WO2019117082A1 - Copolymère à photo-alignement, film photo-aligné et produit stratifié optique - Google Patents

Copolymère à photo-alignement, film photo-aligné et produit stratifié optique Download PDF

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Publication number
WO2019117082A1
WO2019117082A1 PCT/JP2018/045302 JP2018045302W WO2019117082A1 WO 2019117082 A1 WO2019117082 A1 WO 2019117082A1 JP 2018045302 W JP2018045302 W JP 2018045302W WO 2019117082 A1 WO2019117082 A1 WO 2019117082A1
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group
substituent
formula
carbon atoms
repeating unit
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PCT/JP2018/045302
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English (en)
Japanese (ja)
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考浩 加藤
隆史 飯泉
寛 野副
美帆 朝日
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富士フイルム株式会社
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Priority to JP2019559623A priority Critical patent/JP6987883B2/ja
Publication of WO2019117082A1 publication Critical patent/WO2019117082A1/fr

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363Birefringent elements, e.g. for optical compensation
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a photoalignable copolymer, a photoalignment film and an optical laminate.
  • Optical films such as an optical compensation sheet and a retardation film, are used in various image display devices from the viewpoint of image coloration cancellation, viewing angle widening, and the like.
  • a stretched birefringence film has been used as an optical film, but in recent years, it has been proposed to use an optically anisotropic layer using a liquid crystalline compound in place of the stretched birefringence film.
  • Such an optically anisotropic layer is known to be provided with an alignment film on a support forming the optically anisotropic layer in order to align the liquid crystal compound, and rubbing is performed as the alignment film.
  • a photo alignment film which has been subjected to a photo alignment process instead of the process is known.
  • Patent Document 1 discloses a composition for a photoalignment film containing a polymer A having a structural unit a1 containing a cinnamate group, and a low molecular weight compound B having a cinnamate group and having a molecular weight smaller than that of the polymer A.
  • Products are described ([Claim 1]), and the embodiment in which the polymer A has a structural unit a2 containing a crosslinkable group such as an epoxy group and an oxetanyl group is described ([0024] [0028]).
  • the present inventors examined a copolymer having a structural unit a2 containing a crosslinkable group together with a structural unit a1 containing a cinnamate group as the polymer A described in Patent Document 1, the kind of the crosslinkable group is It became clear that the orientation (hereinafter also referred to as “liquid crystal orientation”) of the liquid crystal compound may be inferior when forming the optically anisotropic layer on the obtained photoalignment film depending on the case. In addition, depending on the type of crosslinkable group, the present inventors found that the releasability of the optically anisotropic layer is at the time of transferring the optically anisotropic layer formed on the resulting photo alignment film to another substrate. It became clear that it might be inferior.
  • a photoalignment copolymer which can form a photoalignment film which is excellent in the alignment property of the liquid crystal compound and is also excellent in the removability of the optically anisotropic layer, and using the same It is an object of the present invention to provide a produced photoalignment film and an optical laminate.
  • the present inventors obtained by using a copolymer having a repeating unit containing a specific photoalignable group and a repeating unit containing a specific crosslinkable group.
  • a copolymer having a repeating unit containing a specific photoalignable group and a repeating unit containing a specific crosslinkable group When forming an optically anisotropic layer on the resulting photo alignment film, it is found that the alignment of the liquid crystal compound is good and the releasability of the formed optical anisotropic layer is also excellent, and the present invention is completed.
  • the present inventors found that the above-mentioned subject can be achieved by the following composition.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a substituent. Two adjacent groups among R 2 , R 3 , R 4 , R 5 and R 6 may be combined to form a ring.
  • R 7 represents a hydrogen atom or a methyl group
  • R 8 represents a hydrogen atom, a methyl group or an ethyl group.
  • L 1 in Formula (A) and L 2 in Formula (B) each independently represent a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms which may have a substituent X, At least two or more members selected from the group consisting of an arylene group having 6 to 12 carbon atoms which may have a substituent Y, an ether group, a carbonyl group, and an imino group which may have a substituent Z It represents a divalent linking group in which groups are combined.
  • the substituent X is at least one substituent selected from the group consisting of a halogen atom, an alkyl group and an alkoxy group
  • the substituent Y is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy
  • at least one substituent selected from the group consisting of an alkyl group and an aryl group at least one substituent selected from the group consisting of a group, a cyano group, a carboxy group and an alkoxycarbonyl group It is.
  • L 1 in the formula (A) has at least a linear alkylene group of 1 to 10 carbon atoms which may have a substituent X, and 3 carbons which may have a substituent X
  • L 1 in the formula (A) is at least a linear alkylene group of 1 to 10 carbon atoms which may have a substituent X, or carbon which may have a substituent X
  • the substituents represented by R 2 , R 3 , R 4 , R 5 and R 6 in the formula (A) are each independently a halogen atom or a linear, branched or cyclic C 1 to C 20 carbon atom.
  • the photoalignable copolymer according to any one of [1] to [7], which is a group or a group represented by the following formula (1).
  • * represents a bonding position with a benzene ring in Formula (A)
  • R 9 represents a monovalent organic group.
  • a repeating unit C containing a crosslinkable group represented by the following formula (C), a repeating unit D containing a crosslinkable group represented by the following formula (D), and a table represented by the following formula (E) The photoalignable copolymer according to any one of [1] to [10], having at least one repeating unit selected from the group consisting of repeating units E containing a crosslinkable group.
  • R 10 represents a hydrogen atom or a methyl group
  • L 3 represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms which may have a substituent X
  • It represents a divalent linking group in which groups are combined.
  • R 11 represents a hydrogen atom or a methyl group
  • L 4 represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms which may have a substituent X, 1 or 2 or more selected from the group consisting of an arylene group having 6 to 12 carbon atoms which may have a substituent Y, an ether group, a carbonyl group, and an imino group which may have a substituent Z
  • Q represents any one of —OH, —COOH, and —COOtBu.
  • R 12 represents a hydrogen atom or a methyl group
  • L 5 represents a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms which may have a substituent X, 1 or 2 or more selected from the group consisting of an arylene group having 6 to 12 carbon atoms which may have a substituent Y, an ether group, a carbonyl group, and an imino group which may have a substituent Z
  • S represents a functional group having an ethylenically unsaturated double bond.
