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WO2016099177A1 - Film d'alignement vertical comprenant un (co)polymère à base d'un composé d'oléfine cyclique - Google Patents

Film d'alignement vertical comprenant un (co)polymère à base d'un composé d'oléfine cyclique Download PDF

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Publication number
WO2016099177A1
WO2016099177A1 PCT/KR2015/013877 KR2015013877W WO2016099177A1 WO 2016099177 A1 WO2016099177 A1 WO 2016099177A1 KR 2015013877 W KR2015013877 W KR 2015013877W WO 2016099177 A1 WO2016099177 A1 WO 2016099177A1
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carbon atoms
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unsubstituted
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group
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Korean (ko)
Inventor
박은석
박정하
최대승
황승연
이민형
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020150180478A external-priority patent/KR101746789B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2017520315A priority Critical patent/JP6468525B2/ja
Priority to EP15870344.7A priority patent/EP3196236B1/fr
Priority to CN201580062655.4A priority patent/CN107109231B/zh
Priority to US15/519,982 priority patent/US10131843B2/en
Publication of WO2016099177A1 publication Critical patent/WO2016099177A1/fr
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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
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
    • 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
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • 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

Definitions

  • the present invention relates to a vertical alignment film comprising a (co) polymer of a cyclic olefin compound. More specifically, the present invention relates to a vertical alignment film including a (co) polymer of a cyclic olefin compound having a specific substituent, which may have an orientation even at a low temperature process, and exhibits excellent liquid crystal vertical alignment.
  • the TFT-LCD which is driven by a thin film transistor, can drive individual pixels independently, the response speed of the liquid crystal is very fast, and accordingly, a high quality moving image can be realized.
  • the range is expanding.
  • an alignment film is used under the liquid crystal layer so that the liquid crystal can be used as an optical switch.
  • An alignment (co) polymer or the like is applied to the initial alignment of the liquid crystal molecules in the alignment film.
  • the initial orientation refers to a mechanism in which the main chain of the (co) polymer is aligned in a predetermined direction, whereby the liquid crystal molecules are oriented in a state where no voltage is applied.
  • a display cell in order for a liquid crystal to be used as an optical switch in a TFT-LCD, a display cell is used. Liquid crystals must be initially oriented in a predetermined direction on the innermost layer of the thin film transistor, and an alignment layer including an alignment (co) polymer is used for this purpose.
  • the orientational (co) polymer included in the alignment layer should be able to interact well with the molecules in the liquid crystal layer.
  • liquid crystal alignment a method of applying a polyamic acid heat resistant polymer on a transparent glass and laminating a polyimide polymer alignment film through heat treatment at a high temperature is used.
  • the present invention includes a (co) polymer of a cyclic olefin compound having a specific substituent, to provide a vertical alignment film that can have alignment even in a low temperature process and can exhibit excellent liquid crystal vertical alignment.
  • the present invention provides a display device including the vertical alignment layer. [Measures of problem]
  • the present invention provides a vertical alignment film including a (co) polymer of the cyclic olefin compound represented by the following formula (1).
  • q is an integer from 0 to 4,
  • R 1 to R 4 is a radical represented by Formula 1a, except that R 1 to R 4 are the same as or different from each other, and are radicals of the formula i a , and each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkynyl having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted arylalkyl having 5 to 12 carbon atoms; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron
  • R1 to R4 are hydrogen; halogen; Or when it is not a polar functional group, one or more combinations of R1 and R2 or R3 and R4 are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1 or R2 is connected to any one of R3 and R4 to 4 carbon atoms To form a saturated or unsaturated aliphatic ring of 12 to 12, or an aromatic ring of 6 to 24 carbon atoms,
  • a and C are each independently a simple bond or a substituted or unsubstituted alkylene having 5 carbon atoms, B is ester
  • n1 and n2 are each independently an integer of 0 to 5, n1 + n2 is an integer of 1 to 5,
  • Xl and X2 are substituents substituted in the benzene ring, each independently a fluorine atom (F), alkyl fluoride of 1 to 5 carbon atoms, alkoxy fluoride of 1 to 5 carbon atoms, aryl fluoride of 6 to 20 carbon atoms, or 6 to 20 alkoxy aryl fluoride.
  • F fluorine atom
  • the present invention provides a display device including the vertical alignment layer.
