WO2018198425A1 - Film de cristaux liquides à alignement homéotrope et procédé de fabrication d'un tel film de cristaux liquides à alignement homéotrope - Google Patents

Film de cristaux liquides à alignement homéotrope et procédé de fabrication d'un tel film de cristaux liquides à alignement homéotrope Download PDF

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WO2018198425A1
WO2018198425A1 PCT/JP2017/045457 JP2017045457W WO2018198425A1 WO 2018198425 A1 WO2018198425 A1 WO 2018198425A1 JP 2017045457 W JP2017045457 W JP 2017045457W WO 2018198425 A1 WO2018198425 A1 WO 2018198425A1
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liquid crystal
film
alignment
side chain
group
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PCT/JP2017/045457
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English (en)
Japanese (ja)
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暢 鈴木
敏行 飯田
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日東電工株式会社
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Priority to SG11201900923WA priority Critical patent/SG11201900923WA/en
Priority to CN201780042687.7A priority patent/CN109416429B/zh
Priority to KR1020187032203A priority patent/KR101975402B1/ko
Publication of WO2018198425A1 publication Critical patent/WO2018198425A1/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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/305—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a homeotropic alignment liquid crystal film and a method for producing the same.
  • a liquid crystal film in which a liquid crystal compound is aligned in a predetermined direction is used as an optical film having functions such as optical compensation of a liquid crystal display device and prevention of external light reflection of an organic EL element.
  • the alignment film of a liquid crystal compound has an advantage in reduction in thickness and weight because it has a larger birefringence than a stretched polymer film.
  • a homeotropic alignment liquid crystal film in which liquid crystal molecules having positive refractive index anisotropy are aligned in the normal direction (thickness direction) of the substrate surface has a refractive index (abnormal light refraction) in the thickness direction that is the alignment direction of the liquid crystal molecules.
  • a homeotropic alignment liquid crystal film is produced by applying a liquid crystal compound on a substrate having a vertical alignment film.
  • Patent Document 1 discloses that a composition containing a predetermined side chain type liquid crystal polymer and a photopolymerizable liquid crystal monomer is homeotropically aligned on a substrate having no vertical alignment film. Specifically, a liquid crystalline composition is applied onto a substrate, heated and cooled so that the liquid crystal polymer is in a liquid crystal state to fix the alignment, and the liquid crystal monomer is polymerized or cross-linked by light irradiation. An aligned liquid crystal film is obtained.
  • Patent Document 1 a method for producing a homeotropic alignment liquid crystal film by applying a liquid crystalline composition on a film having a small optical anisotropy such as a norbornene-based film, or a plastic film or a metal film having an optical anisotropy. The method of transferring the aligned liquid crystal film formed on the above onto a plastic film having a small optical anisotropy is described.
  • a liquid crystalline composition is applied on a norbornene-based polymer film or a glass substrate, heated at 130 ° C. to align the liquid crystal, and then irradiated with ultraviolet rays to be homeotropically aligned liquid crystal film. The example which produced was described.
  • an object of the present invention is to provide a homeotropic alignment liquid crystal film with few alignment defects.
  • the present invention relates to a homeotropic alignment liquid crystal film in which a polymer of a side chain type liquid crystal polymer and a photopolymerizable liquid crystal compound is homeotropically aligned, and a method for producing the same.
  • a liquid crystal composition containing a side chain type liquid crystal polymer and a photopolymerizable liquid crystal monomer is applied onto the first main surface of the film substrate not provided with the vertical alignment film (application process), and the liquid crystal polymer and the liquid crystal monomer are applied.
  • a homeotropic alignment liquid crystal film is formed on a film substrate by homeotropic alignment in a liquid crystal state (liquid crystal alignment step) and polymerizing or crosslinking a liquid crystal monomer by light irradiation (photo polymerization step).
  • the side chain type liquid crystal polymer preferably has a monomer unit containing a liquid crystalline fragment side chain and a monomer unit containing a non-liquid crystalline fragment side chain.
