layer”). There is no particular limitation, and examples include conventionally known optically anisotropic layers.
光学異方性層としては、 重合性基を有する液晶化合物を含む液晶組成物を 硬化させて得られる層であるのが好ましい。 The optically anisotropic layer is preferably a layer obtained by curing a liquid crystal composition containing a liquid crystal compound having a polymerizable group.
光学異方性層は、 単層構造であってもよく、 複数層を積層した構造 （積層 体） であってもよい。 The optically anisotropic layer may have a single-layer structure or a structure in which a plurality of layers are laminated (laminate).
以下に、 液晶性合物および任意の添加剤について説明する。 The liquid crystal compound and optional additives will be described below.
[0099] 液晶化合物は、 その形状から、 棒状タイプと円盤状タイプに分類できる。 〇 2020/175620 29 卩（：171? 2020 /008033 The liquid crystal compound can be classified into a rod-shaped type and a disc-shaped type according to its shape. 〇 2020/175 620 29 卩 (：171? 2020 /008033
さらにそれぞれ低分子と高分子タイプがある。 高分子とは一般に重合度が 1 00以上のものを指す （高分子物理 ·相転移ダイナミクス， 土井 正男 著，Furthermore, there are low-molecular type and high-molecular type respectively. Polymers generally refer to polymers with a degree of polymerization of 100 or more (Polymer physics/Phase transition dynamics, Masao Doi,
2頁， 岩波書店， 1 992） 。 2 pages, Iwanami Shoten, 1 992).
本発明においては、 いずれの液晶化合物を用いることもできるが、 棒状液 晶化合物またはディスコティツク液晶化合物を用いるのが好ましく、 棒状液 晶化合物を用いるのがより好ましい。 In the present invention, any liquid crystal compound can be used, but it is preferable to use a rod-shaped liquid crystal compound or a discotic liquid crystal compound, and it is more preferable to use a rod-shaped liquid crystal compound.
［0100］ 液晶化合物は、 重合性基を有することが好ましい。 液晶化合物は 1分子中 に重合性基を 2以上有するのが好ましい。 なお、 液晶化合物が重合によって 固定された後においては、 もはや液晶性を示す必要はない。 [0100] The liquid crystal compound preferably has a polymerizable group. The liquid crystal compound preferably has two or more polymerizable groups in one molecule. Incidentally, after the liquid crystal compound is fixed by polymerization, it is no longer necessary to exhibit liquid crystallinity.
［0101］ 重合性基の種類は特に制限されず、 付加重合反応が可能な官能基が好まし く、 重合性エチレン性不飽和基または環重合性基が好ましく、 （メタ） アク リロイル基、 ビニル基、 スチリル基、 または、 アリル基がより好ましく、 （ メタ） アクリロイル基がさらに好ましい。 [0101] The type of the polymerizable group is not particularly limited, a functional group capable of addition polymerization reaction is preferable, a polymerizable ethylenically unsaturated group or a ring polymerizable group is preferable, and a (meth)acryloyl group, vinyl Group, styryl group, or allyl group is more preferable, and (meth)acryloyl group is further preferable.
［0102］ 棒状液晶化合物としては、 例えば、 特表平 1 1 -5 1 301 9号公報の請 求項 1 または特開 2005-289980号公報の段落 ［ 0026］ 〜 ［ 0 098］ に記載のものを好ましく用いることができ、 ディスコティツク液晶 化合物としては、 例えば、 特開 2007 _ 1 08732号公報の段落 ［00 20］ 〜 ［0067］ または特開 201 0— 244038号公報の段落 ［ 0 01 3］ 〜 ［01 08］ に記載のものを好ましく用いることができる。 [0102] Examples of the rod-shaped liquid crystal compound are those described in claim 1 of Japanese Patent Publication No. 11-513109 or in paragraphs [0026] to [098] of Japanese Patent Laid-Open No. 2005-289980. As the discotic liquid crystal compound, for example, paragraphs [00 20] to [0067] of JP 2007 _ 1 08732 or paragraph [0000 1 of JP 2010-244038 A can be used. ] To [01 08] can be preferably used.
［0103］ 液晶化合物として、 逆波長分散性の液晶化合物を用いることができる。 [0103] As the liquid crystal compound, a reverse wavelength dispersion liquid crystal compound can be used.
ここで、 本明細書において 「逆波長分散性」 の液晶化合物とは、 これを用 いて作製された位相差フィルムの特定波長 （可視光範囲） における面内レタ デーシヨン （［¾ 6） 値を測定した際に、 測定波長が大きくなるにつれて 6 値が同等または高くなるものをいう。 Here, in the present specification, the “reverse wavelength dispersion” liquid crystal compound means an in-plane retardation ([¾ 6) value at a specific wavelength (visible light range) of a retardation film produced by using the liquid crystal compound. In this case, the 6 value becomes equal or higher as the measurement wavelength increases.
［0104］ 液晶化合物としては、 式 （3） で表される液晶化合物が好ましい。
Figure imgf000030_0001
[0104] The liquid crystal compound is preferably a liquid crystal compound represented by the formula (3).
Figure imgf000030_0001
上記式 （3） 中、 0 \ 巳1、 巳 2、 巳 3および巳 4は、 それぞれ独立に 〇 2020/175620 30 卩（：171? 2020 /008033 In the above formula (3), 0 \ M 1 , M 2 , M 3, and M 4 are independent of each other. 〇 2020/175 620 30 boxes (: 171-1? 2020 /008033
、 単結合、 一〇〇一〇一、 一〇 (=3) 〇一、 一〇［^［¾2 -、 一〇［^［¾2 -
Figure imgf000031_0001
, Single bond, 1001 101, 10 (=3) 0 1, 10 [^[¾ 2 -, 10 [^[¾ 2-
Figure imgf000031_0001
_ ［¾1_〇［¾2［¾3—、 または、
Figure imgf000031_0002
および［¾4は、 それぞれ独立に、 水素 原子、 フッ素原子、 または、 炭素数 1〜 4のアルキル基を表す。 _ [¾ 1 _ 〇 [¾ 2 [¾ 3 — or
Figure imgf000031_0002
And [¾ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
〇\ 〇2、 八 1および八2は、 それぞれ独立に、 置換基を有していてもよい 、 炭素数 6〜 1 2の 2価の芳香族炭化水素基、 または、 炭素数 5〜 8の 2価 の脂環式炭化水素基を表し、 脂環式炭化水素基を構成する _〇1~12—の 1個以 上が一〇一、
Figure imgf000031_0003
で置換されていてもよい。 〇 \ 〇 2, eight 1 and eight 2 each independently may have a substituent, a divalent aromatic hydrocarbon group having the number 6-1 2 carbons, or a 5-8 carbon atoms represents a divalent alicyclic hydrocarbon group, ~ _〇_1 constituting the alicyclic hydrocarbon group 1 2 - of one or more on the one hundred and one,
Figure imgf000031_0003
May be substituted with.
3 1および 3 2は、 それぞれ独立に、 単結合、 炭素数 1〜 1 2の直鎖状 もしくは分岐鎖状のアルキレン基、 または、 炭素数 1〜 1 2の直鎖状もしく は分岐鎖状のアルキレン基を構成する _ 01~12—の 1個以上が一〇一、 _ 3 _3 1 and 3 2 are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbons, or a linear or branched chain having 1 to 12 carbons. At least one of _ 01 to 1 2 — constituting the alkylene group of
、 一 (0) —、 もしくは、 一〇〇一に置換された 2価の連結基 を表し、 〇は、 置換基を表す。 , 1(0) —, or a divalent linking group substituted with 1001, and ◯ represents a substituent.
は、 〇〜 2の整数を表し、
Figure imgf000031_0004
複数の巳 3は、 それぞれ同 —であっても異なっていてもよく、 複数の八1は、 それぞれ同一であっても異 なっていてもよい。 Represents an integer from 0 to 2,
Figure imgf000031_0004
A plurality of Snake 3 are the same - or different and a plurality of eight 1 may each become different, even the same.
门は、 〇〜 2の整数を表し、 nが 2である場合、 複数の巳 4は、 それぞれ同 —であっても異なっていてもよく、 複数の八 2は、 それぞれ同一であっても異 なっていてもよい。 门represents an integer of 〇_～ 2, when n is 2, a plurality of snake 4 are the same - or different and a plurality of eight 2 can be the respective same different It may be.
八 は、 置換基を有していてもよい、 芳香族炭化水素環および芳香族複素 環からなる群から選ばれる少なくとも 1つの芳香環を有する有機基を表す。 Eight represents an organic group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, which may have a substituent.
1-1および 1_2は、 それぞれ独立に、 1価の有機基を表す。1 1 and 1_ 2 each independently represents a monovalent organic group.
Figure imgf000031_0005
Figure imgf000031_0005
としては、 例えば、 1， 2 -フエニレン基、 1 , 3 -フエニレン基、 1 , 4 —フエニレン基、 1 , 4—ナフチレン基、 1 , 5—ナフチレン基、 および、 Are, for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, and
2, 6 -ナフチレン基が挙げられ、 なかでも、 1 , 4 -フエニレン基が好ま 〇 2020/175620 31 卩（：171? 2020 /008033 2,6-naphthylene group is mentioned, and among them, 1,4-phenylene group is preferred. 〇 2020/175 620 31 卩(：171? 2020/008033
しく、 トランスー 1 , 4 -フエニレン基がより好ましい。 However, a trans-1,4-phenylene group is more preferable.
また、 〇1、 〇2 % 1および 2が示す炭素数 5〜 8の 2価の脂環式炭化水 素基としては、 5員環基または 6員環基が好ましい。 また、 脂環式炭化水素 基は、 飽和でも不飽和でもよいが飽和脂環式炭化水素基が好ましい。 2価の 脂環式炭化水素基としては、 例えば、 特開 2 0 1 2 _ 2 1 0 6 8号公報の [Further, the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by 0 1 , 0 2 % 1 and 2 is preferably a 5-membered ring group or a 6-membered ring group. The alicyclic hydrocarbon group may be saturated or unsaturated, but a saturated alicyclic hydrocarbon group is preferable. Examples of the divalent alicyclic hydrocarbon group include those described in JP-A No. 20 1 2 _ 210 6 8
0 0 7 8 ] 段落の記載を参酌でき、 この内容は本明細書に組み込まれる。 これらのうち、 シクロヘキシレン基 （シクロヘキサン環） が好ましく、 1 , 4 -シクロヘキシレン基がより好ましく、 トランスー 1 , 4 -シクロヘキ シレン基がさらに好ましい。 [0 0 7 8] The description in the paragraph can be referred to, and the contents thereof are incorporated herein. Of these, a cyclohexylene group (cyclohexane ring) is preferable, a 1,4-cyclohexylene group is more preferable, and a trans-1,4-cyclohexylene group is further preferable.
また、 炭素数 5〜 8の 2価の脂環式炭化水素基が有していてもよい置換基 としては、 後述する式 （八 「_ 1） 中の丫1が有していてもよい置換基と同様 のものが挙げられる。 In addition, as the substituent that the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms may have, a substituent that may be possessed by 丫1 in the formula (8 "_ 1) described later is The same as the group can be mentioned.
