WO2014038868A1 - Polymère de photoalignement, et couche d'alignement et film de retard à cristaux liquides le comprenant - Google Patents

Polymère de photoalignement, et couche d'alignement et film de retard à cristaux liquides le comprenant Download PDF

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WO2014038868A1
WO2014038868A1 PCT/KR2013/008025 KR2013008025W WO2014038868A1 WO 2014038868 A1 WO2014038868 A1 WO 2014038868A1 KR 2013008025 W KR2013008025 W KR 2013008025W WO 2014038868 A1 WO2014038868 A1 WO 2014038868A1
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substituted
carbon atoms
unsubstituted
norbornene
benzyloxy
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PCT/KR2013/008025
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English (en)
Korean (ko)
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한정윤
유동우
이성경
전성호
최대승
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주식회사 엘지화학
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Priority to JP2015531007A priority Critical patent/JP2015533883A/ja
Priority to CN201380046833.5A priority patent/CN104619733A/zh
Priority to US14/419,634 priority patent/US20150210792A1/en
Priority claimed from KR1020130106598A external-priority patent/KR20140032904A/ko
Publication of WO2014038868A1 publication Critical patent/WO2014038868A1/fr

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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1414—Unsaturated aliphatic units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/148—Side-chains having aromatic units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment

Definitions

  • Photo-alignment polymer, alignment film and liquid crystal retardation film comprising the same
  • the present invention relates to a photo-alignment polymer, an alignment film comprising the same, and a liquid crystal retardation film. More specifically, the present invention relates to an optical alignment polymer which can be easily changed in the alignment direction according to the polarization direction and can be preferably applied to an alignment film of a stereoscopic display device, an alignment film including the same, and a liquid crystal retardation film.
  • TFT-LCDs thin film transistor liquid crystal displays
  • liquid crystal As an optical switch in such a TFT-LCD, the liquid crystal must be initially oriented in a predetermined direction on a layer on which the innermost thin film transistor of the display cell is formed, and a liquid crystal alignment layer is used for this purpose.
  • liquid crystal alignment For such liquid crystal alignment, a rubbing process in which a heat-resistant polymer such as polyimide is applied on a transparent glass to form a polymer alignment layer, and a rubbing process of rubbing the alignment layer while rotating a rotating roller wrapped with a rubbing cloth such as nylon or rayon at high speed is performed. It has been applied.
  • the rubbing process may cause mechanical scratches on the surface of the liquid crystal aligning agent during rubbing, or may cause high static electricity, thereby destroying the thin film transistor.
  • defects are generated due to the fine fibers generated in the rubbing cloth, which is an obstacle in improving production yield.
  • a newly designed liquid crystal alignment method is liquid crystal alignment (hereinafter, referred to as "optical alignment") by light such as UV.
  • Photo-alignment refers to a mechanism that forms photopolymerizable liquid crystal alignment layers in which liquid crystals are oriented by the photosensitive groups bonded to a constant photo-alignment polymer by linearly polarized UV, causing photoreactions. Refers to.
  • photoalignment examples include M. Schadt et al. (Jpn. ⁇ Appl. Phys., Vol 31., 1992, 2155), Dae S. Kang et al. (US Pat. Phys. Vol. 34, 1995, UOOO).
  • the photo-oriented polymers used in these patents and papers are mainly polycinnamate-based polymers such as poly (vinyl cinnamate) (PVCN) or poly (inyl methoxycinnamate (PVMC).
  • PVCN poly (vinyl cinnamate)
  • PVMC poly (inyl methoxycinnamate
  • Japanese Patent Laid-Open No. Hei 11-181127 discloses a polymer having a side chain including photosensitive groups such as cinnamate groups in a main chain such as acrylate and methacrylate, and an alignment film containing the same.
  • Korean Patent Laid-Open Publication No. 2002- 0006819 discloses the use of an alignment film made of a polymethacrylic polymer.
  • the present invention is to provide a photo-alignment polymer that can be easily changed in the alignment direction according to the polarization direction and can be preferably applied to the alignment film of the stereoscopic display device.
  • the present invention also provides an alignment film and a liquid crystal retardation film containing the photoalignable polymer.
  • this invention provides the display element containing the said orientation film or liquid crystal retardation film.
  • the present invention relates to a photoalignable polymer comprising a cyclic olefin repeat unit in which at least one photoreactive functional group is substituted, the first UV polarization having a wavelength of 280 to 315 nm and a first polarization direction of 60 mJ / cm 2 or less.
  • the second UV polarized light having a wavelength of 280 to 315 nm and a second polarization direction changed by 90 ° from the first polarization direction to a total amount of light of 60 mJ / cm 2 or less
  • a photoalignable polymer having an absorbance (AR) of at least 0.02 which is defined by Equation 1 below, is provided:
  • A1 represents the absorbance of the photoalignable polymer measured at the maximum absorption wavelength among the wavelengths of 280 to 330 nm after the first photoalignment
  • A2 is the maximum absorption wavelength among the wavelengths of 280 to 330 nm after the secondary photoalignment. The absorbance of the photoalignable polymer measured is shown.
  • the cyclic olefin repeat unit may include a repeat unit of Formula 3a or 3b: [Formula 3a] [Formula 3b]
  • m is 50 to 5000
  • R1, R2, R3, and R4 is a radical selected from the group consisting of Formulas 1a and 1b, and is a radical of Formula 1a or 1b.
  • R1 to R4 except for the same or different from each other, each of which is hydrogen 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; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silicon, and boron, wherein R1 to R4 are hydrogen; halogen; Or when it is not a polar functional group, one or more combinations selected from the group consisting of R1 and R2, R3 and ⁇ 4 are connected to each other to form an
  • Formula 1 a and 1 t » A is a simple bond, oxygen, sulfur or -NH-
  • B is a simple bond, substituted or unsubstituted C 1-20 alkylene, carbonyl, carboxy, ester, substituted Or unsubstituted arylene having 6 to 40 carbon atoms, and substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms
  • X is oxygen or sulfur
  • R9 is a simple bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted alkenylene 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 aralkylene having 7 to 15 carbon atoms, and substituted or unsubstituted alkynylene having 2 to 20 carbon atoms,
  • the present invention also provides an alignment film and a liquid crystal retardation film containing the photoalignable polymer.
  • this invention provides the display element containing the said oriented film or liquid crystal retardation film.
  • the photoalignable polymer of the present invention a change in the orientation direction according to the polarization direction can be quite freely shown.
  • the photo-alignment polymer may be very preferably applied to a patterned retardation film or a patterned cell alignment film applied for realizing a three-dimensional stereoscopic image.
  • the patterned retardation film or the cell alignment film can be produced very efficiently by only one mask process.