  • the content of the photopolymerizable liquid crystal monomer in the liquid crystal composition is preferably 1.1 to 10 times the content of the side chain type liquid crystal polymer.
  • the heating temperature T (° C.) at the time of liquid crystal alignment and the in-plane birefringence ⁇ n of the film substrate satisfy T ⁇ 100 ⁇ 3.5 ⁇ 10 3 ⁇ n.
  • Alignment defects tend to be reduced by using a film substrate having a smooth first main surface (surface on which the liquid crystalline composition is applied).
  • the arithmetic average roughness of the first main surface of the film substrate is preferably 3 nm or less.
  • a stretched film is preferably used as a film substrate having a small arithmetic average roughness and excellent smoothness.
  • the in-plane retardation of the stretched film is, for example, 10 to 500 nm.
  • the film substrate may have a slip layer on the second main surface. It is preferable that an easy slip layer is not provided on the first main surface of the film substrate.
  • a norbornene polymer film is used as the film substrate.
  • the homeotropic alignment liquid crystal film preferably has an arithmetic average roughness of at least one surface of 3 nm or less.
  • the number of alignment defects per 1 cm 2 is preferably 1 or less.
  • a homeotropic alignment liquid crystal film with few fine alignment defects and excellent in-plane uniformity can be obtained.
  • the liquid crystal alignment film is produced by applying a liquid crystalline composition on a substrate and fixing the alignment.
  • the liquid crystalline composition used for producing the homeotropic alignment liquid crystal film includes a side chain type liquid crystal polymer and a photopolymerizable liquid crystal monomer.
  • ⁇ Side-chain liquid crystal polymer As the side chain type liquid crystal polymer, a copolymer having a monomer unit containing a liquid crystalline fragment side chain and a monomer unit containing a non-liquid crystalline fragment side chain is used.
  • the polymer When the polymer has a liquid crystal fragment in the side chain, the polymer is homeotropically aligned when the liquid crystal composition is heated to a predetermined temperature.
  • an alignment force that homeotropically aligns the photopolymerizable liquid crystal monomer contained in the liquid crystalline composition together with the polymer acts.
  • a homeotropic alignment liquid crystal film can be obtained by aligning the liquid crystal monomer accompanying the alignment of the side-chain liquid crystal polymer and fixing the alignment state.
  • Examples of the monomer having a liquid crystalline fragment side chain include a polymerizable compound having a nematic liquid crystalline substituent containing a mesogenic group.
  • Mesogenic groups include biphenyl, phenylbenzoate, phenylcyclohexane, azoxybenzene, azomethine, azobenzene, phenylpyrimidine, diphenylacetylene, diphenylbenzoate, bicyclohexane, cyclohexylbenzene, and terphenyl groups. And the like.
  • the terminal of these cyclic units may have a substituent such as a cyano group, an alkyl group, an alkoxy group, or a halogen group.
  • the mesogenic group those having a biphenyl group or a phenylbenzoate group are preferable.
  • Examples of the monomer having a non-liquid crystalline fragment side chain include a polymerizable compound having a linear substituent such as a long-chain alkyl having 7 or more carbon atoms.
  • Examples of the polymerizable functional group of the liquid crystalline monomer and the non-liquid crystalline monomer include a (meth) acryloyl group.
  • a copolymer having a liquid crystal monomer unit represented by the general formula (I) and a non-liquid crystal monomer unit represented by the general formula (II) is preferably used.
  • R 3 is a hydrogen atom or a methyl group
  • R 4 is an alkyl group having 7 to 22 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, or the following general formula (III) It is a group.
  • R 5 is an alkyl group having 1 to 5 carbon atoms
  • d is an integer of 1 to 6.
  • the ratio of the liquid crystal monomer unit to the non-liquid crystal monomer unit in the side chain type liquid crystal polymer is not particularly limited, but when the ratio of the non-liquid crystal monomer unit is small, the photopolymerizable liquid crystal compound accompanying the alignment of the side chain type liquid crystal polymer The alignment of the liquid crystal layer becomes insufficient, and the alignment of the liquid crystal layer after photocuring may become non-uniform. On the other hand, when the proportion of the liquid crystalline monomer unit is small, the side chain type liquid crystal polymer is difficult to exhibit liquid crystal monodomain alignment.