[0106] 3 1および 3 2が示す炭素数 1〜 1 2の直鎖状または分岐鎖状のアルキ レン基としては、 例えば、 メチレン基、 エチレン基、 プロピレン基、 プチレ ン基、 ペンチレン基、 ヘキシレン基、 メチルヘキシレン基、 および、 ヘプチ レン基が挙げられる。 なお、 3 1および 3 2は、 上述した通り、 炭素数 1 〜 1 2の直鎖状または分岐鎖状のアルキレン基を構成する
Figure imgf000032_0001
The [0106] 3 1 and 3 2 are shown a linear or branched alkylene group of from 1 to 1 2 carbon atoms, for example, methylene group, ethylene group, propylene group, Puchire down, pentylene, hexylene Group, a methylhexylene group, and a heptylene group. Incidentally, 3 1 and 3 2 are as described above, constitute a straight chain or branched chain alkylene group having 1 to 2 carbon atoms
Figure imgf000032_0001
上が一〇一、 一3—、
Figure imgf000032_0002
一 （0） —、 または、 一〇〇一に置換さ れた 2価の連結基であってもよく、 0で表される置換基としては、 後述する 式 （八 「一 1） 中の丫1が有していてもよい置換基と同様のものが挙げられる The top is 101, 13-,
Figure imgf000032_0002
It may be a monovalent (0) — or a divalent linking group substituted with 1001, and a substituent represented by 0 is a group in the formula (8 “1 1) described later. Examples of the substituent which 1 may have include
[0107] !_ 1および !_ 2が示す 1価の有機基としては、 例えば、 アルキル基、 アリー ル基、 および、 ヘテロアリール基が挙げられる。 [0107] Examples of the monovalent organic group represented by !_ 1 and !_ 2 include an alkyl group, an aryl group, and a heteroaryl group.
アルキル基は、 直鎖状、 分岐鎖状または環状であってもよいが、 直鎖状が 好ましい。 アルキル基の炭素数は、 1〜 3 0が好ましく、 1〜 2 0がより好 ましく、 1〜 1 0がさらに好ましい。 The alkyl group may be linear, branched or cyclic, but linear is preferred. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms.
また、 アリール基は、 単環であっても多環であってもよいが単環が好まし い。 アリール基の炭素数は、 6〜 2 5が好ましく、 6〜 1 0がより好ましい 〇 2020/175620 32 卩（：171? 2020 /008033 The aryl group may be monocyclic or polycyclic, but monocyclic is preferred. The carbon number of the aryl group is preferably 6 to 25, more preferably 6 to 10 〇 2020/175 620 32 units (: 171-1? 2020 /008033
また、 ヘテロアリール基は、 単環であっても多環であってもよい。 ヘテロ アリール基を構成するへテロ原子の数は 1〜 3が好ましい。 ヘテロアリール 基を構成するへテロ原子は、 窒素原子、 硫黄原子、 または、 酸素原子が好ま しい。 ヘテロアリール基の炭素数は 4〜 1 8が好ましく、 4〜 1 2がより好 ましい。 また、 アルキル基、 アリール基およびへテロアリール基は、 無置換 であってもよく、 置換基を有していてもよい。 置換基としては、 後述する式 （八 「一 1） 中の丫1が有していてもよい置換基と同様のものが挙げられる。 The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom. The heteroaryl group preferably has 4 to 18 carbon atoms, and more preferably 4 to 12 carbon atoms. Further, the alkyl group, aryl group and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents as the substituent that may be possessed by Ogura 1 in the formula (8 "-1 1") to be described later.
[0108] !_ 1および 1_ 2の少なくとも一方は重合性基であることが好ましい。 [0108] At least one of !_ 1 and 1_ 2 is preferably a polymerizable group.
重合性基は特に制限されないが、 ラジカル重合またはカチオン重合可能な 重合性基が好ましい。 The polymerizable group is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
ラジカル重合性基としては、 一般に知られているラジカル重合性基を用い ることができ、 アクリロイル基またはメタクリロイル基が好ましい。 この場 合、 重合速度はアクリロイル基が一般的に速いことが知られており、 生産性 向上の点から、 アクリロイル基が好ましいが、 メタクリロイル基も重合性基 として同様に使用できる。 As the radically polymerizable group, a generally known radically polymerizable group can be used, and an acryloyl group or a methacryloyl group is preferable. In this case, an acryloyl group is generally known to have a higher polymerization rate, and an acryloyl group is preferable from the viewpoint of improving productivity, but a methacryloyl group can be used as a polymerizable group in the same manner.
カチオン重合性基としては、 一般に知られているカチオン重合性を用いる ことができ、 例えば、 脂環式エーテル基、 環状アセタール基、 環状ラクトン 基、 環状チオエーテル基、 スピロオルソエステル基、 および、 ビニルオキシ 基が挙げられる。 中でも、 脂環式エーテル基、 または、 ビニルオキシ基が好 ましく、 エポキシ基、 オキセタニル基、 または、 ビニルオキシ基がより好ま しい。 As the cationically polymerizable group, generally known cationically polymerizable groups can be used. Examples thereof include alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, and vinyloxy group. Is mentioned. Of these, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is more preferable.
好ましい重合性基の例としては下記が挙げられる。 Examples of preferable polymerizable groups include the following.
[0109] [化 16] [0109] [Chemical 16]
Figure imgf000033_0001
[0110] !_ 1および 1_2はいずれも重合性基であることが好ましく、 アクリロイル基 またはメタクリロイル基であることがより好ましい。
Figure imgf000033_0001
[0110] Both !_ 1 and 1_ 2 are preferably a polymerizable group, and more preferably an acryloyl group or a methacryloyl group.
[0111] は、 置換基を有していてもよい、 芳香族炭化水素環および芳香族複素 環からなる群から選ばれる少なくとも 1つの芳香環を有する有機基を表す。 芳香族炭化水素環としては、 単環であっても、 複環であってもよい。 芳香 族炭化水素環の炭素数は、 6〜 25が好ましく、 6〜 1 0がより好ましい。 芳香族複素環としては、 単環であっても、 複環であってもよい。 芳香族複 素環を構成するへテロ原子は、 窒素原子、 硫黄原子、 または、 酸素原子が好 ましい。 芳香族複素環の炭素数は 4〜 1 8が好ましく、 4〜 1 2がより好ま しい。 [0111] represents an organic group having at least one aromatic ring which may have a substituent and is selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. The aromatic hydrocarbon ring may be a monocyclic ring or a polycyclic ring. The carbon number of the aromatic hydrocarbon ring is preferably 6 to 25, more preferably 6 to 10. The aromatic heterocycle may be a monocycle or a polycycle. The hetero atom forming the aromatic compound ring is preferably a nitrogen atom, a sulfur atom or an oxygen atom. The aromatic heterocycle preferably has 4 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.
置換基としては、 公知の置換基が挙げられる。 Examples of the substituent include known substituents.
[0112] 上記八 「 1としては、 下記式 （八 「一 1） 〜 （八 「一 5） で表される基から なる群から選択されるいずれかの芳香環が好ましい。 [0112] The above-mentioned " 1 " is preferably any aromatic ring selected from the group consisting of groups represented by the following formulas (8"-1" to (8"-15).
なお、 八 「 1が式 （八 「_ 1） 、 式 （八 「_2） 、 式 （八 「_4） および式 （八 1"_5） で表される基からなる群から選択されるいずれかである場合、
Figure imgf000034_0001
Note that eight "1 has the formula (eight" _ 1), Formula (eight "_2), in any one selected from the group consisting of groups represented by the formula (eight" _4) and (eight 1 "_5) If there is
Figure imgf000034_0001
（八 「_3） で表される基である場合、 1_ 1および 1_2ならびに下記式 （八 「 -3） 中の！-3および 1_ 4の少なくとも 1つが重合性基を表すことがより好ま しい。 Is a group represented by (eight "_3), 1_ 1 and 1_ 2 and the following equation (eight" -3) in - 3 and at least one 1_ 4 is correct preferred more may represent a polymerizable group ..
[0113] [0113]
〇 2020/175620 34 卩（：171? 2020 /008033 〇 2020/175 620 34 卩 (：171? 2020 /008033
[化 17] [Chemical 17]
Figure imgf000035_0001
Figure imgf000035_0001
[0114] 式 （八 「一 1） 〜 （八 「一 5） 中、 氺は、 01または〇2との結合位置を表 す。 [0114] In the formulas (8 "1 1) to (8 "1 5), 氺 represents the bonding position with 0 1 or 0 2 .
また、 〇 1は、 1^1または〇1~1を表す。 Further, 0 1 represents 1^1 or 0 1 to 1.
また、 〇 2は、 一3—、 一〇一、 または、 一 （[¾5） —を表し、
Figure imgf000035_0002
水 素原子または炭素数 1〜 6のアルキル基を表す。 In addition, 0 2 represents 1-, 101, or 1 ([¾ 5 )-,
Figure imgf000035_0002
Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
が表す炭素数 1〜 6のアルキル基としては、 例えば、 メチル基、 エチル 基、 プロピル基、 イソプロピル基、
Figure imgf000035_0003
_プチル基、 イソプチル基、 360 - プチル基、 1 6 「 1:—プチル基、 n _ペンチル基、 および、 n _ヘキシル基 が挙げられる。 The alkyl group having 1 to 6 carbon atoms represented by, for example, methyl group, ethyl group, propyl group, isopropyl group,
Figure imgf000035_0003
_ Butyl group, isoptyl group, 360-Putyl group, 16 "1:-Putyl group, n _ pentyl group, and n _ hexyl group.
[0115] 丫1は、 置換基を有してもよい、 炭素数 6〜 1 2の芳香族炭化水素基、 また は、 炭素数 3〜 1 2の芳香族複素環基を表す。 [0115] Reference 1 represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms.
丫1が表す炭素数 6〜 1 2の芳香族炭化水素基としては、 例えば、 フエニル 基、 2, 6—ジェチルフエニル基、 および、 ナフチル基などのアリール基が 挙げられる。 〇 2020/175620 35 卩（：171? 2020 /008033 The aromatic hydrocarbon group having 6-1 2 carbon atoms represented by丫1, for example, phenyl group, 2, 6-Jechirufueniru group, and an aryl group such as a naphthyl group. 〇 2020/175 620 35
丫1が表す炭素数 3〜 1 2の芳香族複素環基としては、 例えば、 チェニル基 、 チアゾリル基、 フリル基、 ピリジル基、 および、 ベンゾフリル基などのへ テロアリール基が挙げられる。 なお、 芳香族複素環基には、 ベンゼン環と芳 香族複素環とが縮合した基も含まれる。 Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by 1 include a heteroaryl group such as a cenyl group, a thiazolyl group, a furyl group, a pyridyl group, and a benzofuryl group. The aromatic heterocyclic group also includes a group in which a benzene ring and an aromatic heterocycle are condensed.
また、 丫1が有していてもよい置換基としては、 例えば、 アルキル基、 アル コキシ基、 ニトロ基、 アルキルスルホニル基、 アルキルオキシカルボニル基 、 シアノ基、 および、 ハロゲン原子が挙げられる。 As the substituent which may be possessed丫1, for example, an alkyl group, alkoxy group, a nitro group, an alkylsulfonyl group, an alkyloxycarbonyl group, a cyano group, and, a halogen atom.
アルキル基としては、 例えば、 炭素数 1〜 1 8の直鎖状、 分岐鎖状または 環状のアルキル基が好ましく、 炭素数 1〜 8のアルキル基 （例えば、 メチル 基、 ェチル基、 プロピル基、 イソプロピル基、
Figure imgf000036_0001
_ブチル基、 イソプチル基 、 3 6 0—ブチル基、 1 _ブチル基、 および、 シクロヘキシル基） がより好 ましく、 炭素数 1〜 4のアルキル基がさらに好ましく、 メチル基またはェチ ル基が特に好ましい。 As the alkyl group, for example, a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group Base,
Figure imgf000036_0001
_Butyl group, isoptyl group, 360-butyl group, 1_butyl group, and cyclohexyl group) are more preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is Particularly preferred.
アルコキシ基としては、 例えば、 炭素数 1〜 1 8のアルコキシ基が好まし く、 炭素数 1〜 8のアルコキシ基 （例えば、 メ トキシ基、 ェトキシ基、 n - ブトキシ基、 および、 メ トキシェトキシ基） がより好ましく、 炭素数 1〜 4 のアルコキシ基がさらに好ましく、 メ トキシ基またはェトキシ基が特に好ま しい。 As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, and methoxetoxy group) Is more preferable, an alkoxy group having 1 to 4 carbon atoms is further preferable, and a methoxy group or an ethoxy group is particularly preferable.