  • the photo-alignment polymer and the alignment film including the same may be very preferably applied to various liquid crystal display devices applied for realizing a stereoscopic image.
  • FIG. 1 schematically shows an example of a conventional alignment layer structure.
  • a photo-alignment polymer comprising a cyclic olefin repeat unit substituted with one or more photo-banung functional groups, the first UV polarization having a wavelength of 280 to 315nm, the first polarization direction)
  • the second UV polarization having a wavelength of 280 to 315 nm and a second polarization direction changed by 90 ° from the first polarization direction is about 60 mJ /
  • A1 represents the absorbance of the photoalignable polymer measured at the maximum absorption wavelength of about 280 to 330 nm, for example, about 300 nm after the first photoalignment, and A2 after the second photoalignment, In a wavelength of about 280-330 nm Absorbance for the photoalignable polymer measured at the maximum absorption wavelength, for example about 300 nm.
  • the photoalignment when the photoalignment is performed by irradiating UV polarization in a predetermined polarization direction with respect to the photoalignment polymer, the double bond included in the photoreactive functional group causes dimerization, and thus the photoalignment polymers are in one direction. Arranged in the form of anisotropy and the optical orientation can proceed.
  • the absorbance after the dimerization and photo-alignment by the UV polarization irradiation, the absorbance is reduced because the structure capable of further photoreaction is reduced. Therefore, the difference between the absorbance after the first photoalignment and the absorbance after the second photoalignment becomes more than a certain level.
  • the photoalignable polymers When the second photoalignment is performed after the first photoalignment, the photoalignable polymers have a dimerization and a second photofold above a certain level. It may reflect that the fragrance is smooth.
  • the absorbance of Equation 1 reaches about 0.02 or more.
  • Such photo-orientable polymers can cause a significant degree of dimerization and secondary photo-alignment by changing the direction of polarization of the photoreactive functional groups, even when the photo-polarization group undergoes secondary photo-alignment. Therefore, in order to provide a patterned retardation film or an alignment film using such a photo-alignment polymer, the mask process does not need to be performed two or more times, and a patterning that shows excellent orientation in each region with a single mask process alone is required. A retardation film, an orientation film, etc. can be manufactured.
  • the first photo-alignment proceeds by irradiating UV polarization in a predetermined direction to the front surface first, only in a certain region through a single mask process
  • the photo-alignment polymer of the above embodiment may be very preferably applied to a patterned retardation film or an alignment film applied for realizing a stereoscopic image.
  • none of the previously known photo-alignment polymers have satisfied the above-mentioned properties.
  • existing photo-alignment polymers are not moved once the alignment direction is determined by polarization. Or, even if it is moving, it was necessary to proceed the secondary photo-alignment with the polarization of the other direction having a very strong light amount. Therefore, in the case of using the existing polymers, in order to obtain a patterned retardation film or the like, it was necessary to irradiate polarizations in one direction different from each other in each region, and at least two mask processes need to be performed for this purpose. there was.
  • optical orientation polymer of one embodiment will be described in more detail.
  • the photo-orientation polymer has an optical absorption rate (AR of at least about 0.02), even though the primary and secondary photo-alignments proceed at a low total light amount of about 60 mJ / cm 2 or less, for example, about 3 to 60 mJ / cm 2 . More specifically, it may be about 0.02 to 0.08.
  • AR optical absorption rate
  • the photo-orientation polymer has an optical absorption rate (AR of at least about 0.02), even though the primary and secondary photo-alignments proceed at a low total light amount of about 60 mJ / cm 2 or less, for example, about 3 to 60 mJ / cm 2 . More specifically, it may be about 0.02 to 0.08.
  • AR optical absorption rate
  • the photo-alignment polymer the light absorption rate when the total light amount in the primary photo-alignment is about 20 to 60 mJ / cm 2 , the total light amount in the secondary photo-alignment is about 3 to 60 mJ / cm 2 (AR) may be about 0.02 to 0.05.
  • the photo-alignment polymer has a light absorption rate when the total light amount of the primary photo-alignment yarn is about 3 to 20 mJ / cm 2 , the total light amount of the secondary photo-alignment is about 3 to 60 mJ / cm 2 ) Is about 0.02 to 0.08, black is about 0.03 to 0.08, and when the total amount of light in the secondary photoalignment is about 15 to 60 mJ / cm 2 , the absorbance (AR) is about 0.04 to 0.08 Can be.
  • the optical alignment polymer exhibits a change in the orientation direction and the secondary photoalignment of a predetermined level or more according to the change in polarization direction even when the total light 1 ⁇ 2 in the primary photoalignment is relatively strong so that no additional light reflection structure remains.
  • the photoalignable polymer has a higher degree of secondary photoalignment and orientation change due to a change in polarization direction when the total amount of light in the primary photoalignment is relatively weak and the total amount of light in the secondary photoalignment is relatively strong. Can be represented.
  • the degree of change in the orientation direction in the first and second optical alignment or the second optical alignment can be controlled. It can be used very efficiently to provide a patterned retardation film or an alignment film exhibiting the desired orientation for each region.
  • the above-described photo-alignment polymer basically exhibits a certain level of absorbance after the first photo-alignment due to the excellent light reflection property and the photo-alignment, and also changes the orientation direction change and the secondary photo-alignment more than a certain level according to the polarization direction change. As shown, the above-described absorbance can be exhibited even after the secondary photoalignment.
  • the photoalignable polymer of one embodiment can be easily provided with a patterned retardation film or an alignment film without two mask processes.
  • the above-described properties of the absorbance (AR), etc. of Formula 1 have not achieved any previously known photo-alignment polymers, it can be achieved by using a photo-alignment polymer obtained from a predetermined cyclic olefin compound .
  • a photo-alignment polymer obtained from a predetermined cyclic olefin compound obtained from a predetermined cyclic olefin compound .
  • q is an integer of 0 to 4
  • at least one of R1, R2, R3, and R4 is a radical selected from the group consisting of Chemical Formulas 1a and 1b and ⁇ R1 except that it is a radical of Chemical Formula 1a or 1b.