  • the molar ratio of the non-liquid crystalline monomer to the total of the liquid crystalline monomer unit and the non-liquid crystalline monomer unit is preferably 0.01 to 0.8, more preferably 0.1 to 0.6, 0.15 Is more preferably 0.5.
  • the weight average molecular weight of the side chain type liquid crystal polymer is preferably about 2000 to 100,000, and more preferably about 2500 to 50,000.
  • the side chain type liquid crystal polymer can be polymerized by various known methods. For example, when the monomer unit has a (meth) acryloyl group as a polymerizable functional group, a side chain liquid crystal polymer having a liquid crystalline fragment and a non-liquid crystalline fragment is obtained by radical polymerization using light or heat.
  • the photopolymerizable liquid crystal compound (monomer) has a mesogenic group and at least one photopolymerizable functional group in one molecule.
  • the mesogenic group include those described above as the liquid crystalline fragments of the side chain type liquid crystal polymer.
  • the photopolymerizable functional group include a (meth) acryloyl group, an epoxy group, and a vinyl ether group. Of these, a (meth) acryloyl group is preferable.
  • the photopolymerizable liquid crystal monomer preferably has two or more photopolymerizable functional groups in one molecule.
  • a liquid crystal monomer containing two or more photopolymerizable functional groups By using a liquid crystal monomer containing two or more photopolymerizable functional groups, a crosslinked structure is introduced into the liquid crystal layer after photopolymerization, so that the durability of the homeotropic alignment liquid crystal film tends to be improved.
  • Examples of the photopolymerizable liquid crystal monomer having a mesogenic group and a plurality of (meth) acryloyl groups in one molecule include compounds represented by the following general formula (IV).
  • R is a hydrogen atom or a methyl group
  • a and D are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group
  • B is a 1,4-phenylene group, 1 , 4-cyclohexylene group, 4,4′-biphenylene group or 4,4′-bicyclohexylene group
  • Y and Z are each independently —COO—, —OCO— or —O—.
  • g and h are each independently an integer of 2 to 6.
  • the ratio of the photopolymerizable liquid crystal compound (monomer) and the side chain type liquid crystal polymer in the liquid crystal composition is not particularly limited.
  • the content of the photopolymerizable liquid crystal compound is preferably larger than the content of the side chain liquid crystal polymer.
  • the content (weight) of the photopolymerizable liquid crystal compound in the liquid crystal composition is 1. It is preferably 5 to 15 times, more preferably 2 to 10 times, and even more preferably 2.5 to 6 times.
  • the liquid crystalline composition preferably contains a photopolymerization initiator.
  • the photopolymerization initiator include Irgacure 907, Irgacure 184, Irgacure 651, and Irgacure 369 manufactured by BASF.
  • the content of the photopolymerization initiator in the liquid crystal composition is usually about 0.5 to 20 parts by weight, preferably about 3 to 15 parts by weight, more preferably 100 parts by weight of the photopolymerizable liquid crystal compound. Is about 5 to 10 parts by weight.
  • a liquid crystalline composition can be prepared by mixing a side chain type liquid crystal polymer, a photopolymerizable liquid crystal compound, a photopolymerization initiator, and a solvent.
  • the solvent is not particularly limited as long as it can dissolve the side chain type liquid crystal polymer and the photopolymerizable liquid crystal compound and does not erode the film substrate (or has low erodibility), such as chloroform, dichloromethane, carbon tetrachloride, Halogenated hydrocarbons such as dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, and orthodichlorobenzene; phenols such as phenol and parachlorophenol; aromatics such as benzene, toluene, xylene, methoxybenzene, and 1,2-dimethoxybenzene Hydrocarbons; ketone solvents such as acetone, methyl ethyl ketone,
  • a film substrate not provided with a vertical alignment film is used as a substrate on which the liquid crystalline composition is applied.