  • the substituent X is at least one substituent selected from the group consisting of a halogen atom, an alkyl group and an alkoxy group
  • the substituent Y is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy
  • at least one substituent selected from the group consisting of an alkyl group and an aryl group at least one substituent selected from the group consisting of a group, a cyano group, a carboxy group and an alkoxycarbonyl group It is.
  • An optical laminate comprising the photoalignment film according to [14] and an optically anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound.
  • a photoalignable copolymer which is capable of producing a photoalignment film excellent in the alignment property of the liquid crystal compound and excellent also in the removability of the optically anisotropic layer, and using the same
  • the produced photo alignment film and optical laminated body can be provided.
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • the photoalignable copolymer of the present invention comprises a repeating unit A containing a photoalignable group represented by the following formula (A) and a repeating unit B containing a crosslinkable group represented by the following formula (B) It is a photoalignable copolymer.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a substituent. Two adjacent groups among R 2 , R 3 , R 4 , R 5 and R 6 may be combined to form a ring.
  • R 7 represents a hydrogen atom or a methyl group
  • R 8 represents a hydrogen atom, a methyl group or an ethyl group.
  • L 1 in the above formula (A) and L 2 in the above formula (B) are each independently a linear, branched or cyclic C 1 to C 10 optionally having substituent X
  • An alkylene group, an arylene group having 6 to 12 carbon atoms which may have a substituent Y, an ether group (-O-), a carbonyl group (-C ( O)-), and a substituent Z
  • the substituent X is at least one substituent selected from the group consisting of a halogen atom, an alkyl group and an alkoxy group
  • the substituent Y is a halogen atom, an alkyl group, an aryl group, an alkoxy group
  • the substituent Z is at least one selected from the group consisting of an alkyl group and an aryl group It is a substituent of the species.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc.
  • 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 (eg, methyl group, ethyl group, propyl group, isopropyl group) N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group and the like are more preferable, an alkyl group having 1 to 4 carbon atoms is still more preferable, and a methyl group or an ethyl group is more preferable Is particularly preferred.
  • the alkoxy group is, for example, preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) More preferably, it is an alkoxy group of the number 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
  • the aryl group includes, for example, an aryl group having a carbon number of 6 to 12, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group and a naphthyl group. Among these, a phenyl group is preferable.
  • aryloxy group examples include phenoxy, naphthoxy, imidazoyloxy, benzimidazoyloxy, pyridin-4-yloxy, pyrimidinyloxy, quinazolinyloxy, purinyloxy, thiophen-3-yloxy and the like.
  • alkoxycarbonyl group for example, methoxycarbonyl, ethoxycarbonyl and the like can be mentioned.
  • linear, branched or cyclic alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and the like. Hexylene group, decylene group and the like can be mentioned.
  • branched alkylene groups include dimethylmethylene, methylethylene, 2,2-dimethylpropylene and 2-ethyl-2-methylpropylene.
  • cyclic alkylene group specifically, for example, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclooctylene group, cyclodecylene group, adamantane-diyl group, norbornane-diyl group And exo-tetrahydrodicyclopentadiene-diyl group etc., among which cyclohexylene group is preferable.
  • arylene group having 6 to 12 carbon atoms include phenylene group, xylylene group, biphenylene group, naphthylene group, 2,2'-methylenebisphenyl group and the like, among which phenylene group is preferable. .
  • L 1 in the above formula (A) is a linear alkylene group having 1 to 10 carbon atoms which may have the above-mentioned substituent X for the reason that the liquid crystal alignment property is better.
  • 2 containing at least one of a cyclic alkylene group of 3 to 10 carbon atoms which may have the above-mentioned substituent X, and an arylene group of 6 to 12 carbon atoms which may have the above-mentioned substituent Y
  • it is a divalent linking group containing at least a cyclic alkylene group of 10 to 10, and it is preferably an unsubstituted linear C 2 to C 6 alkylene group or an unsubstituted trans-1,4-cyclo
  • R 2 , R 3 , R 4 , R 5 and R 6 in the above formula (A) will be described, but R 2 , R 3 , R 4 and R in the above formula (A) will be described.
  • 5 and R 6 may be a hydrogen atom instead of a substituent.
  • the substituent represented by R 2 , R 3 , R 4 , R 5 and R 6 in the above formula (A) is an oxetanyl group or an oxetanyl group from the viewpoint of distinguishing from the repeating unit B represented by the above formula (B) It is preferable that the substituent be a substituent other than the substituent contained, and the photoalignable group easily interacts with the liquid crystal compound, and the liquid crystal alignment property is further improved.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that it is a fluorine atom and a chlorine atom.
  • the linear alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and specifically, for example, a methyl group, ethyl And n-propyl group.
  • the branched alkyl group is preferably an alkyl group having a carbon number of 3 to 6, and specific examples thereof include an isopropyl group and a tert-butyl group.
  • the cyclic alkyl group is preferably an alkyl group having a carbon number of 3 to 6, and specific 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 specifically, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group And perfluorobutyl group etc., among which 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 still more preferably an alkoxy group having 6 to 14 carbon atoms.
  • Preferred examples of the group include n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group and n-tetradecyloxy group.
  • the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group. Among them, a phenyl group is preferable. preferable.
  • the aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and specific examples thereof include a phenyloxy group and a 2-naphthyloxy group. Among them, a phenyloxy group is preferable. Is preferred.
  • amino group examples include: primary amino group (—NH 2 ); secondary amino group such as methylamino group; dimethylamino group, diethylamino group, dibenzylamino group, nitrogen-containing heterocyclic compound (eg, pyrrolidine) , And a tertiary amino group such as a group having a nitrogen atom of piperidine, piperazine and the like as a bond;
  • a linear or cyclic alkyl group having 1 to 20 carbon atoms can be mentioned .
  • the linear alkyl group is preferably an alkyl group having a carbon number of 1 to 6, and specific examples thereof include a methyl group, an ethyl group and an n-propyl group. Among them, a methyl group or an ethyl group is preferable. preferable.
  • the cyclic alkyl group is preferably an alkyl group having a carbon number of 3 to 6, and specific examples thereof include a cyclopropyl group, a cyclopentyl group and a cyclohexyl group.
  • the monovalent organic group represented by R 9 in the above formula (1) may be a combination of the linear alkyl group and the cyclic alkyl group described above directly or via a single bond. Good.