  • R4 are the same as or different from each other, and each independently hydrogen; halogen; Substituted or substituted substituted 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 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; And a polar functional group including at least one selected from oxygen, nitrogen, phosphorus, sulfur, silmecon, and boron, wherein R1 to R4 are hydrogen; halogen; Or when it is not a polar functional group, one or more combinations selected from the group consisting of R1 and R2, R3 and R4 are connected to each other to form an alkylidene group
  • A is a simple bond, oxygen, sulfur or -NH-
  • B is a simple bond, substituted or unsubstituted C 1-20 alkylene, carbonyl, carboxy, ester, substituted or Unsubstituted arylene having 6 to 40 carbon atoms, and substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms
  • X is oxygen or sulfur
  • R9 is a simple bond, substituted or unsubstituted C1-20 and alkylene, substituted or unsubstituted C2-20 alkenylene, substituted or unsubstituted C3-C12 cycloalkylene, substituted or unsubstituted Arylene having 6 to 40 carbon atoms, substituted or unsubstituted aralkylene having 7 to 15 carbon atoms, and substituted or unsubstituted alkynylene having 2 to 20 carbon atoms, and at least one of R10 to R14 is- Radicals
  • aryl is to be a "phenyl It may be a radical represented by 2, in addition to a radical having a variety of aryl and linker L:
  • R15 and R16 are as defined in Formula 1, R17 to R21 are the same as or different from each other, and each independently hydrogen; halogen; Substituted or unsubstituted alkyl having 1 to 20 carbon atoms; Substituted or unsubstituted alkoxy having 1 to 20 carbon atoms; Substituted or unsubstituted aryloxy having 6 to 30 carbon atoms; Substituted or unsubstituted aryl having 6 to 40 carbon atoms; It is selected from the group consisting of hetero aryl having 6 to 40 carbon atoms containing a hetero element of Group 14, 15 or 16, and substituted or unsubstituted alkoxy aryl having 6 to 40 carbon atoms.
  • the radical represented by Formula 2 may be unsubstituted or benzyloxy substituted with halogen or alkoxy having 1 to 3 carbon atoms.
  • Such a cyclic leulevine compound has a substituent represented by -L-R15-R16- (substituted or unsubstituted aryl having 6 to 40 carbon atoms) at the terminal of a photoreactive functional group, such as cinnamate structure.
  • a photoreactive functional group such as cinnamate structure.
  • substituents include those aralkyl structures in which alkyl and aryl are sequentially linked via a linker L.
  • a linker L As a bulky chemical structure such as the aralkyl structure is connected to the end of the photoreactive functional group via a linker L, a large free volume can be secured between the photoreactive functional groups. This may be due to steric hindrance of the bulky aralkyl structures.
  • photoreactive functional groups such as cinnamate structure can be relatively freely moved (flowed) or reacted in a free space largely secured. Inhibition of other reaction groups or substituents is minimized. As a result, the photoreactive functional groups are relatively free with the change of polarization direction.
  • a hetero aryl having 6 to 40 carbon atoms, including a group 14, 15 or 16 hetero element may be selected from the group consisting of the functional groups listed below, and in addition, may be various aryls or hetero aryls:
  • the R '10 to R' 18 are the same or different from each other, and the rest are each independently substituted or unsubstituted linear or branched alkyl having 1 to 20 carbon atoms, substituted or unsubstituted C 1 to 20 carbon atoms Alkoxy, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, and substituted or unsubstituted aryl having 6 to 40 carbon atoms.
  • At least one of R1 to R4 of Formula 1 may be a photoreactive functional group of Formula 1a or 1b, for example, at least one of R1 or R2 may be the photoreactive functional group.
  • 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, trichloromethyl, iodomethyl, bromomethyl and the like.
  • 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-nucenenyl, dodecenyl, and the like.
  • Cycloalkyl is a saturated or unsaturated of 3 to 12 ring carbons It means a non-aromatic monovalent monocyclic, bicyclic or tricyclic hydrocarbon moiety, and may be referred to collectively further substituted by a certain substituent described below. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclonuxyl, cyclonuxenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl (i.e., bicyclo [2,2, 1] hept-5-enyl).
  • Aryl means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having from 6 to 40, preferably from 6 to 12 ring atoms, further substituted by the following substituents 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.
  • alkoxy aryl group examples include mepsicyphenyl, ethoxyphenyl, propoxyphenyl, appendoxyphenyl, pentoxyphenyl, hexoxyphenyl, hepoxy, octoxy, nanoxy, methoxybiphenyl, methoxynaphthalenyl, Methoxy fluorenyl, methoxy anthracenyl, and the like.
  • Alkyl means that at least two hydrogen atoms of the alkyl group as defined above are substituted with an aryl group, and may also be referred to as those further substituted by a specific substituent described below. For example, benzyl, benzhydryl, trityl, etc. are mentioned.
  • Alkynyl 1 is a linear or branched monovalent hydrocarbon moiety containing from 2 to 20 carbon atoms, preferably from 2 to 10, more preferably from 2 to 6 carbon atoms containing at least one carbon-carbon triple bond.
  • An alkynyl group may be bonded through a carbon atom including a carbon-carbon triple bond or through a saturated carbon atom, and alkynyl group may be broadly referred to as further substituted by the following substituents. For example, ethynyl, propynyl, etc. are mentioned.
  • Alkylene '' is 1 to 20, preferably 1 to 10, more Preferably a linear or branched saturated divalent hydrocarbon moiety of 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, nuylene, etc. are mentioned.
  • Alkenylene ' 1 is 2 to 1 containing at least one carbon-carbon double bond
  • 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 '' means a saturated or unsaturated non-aromatic divalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons, encompassing those 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
  • the aromatic moiety includes only carbon atoms, and examples of the arylene group include phenylene and the like.
  • Alkylene '' means a divalent moiety in which at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group, and may also be referred to as being further substituted by a specific substituent described below. , Benzylene and the like.
  • Alkynylene '' is from 2 to containing at least one carbon-carbon triple bond
  • Alkynylene groups are grouped via a carbon atom containing a carbon-carbon triple bond or through a saturated carbon atom. Can be combined through. Alkynylene groups can also be referred to collectively further substituted by certain substituents described below. For example, ethynylene, propynylene, etc. are mentioned.
  • substituted or unsubstituted encompasses not only each of these substituents themselves, but also those further substituted by certain substituents.
  • substituents that may be substituted are halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy , Halocarbonyloxy, aryloxy, haloaryloxy, silyl, siloxy, or the aforementioned polar functional group 11 containing oxygen, nitrogen, phosphorus, sulfur, silicon or boron.
  • the above-mentioned cyclic olephine compound may be prepared according to a conventional method for introducing a cyclic olephine, for example, a predetermined substituent, more specifically, a photoreactive functional group of formula (1a) or (1b), to a norbornene-based compound.
  • a norbornene (alkyl) ol such as norbornene methanol
  • a carboxylic acid compound having a photoreactive functional group of Formula 1a or 1b may be used to prepare the cyclic urelepine compound.
  • the above-described cyclic olefin compound may be prepared by introducing the photoreactive functional group in various ways.