  • the side-chain liquid crystal polymer in the liquid crystalline composition is homeotropically aligned by heating, it is not necessary to provide a vertical alignment film on the substrate.
  • a series of steps from the application of the liquid crystalline composition on the substrate to the curing by photopolymerization of the liquid crystal monomer can be performed by roll-to-roll, so the productivity of homeotropic alignment liquid crystal film can be increased. It can be improved.
  • the film substrate has a first main surface and a second main surface, and the liquid crystalline composition is applied on the first main surface.
  • the resin material constituting the film substrate is not particularly limited as long as it does not dissolve in the solvent of the liquid crystalline composition and has heat resistance during heating for orienting the liquid crystalline composition, polyethylene terephthalate, polyethylene Polyester such as naphthalate; Polyolefin such as polyethylene and polypropylene; Cyclic polyolefin such as norbornene polymer; Cellulosic polymer such as diacetyl cellulose and triacetyl cellulose; Acrylic polymer; Styrene polymer; Polycarbonate, polyamide, polyimide, etc. .
  • a norbornene-based polymer film as the film substrate because a film having excellent fluidity at the time of molding and high smoothness can be easily obtained.
  • a norbornene-based polymer film is preferable because it is excellent in releasability when transferring a homeotropic alignment liquid crystal film to another substrate or the like.
  • Examples of norbornene-based polymers include ZEONOR, ZEONEX manufactured by Nippon Zeon, and ARTON manufactured by JSR.
  • a stretched film may be used as the film substrate.
  • unevenness such as die lines at the time of film formation is leveled, so that the smoothness of the film substrate is improved and the arithmetic average roughness Ra tends to be reduced. Since the surface uniformity is high, it is particularly preferable to use a biaxially stretched film as the film substrate.
  • the in-plane retardation R 0 of a stretched film used as a film substrate is generally 10 nm or more.
  • the film substrate is a stretched film having an in-plane retardation of 10 nm or more
  • liquid crystal molecules are preferentially aligned in a predetermined direction (slow axis direction or fast axis direction).
  • the alignment regulating force that causes homogeneous alignment of the liquid crystal composition is likely to act, and the homeotropic alignment of the liquid crystalline composition tends to be inhibited.
  • a homeotropic alignment liquid crystal film with few alignment defects can be obtained even when a stretched film substrate is used by lowering the heating temperature when the liquid crystal molecules are homeotropically aligned.
  • the in-plane retardation R 0 of the film substrate is preferably 500 nm or less, more preferably 300 nm or less, and further preferably 200 nm or less.
  • the thickness of the film substrate is not particularly limited, but is usually about 10 to 200 ⁇ m in consideration of handling properties.
  • the in-plane birefringence ⁇ n (value obtained by dividing the in-plane retardation R 0 by the thickness) of the stretched film is preferably 0.01 or less, more preferably 0.008 or less, and further preferably 0.006 or less.
  • the arithmetic average roughness Ra of the first main surface of the film substrate is preferably 3 nm or less, more preferably 2 nm or less, and further preferably 1.5 nm or less.
  • Ra of the substrate surface of the homeotropic alignment liquid crystal film is equal to Ra of the first main surface of the substrate. Almost equal. Therefore, when a film substrate having a Ra of the first main surface of 3 nm or less is used, the Ra of the substrate surface of the liquid crystal alignment film is often 3 nm or less. Moreover, Ra of the air surface at the time of application
  • the film substrate preferably contains no filler.
  • a film that does not contain a filler and has a high surface smoothness has low slipperiness, and therefore may cause blocking, and may cause poor conveyance or winding failure in a roll-to-roll process.
  • the second main surface (the surface opposite to the application surface of the liquid crystalline composition) is bonded to the second main surface.
  • the adhesive or the like attached to the second main surface is transferred to the first main surface, which may cause orientation failure or optical defect.