ハロゲン原子としては、 例えば、 フッ素原子、 塩素原子、 臭素原子、 およ び、 ヨウ素原子が挙げられ、 フッ素原子または塩素原子が好ましい。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
[01 16] また、 1、 2および 3は、 それぞれ独立に、 水素原子、 炭素数 1〜 2 0 の 1価の脂肪族炭化水素基、 炭素数 3〜 2 0の 1価の脂環式炭化水素基、 炭 素数 6〜 2 0の 1価の芳香族炭化水素基、 ハロゲン原子、 シアノ基、 ニトロ 基、
Figure imgf000036_0003
または、
Figure imgf000036_0002
を表し、
Figure imgf000036_0004
それぞれ 独立に、 水素原子または炭素数 1〜 6のアルキル基を表し、
Figure imgf000036_0005
[01 16] 1 , 2, and 3 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent alicyclic carbon group having 3 to 20 carbon atoms. Hydrogen group, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, halogen atom, cyano group, nitro group,
Figure imgf000036_0003
Or
Figure imgf000036_0002
Represents
Figure imgf000036_0004
Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
Figure imgf000036_0005
、 互いに結合して芳香環を形成してもよい。 , May combine with each other to form an aromatic ring.
炭素数 1〜 2 0の 1価の脂肪族炭化水素基としては、 炭素数 1〜 1 5のア ルキル基が好ましく、 炭素数 1〜 8のアルキル基がより好ましく、 メチル基 〇 2020/175620 36 卩（：171? 2020 /008033 As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group 〇 2020/175 620 36 卩 (: 171-1? 2020 /008033
、 ェチル基、 イソプロピル基、 6 「 ーペンチル基 （1 , 1 —ジメチルプ ロピル基） 、 I 6 「 I -ブチル基、 または、 1 , 1 -ジメチルー 3, 3 -ジ メチループチル基がさらに好ましく、 メチル基、 ェチル基、 または、 1 6 「, Ethyl group, isopropyl group, 6 "-pentyl group (1, 1-dimethylpropyl group), I 6 "I-butyl group, or 1, 1-dimethyl-3,3-dimethylbutyl group is more preferable, methyl group, Ethyl group, or 1 6 ”
I—ブチル基が特に好ましい。 The I-butyl group is particularly preferred.
炭素数 3〜 20の 1価の脂環式炭化水素基としては、 例えば、 シクロプロ ピル基、 シクロブチル基、 シクロペンチル基、 シクロヘキシル基、 シクロへ プチル基、 シクロオクチル基、 シクロデシル基、 メチルシクロヘキシル基、 および、 ェチルシクロヘキシル基などの単環式飽和炭化水素基；シクロブテ ニル基、 シクロペンテニル基、 シクロヘキセニル基、 シクロヘプテニル基、 シクロオクテニル基、 シクロデセニル基、 シクロペンタジェニル基、 シクロ へキサジェニル基、 シクロオクタジェニル基、 および、 シクロデカジェン基 などの単環式不飽和炭化水素基； ビシクロ ［2. 2. 1］ ヘプチル基、 ビシ クロ ［2. 2. 2］ オクチル基、 トリシクロ ［5. 2. 1. 02, 6］ デシル基 、 トリシクロ ［3. 3. 1. 13, 7］ デシル基、 テトラシクロ ［6. 2. 1.Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group, and , A monocyclic saturated hydrocarbon group such as an ethyl cyclohexyl group; a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclodecenyl group, a cyclopentenyl group, a cyclohexagenyl group, a cyclooctagenenyl group Group and monocyclic unsaturated hydrocarbon group such as cyclodecadiene group; bicyclo [2. 2. 1] heptyl group, bicyclo [2. 2. 2] octyl group, tricyclo [5. 2. 1] .0 2, 6 ] decyl group, tricyclo [3. 3. 1. 1 3, 7 ] decyl group, tetracyclo [6. 2. 1.
13' 6. 〇2, 7］ ドデシル基、 および、 アダマンチル基などの多環式飽和炭化 水素基；が挙げられる。 1 3 ' 6. 0 2, 7 ] Dodecyl group, and polycyclic saturated hydrocarbon group such as adamantyl group;
炭素数 6〜 20の 1価の芳香族炭化水素基としては、 例えば、 フェニル基 、 2, 6 -ジェチルフェニル基、 ナフチル基、 および、 ビフェニル基が挙げ られ、 炭素数 6〜 1 2のアリール基 （特にフェニル基） が好ましい。 Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-ditylphenyl group, a naphthyl group, and a biphenyl group, and an aryl group having 6 to 12 carbon atoms. A group (particularly a phenyl group) is preferred.
ハロゲン原子としては、 例えば、 フッ素原子、 塩素原子、 臭素原子、 およ び、 ヨウ素原子が挙げられ、 フッ素原子、 塩素原子、 または、 臭素原子が好 ましい。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom or a bromine atom is preferable.
—方、
Figure imgf000037_0001
が示す炭素数 1〜 6のアルキル基としては、 例えば、 メチ ル基、 ェチル基、 プロピル基、 イソプロピル基、
Figure imgf000037_0002
_ブチル基、 イソプチル 基、 360—ブチル基、 ㊀ 「 ーブチル基、
Figure imgf000037_0003
および、 11 -ヘキシル基が挙げられる。 — One,
Figure imgf000037_0001
Examples of the alkyl group having 1 to 6 carbon atoms include, for example, methyl group, ethyl group, propyl group, isopropyl group,
Figure imgf000037_0002
_Butyl group, isoptyl group, 360-butyl group, ㊀ “-butyl group,
Figure imgf000037_0003
And 11-hexyl groups.
［0117］ また、 八3および八4は、 それぞれ独立に、 一〇一、
Figure imgf000037_0004
（［¾10） -、 -3 —、 および、
Figure imgf000037_0005
〇一からなる群から選択される基を表し、 は、 水素原 〇 2020/175620 37 卩（：171? 2020 /008033 [0117] In addition, eighty three and eighty four are, independently, 101 and
Figure imgf000037_0004
([¾ 10 )-, -3 —, and,
Figure imgf000037_0005
Represents a group selected from the group consisting of 〇 2020/175 620 37 卩(：171? 2020/008033
子または置換基を表す。Represents a child or a substituent.
Figure imgf000038_0001
上記式 （八 「_ 1） 中の丫1が有していてもよ い置換基と同様のものが挙げられる。
Figure imgf000038_0001
Examples thereof include the same substituents as the substituent 1 may have in the above formula (8 “_ 1 ).
[0118] また、 Xは、 水素原子または置換基が結合していてもよい第 1 4族〜第 1 [0118] Further, X is a hydrogen atom or a Group 14 to Group 1 to which a substituent may be bonded.
6族の非金属原子を表す。 Represents a non-metal atom of Group 6.
また、 Xが示す第 1 4族〜第 1 6族の非金属原子としては、 例えば、 酸素 原子、 硫黄原子、 置換基を有する窒素原子、 および、 置換基を有する炭素原 子が挙げられ、 置換基としては、 上記式 （八 「一 1） 中の丫1が有していても よい置換基と同様のものが挙げられる。 Further, examples of the non-metal atom of Groups 14 to 16 represented by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent. the group, the formula (eight "one 1) those in丫1 is similar to the substituent which may have the like.
[0119] また、 〇3および〇4は、 それぞれ独立に、 単結合、 一〇〇一〇一、 一〇 （ [0119] In addition, 0 3 and 0 4 are, independently of each other, a single bond, a 10101, a 10 (
Figure imgf000038_0002
Figure imgf000038_0002
3[¾4 -、 一 [^-〇[¾2[¾3 -、 または、
Figure imgf000038_0003
を表す。
Figure imgf000038_0004
 3 [¾ 4 -, one [^-〇 [¾ 2 [¾ 3 -, or
Figure imgf000038_0003
Represents.
Figure imgf000038_0004
、 および は、 それぞれ独立に、 水素原子、 フッ素原子、 または、 炭素 数 1〜 4のアルキル基を表す。 , And each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
[0120] また、 3 3および 3 4は、 それぞれ独立に、 単結合、 炭素数 1〜 1 2の 直鎖状もしくは分岐鎖状のアルキレン基、 または、 炭素数 1〜 1 2の直鎖状 もしくは分岐鎖状のアルキレン基を構成する _ 01~12—の 1個以上が一〇一、[0120] Also, 3 3 and 3 4 are each independently a single bond, a linear or branched alkylene group of number 1-1 2 carbons or straight-chain carbon number of 1-1 2 or ~ _ 01 constituting the branched chain alkylene group having 1 2 - of one or more one hundred and one,
- 3— % — 1\11~1—、 一 （0） —、 もしくは、 一〇〇一に置換された 2価の 連結基を表し、 0は、 置換基を表す。 -3 — % — 1\11 ~ 1—, 1 (0) —, or represents a divalent linking group substituted with 1001, and 0 represents a substituent.
[0121] また、 ！_3および !_4は、 それぞれ独立に、 1価の有機基を表す。 [0121] See you again! _ 3 and !_ 4 each independently represent a monovalent organic group.
[0122] また、 は、 芳香族炭化水素環および芳香族複素環からなる群から選ば れる少なくとも 1つの芳香環を有する、 炭素数 2〜 30の有機基を表す。 また、
Figure imgf000038_0005
は、 水素原子、 置換基を有していてもよい炭素数 1〜 1 2のア ルキル基、 または、 芳香族炭化水素環および芳香族複素環からなる群から選 択される少なくとも 1つの芳香環を有する、 炭素数 2〜 30の有機基を表す 〇 2020/175620 38 卩（：171? 2020 /008033 [0122] Further, represents an organic group having 2 to 30 carbon atoms, which has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. Also,
Figure imgf000038_0005
Is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. Represents an organic group having 2 to 30 carbon atoms 〇 2020/175 620 38 卩 (：171? 2020 /008033
また、 Xおよび Vにおける芳香環は、 置換基を有していてもよく、 八 Xと八ソとが結合して環を形成していてもよい。 The aromatic ring in X and V may have a substituent, and 8X and 8so may be bonded to each other to form a ring.
また、 〇3は、 水素原子、 または、 置換基を有していてもよい炭素数 1〜 6 のアルキル基を表す。 Further, 0 3 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
［0123］ 光学異方性層用組成物には、 上述した液晶化合物以外の成分が含まれてい てもよい。 [0123] The composition for the optically anisotropic layer may contain a component other than the above-mentioned liquid crystal compound.
例えば、 光学異方性層用組成物には、 重合開始剤が含まれていてもよい。 使用される重合開始剤は、 重合反応の形式に応じて選択され、 例えば、 熱重 合開始剤、 光重合開始剤が挙げられる。 例えば、 光重合開始剤の例には、 《 —カルボニル化合物、 アシロインエーテル、
Figure imgf000039_0001
炭化水素置換芳香族アシロ イン化合物、 多核キノン化合物、 および、 トリアリールイミダゾールダイマ —と ーアミノフエニルケトンとの組み合わせなどが挙げられる。 For example, the composition for the optically anisotropic layer may contain a polymerization initiator. The polymerization initiator used is selected according to the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator. For example, examples of the photopolymerization initiator include <<-carbonyl compound, acyloin ether,
Figure imgf000039_0001
Examples include a hydrocarbon-substituted aromatic acylloin compound, a polynuclear quinone compound, and a combination of a triarylimidazole dimer and an aminophenyl ketone.
重合開始剤の使用量は、 組成物の全固形分に対して、 〇. 0 1〜 2 0質量 %が好ましく、 〇. 5〜 5質量％がより好ましい。 The amount of the polymerization initiator used is preferably 0.01 to 20% by mass, and more preferably 0.5 to 5% by mass, based on the total solid content of the composition.