  • photo-orientable polymers are cyclic olefinic repeating units, which are the main repeating units, and may include repeating units of the following Chemical Formula 3a or 3b: [Formula 3a] [Formula 3b]
  • Such photo-orientable polymers contain repeating units derived from the above-mentioned cyclic olefin compounds, and because of the bulky aralkyl structure bonded via the linker Lol mediated at the end of the photoreactive functional group, there is a great freedom between the photoreactive functional groups. Space can be secured. For this reason, in the photo-alignment polymer, the photoreactive functional groups can move (flow) or react relatively freely in a free space largely secured. Accordingly, the photo-alignment polymer may exhibit a relatively free change in the orientation direction according to the change in the polarization direction and exhibit excellent secondary photo-alignment, and may satisfy the characteristics of the above-described embodiment.
  • the photoalignable polymer includes a norbornene-based repeating unit of Formula 3a or 3b as a main repeating unit.
  • Such norbornene-based repeating units are structurally hard, and photo-alignment polymers containing the same have a relatively high glass transition temperature (Tg) of about 30 C C or higher, preferably about 300 to 350 ° C. It can exhibit excellent thermal stability compared to the.
  • the photo-alignment polymer is a repeating unit of the formula 3a or 3b although it may include only one or more repeating units selected from the group consisting of, it may be a copolymer further comprising other types of repeating units together.
  • repeating units include, but are not limited to, cinnamate-based chalcone-based or azo-based photoreactive functional groups (e.g., general photoreactive functional groups in which bulky aralkyl structures are not terminally introduced) It may be a fin repeating unit, an acrylate repeating unit or a cyclic ' olefin repeating unit. Examples of such repeating units are disclosed in Patent Publication No. 2010-0021751 and the like.
  • the photo-alignment polymer may be about 50 mol% or more, specifically about 50 to 100 mol%, preferably about 70 mol% so that various properties such as excellent orientation and orientation speed according to Chemical Formula 3a or 3b are not impaired.
  • the above content may include Formula 3a or 3b and a repeating unit.
  • the repeating unit of Formula 3a or 3b constituting the photoalignable polymer may have a polymerization degree of about 50 to 5,000, preferably a polymerization degree of about 100 to 4000, and more preferably about 1000 to 3000.
  • the photo-alignment polymer may have a weight average molecular weight of about 10000 to 1000000, preferably about 20000 to 500000. Accordingly, the photo-alignment polymer may be appropriately included in the coating composition for forming the alignment layer to exhibit excellent coating properties, but the alignment layer formed therefrom may exhibit excellent liquid crystal alignment.
  • the above-described photoalignable polymer may exhibit photoalignment under exposure of polarized light having a wavelength of about 150 to 450 nm, for example, UV Young having a wavelength of about 200 to 400 nm, more specifically, a wavelength of about 280 to 315 nm. Excellent photo-alignment property, orientation speed, etc. can be shown under exposure of the reverse polarization. More specifically, the photo-alignment polymer may absorb UV polarization in the wavelength region of about 270 to 340 nm, more specifically, about 300 nm, and may exhibit the above-described characteristic values with respect to absorbance (AR).
  • polarized light having a wavelength of about 150 to 450 nm, for example, UV Young having a wavelength of about 200 to 400 nm, more specifically, a wavelength of about 280 to 315 nm. Excellent photo-alignment property, orientation speed, etc. can be shown under exposure of the reverse polarization. More specifically, the photo-alignment polymer may absorb UV polarization
  • the above-described photo-alignment polymer is a repeating unit of formula 3a or 3b In the case of inclusion, it may be prepared according to the method described below.
  • one embodiment of the production method is a step of addition polymerization of the monomer of Formula 1 to form a repeating unit of Formula 3a in the presence of a catalyst composition comprising a procatalyst and a cocatalyst comprising a transition metal of Group 10
  • a catalyst composition comprising a procatalyst and a cocatalyst comprising a transition metal of Group 10
  • a catalyst composition comprising a procatalyst and a cocatalyst comprising a transition metal of Group 10
  • Can include:
  • the polymerization reaction may be carried out at a temperature of 10 ° C to 200 ° C. If the reaction temperature is less than 10 ° C. may be lowered the polymerization activity, if the reaction temperature is greater than 200 ° C catalyst is decomposed it is not preferable.
  • the cocatalyst may include a first cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst; And a second co-catalyst for providing a compound comprising a group 15 electron donor ligand may comprise one or more selected from the group consisting of.
  • the cocatalyst may be a catalyst mixture comprising a first cocatalyst that provides the Lewis base, and a second cocatalyst, optionally comprising a neutral Group 15 electron donor ligand.
  • the catalyst mixture may include 1 to 1000 moles of the first cocatalyst and 1 to 1000 moles of the second cocatalyst with respect to 1 mole of the procatalyst.
  • the catalyst activation may not be performed properly, on the contrary, when the content of the first or second cocatalyst is too large, the catalytic activity may be lowered.
  • the first co-catalyst that provides a Lewis base that can be weakly coordinated 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 produced.
  • the weakly coordinated bond with the transition metal compound or a compound providing the same 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 ) alkyl aluminum such as 3 , or transition metal halide such as AgSbF 6 .
  • an alkyl phosphine, a cycloalkyl phosphine, or a phenyl phosphine may be used as a second cocatalyst to provide a compound including the neutral group 15 electron donor ligand.
  • first and second cocatalysts may be used separately, these two cocatalysts may be used as a compound to activate the catalyst by making one salt into one salt.
  • a compound or the like made by ion-bonding alkyl phosphine and borane or borate compound may be used.
  • a repeating unit of Chemical Formula 3a and a photoalignable polymer including the same may be prepared.
  • the photo-alignment polymer further contains an olefin repeat unit, a cyclic olefin repeat unit, an acrylate repeat unit, or the like, these repeat units are formed by a conventional production method of each repeat unit, and the method described above.
  • the photoalignable polymer may be obtained by copolymerization with a repeating unit of Formula 3a.
  • the photo-alignment polymer includes a repeating unit of Formula 3b, it can be prepared according to another embodiment of the manufacturing method.
  • the monomer of Formula 1 in the presence of a catalyst composition comprising a procatalyst and a cocatalyst including a transition metal of Group 4, 6, or 8, the monomer of Formula 1 may be ring-opened to form a repeating unit of Formula 3b. Forming a step.
  • the photo-alignment polymer including the repeating unit represented by Chemical Formula 3b in the presence of a catalyst composition comprising a procatalyst and a cocatalyst comprising a transition metal of Group 4, Group 6, or Group 8, Norbornene (alkyl) ols, such as norbornene methanol, may be prepared by ring-opening polymerization as a monomer to form a ring-opening polymer having a pentagonal ring, and then introducing a photoreactive functional group into the ring-opening polymer.
  • the introduction of the photoreactive functional group may proceed as a reaction to condense the ring-opening polymer with a carboxylic acid compound or an acyl chloride compound having a photoreactive functional group corresponding to Formula 1a or 1b.