  • the vertical alignment layer of the present invention may include an (co) polymer of a cyclic olefin resin having a structure in which a specific cyclic substituent is substituted, and thus may exhibit improved interaction with liquid crystal molecules even at low temperature, and thus have excellent alignment. Can be. [Brief Description of Drawings]
  • FIG. 1 schematically illustrates a structure of a liquid crystal cell including a vertical alignment layer according to an embodiment of the present invention.
  • each layer or element when each layer or element is referred to as being formed “on” or “on” of each charge or element, it means that each layer or element is formed directly on each layer or element, or Or It means that the element can be further formed between the object, the object, the substrate.
  • alkyl means a linear or branched saturated monovalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms.
  • the alkyl group may encompass not only unsubstituted but also further substituted by a certain substituent described below.
  • alkyl groups include methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, nucleus, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, and trichloromethyl, iodo and methyl, bromomethyl.
  • Alkenyl means a linear or branched monovalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms comprising at least one carbon-carbon double bond. . Alkenyl groups may be bonded through a carbon atom comprising a carbon-carbon double bond or through a saturated carbon atom. Alkenyl groups may be broadly referred to as unsubstituted as well as those further substituted by the following substituents. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-nucleenyl, dodecenyl, and the like.
  • Cycloalkyl means a saturated or unsaturated non-aromatic monovalent monocyclic, bicyclic, or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, which also includes those further substituted by certain substituents described below. can do. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclonuxyl, cyclonuxenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl (ie, bicyclo [2,2, 1] hept-5-enyl).
  • Aryl means 6 to 40, preferably 6 to 12 ring atoms
  • a branch means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety, and may be referred to collectively further substituted by a certain substituent described below.
  • Examples of the aryl group include phenyl, naphthalenyl, fluorenyl and the like.
  • Alkoxyaryl means that at least one hydrogen atom of the aryl group as defined above is substituted with an alkoxy group.
  • alkoxyaryl group examples include methoxyphenyl, epoxyphenyl, propoxyphenyl, annexcyphenyl, phenoxyphenyl, nucleooxyphenyl, heptoxy, oxoxy, nanoxy, methoxybiphenyl, methoxynaphthalenyl, Methoxy fluorenyl, methoxycyanracenyl, and the like.
  • Arylalkyl means that at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group, and may be referred to collectively further substituted by a specific substituent described below. For example, benzyl, benzhydryl, trityl, etc. are mentioned.
  • Alkynyl means a linear or branched monovalent hydrocarbon moiety of from 2 to 20 carbon atoms, preferably from 2 to 10, more preferably from 2 to 6, containing at least one carbon-carbon triple bond. do. Alkynyl groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynyl groups may also be referred to collectively further substituted by certain substituents described below. For example, ethynyl, propynyl, etc. are mentioned.
  • Alkylene means a linear or branched saturated divalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms.
  • the alkylene group can also be referred to collectively further substituted by certain substituents described below.
  • methylene, ethylene, propylene, butylene, nuxylene, etc. are mentioned.
  • Alkenylene means a linear or branched divalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms comprising at least one carbon-carbon double bond. do. Alkenylene groups may be bonded through a carbon atom comprising a carbon-carbon double bond and / or through a saturated carbon atom. Alkenylene group can also refer to what is further substituted by the specific substituent mentioned later.
  • Cycloalkylene is a saturated or unsaturated of 3 to 12 ring carbons
  • Non-aromatic divalent means a monocyclic, bicyclic or tricyclic hydrocarbon moiety, and may be referred to collectively further substituted by certain substituents described below. For example, cyclopropylene, cyclobutylene, etc. are mentioned.
  • Arylene means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having from 6 to 20, preferably from 6 to 12 ring atoms, further substituted by the following substituents It may be referred to inclusively.
  • the aromatic moiety contains only carbon atoms. Phenylene etc. are mentioned as an example of an arylene group.
  • Alkynylene means a linear or branched divalent hydrocarbon moiety of 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 6 carbon atoms, which contain at least one carbon-carbon triple bond. do. Alkynylene groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynylene groups can also be referred to collectively further substituted by certain substituents described below. For example, ethynylene, propynylene, etc. are mentioned.
  • Substituent described above "substituted or unsubstituted” is meant to encompass not only each of these substituents themselves, but also those further substituted by a certain substituent.
  • substituents which may be further substituted with each substituent include halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, Arylalkyl, haloarylalkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, siloxy or ⁇ "includes oxygen, nitrogen, phosphorus, sulfur, silicon or boron Polar functional groups ”, and the like.