  • the easy-sliding layer examples include those in which a fine filler having an average particle size of 100 nm or less is contained in a binder such as polyester or polyurethane. From the viewpoint of maintaining the releasability when transferring the homeotropic alignment liquid crystal film to other base materials, etc., and suppressing the transfer of the easy-sliding layer to the homeotropic alignment liquid crystal film at the time of peeling from the film substrate.
  • the film substrate preferably does not have an easy-sliding layer on the surface on which the liquid crystalline composition is applied. That is, it is preferable to use a film substrate having an easy slip layer on the second main surface and no easy slip layer on the first main surface.
  • the method of applying the liquid crystalline composition on the film substrate is not particularly limited, and spin coating, Daiko, kiss roll coating, gravure coating, reverse coating, spray coating, Meyer bar coating, knife roll coating, air knife coating, etc. are adopted. it can.
  • the liquid crystalline composition layer is formed on the film substrate by removing the solvent after applying the solution.
  • the coating thickness is preferably adjusted so that the thickness of the liquid crystalline composition layer after drying the solvent (the thickness of the homeotropic alignment liquid crystal film) is about 0.5 to 5 ⁇ m.
  • the liquid crystalline composition is homeotropically aligned by heating the liquid crystalline composition layer formed on the film substrate to form a liquid crystal phase.
  • the heating temperature is not particularly limited, but is usually about 40 to 200 ° C.
  • the heating temperature is preferably 45 to 100 ° C, more preferably 50 to 95 ° C, and further preferably 55 to 90 ° C.
  • the heating time may be adjusted so that the transition to the liquid crystal phase is sufficient, and is usually about 30 seconds to 30 minutes.
  • the heating temperature T (° C.) during the liquid crystal alignment is preferably 100 ⁇ 3.5 ⁇ 10 3 ⁇ n or less. ⁇ n is the in-plane birefringence of the stretched film substrate.
  • the heating temperature T is more preferably 100-4 ⁇ 10 3 ⁇ n or less, and further preferably 100-4.5 ⁇ 10 3 ⁇ n or less.
  • the heating temperature T is preferably 100-0.1R 0 or less, more preferably 100-0.12R 0 or less, more preferably 100-0.13R 0 or less.
  • R 0 is the in-plane retardation of the stretched film substrate.
  • the orientation of the liquid crystalline compound is fixed by cooling to a temperature not higher than the glass transition temperature of the liquid crystal polymer.
  • the cooling method is not particularly limited, and for example, it may be taken out from the heating atmosphere to room temperature. You may perform forced cooling, such as air cooling and water cooling.
  • the alignment of the photopolymerizable liquid crystal compound is fixed, and the durability of the homeotropic alignment liquid crystal film Will improve.
  • the light to be irradiated light having a wavelength at which the photopolymerization initiator is cleaved may be selected, and ultraviolet light is generally used.
  • the light irradiation is preferably performed in an inert gas atmosphere such as nitrogen gas.
  • the thickness direction retardation R t represented by the product of (nx ⁇ nz) and thickness of the homeotropic alignment liquid crystal film is, for example, about ⁇ 50 to ⁇ 500 nm.
  • the homeotropic alignment liquid crystal film has a light omission (orientation defect) observed under a polarizing microscope of preferably 1 or less per 1 cm 2 , more preferably 0.7 or less, and 0.5 More preferably, it is as follows.
  • the number of orientation failures is obtained as an average value obtained by observing 10 points in the film plane.
  • a homeotropic alignment liquid crystal film with few alignment defects can be obtained by using a stretched film substrate having high smoothness and setting the heating temperature when aligning the liquid crystal within a predetermined range.
  • the homeotropic alignment liquid crystal film can be used as an optical film for display intended for viewing angle compensation and the like.
  • the homeotropic alignment liquid crystal film may be used as it is laminated with the film substrate, or may be used after being peeled off from the film substrate.
  • the homeotropic alignment liquid crystal film may be peeled off from the film substrate and laminated with a substrate such as a retardation film, a polarizing plate or glass.