  • ring-opening polymerization step when hydrogen is added to the divalent bond in the norbornene ring included in the monomer of Chemical Formula 1, ring-opening may proceed, and the polymerization proceeds, so that the repeating unit of Chemical Formula 3b and the photo-oriented polymer including the same Can be prepared.
  • the polymerization and ring opening may be sequentially performed to produce the photoalignable polymer.
  • the ring-opening polymerization is a procatalyst comprising a transition metal of Group 4 (e.g., ⁇ , Zr, Hf), Group 6 (e.g. Mo, W), or Group 8 (e.g. Ru, Os), the metal of the procatalyst
  • a transition metal of Group 4 e.g., ⁇ , Zr, Hf
  • Group 6 e.g. Mo, W
  • Group 8 e.g. Ru, Os
  • linear alkene such as 1-alkene and 2-alkene, which can adjust the molecular weight size
  • linear alkene such as 1-alkene and 2-alkene, which can adjust the molecular weight size
  • Group 4 for example, Ti, Zr
  • Group 8 to Group 10
  • a catalyst containing a transition metal addition of the monomer prepared from 1 to 30 parts by weight 0/0 for example, Ru, Ni, Pd
  • the reaction of hydrogenating the double bond in the norbornene ring can proceed at a temperature.
  • 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, it is not preferable.
  • 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).
  • Activation comprising 1 to 100,000 moles of cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, and elements of neutral Group 15 and 16 which can optionally enhance the activity of the procatalyst metal
  • the activator comprises 1 to 100 moles per mole of procatalyst.
  • the content of the promoter is less than 1 mole there is a problem that the catalyst activation is not made, if larger than 100,000 moles there is a problem that the catalyst activity is lowered is not preferred.
  • the activator may not be necessary depending on the type of procatalyst. If the content of the activator is less than 1 mole there is a problem that the catalyst activation is not made, and if it is larger than 100 moles there is a problem that the molecular weight is lowered is not preferred.
  • Group 4 eg Ti, Zr
  • Group 8 to be used for the hydrogenation reaction
  • Group 10 for example, Ru, Ni, Pd
  • the content of the catalyst is smaller than the monomer prepared 1 weight 0 /. Containing a transition metal and is a problem in that the hydrogenation does not easily made large when poly than 30 weight 0/0 It is not preferable because there is a problem of discoloration of the mer.
  • 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) may be added to the cocatalyst for providing Lewis acid.
  • a transition metal of Group 4 e.g. Ti, Zr, Hf
  • Group 6 e.g. Mo, W
  • Group 8 e.g. Ru, OS
  • M0CI5 0CI5
  • RuCI 3 or ZrCI 4 which have a functional group that readily participates in the Lewis acid-base reaction and is separated from the central metal so that it can be easily separated and converted into a catalytically active species.
  • Transition metal It may refer to a compound.
  • the co-catalyst which provides a Lewis base that can weakly coordinate with the metal of the procatalyst may be borane or borate such as B (C 6 F 5 ) 3 , methylaluminoxane (MAO) or AI (C 2 H 5).
  • Alkyl aluminum, alkyl aluminum halide, and aluminum halide such as AI 3 (CH 3 ) CI 2 can be used.
  • substituents such as lithium, magnesium, germanium, lead, zinc, tin, and silicon may be used.
  • 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 Group 16 elements that can enhance the activity of the procatalyst metal is water, methanol, ethanol, isopropyl alcohol, benzyl alcohol, pemol, ethyl mercaptan ): 2-chloroethanol, trimethylamine, triethylamine, pyridine, ethylene oxide, benzoyl peroxide, t-butyl peroxide and the like.
  • Catalysts containing transition metals of Group 4 (eg Ti, Zr) black or Group 8 to 10 (eg Ru, Ni, Pd) used in hydrogenation reactions are homogeneous forms that can be immediately mixed with the solvent. Or a metal catalyst complex supported on the particulate support.
  • the particulate support is silica, titania, silica / chromia, silica / chromia / titania, silica / alumina, aluminum phosphate gel silanized silica, silica hydrogel montmorillonone clay or zeolite.
  • a repeating unit of Chemical Formula 3b and a photoalignable polymer including the same may be prepared. Moreover, even when the said photo-alignment polymer further contains an olefin type repeating unit, a cyclic olefin type repeating unit, or an acrylate type repeating unit, these repeating units are prepared by the conventional manufacturing method of each repeating unit.
  • the photo-alignment polymer may be obtained by forming and copolymerizing with the repeating unit of Formula 3b prepared by the above-described method.
  • an alignment film comprising the above-described photo-alignment polymer.
  • Such an alignment film may also include an alignment film in the form of a film as well as a thin film.
  • a liquid crystal retardation film comprising such an alignment film and a liquid crystal layer on the alignment film.
  • Such an alignment film and a liquid crystal retardation film may be manufactured using constituents and production methods known in the art, except for including the above-described photoalignable polymer.
  • the alignment layer may be formed by mixing the photo-alignment polymer, the binder resin and the photoinitiator and dissolving it in an organic solvent to obtain a coating composition, then coating the coating composition on a substrate and performing UV curing.
  • the binder resin may be an acrylate-based resin, more specifically, pentaerythritol triacrylate, dipentaerythroxy nuxaacrylate, trimethylolpropane triacrylate, tris (2-acryl Monooxyethyl) isocyanurate or the like can be used.
  • a conventional photoinitiator known to be usable for the alignment layer may be used without particular limitation, and for example, a photoinitiator known under the trade name 13 ⁇ 43) " 690 thereof 819 may be used.
  • organic solvent toluene, anisole, chlorobenzene, dichloroethane, cyclonucleic acid, cyclopentane, propylene glycol methyl ether acetate, and the like can be used. Since the photo-orientation polymer described above exhibits excellent solubility in various organic solvents, various organic solvents may be used without particular limitation.
  • the optical orientation of the polymer, the solid concentration, which comprises a binder resin and a photo-initiator may be about 1 to 15% by weight, about 10 to 15 parts by weight 0/0 in order to cast the film, the alignment film to form Preferably, in order to form a thin film, about 1 to 5 weight 0 /. Is preferable.
  • the alignment layer thus formed may be formed on the substrate, for example, as illustrated in FIG. 1, and may be formed under the liquid crystal to align the same.
  • the substrate may include a substrate including a cyclic polymer, a substrate including an acrylic polymer, or a substrate including a cellulose polymer, and various methods such as bar coating, spin coating, and blade coating of the coating composition. After coating on the substrate to form an alignment film by UV curing.
  • Photo-alignment may occur due to the UV curing.
  • alignment may be performed by irradiating polarized UV in a wavelength range of about 150 to 450 nm.