  • the (co) polymer refers to a polymer encompassing both a homopolymer consisting of a polymerization of a single monomer (Homop ymer) and a copolymer (copolymer, terpolymer) consisting of copolymerization of two or more different monomers.
  • vertical alignment layer refers to a type of alignment layer that determines the alignment state of the liquid crystal molecules before the voltage is applied to the liquid crystal molecules having dielectric anisotropy in the liquid crystal display device.
  • the alignment film is formed to be slightly inclined so that the alignment change occurs while falling through a desired constant direction or falling without a constant direction so that the liquid crystal molecules are parallel to the substrate by voltage application.
  • the vertical alignment optical film including the vertical alignment layer alone is combined with another black film to provide a twisted nematic (TN) mode, a super twisted nematic (STN) mode, an ln plane switching (IPS) mode, and a vertical alignment (VA) mode.
  • TN twisted nematic
  • STN super twisted nematic
  • IPS ln plane switching
  • VA vertical alignment
  • the liquid crystal display (LCD) device such as OCB (Optically Compensated Birefringence) mode, it can be used as an alignment layer for liquid crystal alignment.
  • OCB Optically Compensated Birefringence
  • a vertical alignment layer comprising a (co) polymer of the cyclic olefin compound represented by the following formula (1).
  • q is an integer from 0 to 4,
  • R 1 to R 4 is a radical represented by the following Formula 1a, except that R 1 to R 4 are the same as or different from each other, and are radicals of the formula i a , and each independently hydrogen; Halogen; substituted or unsubstituted linear or branched alkyl of 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenyl having 2 to 20 carbon atoms; Substituted or unsubstituted 2 to 20 carbon atoms Linear or branched alkynyl; Substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; Substituted or unsubstituted arylalkyl having 5 to 12 carbon atoms; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,
  • R1 to R4 are hydrogen; halogen; Or when it is not a polar functional group, one or more combinations of R1 and R2 or R3 and R4 are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1 or R2 is connected to any one of R3 and R4 to 4 carbon atoms It may form a saturated or unsaturated aliphatic ring of 12 to 12, or an aromatic ring of 6 to 24 carbon atoms,
  • a and C are each independently a simple bond or a substituted or unsubstituted alkylene having 1 to 5 carbon atoms,
  • n1 and n2 are each independently an integer of 0 to 5, n1 + n2 is an integer of 1 to 5,
  • ⁇ and X 2 are substituents substituted in a benzene ring, each independently a fluorine atom (F), alkyl having 1 to 5 carbon atoms, alkoxy fluoride having 1 to 5 carbon atoms, aryl fluoride having 6 to 20 carbon atoms, or 6 carbon atoms To 20 alkoxy aryl fluoride.
  • F fluorine atom
  • the compound represented by Chemical Formula 1 may have a predetermined substituent (formula 1a), for example, a substituted benzoic acid ester structure or a phenyl ester structure, in a cyclic olefin structure that may be used as a precursor of various compounds or a monomer of a polymer. It may have a chemical structure introducing a functional group such as. Due to the chemical structure into which such a functional group is introduced, the cyclic olefin compound of Formula 1 may be used as an oriented compound by itself.
  • a predetermined substituent for example, a substituted benzoic acid ester structure or a phenyl ester structure
  • a cyclic olefin structure that may be used as a precursor of various compounds or a monomer of a polymer. It may have a chemical structure introducing a functional group such as. Due to the chemical structure into which such a functional group is introduced, the cyclic olefin compound of Formula 1 may be used as an oriented
  • R 5 is a substituted or unsubstituted linear or branched alkylene having 1 to 20 carbon atoms; Substituted or unsubstituted linear or branched alkenylene having 2 to 20 carbon atoms; Unsubstituted linear or branched alkynylene having 2 to 20 carbon atoms; Substituted or unsubstituted cycloalkylene having 3 to 12 carbon atoms; Substituted or unsubstituted arylene having 6 to 40 carbon atoms; Substituted or unsubstituted carbonyloxyylene having 1 to 20 carbon atoms; Or substituted or unsubstituted alkoxylene having 1 to 20 carbon atoms, and R 6 , R 7 and R 8 are each independently hydrogen; halogen; Substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms; Substi
  • the benzene ring connected to the cyclic olefin through a simple bond or alkylene group of A and C fluorine atom (F alkyl fluoride group, alkoxy fluoride group, corresponding to> d and X 2 , It may be 1 to 5 substituted by an aryl fluoride group or an alkoxy fluoride group, Specifically, for example, X and X 2 are each independently a fluorine atom (F); at least one hydrogen is substituted with the fluorine atom A straight or branched chain alkyl group having 1 to 5 carbon atoms, a straight or branched chain alkoxy group having 1 to 5 carbon atoms, at least one hydrogen substituted with the fluorine atom; An aryl group having 5 to 20 carbon atoms may be an alkoxy fluoride aryl group having 5 to 20 carbon atoms, wherein at least one hydrogen contained in the alkoxy group is substituted with the fluor
  • the cyclic olefin compound of Formula 1 has a strong hydrophobic surface energy, so that the initial orientation of the liquid crystal molecules can be determined in a direction perpendicular to the film. do.