  • R 2 , R 3 , R 4 , R 5 and 5 in the above formula (A) are preferred because the photoalignable group easily interacts with the liquid crystal compound and the liquid crystal alignment becomes better.
  • R 6 it is preferable that at least R 4 represents the above-mentioned substituent, and further, the linearity of the obtained photoalignable copolymer is improved, and it becomes easy to interact with the liquid crystal compound, and liquid crystal alignment It is more preferable that all of R 2 , R 3 , R 5 and R 6 represent a hydrogen atom for the reason that the property is better.
  • R 4 in the above formula (A) is an electron donating substituent, because the reaction efficiency is improved when the resulting photo alignment film is irradiated with light.
  • the electron donating substituent refers to a substituent having a Hammett value (Hammett substituent constant ⁇ p) of 0 or less, and, for example, among the above-mentioned substituents, an alkyl group, A halogenated alkyl group, an alkoxy group, etc. are mentioned. Among them, an alkoxy group is preferable, an alkoxy group having 4 to 18 carbon atoms is more preferable, and an alkoxy group having 6 to 14 carbon atoms is preferable because orientation becomes better. Is more preferred.
  • repeating unit A containing a photoalignable group represented by the above formula (A) include repeating units A-1 to A-116 shown below.
  • Me represents a methyl group.
  • repeating unit B containing a photoalignable group represented by the above formula (B) include repeating units B-1 to B-14 shown below.
  • the content a of the repeating unit A described above and the content b of the repeating unit B described above preferably satisfy the following formula (2) by mass ratio, It is more preferable to satisfy the following formula (3), and it is further preferable to satisfy the following formula (4).
  • the photoalignable copolymer of the present invention further has a repeating unit C containing a crosslinkable group represented by the following formula (C), and the following because the curing reaction at the time of producing the photoalignment film is made more efficient. It is preferable to have at least one of the repeating units D containing a crosslinkable group represented by Formula (D).
  • R 10 represents a hydrogen atom or a methyl group
  • L 3 represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms which may have a substituent X And at least two or more selected from the group consisting of an arylene group having 6 to 12 carbon atoms which may have a substituent Y, an ether group, a carbonyl group, and an imino group which may have a substituent Z
  • R 11 represents a hydrogen atom or a methyl group
  • L 4 represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms which may have a substituent X Or 1 or 2 selected from the group consisting of an arylene group having 6 to 12 carbon atoms which may have a substituent Y, an ether group, a carbonyl group, and an imino group which may have a substituent Z It represents
  • Tu is a notation indicating tert-butyl.
  • substituent X the substituent Y and the substituent Z, and the linear, branched or cyclic alkylene group having 1 to 10 carbon atoms
  • L 1 in the above formula (A) and the above formula It is the same as that described for L 2 in (B).
  • repeating unit C containing a photoalignable group represented by the above formula (C) include repeating units C-1 to C-16 shown below.
  • repeating unit D represented by the above formula (D) include repeating units D-1 to D-12 shown below.
  • the content a of the repeating unit A mentioned above and the content a of the repeating unit A mentioned above are for the purpose of increasing the speed of curing reaction and increasing the crosslinking density after the curing reaction
  • the content b of the repeating unit B described above and the content c of the repeating unit C described above satisfy the following formula (5) by mass ratio, and satisfy the following formula (6) Is more preferred.
  • the content a of the repeating unit A described above and the content a of the repeating unit A described above increase the speed of the curing reaction and increase the crosslinking density after the curing reaction. It is preferable that the content b of the repeating unit B described above and the content d of the repeating unit D described above satisfy the following formula (7) by mass ratio, and satisfy the following formula (8) Is more preferred. 0.01 ⁇ d / (a + b + d) ⁇ 0.3 (7) 0.05 ⁇ d / (a + b + d) ⁇ 0.2 (8)
  • the photoalignable copolymer of the present invention increases the strength of the optical laminate of the present invention described later, peels any support from the optical laminate of the present invention described later, and transfers it to another substrate. It is preferable to further have a repeating unit E represented by the following formula (E) for the reason that the handling property at the time of carrying out becomes good.
  • R 12 represents a hydrogen atom or a methyl group
  • L 5 represents a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms which may have a substituent X Or 1 or 2 selected from the group consisting of an arylene group having 6 to 12 carbon atoms which may have a substituent Y, an ether group, a carbonyl group, and an imino group which may have a substituent Z
  • It represents a divalent linking group in which the above groups are combined
  • S represents a functional group having an ethylenically unsaturated double bond.
  • undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like can be mentioned.
  • Specific examples of the functional group having an ethylenically unsaturated double bond include, for example, a vinyl group, an allyl group, a styryl group, an acryloyl group and a methacryloyl group, and an acryloyl group or a methacryloyl group preferable.
  • repeating unit E containing a photoalignable group represented by the above formula (E) include repeating units E-1 to E-5 shown below.
  • the strength of the optically anisotropic layer including the photoalignment film can be further enhanced while maintaining good liquid crystal alignment and releasability.
  • the content a of the repeating unit A described above, the content b of the repeating unit B described above, and the content e of the repeating unit E described above satisfy the following formula (9) in mass ratio
  • the photoalignable copolymer of the present invention is not limited to the above-mentioned repeating unit A and repeating unit B, and any repeating unit C, repeating unit D and repeating unit E as long as the effects of the present invention are not impaired. It may have a repeating unit.
  • a monomer (radically polymerizable monomer) which forms such other repeating units for example, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, Vinyl compounds and the like can be mentioned.
  • the synthesis method of the photoalignable copolymer of the present invention is not particularly limited.
  • a monomer forming the above-mentioned repeating unit A, a monomer forming the above-mentioned repeating unit B, the above-mentioned repeating unit C, and any It can synthesize
  • the weight average molecular weight (Mw) of the photoalignable copolymer of the present invention is preferably 10,000 to 500,000, and more preferably 30,000 to 200,000 because the orientation is improved.
  • the weight average molecular weight and the number average molecular weight in the present invention are values measured by gel permeation chromatography (GPC) under the conditions shown below.
  • the photoalignment film of the present invention is a composition for a photoalignment film containing the above-described photoalignment copolymer of the present invention (hereinafter, also formally referred to as "the composition for photoalignment film of the present invention"). It is a photo alignment film formed using.