  • the intensity of the exposure may be about 50 mJ / cin 2 to 10 J / cuf of energy, preferably about 500 mJ / cu to 5J / crf.
  • 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 polarizer plate finely deposited aluminum or metal wire, or 3 quartz Polarized UV selected from polarized UV may be applied by passing or reflecting the Brewster polarizer round due to the reflection of the glass.
  • a transparent substrate such as quartz glass, soda lime glass, soda lime free glass, 2 a polarizer plate finely deposited aluminum or metal wire, or 3 quartz Polarized UV selected from polarized UV may be applied by passing or reflecting the Brewster polarizer round due to the reflection of the glass.
  • the substrate temperature at the time of irradiating the said UV normal temperature is preferable. However, in some cases, it may be irradiated with UV in a heated state within a temperature range of 100 ° C or less.
  • the film thickness of the final coating film formed by the above series of processes is preferably 30 to 1000 rai.
  • An alignment film is formed by the method mentioned above, a liquid crystal layer is formed on it, and a liquid crystal phase difference film can be manufactured in accordance with a conventional method.
  • a liquid crystal retardation film may be a patterned liquid crystal retardation film applied for realizing a stereoscopic image or the like.
  • the alignment layer includes two types of alignment layers having different alignment directions of the photo-alignment polymers, and the liquid crystal layer is divided into two regions oriented by each alignment layer and patterned. Can be.
  • the photoalignable polymer of one embodiment using the photoalignable polymer of one embodiment,
  • the patterned liquid crystal retardation film can be produced very easily and efficiently through the front exposure of UV polarization and the secondary exposure of UV polarization applying a single mask process.
  • such a patterned liquid crystal retardation film may exhibit excellent orientation and the like for each region, and may greatly contribute to the implementation of a good stereoscopic image.
  • the above-described alignment film or liquid crystal retardation film may be applied to an optical film or an optical filter for realizing a stereoscopic image.
  • a display device including the alignment layer or the liquid crystal retardation film is provided.
  • the display device may be a liquid crystal display device in which the alignment film is included for alignment of liquid crystals, or a stereoscopic image display device included in an optical film or a filter such as a liquid crystal retardation film for realizing a stereoscopic image.
  • the configuration of these display elements is in accordance with the configuration of the conventional elements, except that the above-described photo-alignment polymer, the alignment film and the like, and the like, detailed description thereof will be omitted.
  • preferred embodiments are presented to help understand the invention. However, the following examples are only to illustrate the invention, not limited to the invention only.
  • Example 1 Except for using norbornene-5-methanol instead of norbornene-5-ol in Example 1, the reaction was carried out in the same manner and conditions to prepare 4-benzyloxy-cinnamate-5-methyl norbornene.
  • Example 3 Preparation of 4-benzyloxy-cinnamate-5-ethyl norbornene (Preparation of Cyclic Olefin Compound)
  • Example 7 except that norbornene-5-ethanol was used instead of ⁇ 1 ", the reaction was carried out in the same manner and under the same procedure. 4- (4-methyl-bennzyloxy) -cinnamate-5-ethyl norbomene was prepared.
  • Example 1 In Example 1, except that 4- (4-methoxy-benzyloxy) -benzaldehyde was used instead of 4-Benzyloxy-benzaldehyde, the reaction was carried out in the same manner and conditions. 4- (4-methoxy-benzyloxy) -cinnamate -5-norbornene was prepared. NMR (CDCI 3 (500 MHz), ppm): 0.6 (1, m) 1.20 to 1.27 (2, m)
  • Example 20 Preparation of 4- (1-phenyl perfluoroheptyloxy) -cinnamate-5-methyl norbornene (prepared with a cyclic olefin compound) Except for using norbornene-5-methanol instead of norbornene-5-ol in Example 19, 4- (1-phenyl perfluoroheptyloxy) -cinnamate-5-methyl norbornene was prepared in the same manner and reaction. .
  • Example 19 except that norbornene-5-ethanol-i- was used instead of norbornene-5-ol, the reaction was carried out according to the same method and conditions as for 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-ethyl norbornene. Prepared.
  • Example ⁇ The reaction was carried out in the same manner and conditions except that 4- (4-benzyloxy) -benzyloxy-benzaldehyde was used instead of 4-Benzyloxy-benzaldehyde in Example 1, and 4- (4-benzyloxy) -benzyloxy-cinnamate -5- norbornene was prepared.
  • Example 22 In Example 22, norbornene-5-methanol instead of norbornene-5-ol Except for those used, the reaction was carried out in the same manner and conditions to prepare 4- (4-benzyloxy) -benzyloxy-cinnamate-5-methyl norbornene.
  • Example 24 Preparation of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-ethyl norbornene (Preparation of Cyclic Olefin Compound)
  • Example 22 except for using norbornene-5-ethanol ⁇ r instead of norbornene-5-ol, the reaction was carried out according to the same method and conditions to obtain 4- (4-benzyloxy) -benzyloxy-cinnamate-5-ethyl norbornene. Prepared.
  • Example 25 norbornene-5-methanol instead of norbornene-5-ol Except for the use, reaction was carried out in the same manner and conditions to prepare 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-methyl norbornene.
  • Example 28 the reaction was carried out by the same method and conditions except for the use of norbornene-5-methanol instead of norbornene-5-ol, to obtain 4- (4- Trifluoromethyl) -benzyloxy-cinnamate-5-methyl norbornene was prepared.
  • Example 30 Preparation of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene (prepared with a cyclic olefin compound)
  • Example 28 except that norbornene-5-ol was used instead of norbornene-5-ethan, the reaction was carried out by the same method and conditions to prepare 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene. All.
  • reaction product was added to an excess of ethanol to obtain a white polymer precipitate.
  • Example 36 4-benzyloxy-cinnamate-5-ethyl norbornene ⁇ l thickening
  • Example 37 4- (4-fluoro-benzyloxy) -cinnamate-5-norbornene ⁇ Polymerization 4-benzyloxy-cinnamate-5-norbornene of Example 1 .
  • Example 38 Polymerization of 4- (4-fluoro-benzyloxy) -cinnamate-5-methyl norbornene
  • Example 39 Polymerization of 4- (4-fluoro-benzyloxy) -cinnamate-5-ethyl norbornene
  • Example 4 except that 4- (4-fluoro-benzyloxy) -cinnamate-5-ethyl norbornene (50mmol) of Example 6 was used instead of 4-benzyloxy-cinnamate-5-norbornene of Example I 1.
  • Example 41 Polymerization of 4- (4-methyl-benzyloxy) -cinnamate-5-methyl norbomene
  • Example 42 Incorporation of 4- (4-methyl-benzyloxy) -cinnamate-5-ethyl norbomene
  • Example 1 except that 4- (4-methyl-benzyloxy) -cinnamate-5-ethyl norbomene (50mmol) of Example 9 was used instead of 4-benzyloxy-cinnamate-5-norbornene as a monomer.