  • Example 1 An unstretched norbornene-based film (“Zeonor film” manufactured by Nippon Zeon Co., Ltd., thickness: 50 ⁇ m, in-plane retardation: 0 nm, arithmetic average roughness: 2.3 nm), the above-mentioned liquid crystalline composition has a thickness after drying. It was applied by a bar coater so as to have a thickness of 1 ⁇ m, and heated at the temperature shown in Table 1 (50 to 100 ° C.) for 2 minutes to align the liquid crystal. Then, it cooled to room temperature, the orientation was fixed, 700 mJ / cm ⁇ 2 > ultraviolet-ray was irradiated in nitrogen atmosphere, the liquid crystal monomer was photocured, and the liquid crystal aligning film was produced.
  • Zeonor film manufactured by Nippon Zeon Co., Ltd., thickness: 50 ⁇ m, in-plane retardation: 0 nm, arithmetic average roughness: 2.3 nm
  • Example 5 The liquid crystal composition was applied on a biaxially stretched polyethylene terephthalate film (“Diafoil T302” manufactured by Mitsubishi Chemical Co., Ltd., thickness: 75 ⁇ m), and a liquid crystal alignment film was produced in the same manner as in Experimental Example 1.
  • Example 6 A liquid crystalline composition whose composition was changed to 50 parts by weight of a side chain type liquid crystal polymer and 50 parts by weight of a polymerizable liquid crystal compound was applied on the same biaxially stretched film as used in Experimental Example 2, and 2 After minute heating, cooling and photocuring were performed to prepare a liquid crystal alignment film.
  • Arithmetic mean roughness was determined from an AFM observation image of 1 ⁇ m square using a scanning probe microscope (AFM).
  • the liquid crystal alignment film was transferred onto the surface of the glass plate provided with an adhesive on the surface, and an area of 1 cm 2 was observed under a crossed Nicol polarizing microscope, and the number of local light leakage was counted. A sample was observed with a polarizing microscope at 10 locations (total 10 cm 2 ) per sample, and the average number of light omissions was defined as the number of alignment defects per cm 2 . Table 1 shows the number of alignment defects per 1 cm 2 of the liquid crystal alignment film obtained in each experimental example.
  • the orientation defects in Experimental Example 2 decreased in the temperature range of 50 to 90 ° C.
  • the number of orientation defects in Experimental Example 2 increased.
  • the temperature range in which the alignment defect is reduced is 50 to 80 ° C.
  • the temperature range in which the alignment defect is reduced is 50 to 70 ° ° C.

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  • Chemical Kinetics & Catalysis (AREA)
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  • General Physics & Mathematics (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un film de cristaux liquides à alignement homéotrope produit de la manière suivante : une composition cristalline liquide contenant un polymère à cristaux liquides de type à chaîne latérale et un monomère à cristaux liquides photopolymérisable est appliquée sur un substrat de film sans film d'alignement vertical disposé sur ce dernier ; le polymère de cristaux liquides et le monomère de cristaux liquides sont alignés de manière homéotrope dans un état de cristaux liquides ; le monomère de cristaux liquides est polymérisé ou réticulé par exposition à la lumière afin d'obtenir un film de cristaux liquides à alignement homéotrope. Le polymère à cristaux liquides de type à chaîne latérale comprend une unité monomère contenant une chaîne latérale de fragment cristallin liquide, et une unité monomère contenant une chaîne latérale de fragment cristallin non liquide. Il est préférable qu'un film étiré soit utilisé en tant que substrat de film, et que la température de chauffage destinée à aligner un composé de cristaux liquides soit comprise dans une plage prescrite.