  • the thickness of the photoalignment film is not particularly limited and may be appropriately selected depending on the purpose, but it is preferably 10 to 1000 nm, and more preferably 10 to 700 nm.
  • the content of the photoalignable copolymer of the present invention in the composition for photoalignment film of the present invention is not particularly limited, but in the case of containing the organic solvent described later, 0.1 to 50 with respect to 100 parts by mass of the organic solvent It is preferable that the amount is in the range of 0.5 to 10 parts by mass.
  • the composition for a photoalignment film of the present invention preferably contains an organic solvent from the viewpoint of workability for producing a photoalignment film.
  • an organic solvent specifically, for example, ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (eg, dioxane, tetrahydrofuran etc.), aliphatic hydrocarbons (Eg, hexane), alicyclic hydrocarbons (eg, cyclohexane), aromatic hydrocarbons (eg, toluene, xylene, trimethylbenzene etc.), halogenated carbons (eg, dichloromethane, dichloroethane, di) Chlorobenzene, chlorotoluene etc., esters (eg methyl acetate, ethyl acetate, butyl acetate etc), water, alcohols (eg ethanol, isopropan
  • composition for photo alignment film of the present invention may contain other components other than the above, and examples thereof include a crosslinking catalyst, an adhesion improver, a leveling agent, a surfactant, a plasticizer and the like.
  • the photoalignment film of the present invention can be produced by a conventionally known production method except that the composition for photoalignment film of the present invention described above is used.
  • the composition for photoalignment film of the present invention described above is supported Producing by a manufacturing method including a coating step of coating on a body surface, and a light irradiation step of irradiating non-polarized light in a direction oblique to the polarized light or the coated film surface with respect to the coated film of the composition for photo alignment film it can.
  • the support will be described in the optical laminate of the present invention described later.
  • the coating method in the coating step is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include spin coating, die coating, gravure coating, flexographic printing, and inkjet printing.
  • the polarized light irradiated to the coating film of the composition for photo alignment film is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, elliptically polarized light and the like, among which 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 at a polar angle ⁇ (0 ⁇ ⁇ 90 °) with respect to the normal direction of the coating film surface. Can be selected as appropriate, but preferably ⁇ is 20 to 80 °.
  • the wavelength in polarized light or non-polarized light is not particularly limited as long as the coating film of the composition for photo alignment film can be provided with the ability to control the alignment of liquid crystalline molecules, for example, ultraviolet light, near ultraviolet light, visible light Etc. Among them, near ultraviolet light of 250 nm to 450 nm is particularly preferable.
  • a light source for irradiating polarized light or non-polarized light for example, a xenon lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp and the like can be mentioned.
  • the wavelength range to be irradiated can be limited by using an interference filter, a color filter, or the like for ultraviolet light or visible light obtained from such a light source.
  • linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources.
  • the integrated light quantity of polarized light or non-polarized light is not particularly limited as long as the coating of the composition for photo alignment film can be given the ability to control the alignment of liquid crystalline molecules, and is not particularly limited. / Cm 2 is preferable, and 5 to 100 mJ / cm 2 is more preferable.
  • the illumination intensity of polarized light or non-polarized light is not particularly limited as long as the coating of the composition for photo alignment film can be provided with the ability to control the alignment of liquid crystalline molecules, but 0.1 to 300 mW / cm 2 Preferably, 1 to 100 mW / cm 2 is more preferable.
  • the optical laminate of the present invention is an optical laminate having the above-described photoalignment film of the present invention and an optically anisotropic layer formed using a liquid crystal composition containing a liquid crystalline compound.
  • the optical laminate of the present invention preferably further comprises a support, and specifically preferably comprises a support, an optical alignment film and an optically anisotropic layer in this order. .
  • optically anisotropic layer included in the optical laminate of the present invention is not particularly limited as long as it is an optically anisotropic layer containing a liquid crystalline compound, and conventionally known optically anisotropic layers may be appropriately employed and used it can.
  • Such an optically anisotropic layer is a layer obtained by curing a composition containing a liquid crystal compound having a polymerizable group (hereinafter, also referred to as a “composition for forming an optically anisotropic layer”). And may be a single layer structure or a structure (laminated body) in which a plurality of layers are laminated.
  • the liquid crystal compound and optional additives contained in the composition for forming an optically anisotropic layer are described below.
  • the liquid crystalline compound contained in the composition for forming an optically anisotropic layer is a liquid crystalline compound having a polymerizable group.
  • liquid crystal compounds can be classified into rod-like types and discotic types according to their shapes. Furthermore, there are low molecular weight and high molecular type respectively.
  • a polymer refers to one having a degree of polymerization of 100 or more (Polymer physics / phase transition dynamics, Masao Doi, page 2, Iwanami Shoten, 1992).
  • any liquid crystal compound can be used, but it is preferable to use a rod-like liquid crystal compound or a discotic liquid crystal compound, and it is more preferable to use a rod-like liquid crystal compound.
  • liquid crystal compound having a polymerizable group is used to fix the above-mentioned liquid crystal compound, it is more preferable that the liquid crystal compound has two or more polymerizable groups in one molecule. In the case where the liquid crystal compound is a mixture of two or more types, it is preferable that at least one type of liquid crystal compound has two or more polymerizable groups in one molecule. In addition, 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, and a functional group capable of addition polymerization reaction is preferable, and a polymerizable ethylenically unsaturated group or a ring polymerizable group is preferable. More specifically, (meth) acryloyl group, vinyl group, styryl group, allyl group and the like are preferably mentioned, and (meth) acryloyl group is more preferable. In addition, a (meth) acryloyl group is a description which means a methacryloyl group or an acryloyl group.
  • rod-like liquid crystalline compound for example, those described in claim 1 of JP-A-11-513019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used, and
  • tick liquid crystal compound for example, those described in paragraphs [0020] to [0067] of JP2007-108732A and paragraphs [0013] to [0108] of JP2010-244038A are preferably used. But not limited thereto.
  • a liquid crystal compound having reverse wavelength dispersion can be used as the liquid crystal compound.
  • the “reverse wavelength dispersive” liquid crystal compound refers to the in-plane retardation (Re) value at a specific wavelength (visible light range) of a retardation film produced using this In this case, the Re value becomes equal or higher as the measurement wavelength increases.