［0124］ また、 光学異方性層用組成物には、 重合性モノマーが含まれていてもよい 重合性モノマーとしては、 ラジカル重合性またはカチオン重合性の化合物 が挙げられる。 好ましくは、 多官能性ラジカル重合性モノマーであり、 上記 の重合性基含有の液晶化合物と共重合性のものが好ましい。 例えば、 特開 2 0 0 2— 2 9 6 4 2 3号公報中の段落 ［0 0 1 8］ 〜 ［0 0 2 0］ に記載の ものが挙げられる。 [0124] Further, the composition for the optically anisotropic layer may contain a polymerizable monomer. Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. A polyfunctional radically polymerizable monomer is preferable, and one that is copolymerizable with the above-mentioned polymerizable group-containing liquid crystal compound is preferable. For example, those described in paragraphs [0 0 1 8] to [0 0 2 0] of JP-A-2000-2296423 can be mentioned.
重合性モノマーの含有量は、 液晶化合物の全質量に対して、 1〜 5 0質量 %であることが好ましく、 2〜 3 0質量％であることがより好ましい。 The content of the polymerizable monomer is preferably 1 to 50 mass% and more preferably 2 to 30 mass% with respect to the total mass of the liquid crystal compound.
［0125］ また、 光学異方性層用組成物には、 塗膜の均一性、 膜の強度の点から、 界 面活性剤が含まれていてもよい。 [0125] Further, the composition for the optically anisotropic layer may contain a surfactant from the viewpoint of the uniformity of the coating film and the strength of the film.
界面活性剤としては、 従来公知の化合物が挙げられるが、 特にフッ素系化 合物が好ましい。 例えば特開 2 0 0 1 - 3 3 0 7 2 5号公報中の段落 ［0 0 2 8］ 〜 ［0 0 5 6］ に記載の化合物、 特開 2 0 0 5 - 0 6 2 6 7 3号公報 〇 2020/175620 39 卩（：171? 2020 /008033 As the surfactant, conventionally known compounds can be mentioned, but a fluorine compound is particularly preferable. For example, the compounds described in paragraphs [0 0 2 8] to [0 0 5 6] of JP-A-2000 0-3300 7 25, JP-A-2000 5-0 6 2 6 7 3 Publication 〇 2020/175 620 39 卩 (：171? 2020 /008033
の段落 ［0 0 6 9］ 〜 ［0 1 2 6］ に記載の化合物が挙げられる。 The compounds described in paragraphs [0 0 6 9] to [0 1 2 6] of the above.
［0126］ また、 光学異方性層用組成物には、 光学異方性層を偏光子として機能させ る点から、 二色性物質が含まれていてもよい。 [0126] Further, the composition for an optically anisotropic layer may contain a dichroic substance from the viewpoint of causing the optically anisotropic layer to function as a polarizer.
上記二色性物質は特に制限されず、 可視光吸収物質 （二色性色素） 、 発光 物質 （蛍光物質、 燐光物質） 、 紫外線線吸収物質、 赤外線吸収物質、 非線形 光学物質、 力ーボンナノチューブ、 および、 無機物質 （例えば量子ロッ ド） が挙げられ、 従来公知の二色性物質 （二色性色素） を使用できる。 The above-mentioned dichroic substance is not particularly limited, and visible light absorbing substance (dichroic dye), light emitting substance (fluorescent substance, phosphorescent substance), ultraviolet ray absorbing substance, infrared absorbing substance, non-linear optical substance, carbon nanotube, In addition, inorganic substances (for example, quantum rods) can be mentioned, and conventionally known dichroic substances (dichroic dyes) can be used.
［0127］ また、 光学異方性層用組成物には有機溶媒が含まれていてもよい。 有機溶 媒としては、 上述した本発明の光配向膜用組成物において説明したものと同 様のものが挙げられる。 [0127] The composition for the optically anisotropic layer may contain an organic solvent. Examples of the organic solvent include the same ones as described in the above-mentioned composition for photoalignment film of the present invention.
［0128］ また、 光学異方性層用組成物には、 偏光子界面側垂直配向剤および空気界 面側垂直配向剤などの垂直配向促進剤、 ならびに、 偏光子界面側水平配向剤 および空気界面側水平配向剤などの水平配向促進剤などの各種配向剤が含ま れていてもよい。 [0128] Further, the composition for the optically anisotropic layer includes a vertical alignment promoter such as a polarizer interface side vertical aligning agent and an air interface side vertical aligning agent, and a polarizer interface side horizontal aligning agent and an air interface. Various aligning agents such as a horizontal alignment promoting agent such as a side horizontal aligning agent may be contained.
光学異方性層用組成物には、 上記成分以外に、 密着改良剤、 可塑剤、 およ び、 ポリマーなどが含まれていてもよい。 The composition for an optically anisotropic layer may contain an adhesion improver, a plasticizer, a polymer and the like in addition to the above components.
［0129］ 光学異方性層用組成物を用いた光学異方性層の形成方法は特に制限されず 、 例えば、 上述した光配向膜上に、 光学異方性層用組成物を塗布して塗膜を 形成し、 得られた塗膜に対して硬化処理 （紫外線の照射 （光照射処理） また は加熱処理） を施して光学異方性層を形成する方法が挙げられる。 [0129] The method for forming the optically anisotropic layer using the composition for optically anisotropic layer is not particularly limited. For example, the composition for optically anisotropic layer may be applied onto the above-mentioned photo-alignment film. Examples include a method of forming a coating film and subjecting the obtained coating film to a curing treatment (irradiation with ultraviolet rays (light irradiation treatment) or heat treatment) to form an optically anisotropic layer.
光学異方性層用組成物の塗布は、 公知の方法 （例えば、 ワイヤーバーコー ティング法、 押し出しコーティング法、 ダイレクトグラビアコーティング法 、 リバースグラビアコーティング法、 ダイコーティング法） により実施でき る。 The composition for the optically anisotropic layer can be applied by a known method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).
［0130］ 光学異方性層の膜厚は特に制限されず、 〇. 1〜 1 〇 が好ましく、 0 . 5〜 5 がより好ましい。 [0130] The film thickness of the optically anisotropic layer is not particularly limited, and is preferably 0.1 to 10 and more preferably 0.5 to 5.
光学異方性層の波長 5 5 0 n における面内レタデーシヨンは特に制限さ れないが、 1 1 0〜 1 6 0门 が好ましい。 〇 2020/175620 40 卩（：171? 2020 /008033 The in-plane retardation of the optically anisotropic layer at a wavelength of 550 n is not particularly limited, but 110 to 160 is preferable. 〇 2020/175 620 40 卩 (: 171? 2020 /008033
[0131] ＜用途＞ [0131] <Use>
上記積層体は種々の用途に適用できる。 例えば、 表示素子と、 積層体とを 含む画像表示装置が挙げられる。 The laminated body can be applied to various uses. For example, an image display device including a display element and a laminated body can be mentioned.
本発明の画像表示装置に用いられる表示素子は特に制限されず、 例えば、 液晶セル、 有機エレクトロルミネッセンス （以下、 「巳 !_」 と略す。 ） 表示 パネル、 および、 プラズマディスプレイパネル等が挙げられ、 液晶セルまた は有機巳 !_表示パネルが好ましい。 すなわち、 本発明の画像表示装置として は、 表示素子として液晶セルを用いた液晶表示装置、 表示素子として有機巳 !_表示パネルを用いた有機日 !_表示装置が好ましい。 The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter, abbreviated as “M!”) display panel, and a plasma display panel. Liquid crystal cells or organic display panels are preferred. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, and an organic date display device using an organic semiconductor display panel as a display element.
[0132] 液晶表示装置に利用される液晶セルとしては、 八 （V 6 「 1: 丨
Figure imgf000041_0001
丨 八 [0132] As a liquid crystal cell used in a liquid crystal display device, there are eight (V 6 "1:
Figure imgf000041_0001
Hachi
I 1 9 门 1116 11 1：） モード、 〇〇巳 （〇 \ 〇 a \ I ）/ 〇〇 01 6 门 3 3 ㊀〇! 巳㊀门 〇!） モード、 I
Figure imgf000041_0002
1 门 9I 1 9 门 1116 11 1:) mode, 〇 〇 跳 (〇 \ 〇 a \ I )/ 〇 〇 01 6 门 3 3 ㊀ 〇! 巳 ㊀ 门 〇!) mode, I
Figure imgf000041_0002
1 door 9
） モード、 または、 丁 （丁 \« 丨 3 I 6〇1
Figure imgf000041_0003
I 〇） モードであるこ とが好ましい。 ) Mode or Ding (Ding \« 丨 3 I 60 1
Figure imgf000041_0003
It is preferable that it is in I 0) mode.
[0133] 本発明の画像表示装置の一例である有機巳 !_表示装置としては、 例えば、 視認側から、 偏光子、 本発明の積層体、 および、 有機日 !_表示パネルをこの 順で有する態様が好ましい。 [0133] An organic semiconductor display device which is an example of the image display device of the present invention includes, for example, a polarizer, the laminate of the present invention, and an organic solar display panel in this order from the viewing side. Aspects are preferred.
[0134] 上記偏光子は、 光を特定の直線偏光に変換する機能を有する部材であれば 特に制限されず、 従来公知の吸収型偏光子および反射型偏光子を利用できる 吸収型偏光子としては、 ヨウ素系偏光子、 二色性染料を利用した染料系偏 光子、 およびポリエン系偏光子などが用いられる。 ヨウ素系偏光子および染 料系偏光子には、 塗布型偏光子および延伸型偏光子があり、 いずれも適用で きる。 [0134] The above-mentioned polarizer is not particularly limited as long as it is a member having a function of converting light into a specific linearly polarized light, and as an absorption-type polarizer that can utilize a conventionally known absorption-type polarizer and reflection-type polarizer, An iodine-based polarizer, a dye-based polarizer using a dichroic dye, and a polyene-based polarizer are used. The iodine-based polarizer and the dye-based polarizer include a coating-type polarizer and a stretch-type polarizer, both of which are applicable.
また、 基材上にポリビニルアルコール層を形成した積層フィルムの状態で 延伸および染色を施すことで偏光子を得る方法として、 特許第 50481 2 〇号公報、 特許第 5 1 439 1 8号公報、 特許第 469 1 205号公報、 特 許第 475 1 481号公報、 特許第 475 1 486号公報を挙げることがで 〇 2020/175620 41 卩（：171? 2020 /008033 Further, as a method of obtaining a polarizer by stretching and dyeing in the state of a laminated film in which a polyvinyl alcohol layer is formed on a substrate, Patent No. 50481 2 0 Publication, Patent 5 1 439 18 Publication, Patent No. 469 1 205, Japanese Patent No. 475 1 481 and Japanese Patent No. 475 1 486 can be mentioned. 〇 2020/175 620 41 卩(：171? 2020/008033
き、 これらの偏光子に関する公知の技術も好ましく利用できる。 However, known techniques regarding these polarizers can also be preferably used.
反射型偏光子としては、 例えば、 複屈折の異なる薄膜を積層した偏光子、 ワイヤ—グリッ ド型偏光子、 および、 選択反射域を有するコレステリック液 晶と 1 / 4波長板とを組み合わせた偏光子が挙げられる。 Examples of reflective polarizers include a polarizer in which thin films having different birefringence are laminated, a wire-grid polarizer, and a polarizer in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wavelength plate are combined. Is mentioned.
これらのうち、 密着性がより優れる点で、 ポリビニルアルコール系樹脂 （
Figure imgf000042_0001
特に、 ポリビニル アルコールおよびエチレンービニルアルコール共重合体からなる群から選択 される少なくとも 1つ） を含む偏光子が好ましい。 Of these, polyvinyl alcohol resin (
Figure imgf000042_0001
In particular, a polarizer containing at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymer) is preferable.