PCT/JP2017/045457 2017-04-24 2017-12-19 Film de cristaux liquides à alignement homéotrope et procédé de fabrication d'un tel film de cristaux liquides à alignement homéotrope WO2018198425A1 (fr)

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SG11201900923WA SG11201900923WA (en) 2017-04-24 2017-12-19 Homeotropically-aligned liquid crystal film and method for manufacturing the same
CN201780042687.7A CN109416429B (zh) 2017-04-24 2017-12-19 垂直取向液晶膜及其制造方法
KR1020187032203A KR101975402B1 (ko) 2017-04-24 2017-12-19 호메오트로픽 배향 액정 필름 및 그 제조 방법

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JP2017-085697 2017-04-24

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JP6769921B2 (ja) * 2017-04-28 2020-10-14 日東電工株式会社 液晶配向フィルムの製造方法
JP6686083B2 (ja) * 2018-08-27 2020-04-22 日東電工株式会社 配向液晶フィルムおよびその製造方法、粘着剤付き光学フィルムおよびその製造方法、ならびに画像表示装置
KR20210079273A (ko) * 2018-10-26 2021-06-29 도요보 가부시키가이샤 액정 화합물 배향층 전사용 필름

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JP2007206605A (ja) * 2006-02-06 2007-08-16 Nitto Denko Corp 液晶パネルおよび液晶表示装置
JP2008523443A (ja) * 2004-12-11 2008-07-03 エルジー・ケム・リミテッド 配向膜の要らないホメオトロピック配向液晶フィルム及びその製造方法
JP2008158310A (ja) * 2006-12-25 2008-07-10 Nitto Denko Corp 積層体、液晶パネル、および液晶表示装置
WO2011024683A1 (fr) * 2009-08-31 2011-03-03 コニカミノルタオプト株式会社 Film de compensation optique, plaque de polarisation et dispositif d'affichage à cristaux liquides
JP2014197119A (ja) * 2013-03-29 2014-10-16 Ｊｘ日鉱日石エネルギー株式会社 光学フィルム、偏光板、画像表示装置及び光学フィルムの製造方法
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US6885423B2 (en) * 2000-12-06 2005-04-26 Nitto Denko Corporation Method for manufacturing homeotropic alignment liquid crystal film
JP4174192B2 (ja) 2001-05-08 2008-10-29 日東電工株式会社 ホメオトロピック配向液晶性組成物、ホメオトロピック配向液晶フィルムの製造方法およびホメオトロピック配向液晶フィルム
JP3899482B2 (ja) * 2001-06-11 2007-03-28 日東電工株式会社 ホメオトロピック配向液晶フィルムの製造方法およびホメオトロピック配向液晶フィルム
JP4266289B2 (ja) 2002-01-16 2009-05-20 日東電工株式会社 ホメオトロピック配向液晶フィルムの製造方法、ホメオトロピック配向液晶フィルムおよび光学フィルム
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JP2006126770A (ja) * 2004-05-26 2006-05-18 Nitto Denko Corp 楕円偏光板および画像表示装置
JP2008523443A (ja) * 2004-12-11 2008-07-03 エルジー・ケム・リミテッド 配向膜の要らないホメオトロピック配向液晶フィルム及びその製造方法
JP2007206605A (ja) * 2006-02-06 2007-08-16 Nitto Denko Corp 液晶パネルおよび液晶表示装置
JP2008158310A (ja) * 2006-12-25 2008-07-10 Nitto Denko Corp 積層体、液晶パネル、および液晶表示装置
WO2011024683A1 (fr) * 2009-08-31 2011-03-03 コニカミノルタオプト株式会社 Film de compensation optique, plaque de polarisation et dispositif d'affichage à cristaux liquides
JP2014197119A (ja) * 2013-03-29 2014-10-16 Ｊｘ日鉱日石エネルギー株式会社 光学フィルム、偏光板、画像表示装置及び光学フィルムの製造方法
JP2015163957A (ja) * 2014-01-31 2015-09-10 住友化学株式会社 光学異方性シート

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KR20180125172A (ko) 2018-11-22
CN109416429B (zh) 2019-12-31
JP2018185375A (ja) 2018-11-22
TWI645020B (zh) 2018-12-21
CN109416429A (zh) 2019-03-01
KR101975402B1 (ko) 2019-05-07
JP6363252B1 (ja) 2018-07-25
SG11201900923WA (en) 2019-02-27

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