  • the liquid crystal compound having reverse wavelength dispersion is not particularly limited as long as it can form a film having reverse wavelength dispersion as described above, and, for example, the general formula (I) described in JP-A-2008-297210 Compounds represented by the general formula (1) described in JP 2010-084032 A (especially, compounds described in paragraph Nos.
  • the composition for forming an optically anisotropic layer may contain components other than the liquid crystal compound described above.
  • the composition for forming an optically anisotropic layer may contain a polymerization initiator.
  • the polymerization initiator to be 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 compounds, acyloin ethers, ⁇ -hydrocarbon substituted aromatic acyloin compounds, polynuclear quinone compounds, combinations of triarylimidazole dimers and p-aminophenyl ketones, etc.
  • Be The amount of the polymerization initiator used is preferably 0.01 to 20% by mass, and more preferably 0.5 to 5% by mass, with respect to the total solid content of the composition.
  • the composition for forming an optically anisotropic layer may contain a polymerizable monomer from the viewpoint of the uniformity of the coating film and the strength of the film.
  • the polymerizable monomer include radically polymerizable or cationically polymerizable compounds.
  • Preferred are polyfunctional radically polymerizable monomers, and those copolymerizable with the above-mentioned polymerizable group-containing liquid crystal compound.
  • the content of the polymerizable monomer is preferably 1 to 50% by mass, and more preferably 2 to 30% by mass, with respect to the total mass of the liquid crystal compound.
  • a surfactant may be contained in the composition for forming an optically anisotropic layer from the viewpoint of the uniformity of the coating film and the strength of the film.
  • surfactant although a conventionally well-known compound is mentioned, especially a fluorine-type compound is preferable. Specifically, for example, compounds described in paragraphs [0028] to [0056] in JP-A-2001-330725, and compounds described in paragraphs [0069]-[0126] of JP-A-2005-062673 are listed.
  • an organic solvent may be contained in the composition for forming an optically anisotropic layer.
  • an organic solvent the thing similar to what was demonstrated in the composition for photoalignment films of this invention mentioned above can be mentioned.
  • composition for forming an optically anisotropic layer a polarizer interface side vertical alignment agent, a vertical alignment promoter such as an air interface vertical side alignment agent, a polarizer interface side horizontal alignment agent, and air Various alignment agents such as a horizontal alignment promoter such as an interface-side horizontal alignment agent may be included.
  • the composition for forming an optically anisotropic layer may contain an adhesion improver, a plasticizer, a polymer and the like.
  • the formation method of the optically anisotropic layer using the composition for optically anisotropic layer formation which has such a component is not specifically limited,
  • an optically anisotropic layer The composition for formation can be applied to form a coating film, and the resulting coating film can be formed by curing treatment (irradiation with ultraviolet light (light irradiation treatment) or heat treatment).
  • the application of the composition for forming an optically anisotropic layer can be carried out by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method).
  • the thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.1 to 10 ⁇ m, and more preferably 0.5 to 5 ⁇ m.
  • the optical layered product of the present invention may have a support as a substrate for forming an optically anisotropic layer as described above.
  • a support include a polarizer, a polymer film and the like, and combinations thereof, such as a laminate of a polarizer and a polymer film, a laminate of a polymer film, a polarizer and a polymer film It may be a body or the like.
  • the support may be a temporary support which may be peeled off (hereinafter, it may simply be referred to simply as a “temporary support”) after the formation of the optically anisotropic layer.
  • the optically anisotropic layer may be provided by peeling the polymer film functioning as a temporary support from the optical laminate. For example, after preparing an optical laminate including an optically anisotropic layer and a temporary support, and bonding the optically anisotropic layer side of the optical laminate to a support including a polarizer with an adhesive or an adhesive, By peeling off the temporary support contained in the optically anisotropic layer, a laminate of a support including a polarizer and an optically anisotropic layer may be provided.
  • a polarizer is not particularly limited as long as it is a member having a function of converting light into specific linear polarization, and conventionally known absorption polarizers and reflection polarizers can be used.
  • absorption type polarizer an iodine based polarizer, a dye based polarizer using a dichroic dye, a polyene based polarizer and the like are used.
  • iodine type polarizers and dye type polarizers there are coating type polarizers and stretching type polarizers, either of which can be applied, but polarized light produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching it Preferably a child.
  • multilayer film which formed the polyvinyl alcohol layer on the base material patent 5048120, patent 5143918, patent 5048120, patent No. 4,691,205, Japanese Patent No. 4,751,481, Japanese Patent No.
  • a reflection type polarizer a polarizer in which thin films different in birefringence are laminated, a wire grid type polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection area and a quarter wavelength plate are combined, etc. are used.
  • a polymer containing polyvinyl alcohol resin (-CH 2 -CHOH- as a repeating unit) is intended, in particular, at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymer It is preferable that it is a polarizer containing one is preferable.
  • the polarizing plate can be produced, for example, as follows.
  • the support is peeled off from the above-mentioned optical laminate, and the layer containing the optically anisotropic layer is laminated on the support containing a polarizer.
  • the above-mentioned optical laminate is laminated on a support including a polarizer, and then the peelable support contained in the optical laminate is peeled off.
  • both layers may be adhered by an adhesive or the like.
  • the adhesive is not particularly limited, but as described in JP-A-2004-245925, a curable adhesive of an epoxy compound having no aromatic ring in the molecule, as described in JP-A-2008-174667, 360 to An active energy ray-curable adhesive comprising a photopolymerization initiator having a molar absorption coefficient of 400 or more at a wavelength of 450 nm and an ultraviolet curable compound as essential components, (meth) acrylic compound described in JP-A-2008-174667 (A) a (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule, and (b) a hydroxyl group in the molecule in a total amount of 100 parts by mass, and only one polymerizable double bond And (c) phenol ethylene oxide modified acrylate or nonyl phenol ethylene oxide modified acrylic Such as an active energy ray-curable adhesive containing a chromatography bets and the like.
  • the thickness of the polarizer is not particularly limited, but is preferably 1 to 60 ⁇ m, more preferably 1 to 30 ⁇ m, and still more preferably 2 to 20 ⁇ m.
  • the polymer film is not particularly limited, and a commonly used polymer film (for example, a polarizer protective film or the like) can be used.