[0135] 偏光子の厚みは特に制限されず、 3〜 6 0 が好ましく、 5 〜 3 0 より好ましい。 [0135] The thickness of the polarizer is not particularly limited and is preferably 3 to 60, more preferably 5 to 30.
[0136] 有機巳 !_表示パネルは、 陽極および陰極の一対の電極間に、 発光層または 発光層を含む複数の有機化合物薄膜を形成した部材である。 有機日 !_表示パ ネルは、 発光層のほか正孔注入層、 正孔輸送層、 電子注入層、 電子輸送層、 および、 保護層などを有してもよく、 またこれらの各層はそれぞれ他の機能 を備えたものであってもよい。 [0136] An organic semiconductor display panel is a member in which a light emitting layer or a plurality of organic compound thin films including the light emitting layer are formed between a pair of electrodes of an anode and a cathode. In addition to the light emitting layer, the organic display panel may have a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a protective layer, and the like, and each of these layers is different. It may have the function of.
実施例 Example
[0137] 以下に実施例に基づいて本発明をさらに詳細に説明する。 以下の実施例に 示す材料、 使用量、 割合、 処理内容、 および、 処理手順は、 本発明の趣旨を 逸脱しない限り適宜変更することができる。 従って、 本発明の範囲は以下に 示す実施例により限定的に解釈されるべきものではない。 [0137] Hereinafter, the present invention will be described in more detail with reference to Examples. The materials, used amounts, ratios, treatment contents, and treatment procedures shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following examples.
[0138] （モノマー 八一 1 の合成） [0138] (Synthesis of Monomer 81)
撹拌羽、 温度計、 滴下口一卜および還流管を備えた 2 !_三ロフラスコに、 In a 2!_ 3 flask equipped with a stirring blade, a thermometer, a dropping port and a reflux tube,
4—アミノシクロへキサノール （5〇. 〇 9） 、 トリエチルアミン （4 8 . 3 ） 、 および、 1\1 , 1\! -ジメチルアセトアミ ド （8 0 0 9） を量りとり、 氷冷下で撹拌した。 4-Aminocyclohexanol (50.09.0), triethylamine (48.3), and 1\1, 1\!-dimethylacetamide (8009) were weighed and cooled on ice. It was stirred.
次に、 滴下口一卜を用いてメタクリル酸クロリ ド （4 7 . 5 9） を 4 0分 かけて上記フラスコ内に滴下し、 滴下終了後、 反応液を 4 0 °〇で 2時間撹拌 した。 〇 2020/175620 42 2020 /008033 Next, methacryloyl chloride (47.5.9) was added dropwise to the above flask over 40 minutes using one drop port, and after the addition was complete, the reaction solution was stirred at 40 ° for 2 hours. .. 〇 2020/175 620 42 2020/008033
反応液を室温 （2 3 °〇 まで冷却した後、 反応液を吸引ろ過して、 析出し た塩を除去した。 得られた有機層を撹拌羽、 温度計、 滴下口一卜および還流 管を備えた 2 1_三ロフラスコに移し、 水冷下で撹拌した。 After the reaction solution was cooled to room temperature (23 ° C), the reaction solution was suction filtered to remove the precipitated salt. The obtained organic layer was stirred with a stirring blade, a thermometer, a dropping port and a reflux tube. It was transferred to a 2 1_3 flask equipped with it and stirred under water cooling.
次いで、 フラスコ内に、 1\1 , 1\1—ジメチルアミノビリジン （1 0 . 6 9） およびトリエチルアミン （6 5 . 9 9） を添加し、 滴下口一卜を用いて、 あ らかじめテトラヒドロフラン （1 2 5 9） に溶解させた 4 -
Figure imgf000043_0001
-オクチルオ キシ桂皮酸クロリ ド （1 2 7 . 9 9） を 3 0分かけて上記フラスコ内に滴下 し、 滴下終了後、 反応液を 5 0 °◦で 6時間撹拌した。 反応液を室温まで冷却 した後、 水で分液洗浄し、 得られた有機層を無水硫酸マグネシウムで乾燥し 、 得られた溶液を濃縮することにより黄白色固体を得た。 Then, into the flask, 1 \ 1, 1 \ 1-dimethylamino-bi-lysine (1 0.6 9) and triethylamine (6 5.9 9), by using a dropping port one Bok, nitrous et beforehand tetrahydrofuran 4 dissolved in (1 2 5 9)
Figure imgf000043_0001
- Okuchiruo carboxy cinnamic acid Kurori de (. 1 2 7 9 9) over 3 0 minutes was dropped into the flask. After completion of the dropwise addition, the mixture was stirred for 6 hours at a reaction 5 0 ° ◦. After the reaction solution was cooled to room temperature, it was separated and washed with water, the obtained organic layer was dried over anhydrous magnesium sulfate, and the obtained solution was concentrated to obtain a yellowish white solid.
得られた黄白色固体をメチルエチルケトン （4 0 0 9） に加熱溶解させ、 再結晶を行うことで、 以下に示すモノマー 八_ 1 を白色固体として 7 6 9 得た （収率 4 0 %） 。 The obtained yellowish white solid was heated and dissolved in methyl ethyl ketone (409) and recrystallized to obtain 769 as a white solid of Monomer 8_1 shown below (yield 40%).
なお、 以下のモノマー 八_ 1は、 上述した繰り返し単位八_ 1 を形成す るモノマーに該当する。 The following monomer 8_1 corresponds to the monomer forming the above-mentioned repeating unit 8_1.
[0139] [化 18] [0139] [Chemical 18]
Figure imgf000043_0002
Figure imgf000043_0002
[0140] （他のモノマー） [0140] (Other monomers)
繰り返し単位巳一 1 を形成する下記モノマー 巳一 1 として、 サイクロマ
Figure imgf000043_0003
（ダイセル社製） を用いた。 The following monomer, which forms the repeating unit, Minichi 1, is used as
Figure imgf000043_0003
(Manufactured by Daicel) was used.
[0141 ] 〇 2020/175620 43 卩（：171? 2020 /008033 [0141] 〇 2020/175 620 43 卩 (：171? 2020 /008033
[化 19] [Chemical 19]
Figure imgf000044_0001
Figure imgf000044_0001
-1 -1
[0142] （重合体
Figure imgf000044_0002
の合成） [0142] (Polymer
Figure imgf000044_0002
Of)
冷却管、 温度計、 および撹拌機を備えたフラスコに、 溶媒として 2—ブタ ノン （5質量部） を仕込み、 フラスコ内に窒素を
Figure imgf000044_0003
流しながらCharge 2-butanone (5 parts by mass) as a solvent into a flask equipped with a cooling tube, thermometer, and stirrer, and add nitrogen to the flask.
Figure imgf000044_0003
Flowing
、 水浴加熱により還流させた。 ここに、 モノマー〇1八_ 1 （ 1 . 2質量部）The mixture was refluxed by heating in a water bath. Here, the monomer 0 18 _ 1 (1.2 parts by mass)
、 モノマー 巳一 1 （8 . 8質量部） 、 重合開始剤として 2 , 2’ ーアゾビ ス （イソプチロニトリル） （1質量部） と、 溶媒として 2—ブタノン （5質 量部） を混合した溶液を、 3時間かけて滴下し、 さらに 3時間還流状態を維 持したまま、 得られた反応液を撹拌した。 反応終了後、 反応液を室温まで放 冷し、 反応液に 2 -ブタノン （3 0質量部） を加えて希釈することで、 重合 体濃度が約 2 0質量％の重合体溶液を得た。 得られた重合体溶液を大過剰の メタノール中へ投入して重合体を沈殿させ、 沈殿物をろ別し、 得られた固形 分を大量のメタノールで洗浄した後、 5 0 °〇において 1 2時間送風乾燥する ことにより、 光配向性基を有する重合体 1 を得た。 , A solution of a mixture of a monomer, Miichi 1 (8.8 parts by mass), a polymerization initiator, 2,2'-azobis (isoptyronitrile) (1 part by mass), and a solvent, 2-butanone (5 parts by mass) Was added dropwise over 3 hours, and the resulting reaction solution was stirred while maintaining the reflux state for 3 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and 2-butanone (30 parts by mass) was added to the reaction solution to dilute it to obtain a polymer solution having a polymer concentration of about 20% by mass. The obtained polymer solution was poured into a large excess of methanol to precipitate the polymer, the precipitate was filtered off, and the obtained solid content was washed with a large amount of methanol, and then the solid content was measured at 50 ° C. Polymer 1 having a photoalignable group was obtained by drying with air blowing for a period of time.
[0143] <実施例 1 > [0143] <Example 1>
（光配向膜用組成物の調製） (Preparation of composition for photo-alignment film)
下記のように光配向膜用組成物 1 を調製した。 光配向膜用組成物 1 重合体 _ 1 1 0 0 . 0 0質量部 下記熱酸発生剤口 _ 1 3 . 0 0質量部 ジイソプロピルェチルアミン 〇. 6 0質量部 酢酸プチル 9 5 3 . 1 2質量部 〇 2020/175620 44 卩（：171? 2020 /008033 Composition 1 for photo-alignment film was prepared as follows. Composition for photo-alignment film 1 Polymer _ 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Part by mass Thermal acid generator port _ 1 3.0 0 parts by mass Diisopropylethylamine 0.60 parts by mass Putyl acetate 9 5 3.1 2 parts by mass 〇 2020/175 620 44 卩 (：171? 2020 /008033
メチルェチルケトン 2 3 8 . 2 8質量部 Methyl ethyl ketone 2 3 8 .2 8 parts by mass
[0144] 熱酸発生剤口 - 1 [0144] Thermal acid generator mouth-1
[0145] [化 20]
Figure imgf000045_0001
[0145] [Chemical 20]
Figure imgf000045_0001
[0146] 調製した光配向膜用組成物 1 を、 ガラスビンに封入し、 密閉した状態で常 温下 7日間保存した。 [0146] The prepared composition for photo-alignment film 1 was sealed in a glass bottle and stored in a sealed state at normal temperature for 7 days.
[0147] （積層体の作製） [0147] (Preparation of laminate)
セルロースアシレートフィルムとして、 特開 2 0 1 2— 2 1 5 6 8 9号公 報の実施例 6と同じものを用いた。 このフィルムの片側の面に、 上記 7日間 保存した光配向膜用組成物 1 をバーコーターで塗布した。 その後、 光配向膜 用組成物 1が塗布されたフィルムを 1 2 5 °〇のホッ トプレート上で 2分間乾 燥して溶媒を除去し、 厚さ 0 . 3 の前駆体膜を形成した。 得られた前駆 体膜に偏光紫外線照射
Figure imgf000045_0002
超高圧水銀ランプ使用） することで 、 光配向膜を形成した。 As the cellulose acylate film, the same film as that used in Example 6 of Japanese Patent Laid-Open No. 20 1 2-2 15 6 8 9 was used. On one surface of this film, the composition for photo-alignment film 1 stored for 7 days was applied by a bar coater. Then, the film coated with the composition for photo-alignment film 1 was dried on a hot plate at 125° for 2 minutes to remove the solvent, and a precursor film having a thickness of 0.3 was formed. Irradiation of the obtained precursor film with polarized ultraviolet light
Figure imgf000045_0002
By using an ultra-high pressure mercury lamp), a photo-alignment film was formed.