  • Example 44 4- (4-methoxy-benzyloxy) -cinnamate-5-methyl norbomene polymerization
  • Example 45 Polymerization of 4- (4-methoxy-benzyloxy) -cinnamate-5-ethyl norbornene
  • Example 34 except that 4- (4-methoxy-benzyloxy) -cinnamate-5-ethyl norbornene ⁇ (50 mmol) of Example 12 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1
  • Example 46 4- (2-naphthalene-methyloxy) -cinnamate-5-norbornene ⁇ polymerization
  • Example 47 Integration of 4- (2-naphthalene-methyloxy) -cinnamate-5-methyl norbornene
  • Example 48 4- (2-naphthalene-methyloxy) -cinnamate-5-ethyl norbornene ⁇ 9uaujoqjou-g-9iBUJBUU! 0- (Axo
  • Example 52 4-benzyloxy-cinnamate-5-norbornene of Example 1.
  • Example 53 Polymerization of 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-methyl norbornene
  • Example 54 Polymerization of 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-ethyl norbornene
  • Example 55 Polymerization of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-norbornene
  • Example 56 4- (4-benzyloxy) -benzyloxy-cinnamate-5-methyl norbornene // u O sssooS O SMld 8988sAV
  • Example 34 except that 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 27 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1
  • Example 61 Polymerization of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-norbornene
  • Example 62 Polymerization of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-methyl norbornene
  • Example 63 Incorporation of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene
  • Example 63 Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1 , except that 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 30 was used as the monomer, and was the same as that of Example 34.
  • Example 65 Polymerization of 4- (4-bromo-benzyloxy) -cinnamate-5-methyl norbomene
  • Example 34 and 34 except that 4- (4-bromo-benzyloxy) -cinnamate-5-methyl norbomene (50 mmol) of Example 32 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1 1.
  • Example 66 Polymerization of 4- (4-bromo-benzyloxy) -cinnamate-5-ethyl norbomene
  • Example 67 Preparation of Polymers by 4-benzyloxy-cinnamate-5-norbornene ⁇ l ring opening methathesis polymerization and hydrogenation reaction
  • Example 69 Preparation of polymers by ring-opening polymerization of 4-benzyloxy-cinnamate-5-ethyl norbornene and hydrogenation reaction
  • Example 70 Polymerization by 4- (4-fluoro-benzyloxy) -cinnamate-5-norbornene and Polymer Preparation by Hydrogenation Same as Example 67 except for using the 4- (4-fluoro-benzyloxy) -cinnamate-5-norbornene (50mmol) 3 ⁇ 4- monomer of Example 4 instead of the 4-benzyloxy-cinnamate-5-norbornene of Example 1
  • Example 71 Polymerization by Ring Opening Polymerization of 4- (4-fluoro-benzyloxy) -cinnamate-5-methyl norbornene and Hydrogenation
  • Example 72 Preparation of Polymer by Ring Opening Polymerization Hydrogenation of 4- (4-fluoro-benzyloxy) -cinnamate-5-ethyl norbornene
  • Example 73 Preparation of Polymers by 4- (4-methyl-benzyloxy) -cinnamate-5-norbornene ⁇ l Ring Opening Polymerization and Hydrogenation
  • Example 67 and except that 4- (4-methyl-benzy! Oxy) -cinnamate-5-norbornene (50 mmol) of Example 7 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1
  • Example 75 Polymerization by Ring Opening Polymerization of 4- (4-methyl-benzyloxy) -cinnamate-5-ethyl norbornene and Hydrogenation
  • Example 76 Preparation of Polymers by 4- (4-methoxy-benzyloxy) -cinnamate-5-norbornene ⁇ 'Ring Opening Polymerization and Hydrogenation
  • Example 77 Preparation of polymer by ring-opening polymerization of 4- (4-m ethoxy-benzyloxy) -ci n mate-5-methyl norbornene and hydrogenation reaction
  • Example 77 Same as Example 67 except that 4- (4-methoxy-benzyloxy) -cinnamate-5-methyl norbornene (50mmol) of Example 11 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1
  • Example 79 Polymer preparation by 4- (2-naphthalene-methyloxy) -cinnamate-5-norbornene ⁇ ring-opening polymerization and hydrogenation reaction
  • Example 80 Polymerization by Ring Opening Polymerization of 4- (2-naphthalene-methyloxy) -cinnamate-5-methyl norbornene and Hydrogenation
  • Example 81 Polymerization by Ring Opening Polymerization and Hydrogenation of 4- (2-naphthalene-methyloxy) -cinnamate-5-ethyl norbornene
  • Example 81 Same as Example 67, except that 4- (2-naphthalene-methyloxy) -cinnamate-5-ethyl norbornene (50 mmol) of Example 15 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1
  • Example 82 Preparation of Polymers by Ring Opening Polymerization and Hydrogenation of 4- (4-methylketone benzyloxy) -cinnamate-5-norbornene
  • Example 83 Polymer Preparation by Ring Opening Polymerization and Hydrogenation of 4- (4-methylketone benzyloxy) -cinnamate-5-methyl norbornene
  • Example 84 Polymer Preparation by 4- (4-methylketone benzyloxy) -cinnamate-5-ethyl norbornene ring-opening polymerization and hydrogenation reaction
  • Example 85 Polymerization by Ring Opening and Hydrogenation of 4- (1 -phenyl perfluoroheptyloxy) -cinnamate-5-norbornene
  • Example 87 Preparation of polymers by ring-opening polymerization of 4- (1-phenyl perfluoroheptyloxy) -cinnamate-5-ethyl norbornene and hydrogenation reaction
  • Example 87 Preparation of polymer by ring-opening synthesis of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-norbornene and hydrogenation reaction
  • Example 89 Preparation of Polymer by Ring Opening and Hydrogenation of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-methyl norbornene
  • Example 89 Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (4-benzyloxy) -benzyloxy-cinnamate-5-methyl norbornene (50 mmol) of Example 23 was used as the monomer, and was the same as that of Example 67.
  • Example 90 Ring-opening polymerization of 4- (4-benzyloxy) -benzyloxy-cinnamate-5-ethyl norbornene and polymer preparation by hydrogenation reaction Except for 4-benzyloxy-cinnamate-5-norbornene of Example 1, except that 4- (4-benzyloxy) -benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 24 was used as the monomer, and was the same as that of Example 67.
  • Example 91 Preparation of Polymer by Ring Opening Polymerization and Hydrogenation of 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-norbornene
  • Example 67 except that 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-norbornene (50 mmol) of I 25 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1
  • Example 92 Preparation of Polymers by Ring Opening Polymerization and Hydrogenation of 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-methyl norbornene
  • Example 1 except that 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-methyl norbornene (50 mmol) of Example 26 was used instead of 4-benzyloxy-cinnamate-5-norbomene of Example 1 1.