  • a polymer which comprises a polymer film For example, A cellulose polymer; An acrylic polymer which has acrylic acid ester polymers, such as a polymethyl methacrylate and a lactone ring containing polymer; A thermoplastic norbornene-type polymer; A polycarbonate system Polymers; Polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; Styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin); Polyolefin-based polymers such as polyethylene, polypropylene and ethylene-propylene copolymer; Vinyl chloride Based polymers; amide based polymers such as nylon and aromatic polyamides; imide based polymers; sulfone based polymers; polyether sulf
  • a cellulose-based polymer (hereinafter, also referred to as “cellulose acylate”) represented by triacetyl cellulose can be preferably used.
  • cellulose acylate represented by triacetyl cellulose
  • acrylic polymer examples include polymethyl methacrylate, and lactone ring-containing polymers described in paragraphs [0017] to [0107] of JP 2009-98605 A, and the like.
  • the thickness of the polymer film used for a polarizer protective film etc. is not specifically limited, 40 micrometers or less are preferable from the reasons that thickness of an optical laminated body can be made thin.
  • the lower limit is not particularly limited, but is usually 5 ⁇ m or more.
  • the thickness of the support is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, and still more preferably 5 to 20 ⁇ m.
  • the thickness of the said support body means the thickness of the sum total of these thickness, when it has both a polarizer and a polymer film.
  • a cellulose polymer or a polyester polymer can be preferably used.
  • the thickness of the polymer film is not particularly limited, but is preferably 5 ⁇ m to 100 ⁇ m and more preferably 20 ⁇ m to 90 ⁇ m from the viewpoint of handling at the time of production and the like.
  • the interface to be peeled off may be between the support and the photoalignment film, may be between the photoalignment film and the optically anisotropic layer, or may be another interface.
  • the optical layered body of the present invention can be used preferably in the production of an image display device because the thickness of the support can be peeled off.
  • the display element used for an image display apparatus is not specifically limited, For example, a liquid crystal cell, organic electroluminescence (it abbreviates to "EL" hereafter) display panel, a plasma display panel etc. are mentioned. Among these, a liquid crystal cell and an organic EL display panel are preferable, and a liquid crystal cell is more preferable. That is, the image display device is preferably a liquid crystal display device using a liquid crystal cell as a display element, and an organic EL display device using an organic EL display panel as a display element, and more preferably a liquid crystal display device.
  • the liquid crystal display device which is an example of an image display device is a liquid crystal display device which has the optical laminated body of this invention mentioned above, and a liquid crystal cell.
  • the optical laminate of the present invention it is preferable to use the optical laminate of the present invention as a polarizing plate on the front side.
  • the liquid crystal cell constituting the liquid crystal display device will be described in detail.
  • the liquid crystal cell used for the liquid crystal display device is preferably a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. It is not limited to In the TN mode liquid crystal cell, rod-like liquid crystalline molecules (rod-like liquid crystalline compounds) are substantially horizontally aligned when no voltage is applied, and are further twisted at 60 to 120 °.
  • the TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.
  • VA mode liquid crystal cell rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied.
  • a narrow definition VA mode liquid crystal cell in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and substantially horizontally aligned when a voltage is applied
  • a liquid crystal cell (in multi-domain vertical alignment (MVA) mode) liquid crystal cell (SID 97, Digest of tech. Papers (preliminary paper)) in which the VA mode is multi-domained in order to widen the viewing angle.
  • n-ASM mode Analy symmetric aligned microcell
  • LCD International Liquid Crystal Display
  • PSA Polymer-Sustained Alignment
  • JP-A-2006-215326 and JP-A-2008-538819 The details of these modes are described in detail in JP-A-2006-215326 and JP-A-2008-538819.
  • the liquid crystal cell of the IPS mode rod-like liquid crystalline molecules are aligned substantially parallel to the substrate, and the liquid crystalline molecules respond in a planar manner by the application of an electric field parallel to the substrate surface.
  • black is displayed when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other.
  • Japanese Patent Application Laid-Open Nos. 10-54982, 11-202323 and 9-292522 are methods for reducing the leaked light during black display in an oblique direction using an optical compensation sheet to improve the viewing angle. No. 11-133408, 11-305217, 10-307291 and the like.
  • Cyclomer M100 (manufactured by Daicel) was used as the following monomer mC-3 for forming the above-mentioned repeating unit C-3.
  • the following monomer mD-1 uses commercially available methacrylic acid (Wako Pure Chemical Industries, Ltd.), and the following monomer mD-3 uses commercially available 2-hydroxyethyl methacrylate (Tokyo Kasei Reagent), and the following monomer mD-4 uses commercially available 2-methacryloyl ester.
  • the following monomer mD-5 uses commercially available -butyl methacrylate (Wako Pure Chemical Industries, Ltd.) using oxyethyl succinate (Shin-Nakamura Chemical Co., Ltd.), and the following monomer mD-7 uses commercially available 2-methacryloyloxyethyl phthalic acid (New The following monomer mD-12 used commercially available 2-hydroxyethyl methacrylamide (Tokyo Kasei Kogyo Co., Ltd.). The following monomers mD-1 and the like correspond to the monomers forming the above-described repeating unit D-1 and the like.
  • mE-1 85 g of mE-1 was obtained as a pale yellow liquid (yield 88%).
  • the following monomer mE-1 corresponds to the monomer forming the precursor of the above-mentioned repeating unit E-1 (ie, the unit before changing to an acryloyl group by deprotection).
  • the above-mentioned monomers mF-1 and mF-2 correspond to monomers forming the repeating units F-1 and F-2 shown below, respectively.
  • Example 1 In a flask equipped with a condenser, a thermometer and a stirrer, 5 parts by mass of 2-butanone as a solvent was charged, and the flask was heated to reflux with a nitrogen bath flowing at 5 mL / min.
  • 3 parts by mass of monomer mA-1, 7 parts by mass of monomer mB-3, 1 part by mass of 2,2'-azobis (isobutyronitrile) as a polymerization initiator, and 5 parts of 2-butanone as a solvent The solution which mixed parts was dripped over 3 hours, and it stirred, maintaining reflux condition for another 3 hours.
  • reaction solution was allowed to cool to room temperature, and 30 parts by mass of 2-butanone was added and diluted to obtain a polymer solution of about 20% by mass.