  • the cyclic olefin compound described above may be prepared according to a conventional method of introducing a predetermined substituent, more specifically, a functional group represented by Chemical Formula 1a, to a cyclic olefin, for example, a norbornene-based compound.
  • a cyclic olefin for example, a norbornene-based compound.
  • condensation reaction of norbornene alkyl, such as norbornene methanol, with a carboxylic acid compound or an acyl chloride compound having a functional group corresponding to Formula 1 a may be used to prepare the cyclic urelepine compound.
  • the aforementioned cyclic olefin compound may be prepared by introducing the functional group in various ways.
  • the (co) polymer of the cyclic olefin compound represented by the formula (1) may be an orientation (co) polymer containing a repeating unit of the formula (2a) or 2b.
  • m 50 to 5000
  • Such an oriented (co) polymer includes repeating units derived from the above-described cyclic olefin compound, and can exhibit excellent orientation.
  • a and C in the substituent of Formula 1a are selected and controlled by alkylene of various lengths, and the substituents of the benzene ring are substituted with fluorine atom (F), alkyl fluoride, alkoxy fluoride, aryl fluoride, or alkoxy fluoride.
  • the oriented (co) polymer includes a norbornene-based repeating unit of Formula 2a or 2b as a main repeating unit.
  • Such norbornene-based repeat units are structurally rigid, and the orientation (co) polymers comprising them have a relatively high glass transition temperature (Tg) of about 30 C C or higher, preferably about 300 to 35 CTC, and thus are known in the art. It can exhibit excellent thermal stability compared to the polymer and the like.
  • the alignment (co) polymer may exhibit excellent orientation because the functional group can move relatively freely in the polymer backbone due to the structural characteristics of the functional group bonded to the norbornene-based repeating unit.
  • the alignment (co) polymer can be preferably used in the liquid crystal alignment layer for the alignment, it can be preferably applied to a variety of other optical field. Since the definition of each substituent bonded to the alignment (co) polymer has already been described in detail with respect to Formula 1, further description thereof will be omitted.
  • the repeating unit of Formula 2a or 2b constituting the orientation (co) polymer has a degree of polymerization of about 50 to about 5,000, preferably a degree of polymerization of about 100 to about 4,000, more preferably about 1,000 to about 3,000 It can have Accordingly, while the alignment (co) polymer is suitably included in the coating composition for forming the alignment film to exhibit excellent coating properties, the alignment film formed therefrom may exhibit excellent liquid crystal alignment.
  • the above-mentioned orientation (co) polymer can be manufactured by the following method.
  • One embodiment of the manufacturing method includes the step of addition polymerization of the monomer of Formula 1 to form a repeating unit of Formula 2a in the presence of a catalyst composition comprising a procatalyst and a cocatalyst comprising a transition metal of Group 10 do.
  • the polymerization reaction may be carried out in a silver degree of 10 ° C to 200 ° C. If the reaction temperature is less than 10 ° C. polymerization activity may be lowered, if the reaction temperature is greater than 20 CTC catalyst is decomposed it is not preferred.
  • the cocatalyst is one of the cocatalyst to provide a low-cost Lewis bond that can be weakly coordinated with the metal of the procatalyst; And providing a compound comprising a Group 15 electron donor ligand may include one or more selected from the group consisting of two cocatalysts.
  • the cocatalyst may be a catalyst mixture comprising a coarse 11 cocatalyst providing the Lewis base, and optionally a compound crab cocatalyst comprising a neutral Group 15 electron donor ligand.