  • Example 93 Polymerization by Ring Opening Polymerization of 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-ethyl norbornene and Hydrogenation
  • Example 67 except that 4- (4-fluoro-phenyloxy) -benzyloxy-cinnamate-5-ethyl norbornene (50 mmol) of Example 27 was used as the monomer instead of 4-benzyloxy-cinnamate-5-norbornene of Example 1
  • Example 94 Polymerization by Ring Opening Polymerization of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-norbornene and Hydrogenation
  • Example 67 Polymerization by Ring Opening Polymerization of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-norbornene and Hydrogenation
  • Example 95 Polymerization by Ring Opening Polymerization and Hydrogenation of 4- (4-trifluoromethyl) -benzyloxy-cinnamate-5-ethyl norbornene
  • Example 97 Polymerization by Ring Opening Polymerization of 4- (4-bromo-benzyloxy) -cinnamate-5-norbomene and Hydrogenation
  • Example .99 Preparation of Polymer by Ring Opening Polymerization and Hydrogenation of 4- (4-bromo-benzyloxy) -cinnamate-5-ethyl norbornene
  • the toluene solution in which the photo-oriented polymers (2 to 3 wt% of the solution) of Examples 35 and 44 were dissolved on the glass substrate was dropped, and spin coating was performed. After drying for 2 minutes at 10C C, the wavelength of 280 to 315nm and UV polarization having a predetermined polarization direction was irradiated to proceed with the first photoalignment, and the alignment layer was rotated by 90 ° to turn the polarization direction. UV polarization was performed under the same conditions as the primary photoalignment to proceed the secondary photoalignment. The total light amount during the primary and secondary photo-alignment was adjusted through the irradiation time, the total light amount was as summarized in Table 1 below.
  • absorbance was measured through UV absorbance after the first and second photo alignment.
  • the reference wavelength was used 300nm, and the absorbance was measured using a UV-vis spectrometer. From these absorbance measurement results, the absorbances A1 and A2 after primary and secondary photoalignment were derived, and absorbance (AR) was obtained from Equation 1 below and is shown in Table 1 below.
  • A1 represents the absorbance of the photoalignable polymer measured after the first photoalignment at the maximum absorption wavelength (about 300 nm in this test example) of about 280 to 330 nm
  • the area ratio of the unoriented part (visual discrimination) to the area of the entire alignment layer is calculated, and accordingly, the orientation is evaluated on a five-point basis, and the results are shown in Table 1 below. .
  • ENTRY 1 to 33 that satisfies the absorbance (AR) of about 0.02 or more, as an experimental result using the photoalignable polymer of the embodiment, it was confirmed that exhibits excellent orientation after the primary and secondary orientation, In particular, it was confirmed that even after the secondary alignment, the change in the orientation direction according to the polarization direction was free, thereby showing excellent orientation.

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Abstract

La présente invention concerne un polymère de photoalignement dans lequel une direction d'alignement selon une direction de polarisation peut être changée facilement, et lequel polymère de photoalignement peut être appliqué de façon souhaitable à une couche d'alignement ou similaire d'un dispositif d'affichage stéréoscopique. La présente invention concerne également une couche d'alignement et un film de retard à cristaux liquides comprenant le polymère de photoalignement. Le polymère de photoalignement comprend une unité de répétition à base d'oléfine cyclique substituée par un ou plusieurs groupes fonctionnels photoréactifs. Le polymère de photoalignement a un taux d'absorption (AR) de 0,02 ou plus défini par une formule spécifique lorsque un photoalignement primaire est effectué par irradiation d'une première lumière UV polarisée ayant une longueur d'onde de 280 à 315 nm et une première direction de polarisation dans la quantité totale de lumière de 60 mJ/cm2 ou moins, et un second photoalignement est réalisé par irradiation d'une seconde lumière UV polarisée ayant une longueur d'onde de 280 à 315 nm et une seconde direction de polarisation qui est changée de 90° à partir de la première direction de polarisation dans la quantité totale de lumière de 60 mJ/cm2 ou moins.
PCT/KR2013/008025 2012-09-07 2013-09-05 Polymère de photoalignement, et couche d'alignement et film de retard à cristaux liquides le comprenant WO2014038868A1 (fr)

Priority Applications (3)

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JP2015531007A JP2015533883A (ja) 2012-09-07 2013-09-05 光配向性重合体、これを含む配向膜および液晶位相差フィルム
CN201380046833.5A CN104619733A (zh) 2012-09-07 2013-09-05 光取向聚合物、取向层及包含其的液晶延迟膜
US14/419,634 US20150210792A1 (en) 2012-09-07 2013-09-05 Photo-alignment polymer, alignment layer and liquid crystal retardation film comprising the same

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KR20120099570 2012-09-07
KR10-2012-0099570 2012-09-07
KR1020130106598A KR20140032904A (ko) 2012-09-07 2013-09-05 광배향성 중합체, 이를 포함하는 배향막 및 액정 위상차 필름
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990030881A (ko) * 1997-10-07 1999-05-06 윤종용 광시야각 액정 표시 장치
KR19990045029A (ko) * 1997-11-05 1999-06-25 가나이 쓰도무 액정표시장치와 편광조사방법 및 그 장치
KR20030095403A (ko) * 2001-05-10 2003-12-18 니폰 가야꾸 가부시끼가이샤 액정성 화합물 및 이를 사용한 위상차 필름
KR20100083103A (ko) * 2009-01-12 2010-07-21 주식회사 엘지화학 할로겐계 치환기를 갖는 광반응성 작용기를 포함하는 노보넨계 중합체, 이의 제조방법 및 이를 이용한 배향막
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
KR19990030881A (ko) * 1997-10-07 1999-05-06 윤종용 광시야각 액정 표시 장치
KR19990045029A (ko) * 1997-11-05 1999-06-25 가나이 쓰도무 액정표시장치와 편광조사방법 및 그 장치
KR20030095403A (ko) * 2001-05-10 2003-12-18 니폰 가야꾸 가부시끼가이샤 액정성 화합물 및 이를 사용한 위상차 필름
KR20100083103A (ko) * 2009-01-12 2010-07-21 주식회사 엘지화학 할로겐계 치환기를 갖는 광반응성 작용기를 포함하는 노보넨계 중합체, 이의 제조방법 및 이를 이용한 배향막
KR20120069652A (ko) * 2010-09-27 2012-06-28 주식회사 엘지화학 고리형 올레핀 화합물, 광반응성 중합체 및 이를 포함하는 배향막

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