  • the resulting polymer solution is poured into a large excess of methanol to precipitate the polymer, and the collected precipitate is separated by filtration, washed with a large amount of methanol and then air-dried at 50 ° C. for 12 hours, A polymer P-1 having a photoalignable group was obtained.
  • Examples 2 to 28 and Comparative Examples 1 to 4 As the monomers forming the repeating units shown in Table 1 below, using the synthesized monomers, the addition amount of the polymerization initiator is changed so as to obtain the weight average molecular weight shown in Table 1 below, A polymer was synthesized in the same manner as the polymer P-1 synthesized in Example 1 except that the blending amount of the monomers was changed so as to be the content.
  • the ratio of the blending amounts (parts by mass) of the respective monomers forming the repeating units A, B and C in Example 25 is 0.5: 0.4: 0.1.
  • the weight average molecular weight of each of the synthesized polymers was measured by the method described above. The results are shown in Table 1 below.
  • composition for photo alignment film 1 part by mass of the polymer P-2 synthesized in Example 2 and 0.05 parts by mass of a thermal acid generator represented by the following structural formula with respect to 100 parts by mass of tetrahydrofuran, and a composition for photo alignment film Prepared.
  • a thermal acid generator represented by the following structural formula with respect to 100 parts by mass of tetrahydrofuran
  • a composition for photo alignment film Prepared.
  • 1 part by mass of light added to 100 parts by mass of tetrahydrofuran A composition for alignment film was prepared.
  • Optical laminates of Examples 2, 5, 7 to 9, 11, 14, 16, 20 to 28 and Comparative Examples 1 to 4 were produced by the following procedure.
  • a cellulose acylate film the same one as Comparative Example 1 of JP-A-2014-164169 was used.
  • the composition for each light alignment film prepared above was applied to one side of this film by a bar coater. After application, the solvent was removed by drying for 5 minutes on a hot plate at 80 ° C. to form a 0.2 ⁇ m thick photoisomerization composition layer.
  • the obtained photoisomerization composition layer was irradiated with polarized ultraviolet light (10 mJ / cm 2 , using an ultra-high pressure mercury lamp) to form a photo alignment film.
  • a nematic liquid crystal compound (ZLI-4792, manufactured by Merck) was coated on the photoalignment film with a bar coater to form a composition layer.
  • the composition layer thus formed was heated to 90 ° C. on a hot plate and then cooled to 60 ° C. to stabilize the orientation. Thereafter, the temperature is maintained at 60 ° C., and the orientation is fixed by ultraviolet irradiation (500 mJ / cm 2 , using an ultra-high pressure mercury lamp) under nitrogen atmosphere (oxygen concentration 100 ppm) to form a 2.0 ⁇ m thick optically anisotropic layer , And an optical laminate was produced.
  • Example 29 An optical laminate was produced in the same manner as in Example 16, except that the coating liquid for an optically anisotropic layer (liquid crystal 101) shown below was used in place of the nematic liquid crystal compound coated on the photoalignment film. did. This optical laminate is referred to as the optical laminate of Example 29.
  • Example 30 An optical laminate was produced in the same manner as in Example 16, except that the coating liquid for an optically anisotropic layer (liquid crystal 102) shown below was used in place of the nematic liquid crystal compound coated on the photoalignment film. did. This optical laminate is referred to as the optical laminate of Example 30.
  • the term “stable planar shape” refers to unevenness or orientation when observed by placing an optical laminate between two polarizing plates arranged in crossed nicols. It is intended that there is no defect such as a defect. Further, in the specification of the present application, a liquid crystal director intends a vector in a direction (alignment main axis) in which the major axis of liquid crystalline molecules is aligned.
  • Example 31 As a monomer which forms a repeating unit shown in the following Table 3, it synthesize
  • Polymer P-29 was synthesized in the same manner as for polymer P-1. The weight average molecular weight of the synthesized polymer P-29 was 36000.
  • Examples 32 to 36 As a monomer which forms a repeating unit shown in the following Table 3, it synthesize
  • composition for photo alignment layers were prepared in the same manner as in Example 2 except that Polymers P-29 to P-34 were used instead of Polymer P-2.
  • optical laminates of Examples 31 to 36 and Example 7 were produced by the following procedure.
  • a cellulose acylate film the same one as Comparative Example 1 of JP-A-2014-164169 was used.
  • the composition for each light alignment film prepared above was applied to one side of this film by a bar coater. After application, the solvent was removed by drying for 5 minutes on a hot plate at 80 ° C. to form a 0.2 ⁇ m thick photoisomerization composition layer.
  • the obtained photoisomerization composition layer was irradiated with polarized ultraviolet light (10 mJ / cm 2 , using an ultra-high pressure mercury lamp) to form a photo alignment film.
  • a nematic liquid crystal compound (ZLI-4792, manufactured by Merck) was coated on the photoalignment film with a bar coater to form a composition layer.
  • the composition layer thus formed was heated to 90 ° C. on a hot plate and then cooled to 60 ° C. to stabilize the orientation. Thereafter, the temperature is maintained at 60 ° C., and the orientation is fixed by ultraviolet irradiation (5 mJ / cm 2 , using ultra-high pressure mercury lamp) under nitrogen atmosphere (oxygen concentration 100 ppm) to form a 2.0 ⁇ m thick optically anisotropic layer , And an optical laminate was produced.
  • AAA The liquid crystal director is uniformly aligned and aligned, and the surface condition and display performance are extremely excellent.
  • AA the liquid crystal director is uniformly aligned and aligned, and the display performance is excellent.
  • A the liquid crystal director is not disturbed and the surface condition is stabilized.
  • B The disturbance of the liquid crystal director is minimal and the surface is stable
  • C The disturbance of the liquid crystal director is partial and the surface is stable
  • D the liquid crystal director is largely disturbed and the surface Is unstable and display performance is very poor
  • Example 37 A 100 mL three-necked flask equipped with a condenser, a thermometer, and a stirrer was charged with 5 parts by mass of 2-butanone as a solvent, and the bath was heated to reflux while flowing nitrogen at 5 mL / min.
  • 4.17 parts by mass of monomer mA-98, 5.47 parts by mass of monomer mB-2, 0.36 parts by mass of monomer mE-1, and 2,2'-azobis (isobutyro) as a polymerization initiator.
  • a solution prepared by mixing 1 part by mass of nitrile) and 5 parts by mass of 2-butanone as a solvent was added dropwise over 3 hours, and the mixture was further stirred for 3 hours while maintaining the reflux state.