  • the catalyst mixture may include about 1 to about 1000 moles of the first cocatalyst, and about 1 to about 1000 moles of the second cocatalyst with respect to 1 mol of the procatalyst.
  • the catalyst activation may not be properly performed.
  • the excessively large catalyst may lower the catalytic activity.
  • the procatalyst including the Group 10 transition metal may be easily separated by the first procatalyst providing a Lewis base so that the central transition metal may be converted into a catalytically active species.
  • Lewis base functional groups can be used. for example
  • the first procatalyst which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, is easily reacted with the Lewis base to form a vacancy in the transition metal, and also to stabilize the transition metal thus formed.
  • Compounds that provide weak coordination with metal compounds or compounds that provide them can be used.
  • borate such as B (C 6 F 5 ) 3 or borate such as dimethylanilinium tetrakis (pentafluorophenyl) borate, methylaluminoxane (MAO) or AI (C 2 H 5 ) there is a transition metal halide such as an alkyl aluminum, or AgSbF 6, such as 3.
  • an alkyl phosphine, cycloalkyl phosphine, or phenyl phosphine may be used as the cocatalyst to provide a compound including the neutral group 15 electron donor ligand.
  • the first and second cocatalysts may also be used separately, but these two cocatalysts may be used as a compound to make a salt to activate a catalyst.
  • a compound made by ion bonding an alkyl phosphine and a borane or a borate compound may be used.
  • the alignment unit (co) polymer of one embodiment including the repeating unit of Formula 2a and the same may be prepared.
  • the orienting (co) polymer further includes an olefinic repeating unit, a cyclic olefinic repeating unit, an acrylate repeating unit, or the like, these repeating units are formed by a conventional method for producing each repeating unit,
  • the alignment (co) polymer may be obtained by copolymerization with the repeating unit of Formula 2a prepared by one method.
  • orientation (co) polymer comprises a repeating unit of Formula 2b
  • it can be prepared according to another embodiment of the preparation method.
  • the production method of this other embodiment is based on the norbornenol system in the presence of a catalyst composition comprising a procatalyst and a cocatalyst comprising a transition metal of Group 4, 6, or 8 Ring-opening polymerizing the monomer or the norbornenealkylol monomer to form a ring-opening polymer; And introducing a functional group represented by Formula 1a into the ring-opening polymer to form a repeating unit of Formula 2b.
  • the introduction of the functional group may be carried out by a condensation reaction of the ring-opening polymer with a carboxylic acid compound or an acyl chloride compound having a functional group represented by Formula 1 a.
  • the monomer of Formula 1 may be ring-opened and polymerized to repeat the repeating unit of Formula 2b in the presence of a catalyst composition comprising a procatalyst and a promoter comprising a transition metal of Group 4, 6, or 8 Through the forming step, it may be manufactured.
  • the ring opening may proceed, and the polymerization proceeds together with the repeating unit of Formula 2b and the like; Co) polymers can be prepared.
  • the ring-opening polymerization can be carried out in Group 4 (eg Ti, Zr, Hf), Group 6 (eg Mo, W), or
  • Procatalysts comprising transition metals of Group 8 (e.g. Ru, Os), cocatalysts that provide Lewis bases capable of weakly coordinating with the metals of the procatalysts and optionally enhance the activity of the procatalyst metals. It can proceed in the presence of a catalyst mixture consisting of neutral group 15 and group 16 activators and the like.
  • Group 8 e.g. Ru, Os
  • cocatalysts that provide Lewis bases capable of weakly coordinating with the metals of the procatalysts and optionally enhance the activity of the procatalyst metals. It can proceed in the presence of a catalyst mixture consisting of neutral group 15 and group 16 activators and the like.
  • the linear alkenes such as the molecular weight 1-alkenes, 2-alkenes that can be adjusted over about 1 to about 100mol% monomers, about 10 ° C to about 20C C and to proceed with the polymerization at a temperature
  • Group 4 for example, Ti, Zr
  • Group 8 is Group 8 to Group 10 of about 1 to about 30 increased 0 compared to monomers
  • a catalyst containing a transition metal e.g., Ru, Ni, Pd
  • reaction temperature is too low, there is a problem that the polymerization activity is lowered, and if the reaction temperature is too high, the catalyst is decomposed, which is not preferable.