次いで、 光配向膜上に、 下記光学異方性層用塗布液 1 を、 バーコーターを 用いて塗布した。 光配向膜上に形成された塗膜を温風にて 1 2 0 °〇に加熱し 、 次に、 6 0 °〇に冷却した後に、 窒素雰囲気下で高圧水銀灯を用いて、 波長 続いて 1 2 0 °〇
Figure imgf000045_0003
上記手順によ って、 液晶化合物の配向を固定化し、 光学異方性層を含む実施例 1の積層体 を作製した。 得られた積層体の 8 6 （5 5 0）
Figure imgf000045_0004
であった。 光学異方性層用塗布液 1 Next, the following coating solution 1 for optically anisotropic layer was coated on the photo-alignment film using a bar coater. The coating film formed on the photo-alignment film is heated to 120 ° 〇 with warm air and then cooled to 60 ° 〇, and then a high-pressure mercury lamp is used in a nitrogen atmosphere for a wavelength of 1 20 ° 〇
Figure imgf000045_0003
According to the above procedure, the alignment of the liquid crystal compound was fixed, and the laminate of Example 1 including the optically anisotropic layer was produced. 8 6 (550) of the obtained laminate
Figure imgf000045_0004
Met. Coating liquid for optically anisotropic layer 1
-下記重合性液晶化合物!-一 1 3 9 . 0 0質量部 〇 2020/175620 45 2020 /008033 -The following polymerizable liquid crystal compounds!- 1 13 9.00 parts by mass 〇 2020/175 620 45 2020/008033
-下記重合性液晶化合物 1- _ 2 39 00質量部 -下記重合性液晶化合物 1- _ 3 1 7. 00質量部 -下記重合性液晶化合物 _ 1 5. 00質量部 下記重合開始剤 3_ 1 （ォキシム型） 〇. 50質量部 - レベリング剤 （下記化合物丁 _ 1） 〇. 20質量部-The following polymerizable liquid crystal compound 1- _ 2 39 00 parts by mass-The following polymerizable liquid crystal compound 1- _ 3 1 7.00 parts by mass-The following polymerizable liquid crystal compound _ 1 5.00 parts by mass The following polymerization initiator 3_ 1 ( Oxime type) 〇.50 parts by mass-Leveling agent (the following compound _ 1) 〇.20 parts by mass
-シクロペンタノン 235. 00質量部 -Cyclopentanone 235.00 parts by mass
[0148] 重合性液晶化合物！-一 1 [0148] Polymerizable liquid crystal compound! -One 1
[0149] [化 21] [0149] [Chemical 21]
Figure imgf000046_0001
Figure imgf000046_0001
[0150] 重合性液晶化合物 _ 2 [0150] Polymerizable liquid crystal compound _ 2
[0151] [化 22] [0151] [Chemical 22]
Figure imgf000046_0002
Figure imgf000046_0002
[0152] 重合性液晶化合物 _ 3 [0152] Polymerizable liquid crystal compound _ 3
[0153] [化 23]
Figure imgf000046_0003
[0153] [Chemical 23]
Figure imgf000046_0003
[0154] 重合性液晶化合物八 _ 1 [0154] Polymerizable liquid crystal compound _ 1
[0155] [化 24]
Figure imgf000046_0004
[0155] [Chemical 24]
Figure imgf000046_0004
[0156] 重合開始剤 3 _ 1 〇 2020/175620 46 卩（：171? 2020 /008033 [0156] Polymerization initiator 3 _ 1 〇 2020/175 620 46 卩 (: 171? 2020 /008033
[0157] [化 25] [0157] [Chemical 25]
Figure imgf000047_0001
Figure imgf000047_0001
[0160] <実施例 2> [0160] <Example 2>
光配向膜用組成物 1 を下記の光配向膜用組成物 2に変更した以外は、 実施 例 1 と同様の方法により、 積層体を作製した。 光配向膜用組成物 2 重合体 _ 1 1 00. 00質量部 上記熱酸発生剤口 _ 1 3. 00質量部 ジイソプロピルェチルアミン 0. 01 3質量部 酢酸プチル 953. 1 2質量部 メチルェチルケトン 238. 28質量部 A laminate was produced in the same manner as in Example 1 except that the composition 2 for a photo-alignment film was changed to the composition 2 for a photo-alignment film. Composition for photo-alignment film 2 Polymer _ 1 1 00.00 parts by weight The above thermal acid generator port _ 1 3.00 parts by weight Diisopropylethylamine 0.011 3 parts by weight Putyl acetate 953.1.2 parts by weight Methyl Tyrketone 238. 28 parts by mass
[0161] <実施例 3> [0161] <Example 3>
光配向膜用組成物 1 を下記の光配向膜用組成物 3に変更した以外は、 実施 例 1 と同様の方法により、 積層体を作製した。 光配向膜用組成物 3 〇 2020/175620 47 卩（：171? 2020 /008033 A laminate was produced in the same manner as in Example 1 except that the composition 3 for a photo-alignment film was changed to the composition 3 for a photo-alignment film. Composition for photo-alignment film 3 〇 2020/175 620 47 卩(：171? 2020/008033
重合体 _ 1 1 00. 00質量部 上記熱酸発生剤口 _ 1 3. 00質量部 ジイソプロピルェチルアミン 2. 03質量部 酢酸プチル 953. 1 2質量部 メチルェチルケトン 238. 28質量部 Polymer _ 1 10.00 0.00 parts by mass Thermal acid generator port _ 1 3.00 parts by mass Diisopropylethylamine 2.03 parts by mass Putyl acetate 953. 1 2 parts by mass Methyl ethyl ketone 238. 28 parts by mass
[0162] <実施例 4> [0162] <Example 4>
光配向膜用組成物 1 を下記の光配向膜用組成物 4に変更した以外は、 実施 例 1 と同様の方法により、 光学積層体を作製した。 この光学積層体を実施例 4の光学積層体とした。 光配向膜用組成物 4 重合体 _ 1 1 00. 00質量部 上記熱酸発生剤口 _ 1 3. 00質量部 トリプチルアミン 〇. 86質量部 酢酸プチル 953. 1 2質量部 メチルェチルケトン 238. 28質量部 An optical layered body was produced in the same manner as in Example 1 except that the composition 4 for the photo-alignment film was changed to the composition 4 for the photo-alignment film. This optical laminate was used as the optical laminate of Example 4. Composition for photo-alignment film 4 Polymer _ 1 1 00.00 parts by mass Thermal acid generator mouth _ 1 3.00 parts by mass Triptylamine 〇.86 parts by mass Putyl acetate 953.1.2 parts by mass Methyl ethyl ketone 238. 28 parts by mass
[0163] <実施例 5> [0163] <Example 5>
実施例 1で使用した光学異方性層用塗布液 1 に代えて、 以下に示す光学異 方性層用塗布液 2を用いて、 実施例 1 と同様の手順に従って、 バーコーター を用いて、 光学異方性層用塗布液 2を塗布した。 配向膜上に形成された塗膜 を温風にて 1 0〇°〇に加熱し、 次に、 90°〇に冷却した後に窒素雰囲気下で 高圧水銀灯を用いて、
Figure imgf000048_0001
Instead of the optically anisotropic layer coating liquid 1 used in Example 1, the following optically anisotropic layer coating liquid 2 was used, and following the same procedure as in Example 1, using a bar coater, Coating solution 2 for optically anisotropic layer was applied. The coating film formed on the alignment film was heated to 1 0_Rei ° 〇 with warm air, then, using a high pressure mercury lamp under a nitrogen atmosphere was cooled to 90 ° 〇,
Figure imgf000048_0001
に照射し、 続いて
Figure imgf000048_0002
の紫外線を塗膜 に照射した。 上記手順によって、 液晶化合物の配向を固定化し、 実施例 5の 積層体を作製した。 得られた積層体の 86 (550)
Figure imgf000048_0003
\¥02020/175620 48 2020/008033 And then irradiate
Figure imgf000048_0002
The coating film was irradiated with the ultraviolet rays. By the above procedure, the alignment of the liquid crystal compound was fixed, and the laminate of Example 5 was produced. 86 (550) of the obtained laminate
Figure imgf000048_0003
\\02020/175 620 48 2020/008033
光学異方性層用塗布液 2 下記重合性液晶化合物 1- _ 4 40. 00質量部 下記重合性液晶化合物 1- _ 5 40. 00質量部 上記重合性液晶化合物 - 1 20. 00質量部 上記重合開始剤 3 _ 1 〇. 60質量部 下記重合性化合物巳 _ 1 7. 00質量部 レベリング剤 （上記化合物丁 _ 1） 〇. 1 〇質量部 メチルェチルケトン 200. 00質量部 シクロペンタノン 200. 00質量部 Coating liquid for optically anisotropic layer 2 Polymerizable liquid crystal compound 1-_ 4 40.00 parts by mass Polymerizable liquid crystal compound 1-_ 5 40.00 part by mass Polymerizable liquid crystal compound-1-20.00 part by mass Above Polymerization initiator 3 _ 1 〇.60 parts by mass Polymerizable compound below _ 1 7.00 parts by mass Leveling agent (above compound _ 1) 〇.1 〇 parts by mass Methyl ethyl ketone 200.00 parts by mass Cyclopentanone 200.00 parts by mass
[0164] 重合性液晶化合物 _ 4 [0164] Polymerizable liquid crystal compound _ 4
[0165] [化 27] [0165] [Chemical 27]
Figure imgf000049_0001
Figure imgf000049_0001
[0166] 重合性液晶化合物 _ 5 [0166] Polymerizable liquid crystal compound _ 5
[0167] [化 28] [0167] [Chemical 28]
Figure imgf000049_0002
Figure imgf000049_0002
[0168] 重合性化合物巳 _ 1 [0168] Polymerizable compound _ 1
[0169] 〇 2020/175620 49 卩（：171? 2020 /008033 [0169] 〇 2020/175 620 49 卩 (：171? 2020 /008033
[化 29] [Chemical 29]
Figure imgf000050_0001
Figure imgf000050_0001
[0170] <比較例 1 > [0170] <Comparative example 1>
光配向膜用組成物 1 を下記の光配向膜用組成物 5に変更した以外は、 実施 例 1 と同様の方法により、 積層体を作製した。 光配向膜用組成物 5 重合体 _ 1 1 00. 00質量部 上記熱酸発生剤口 _ 1 3. 00質量部 酢酸プチル 953. 1 2質量部 メチルェチルケトン 238. 28質量部 A laminate was produced in the same manner as in Example 1 except that the composition for photoalignment film 1 was changed to the following composition for photoalignment film 5. Composition for photo-alignment film 5 Polymer _ 1 1 00.00 parts by mass The above thermal acid generator mouth _ 1 3.00 parts by mass Putyl acetate 953. 1 2 parts by mass Methyl ethyl ketone 238. 28 parts by mass
[0171] <比較例 2> [0171] <Comparative example 2>
光配向膜用組成物 1 を下記の光配向膜用組成物 6に変更した以外は、 実施 例 1 と同様の方法により、 積層体を作製した。 光配向膜用組成物 6 重合体 _ 1 1 00. 00質量部 上記熱酸発生剤口 _ 1 3. 00質量部 —ブチルアミン 〇. 34質量部 酢酸プチル 953. 1 2質量部 〇 2020/175620 50 卩（：171? 2020 /008033 A laminate was produced in the same manner as in Example 1 except that the composition for photoalignment film 1 was changed to the composition for photoalignment film 6 below. Composition for photo-alignment film 6 Polymer _ 1 1 00.00 parts by mass The above thermal acid generator mouth _ 1 3.00 parts by mass — Butylamine 〇.34 parts by mass Putyl acetate 953.1.2 parts by mass 〇 2020/175 620 50 卩 (: 171? 2020 /008033
メチルェチルケトン 2 3 8 . 2 8質量部 Methyl ethyl ketone 2 3 8 .2 8 parts by mass
[0172] ＜評価＞ [0172] <Evaluation>
（液晶配向性評価） (Liquid crystal orientation evaluation)
各実施例および比較例で得られた積層体から幅 4 0
Figure imgf000051_0001
、 の フィルムを切り出した。 試料をクロスニコル下の偏光顕微鏡 （ 1 0倍の対物 レンズ使用） で観察し、 下記の基準で液晶配向性を評価した。 From the laminates obtained in each Example and Comparative Example, width 40
Figure imgf000051_0001
The film was cut out. The sample was observed with a polarizing microscope under a crossed Nicol (using a 10× objective lens), and the liquid crystal orientation was evaluated according to the following criteria.