  • 10 mg of dibutylhydroxytoluene (BHT) was added to the reaction solution to make the temperature 60 ° C.
  • 0.49 g of triethylamine was added, and the mixture was stirred at 60 ° C. for 5 hours.
  • the reaction solution was allowed to cool to room temperature, and 30 parts by mass of 2-butanone was added for dilution to obtain an about 20% by mass polymer solution.
  • the resulting polymer solution is poured into a large excess of methanol to precipitate the polymer, and the collected precipitate is separated by filtration, washed with a large amount of methanol and then air-dried at 50 ° C. for 12 hours, A polymer P-35 having a photoalignable group was obtained.
  • the compositional ratio (weight ratio) calculated by 1 H-NMR was 42/55/3.
  • Example 38 A 100 mL three-necked flask equipped with a condenser, a thermometer, and a stirrer was charged with 5 parts by mass of 2-butanone as a solvent, and the bath was heated to reflux while flowing nitrogen at 5 mL / min.
  • the resulting polymer solution is poured into a large excess of methanol to precipitate the polymer, and the collected precipitate is separated by filtration, washed with a large amount of methanol and then air-dried at 50 ° C. for 12 hours, A polymer P-36 having a photoalignable group was obtained.
  • the compositional ratio (weight ratio) calculated by 1 H-NMR was 40/53/7.
  • composition for photo alignment film Each composition for photo alignment film was prepared in the same manner as in Example 2 except that Polymers P-35 to P-36 were used instead of Polymer P-2.
  • Optical Laminate As a cellulose acylate film, the same one as Comparative Example 1 of JP-A-2014-164169 was used. The composition for each light alignment film prepared above was applied to one side of this film by a bar coater. After application, the solvent was removed by drying for 5 minutes on a hot plate at 80 ° C. to form a 0.2 ⁇ m thick photoisomerization composition layer.
  • the obtained photoisomerization composition layer was irradiated with polarized ultraviolet light (10 mJ / cm 2 , using an ultra-high pressure mercury lamp) to form a photo alignment film.
  • the coating solution for the optically anisotropic layer (liquid crystal 101) similar to that of Example 29 was coated on the photoalignment film with a bar coater to form a composition layer.
  • the composition layer thus formed was heated to 90 ° C. on a hot plate and then cooled to 60 ° C. to stabilize the orientation.
  • the temperature is maintained at 60 ° C., and the orientation is fixed by ultraviolet irradiation (500 mJ / cm 2 , using an ultra-high pressure mercury lamp) under nitrogen atmosphere (oxygen concentration 100 ppm) to form a 2.0 ⁇ m thick optically anisotropic layer , And an optical laminate was produced.
  • the prepared 80 mm ⁇ 25 mm optical laminate was evaluated for liquid crystal alignment and releasability in the same manner as in Example 2 and the like. The results are shown in Table 4 below.
  • TAC cellulose cellulose acylate film
  • an adhesive SK Dyne 2057, manufactured by Soken Chemical Co., Ltd.
  • TAC the same one as in Comparative Example 1 of JP-A-2014-164169 was used.
  • a laminate for evaluation having a TAC, a pressure-sensitive adhesive, a photoalignment film, an optically anisotropic layer, a pressure-sensitive adhesive and a glass substrate in this order was produced.
  • A The component of the optically anisotropic layer or the photoalignment film is not released even with a force of 5 N / 25 mm.
  • B The component of the optically anisotropic layer or the photo alignment film is released by the force of 0.5 N or more and 5 N / 25 mm.
  • a component of the optically anisotropic layer or photo alignment film is released with a force of less than 0.5 N / 25 mm
  • the photo alignment film using the copolymer having the repeating unit E represented by the above formula (E) has good liquid crystal alignment and releasability. I found that. Also, from the comparison results with Example 24, it was found that the strength of the optical laminate was also improved.

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Abstract

Le problème à la base de la présente invention concerne : un copolymère à photo-alignement capable de former un film photo-aligné qui a la propriété d'aligner de manière satisfaisante des composés cristallins liquides et d'empêcher grandement le détachement de la couche optiquement anisotrope ; et un film photo-aligné et un produit stratifié optique produits chacun à l'aide du copolymère à photo-alignement. Le copolymère à photo-alignement comprend un motif récurrent A, représenté par la formule (A) et comprenant un groupe à photo-alignement et un motif récurrent B représenté par la formule (B) et comprenant un groupe réticulable.
PCT/JP2018/045302 2017-12-15 2018-12-10 Copolymère à photo-alignement, film photo-aligné et produit stratifié optique WO2019117082A1 (fr)

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Cited By (9)

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JP7033198B2 (ja) 2018-05-25 2022-03-09 富士フイルム株式会社 光配向性共重合体、光配向膜および光学積層体
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JPWO2019225632A1 (ja) * 2018-05-25 2021-05-13 富士フイルム株式会社 光配向性共重合体、光配向膜および光学積層体
JP2020201335A (ja) * 2019-06-07 2020-12-17 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
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JPWO2021153402A1 (fr) * 2020-01-30 2021-08-05
WO2021153402A1 (fr) * 2020-01-30 2021-08-05 富士フイルム株式会社 Polymère à photo-alignement, composition de liant, couche de liant, stratifié optique, procédé de fabrication de stratifié optique, et dispositif d'affichage d'image
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JPWO2021166619A1 (fr) * 2020-02-20 2021-08-26
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CN115104050A (zh) * 2020-02-20 2022-09-23 富士胶片株式会社 光学层叠体、偏振片及图像显示装置
CN115104050B (zh) * 2020-02-20 2023-11-14 富士胶片株式会社 光学层叠体、偏振片及图像显示装置
JP7385729B2 (ja) 2020-02-20 2023-11-22 富士フイルム株式会社 光学積層体、偏光板および画像表示装置
WO2022071042A1 (fr) * 2020-09-30 2022-04-07 富士フイルム株式会社 Composition pour film de photo-alignement, film de photo-alignement, et stratifié optique
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JPWO2022071042A1 (fr) * 2020-09-30 2022-04-07
JP7454695B2 (ja) 2020-09-30 2024-03-22 富士フイルム株式会社 光配向膜用組成物、光配向膜および光学積層体
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