  • the hydrogenation reaction temperature is too low, there is a problem that the activity of the hydrogenation reaction is lowered, if too high a problem that the catalyst is decomposed Not desirable
  • the catalyst mixture may be added to one mole of the procatalyst comprising a transition metal of Group 4 (e.g. Ti, Zr, Hf), Group 6 (e.g. Mo, W), or Group 8 (e.g. Ru, Os).
  • a transition metal of Group 4 e.g. Ti, Zr, Hf
  • Group 6 e.g. Mo, W
  • Group 8 e.g. Ru, Os
  • From about 1 to about 100,000 moles of cocatalyst, which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, and optionally a group of neutral Group 15 and 16 elements that can enhance the activity of the procatalyst metal Activator comprises about 1 to about 100 moles per mole of procatalyst.
  • the content of the promoter is less than about 1 mole, there is a problem that the catalyst activation is not made, and when the content of the promoter is greater than about 100,000 moles, the catalyst activity is lowered, which is not preferable.
  • the activator may not be necessary depending on the type of procatalyst.
  • the content of the activator is less than about 1 mole, there is a problem that the catalyst activation is not made, and when the content of the activator is greater than about 100 moles, the molecular weight is lowered, which is not preferable.
  • Group 4 (eg, Ti, Zr) black used in the hydrogenation reaction contains a catalyst containing a transition metal of Groups 8 to 10 (eg, Ru, Ni, Pd) than about 1 weight 0 /. If a problem is less the hydrogenation does not easily achieved and greater than about 30 weight 0/0 it is not preferable because of a problem that increased polymer discoloration.
  • a catalyst containing a transition metal of Groups 8 to 10 eg, Ru, Ni, Pd
  • Procatalysts comprising transition metals of Group 4 (e.g. Ti, Zr), Group 6 (e.g. Mo, W), or Group 8 (e.g. Ru, Os) are readily available by cocatalysts providing Lewis acids.
  • a transition metal compound such as a base reaction to easily join the TiCI with a functional group falling off from the central metal 4
  • WCI 6l M0CI5 black has RuCI 3 and ZrCI 4 - off jeungsim to transition metal can be replaced by the catalytically active species, a Lewis acid May be referred to.
  • the co-catalyst which provides a Lewis base that can weakly coordinate with the metal of the procatalyst is borane or borate such as B (C 6 F 5 ) 3 , methylaluminoxane (MAO) or AI (C 2 H 5 Alkyl aluminum, alkyl aluminum halide, aluminum halide such as AI 3 (CH 3 ) CI 2, and the like.
  • B C 6 F 5
  • MAO methylaluminoxane
  • AI C 2 H 5 Alkyl aluminum, alkyl aluminum halide, aluminum halide such as AI 3 (CH 3 ) CI 2, and the like.
  • substituents such as lithium, magnesium magnesium, germanium, lead, zinc, tin, and silicon may be used.
  • it reacts easily with Lewis base to make the transition metal vacancies and also In order to stabilize, it is a compound which weakly coordinates with a transition metal compound or a compound providing the same.
  • An activator of polymerization can be added, it may not be necessary depending on the kind of procatalyst.
  • An activator containing neutral Group 15 and 16 elements that can enhance the activity of the procatalyst metal is water, methanol, ethanol, isopropyl alcohol, benzyl alcohol, phenol, ethyl mercaptan ), 2-chloroethanol, trimethylamine, triethylamine, pyridine, ethylene oxide, benzoyl peroxide, t-butyl peroxide and the like.
  • Group 4 eg Ti, Zr
  • Group 8 to be used for the hydrogenation reaction
  • Catalysts containing transition metals of Group 10 may be homogeneous in form that can be immediately mixed with a solvent, or the metal catalyst complex may be supported on a particulate support.
  • the particulate support is silica, titania, silica / chromia, silica / chromia / titania, silica / alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite.
  • the repeating unit of Formula 2b and an orientation (co) polymer of one embodiment including the same may be prepared.
  • the oriented (co) polymer further includes an olefinic repeating unit, a cyclic olefinic repeating unit, an acrylate repeating unit, or the like, these repeating units are formed by a conventional production method of each repeating unit,
  • the orientational (co) polymer can be obtained by copolymerization with repeating units of formula (2b) prepared in one way.
  • the vertical alignment film comprising the above-mentioned alignment (co) polymer may encompass not only the shape of a thin film but also the alignment film in the form of a film.