八 ：観察視野内で光漏れなし。 クロスニコルから検光子を 4 ° ずらして観察 したときの光学模様が観察視野内で均一であった。 Eight: No light leakage within the observation field. The optical pattern observed when the analyzer was shifted 4° from the crossed Nicols was uniform within the observation field.
巳 ：観察視野内で光漏れがごくわずかにある。 クロスニコルから検光子を 4 ° ずらして観察したときの光学模様は観察視野内で均一であった。 Minami: There is very little light leakage in the observation field of view. The optical pattern observed when the analyzer was shifted 4° from the crossed Nicols was uniform within the observation field.
〇 ：観察視野内で光漏れあり。 クロスニコルから検光子を 4 ° ずらして観察 したときに光学模様が観察視野内で不均一であった （配向不良が観察された ◯: There is light leakage in the observation visual field. The optical pattern was non-uniform in the observation field when the analyzer was shifted from the crossed Nicols by 4° (alignment failure was observed.
[0173] （耐久性評価） [0173] (Durability evaluation)
各実施例および比較例で得られた積層体に粘着剤を貼合し、 その粘着面を ガラスに貼合し、 積層体とガラスとの貼合物を温度 8 5 °〇および湿度 8 5 % の環境下で 7 2時間保持した後の積層体の 6 （5 5 0） を下記の基準で評 価した。 A pressure-sensitive adhesive was attached to the laminate obtained in each of the examples and comparative examples, the adhesive surface was attached to glass, and the laminate and the glass were attached to each other at a temperature of 85 ° C and a humidity of 85%. 6 (550) of the laminate after holding for 72 hours in the above environment was evaluated based on the following criteria.
八 ：温度
Figure imgf000051_0002
（5 5 0） に対し 、 保持後の 8 6 （5 5 0） の割合が 9 8 %以上である場合 Eight: temperature
Figure imgf000051_0002
When the ratio of 8 6 (5 50) after holding to (550) is 98% or more
巳 ：温度 8 5 °〇および湿度 8 5 %の環境下保持前の 6 （5 5 0） に対し、 保持後の 8 ㊀ （5 5 0） の割合が 9 8 %未満である場合 Min: When the ratio of 8 ㊀ (550) after holding is less than 98% under 6 (550) before holding in an environment of temperature 85 ° and humidity 85%.
[0174] 表 1中、 「酸発生剤」 の 「添加量」 欄は、 光配向性共重合体の全質量に対 する酸発生剤の含有量 （質量％） を表す。 [0174] In Table 1, the "addition amount" column of "acid generator" represents the content (% by mass) of the acid generator with respect to the total mass of the photoalignable copolymer.
表 1中、 「アミン化合物」 の 「添加量」 欄は、 酸発生剤の全モルに対する アミン化合物の含有量 （モル量） を表す。 In Table 1, the "addition amount" column of "amine compound" represents the content (molar amount) of the amine compound with respect to the total moles of the acid generator.
表 1中、 「液晶 1」 は光学異方性層用塗布液 1 を用いたことを意味し、 「 〇 2020/175620 51 卩(：171? 2020 /008033 In Table 1, "Liquid crystal 1" means that the coating liquid 1 for optically anisotropic layer was used, 〇 2020/175 620 51 卩(: 171? 2020/008033
液晶 2」 は光学異方性層用塗布液 2を用いたことを意味する。 "Liquid crystal 2" means that the coating liquid 2 for optically anisotropic layer was used.
表 1中、 「繰り返し単位 」 欄に記載した繰り返し単位の含有量を 3とし 、 「繰り返し単位巳」 欄に記載した繰り返し単位の含有量を とした。 In Table 1, the content of the repeating unit described in the "Repeating unit" column was set to 3, and the content of the repeating unit described in the "Repeating unit" column was set to.
［0175］ ［表 1］ [0175] [Table 1]
Figure imgf000052_0001
Figure imgf000052_0001
［0176］ 上記表 1 に示すように、 本発明の光配向膜用組成物においては、 所望の効 果が得られることが確認された。 [0176] As shown in Table 1 above, it was confirmed that the composition of the present invention for a photo-alignment film could achieve desired effects.
特に、 実施例 1〜 3の比較より、 アミン化合物の含有量が、 酸発生剤の含 有モル量に対して、 5〜 4 0 0モル％である場合、 より効果が優れていた。 一方で、 アミン化合物を使用していない比較例 1、 窒素原子上にプロトン を有するアミン化合物を使用した比較例 2においては、 所望の効果は得られ なかった。 In particular, as compared with Examples 1 to 3, the effect was more excellent when the content of the amine compound was 5 to 400 mol% with respect to the content molar amount of the acid generator. On the other hand, in Comparative Example 1 in which the amine compound was not used and Comparative Example 2 in which the amine compound having a proton on the nitrogen atom was used, the desired effect was not obtained.
［0177］ ＜実施例 6＞ [0177] <Example 6>
（連続塗布フィルムの作製） (Production of continuous coating film)
〇 2 0 1 6 / 1 5 8 9 4 0号の段落 ［0 0 5 9］ 〜 ［0 0 6 6］ に記載の 方法で、 延伸倍率を 8 %とし、 口ール状に巻いた長尺セルロースアシレート フィルム 1 （幅 1 3 4 0 〇〇 を作製した。 〇 Long stretched in a round shape with a stretching ratio of 8% by the method described in paragraphs [0 0 5 9] to [0 0 6 6] of No. A cellulose acylate film 1 (width 1340.000 was produced.
次に、 セルロースアシレートフィルム 1 に、 スリッ トダイコーターにより 、 塗布幅 1 3 1 〇 で、 光配向膜用組成物 1 を塗布した。 その後、 光配向 〇 2020/175620 52 卩（：171? 2020 /008033 Next, the composition for photo-alignment film 1 was applied to the cellulose acylate film 1 with a slit die coater so as to have a coating width of 1310. Then photo-alignment 〇 2020/175 620 52 卩 (：171? 2020 /008033
膜用組成物 1が塗布されたフィルムに 1 2 5 °〇の温風を当てて 2分間乾燥し て溶媒を除去し、 厚さ〇. 3 の前駆体膜を形成した。 得られた前駆体膜 に偏光紫外線照射
Figure imgf000053_0001
超高圧水銀ランプ使用） することで、 長 尺光配向膜を形成した。 The film coated with the film composition 1 was blown with hot air at 125 ° to dry for 2 minutes to remove the solvent and form a precursor film having a thickness of 0.3. Irradiation of the obtained precursor film with polarized ultraviolet light
Figure imgf000053_0001
By using an ultra-high pressure mercury lamp), a long photo-alignment film was formed.
次に、 スリッ トダイコーターにより、 塗布幅 1 3 2 0 で、 光学異方性 層用塗布液 2を光配向膜の両サイ ドを完全に覆う形で塗布した。 次に、 塗膜 を温風にて 1 0〇°〇に加熱し、 次に、 9 0 °〇に冷却した後に窒素雰囲気下で 高圧水銀灯を用いて、 波長 3 6 5 n mにて
Figure imgf000053_0002
Next, a slit die coater was used to apply the coating liquid 2 for optically anisotropic layer with a coating width of 1320 so as to completely cover both sides of the photo-alignment film. Next, a coating film with hot air heated to 1 0_Rei ° 〇, then using a high-pressure mercury lamp under a nitrogen atmosphere and the mixture was cooled to 9 0 ° 〇 at wavelength 3 6 5 nm
Figure imgf000053_0002
に照射し、 続いて 1 2 5 °〇に加熱しながら 5〇〇 」/〇 2の紫外線を塗膜 に照射した。 上記手順によって、 液晶化合物の配向を固定化し、 実施例 6の 積層体 （長尺フィルム） を作製した。 得られた積層体の
Figure imgf000053_0003
（5 5 0） は 1 4 0 光学異方性層の厚みは 2 . 5 ^Ji rr\ s （メタ） アクリロイル反応率 は 8 5 %であった。 Then, the coating film was irradiated with UV of 50,000"/○ 2 while heating it to 125°. By the above procedure, the orientation of the liquid crystal compound was fixed, and the laminate (long film) of Example 6 was produced. Of the obtained laminate
Figure imgf000053_0003
In the case of (550), the thickness of the 140 optically anisotropic layer was 2.5 ^Ji rr\ s (meth)acryloyl reaction rate was 85 %.
[0178] <実施例 7 > [0178] <Example 7>
実施例 6と同様の方法で、 塗布幅
Figure imgf000053_0004
光学異方性層用塗布液In the same manner as in Example 6, the coating width
Figure imgf000053_0004
Coating liquid for optically anisotropic layer
2を光配向膜の両サイ ドを完全に覆う形で塗布した。 塗布液が未乾燥状態の うちに、 フィルムの両端部に、 搔き取り部材としてスクレーパーを押し当て て、 光学異方性層用塗布液 2の厚みを薄く した。 なお、 本実施例 7において は、 基材の一方の端部より 1 〇〜 3
Figure imgf000053_0005
の範囲が薄塗りとなっている。 続いて、 実施例 6と同様の方法で塗膜を乾燥、 配向を固定化し、 実施例 7 の積層体を作製した。 得られた積層体の
Figure imgf000053_0006
（5 5 0） は 1 4 0 n m、 光学 異方性層の中心厚みは 2 . 5 《1、 光学異方性層の端部で上述した方法で薄塗 りした部分の厚みは 1 、 （メタ） アクリロイル反応率は 8 5 %であった 2 was applied so as to completely cover both sides of the photo-alignment film. While the coating liquid was in an undried state, a scraper was pressed against both ends of the film as a scraping member to thin the coating liquid 2 for the optically anisotropic layer. In addition, in the present Example 7, from one end of the substrate to 10 ~ 3
Figure imgf000053_0005
The range is lightly coated. Subsequently, the coating film was dried and the orientation was fixed in the same manner as in Example 6 to produce the laminate of Example 7. Of the obtained laminate
Figure imgf000053_0006
(5 5 0) 1 4 0 n m, 2 is the center thickness of the optical anisotropic layer. 5 "1, part of the thickness 1 interest thin coating in the manner described above at the end of the optically anisotropic layer, (Meth) acryloyl reaction rate was 85%
[0179] <実施例 8 > [0179] <Example 8>
実施例 6と同様の方法で、 光学異方性層用塗布液 2を光配向膜に塗布した 。 その後、 配向膜上に形成された塗膜を温風にて 1 〇〇°〇に加熱し、 9 0 °〇 に冷却した後に窒素雰囲気下で、 ウェブ端部〜 3 0
Figure imgf000053_0007
の位置に左右それぞ れに遮光板を設けた高圧水銀灯を用いて、 波長 365 n mにて 1 00 m J / c m2の紫外線を塗膜に照射し、 続いて 2回目の照射は 1 25 °Cに加熱しなが ら遮光板を設けず塗膜全面に 500m J / c m 2の紫外線を照射した。 上記手 順によって、 液晶化合物の配向を固定化し、 実施例 8の積層体を作製した。 得られた積層体の R e （550） は 1 40 n m、 厚みは 2. 5 ^m、 （メタ ） アクリロイル反応率は 85%であった。 また、 遮光板により 1回目の紫外 線照射がなされなかった領域は、 複屈折性がなく、 厚みは 2. 5 Mm、 （メ 夕） アクリロイル反応率は 87 %であった。 The coating liquid 2 for optically anisotropic layer was applied to the photo-alignment film in the same manner as in Example 6. After that, the coating film formed on the orientation film is heated to 100 ° with hot air and cooled to 90 ° , and then the web edge part to 30
Figure imgf000053_0007
To the left and right Using a high-pressure mercury lamp equipped with a shading plate, irradiate the coating film with 100 mJ / cm 2 of ultraviolet light at a wavelength of 365 nm, and then do not heat it to 125 °C for the second irradiation. The entire surface of the coating film was irradiated with ultraviolet rays of 500 m J / cm 2 without providing a light shielding plate. By the above procedure, the alignment of the liquid crystal compound was fixed, and the laminate of Example 8 was produced. The R e (550) of the obtained laminate was 140 nm, the thickness was 2.5 ^m, and the (meth)acryloyl reaction rate was 85%. The region where the first UV irradiation was not performed by the shading plate had no birefringence, the thickness was 2.5 Mm, and the (acryl)acryloyl reaction rate was 87%.
[0180] ＜実施例 9＞ [0180] <Example 9>
実施例 6と同様の方法で、 光学異方性層用塗布液 2を光配向膜に塗布した 。 その後、 配向膜上に形成された塗膜を温風にて 1 〇〇°Cに加熱し、 90°C に冷却した後に窒素雰囲気下で、 高圧水銀灯を用いて、 波長 365 n mにて 1 00 mJ/c m 2の紫外線を塗膜全面に照射し、 続いて 1 25°Cに加熱しな がらウェブ端部〜 3 Ommの位置に遮光板を設けた高圧水銀灯を用いて 50 OmJ/c m2の紫外線を塗膜に照射した。 上記手順によって、 液晶化合物の 配向を固定化し、 実施例 9の積層体を作製した。 得られた積層体の遮光板に より 2回目の紫外線照射がなされなかった領域は、 R e （550） は 1 40 n m、 光学異方性層の厚みは 2. 5 Mm、 （メタ） アクリロイル反応率は 6 0 %であった。 In the same manner as in Example 6, the coating liquid 2 for optically anisotropic layer was applied to the photo-alignment film. After that, the coating film formed on the alignment film was heated to 100 ° C with warm air, cooled to 90 ° C, and then, under a nitrogen atmosphere, a high pressure mercury lamp was used to set a wavelength of 100 nm. Irradiate the entire surface of the coating with mJ/cm 2 of UV light, and then heat it to 125°C while using a high pressure mercury lamp equipped with a light shield plate at a position of 3 Omm from the edge of the web to 50 OmJ/cm 2 . The coating film was irradiated with ultraviolet rays. By the above procedure, the orientation of the liquid crystal compound was fixed, and the laminate of Example 9 was produced. The region where the second layer was not irradiated with UV light from the light-shielding plate of the obtained laminate had a Re (550) of 140 nm, an optically anisotropic layer thickness of 2.5 Mm, and a (meth)acryloyl reaction. The rate was 60%.
[0181] ＜評価＞ [0181] <Evaluation>
（ （メタ） アクリロイル反応率） ((Meth) Acryloyl reaction rate)
（メタ） アクリロイル基を有する各成分の全ての重合性基のうち、 光学異 方性層を形成する際の重合によって消費されたものの比率をいい、 フーリエ 変換赤外分光 （F T - I R） 光度計 〔N i c o l e t 6700 （Thermo Fish er Science社製） 〕 を用いて測定し、 得られたスペクトルの C = C基由来の ピーク面積から、 （メタ） アクリロイル基の反応率を算出した。 反応率の算 出は、 C = C基由来の吸収、 すなわち、 81 0 c m-1、 1 4 1 0 c m-1およ び 1 635 c m-1のいずれかのピークの面積の減少を、 反応前後で変化しな \¥0 2020/175620 54 卩（：17 2020 /008033 Of all the polymerizable groups of each component having a (meth)acryloyl group, the ratio of those consumed by polymerization when forming the optically anisotropic layer. Fourier Transform Infrared Spectroscopy (FT-IR) Photometer The reaction rate of the (meth)acryloyl group was calculated from the peak area derived from the C=C group in the obtained spectrum, which was measured using [Nicolet 6700 (manufactured by Thermo Fisher Science)]. The reaction rate was calculated by the absorption from the C = C group, that is, the decrease in the area of any of the peaks of 81 0 cm- 1 , 1140 cm- 1 and 1635 cm- 1. , Before and after the reaction \¥0 2020/175 620 54 卩 (: 17 2020 /008033
い液晶成分の二トリル基の吸収 2 2 1 5〇 - 1の面積を基準として計算した There absorbed 2 2 1 5_Rei the nitrile group of the liquid crystal component - was calculated based on the first area
[0182] （端部力ール） [0182] (End force)
搬送中の支持体の端部を目視で評価した。 The edge of the support during transportation was visually evaluated.
八 ：搬送用口ールの間の、 支持されていない領域で、 ウェブ端部に変形 なし Eight: Unsupported area between the transfer ports, no deformation at the web edge
巳 ：搬送用口ールの間の、 支持されていない領域で、 ウェブ端部が力一 ノレ Mami: The unsupported area between the transport ports, where the web edge is
〇 ：搬送用口ールに支持された領域で、 ウェブ端部が力ール 〇 :端部の力ールが大きく、 搬送できない ◯: The area supported by the transfer port, the edge of the web is strong.
[0183] [表 2] [0183] [Table 2]
Figure imgf000055_0001
Figure imgf000055_0001
[0184] 上記表 2に示すように、 本発明の光配向膜用組成物は、 積層体が長尺フィ ルムであっても、 所望の効果が得られることが確認された。 [0184] As shown in Table 2 above, it was confirmed that the composition for a photo-alignment film of the present invention could achieve a desired effect even if the laminate had a long film.
一方、 実施例 6に示すように、 本発明の光配向膜用組成物を塗工した長尺 フィルムでは、 端部に力ールが発生しやすいが、 実施例 7〜 9に示すような 端部処理によって、 改良できる。 On the other hand, as shown in Example 6, in the long film coated with the composition for a photo-alignment film of the present invention, a force is likely to be generated at the end portion, but as shown in Examples 7 to 9, It can be improved by partial processing.

Claims

\¥0 2020/175620 55 卩（：17 2020 /008033 請求の範囲 \¥0 2020/175 620 55 卩(: 17 2020/008033 Claims
［請求項 1］ 光配向性基を含む繰り返し単位 と、 架橋性基を含む繰り返し単位 巳とを有し、 [Claim 1] having a repeating unit containing a photoalignable group and a repeating unit containing a crosslinkable group,
前記繰り返し単位 の含有量 8と、 前記繰り返し単位巳の含有量匕 とが、 質量比で下記式 （1） を満たす光配向性共重合体と、 The content of the repeating unit 8 and the content of the repeating unit 茕, a photo-alignable copolymer that satisfies the following formula (1) in a mass ratio,
〇. 7 0 £匕/ （3 + 13） £〇. 9 7 · · · （1） ○ 0.70 匕 / (3 + 13) £ ○. 9 7 ··· (1)
酸発生剤と、 An acid generator,
沸点が 5 0〜 2 3 0 °〇であり、 窒素原子上にプロトンを有さないア ミン化合物と、 を含む光配向膜用組成物。 A composition for a photo-alignment film, which comprises an amine compound having a boiling point of 50 to 230° and having no proton on a nitrogen atom.
［請求項 2］ 前記アミン化合物が下記式 （2） で表される化合物を含む、 請求項 [Claim 2] The amine compound contains a compound represented by the following formula (2):
1 に記載の光配向膜用組成物。 The composition for a photo-alignment film according to 1.
［化 1］ [Chemical 1]
Figure imgf000056_0001
それぞれ独立に、 炭 素数 1〜 2 0の直鎖状、 分岐鎖状または環状のアルキル基を表す。 ［請求項 3］ 前記アミン化合物の含有量が、 前記酸発生剤の含有モル量に対して
Figure imgf000056_0001
Each independently represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. [Claim 3] The content of the amine compound is relative to the content molar amount of the acid generator.
、 5〜 4 0 0モル％である、 請求項 1 または 2に記載の光配向膜用組 成物。 The composition for a photo-alignment film according to claim 1, wherein the composition is 5 to 400 mol %.
［請求項 4］ 前記光配向性基を含む繰り返し単位 が、 下記式 （ ） で表される 繰り返し単位を含み、 [Claim 4] The repeating unit containing a photo-alignment group includes a repeating unit represented by the following formula (),
前記架橋性基を含む繰り返し単位巳が、 下記式 （巳） で表される繰 り返し単位を含む、 請求項 1〜 3のいずれか 1項に記載の光配向膜用 組成物。 〇 2020/175620 56 卩（：171? 2020 /008033 The composition for a photo-alignment film according to any one of claims 1 to 3, wherein the repeating unit containing the crosslinkable group contains a repeating unit represented by the following formula (M). 〇 2020/175 620 56 卩 (：171? 2020 /008033
[化 2] [Chemical 2]
Figure imgf000057_0001
、 、 水素原子またはメチル基を表す。
Figure imgf000057_0001
, Represents a hydrogen atom or a methyl group.
1- 1は、 窒素原子とシクロアルカン環とを含む 2価の連結基を表し 、 前記シクロアルカン環を構成する炭素原子の一部が、 窒素原子、 酸 素原子および硫黄原子からなる群から選択されるへテロ原子で置換さ れていてもよい。1 1 Select represents a divalent linking group containing a nitrogen atom and a cycloalkane ring, a part of carbon atoms constituting the cycloalkane ring, from the group consisting of nitrogen atom, oxygen radicals, and a sulfur atom It may be substituted with a hetero atom.
Figure imgf000057_0002
［¾ 8、 ［¾ 9および［^。は、 それぞれ独立に、 水素原子ま たは置換基を表し、 ［¾ 6、 ［¾ 7、 ［¾ 8、
Figure imgf000057_0003
および
Figure imgf000057_0004
のうち、 隣接す る 2つの基が結合して環を形成していてもよい。
Figure imgf000057_0002
[¾ 8 , [¾ 9 and [^. Each independently represents a hydrogen atom or a substituent, and is represented by [¾ 6 , [¾ 7 , [¾ 8 ,
Figure imgf000057_0003
and
Figure imgf000057_0004
Of these, two adjacent groups may be bonded to each other to form a ring.
前記式 （巳） 中、
Figure imgf000057_0005
は、 水素原子またはメチル基を表す。 In the formula (Mimi),
Figure imgf000057_0005
Represents a hydrogen atom or a methyl group.
し2は、 2価の連結基を表す。 2 represents a divalent linking group.
Xは、 架橋性基を表す。 X represents a crosslinkable group.
［請求項 5］ 前記架橋性基を含む繰り返し単位巳が、 下記式 （X I） 〜 （乂3） のいずれかで表される架橋性基を含む、 請求項 1〜 4のいずれか 1項 に記載の光配向膜用組成物。 [Claim 5] The repeating unit containing a crosslinkable group contains a crosslinkable group represented by any one of the following formulas (XI) to (3). The composition for a photo-alignment film described.
[化 3] [Chemical 3]
Figure imgf000057_0006
Figure imgf000057_0006
（XI） （¾2） 网 (XI) (¾2) network
前記式 （X I） 〜 （乂3） 中、 氺は結合手を表し、
Figure imgf000057_0007
水素原 子、 メチル基、 または、 エチル基を表す。 〇 2020/175620 57 卩（：171? 2020 /008033 In the formulas (XI) to (3), Ai represents a bond,
Figure imgf000057_0007
Represents hydrogen atom, methyl group, or ethyl group. 〇 2020/175 620 57 卩 (：171? 2020 /008033
[請求項 6] 請求項 1〜 5のいずれか 1項に記載の光配向膜用組成物を用いて形 成した、 光配向膜。 [Claim 6] A photo-alignment film formed using the composition for a photo-alignment film according to any one of claims 1 to 5.
[請求項 7] 請求項 6に記載の光配向膜と、 [Claim 7] The photo-alignment film according to claim 6,
液晶化合物を含む液晶組成物を用いて形成される光学異方性層と、 を有する、 積層体。 An optically anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound, and a laminate.
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