  • the liquid crystal cell includes a substrate 100, a vertical alignment layer 200 formed on the substrate, and a liquid crystal layer 300 on the vertical alignment layer. Specifically, the alignment layer 200 is formed. It can be seen that two substrates 100 overlap each other, and a liquid crystal is injected therebetween to form the liquid crystal layer 300.
  • a vertical alignment film except for including the above-described alignment (co) polymer as an alignment polymer, it can be prepared using the components and manufacturing methods known in the art.
  • the vertical alignment layer may be formed by mixing the oriented (co) polymer, the binder resin and the photoinitiator and dissolving it in an organic solvent to obtain a coating composition, and then coating the coating composition on a substrate and proceeding with UV curing. have.
  • the binder resin may be used an acrylate resin, and more specifically, pentaerythritol triacrylate, dipentaerythroxy nuxaacrylate, trimethyl propane triacrylate, tris (2-acryl Monooxyethyl) isocyanurate or the like can be used.
  • photoinitiator a conventional photoinitiator known to be usable for the vertical alignment layer may be used without particular limitation.
  • Photoinitiators known as 1 3 (; 1 ⁇ 907, 819 can be used.
  • organic solvent toluene, anisole, chlorobenzene, dichloroethane, cyclonucleic acid, cyclopentane, propylene glycol methyl ether acetate and the like can be used. Since the above-described oriented norbornene-based copolymer exhibits excellent solubility in various organic solvents, various organic solvents may be used without particular limitation.
  • the solid content concentration including the alignment (co) polymer, the binder resin and the photoinitiator may be 1 to 15% by weight 0 /.
  • the vertical alignment layer in the form of a film 10 to 15% by weight 0 / 0 is preferable, and 1 to 5 parts by weight 0/0 is preferred in order to form a thin-film form.
  • the vertical alignment layer thus formed may be formed on the substrate, for example, as shown in FIG. 1, and may be formed under the liquid crystal to align the same.
  • the substrate may be a substrate containing a cyclic polymer, a substrate containing an acrylic polymer or a substrate containing a cellulose polymer, etc., AgNW substrate, ITO conductive to electrically drive the liquid crystal, ITO Substrate, FTO substrate and the like can also be used.
  • the coating composition may be coated on a substrate by various methods such as bar coating, spin coating, and blade coating, and then UV cured to form a vertical alignment layer.
  • the UV is a polarizing device using a substrate coated with a dielectric anisotropic material on the surface of a transparent substrate, such as quartz glass, soda lime glass, soda lime free glass, 2 a polarizing plate on which fine aluminum or metal wire is deposited, or 3 quartz Polarized UV selected from polarized UV may be applied by passing or reflecting through a Brewster polarizer or the like due to reflection of glass.
  • a transparent substrate such as quartz glass, soda lime glass, soda lime free glass, 2 a polarizing plate on which fine aluminum or metal wire is deposited, or 3 quartz Polarized UV selected from polarized UV may be applied by passing or reflecting through a Brewster polarizer or the like due to reflection of glass.
  • phase silver is preferable.
  • UV may be irradiated in a heated state within a silver range of 10 C C or less.
  • the film thickness of the final coating film formed by the above series of processes is about
  • the liquid crystal cell can be manufactured by the conventional method of forming a vertical alignment film by the above-mentioned method, superimposing two sheets, and injecting a liquid crystal.
  • the vertical alignment layer includes the alignment (co) polymer
  • the vertical alignment layer may exhibit excellent interaction with the liquid crystal molecules, thereby enabling effective initial alignment of the liquid crystal molecules.
  • the above-described vertical alignment layer or liquid crystal cell may be applied to an optical film or an optical filter for implementing a stereoscopic image.
  • a display device including the vertical alignment layer is provided.
  • the display device may be a liquid crystal display device in which the vertical alignment layer is included for alignment of liquid crystals, or a stereoscopic image display device in which the vertical alignment layer is included in an optical film or a filter for realizing a stereoscopic image.
  • the configuration of these display elements includes the above-described alignment (co) polymer and the vertical alignment layer, the configuration of the display elements is a conventional device, and thus detailed description thereof will be omitted.
  • preferred embodiments will be presented to aid in understanding the invention. However, the following examples are only to illustrate the invention, not limited to the invention only.
  • Methyl-4 '-(trifluoromethoxy)-[1,1'-biphenyl] -4-carboxylate 18.4 g (0.06 mol) was added to methanol and dissolved at 50 ° C while stirring.
  • KOH (20.90 g, 0.37 mol) was dissolved in methanol and then placed in the flask stirred above.
  • the sealant epoxy resin
  • the sealant was applied to the edge of the ITO substrate coated with the alignment layer, and another ITO substrate coated with the alignment layer was folded and pressed, followed by UV (100mW / cm 2 ).
  • UV 100mW / cm 2
  • a high-pressure mercury lamp of 100mW / cm 2 intensity was used as the light source, the amount of UV light was adjusted by time.
  • each cell prepared above was placed, and the degree of light leakage was measured by observing with a polarizing microscope how much the incident light passes through the polarizer and Sal.
  • Example 3-4 10 10 (Manufacture example 3-4)

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Abstract

La présente invention concerne un film d'alignement vertical comprenant un (co)polymère à base d'un composé d'oléfine cyclique. Plus particulièrement, la présente invention concerne un film d'alignement vertical qui est capable d'alignement même dans un procédé à basse température, et qui est capable de présenter un excellent alignement vertical de cristaux liquides, ledit film d'alignement vertical étant caractérisé en ce qu'il comprend un (co)polymère à base d'un composé d'oléfine cyclique portant un substituant spécifique.
PCT/KR2015/013877 2014-12-18 2015-12-17 Film d'alignement vertical comprenant un (co)polymère à base d'un composé d'oléfine cyclique Ceased WO2016099177A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2017520315A JP6468525B2 (ja) 2014-12-18 2015-12-17 環状オレフィン化合物の（共）重合体を含む垂直配向膜
EP15870344.7A EP3196236B1 (fr) 2014-12-18 2015-12-17 Film d'alignement vertical comprenant un (co)polymère à base d'un composé d'oléfine cyclique
CN201580062655.4A CN107109231B (zh) 2014-12-18 2015-12-17 包含环烯烃(共)聚物的垂直取向层
US15/519,982 US10131843B2 (en) 2014-12-18 2015-12-17 Vertical alignment layer comprising cyclic olefin copolymer

Applications Claiming Priority (4)

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KR10-2014-0183431 2014-12-18
KR20140183431 2014-12-18
KR10-2015-0180478 2015-12-16
KR1020150180478A KR101746789B1 (ko) 2014-12-18 2015-12-16 고리형 올레핀 화합물의 (공)중합체를 포함하는 수직 배향막

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19980057674A (ko) * 1996-12-30 1998-09-25 손욱 배향막 형성용 조성물, 이로부터 형성되는 배향막과 이 배향막을 구비한 액정표시소자
KR20080081731A (ko) * 2007-03-06 2008-09-10 주식회사 엘지화학 고리형 올레핀계 화합물, 이를 포함하는 중합체, 및 상기중합체를 포함하는 액정배향막
KR20090019721A (ko) * 2007-08-20 2009-02-25 후지필름 가부시키가이샤 광학 보상 필름, 그 제조 방법, 그리고 그것을 사용한 편광판 및 액정 표시 장치
KR20110033183A (ko) * 2008-06-13 2011-03-30 제이엑스 닛코닛세키에너지주식회사 타원 편광판 및 이를 이용한 수직 배향형 액정 표시 장치
KR20120069652A (ko) * 2010-09-27 2012-06-28 주식회사 엘지화학 고리형 올레핀 화합물, 광반응성 중합체 및 이를 포함하는 배향막

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19980057674A (ko) * 1996-12-30 1998-09-25 손욱 배향막 형성용 조성물, 이로부터 형성되는 배향막과 이 배향막을 구비한 액정표시소자
KR20080081731A (ko) * 2007-03-06 2008-09-10 주식회사 엘지화학 고리형 올레핀계 화합물, 이를 포함하는 중합체, 및 상기중합체를 포함하는 액정배향막
KR20090019721A (ko) * 2007-08-20 2009-02-25 후지필름 가부시키가이샤 광학 보상 필름, 그 제조 방법, 그리고 그것을 사용한 편광판 및 액정 표시 장치
KR20110033183A (ko) * 2008-06-13 2011-03-30 제이엑스 닛코닛세키에너지주식회사 타원 편광판 및 이를 이용한 수직 배향형 액정 표시 장치
KR20120069652A (ko) * 2010-09-27 2012-06-28 주식회사 엘지화학 고리형 올레핀 화합물, 광반응성 중합체 및 이를 포함하는 배향막

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