CN116261681A - Oriented liquid crystal film, method for producing the same, and image display device - Google Patents
Oriented liquid crystal film, method for producing the same, and image display device Download PDFInfo
- Publication number
- CN116261681A CN116261681A CN202180053493.3A CN202180053493A CN116261681A CN 116261681 A CN116261681 A CN 116261681A CN 202180053493 A CN202180053493 A CN 202180053493A CN 116261681 A CN116261681 A CN 116261681A
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- liquid crystal
- layer
- alignment
- resin
- film according
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- 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
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- 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
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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- 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
-
- 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
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
-
- 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
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
- H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Liquid Crystal (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
Abstract
A liquid crystal alignment film (100) is provided with: the liquid crystal display device comprises a first alignment liquid crystal layer (1) in which liquid crystal molecules are aligned, a resin coating layer (6) in contact with a first main surface of the first alignment liquid crystal layer, and an optical layer (4) bonded to the resin coating layer (6) via an adhesive layer (3). The resin coating is a non-curable resin layer. The glass transition temperature of the resin coating may be 20 ℃ or higher. The first alignment liquid crystal layer may be one in which liquid crystal molecules are aligned in parallel. In one embodiment, the alignment liquid crystal film is formed by applying a resin solution containing a resin and an organic solvent to the first main surface of the first alignment liquid crystal layer to form the resin coating layer, and bonding the resin coating layer and the optical layer via an adhesive.
Description
Technical Field
The present invention relates to an alignment liquid crystal film in which liquid crystal molecules are aligned, a method for manufacturing the alignment liquid crystal film, and an image display device including the alignment liquid crystal film.
Background
As an optical film having functions of optically compensating a liquid crystal display device, preventing reflection of external light of an organic EL element, and the like, a liquid crystal film (alignment liquid crystal film) in which a liquid crystal compound is aligned in a predetermined direction is used. Since the birefringence of the oriented liquid crystal film is larger than that of the stretched film of the polymer, the oriented liquid crystal film is advantageous in thinning and weight saving. In an image display device, an alignment liquid crystal film is bonded to an organic EL panel or a liquid crystal display panel as a polarizer integrally laminated with a polarizer via an adhesive (pressure sensitive adhesive) or an adhesive (for example, patent document 1).
The liquid crystal compound can orient the liquid crystal molecules in a predetermined direction by a shearing force, an orientation regulating force of an orientation film, or the like at the time of coating on a substrate, and an orientation liquid crystal film having various optical anisotropies can be obtained. For example, a parallel alignment (horizontal alignment) liquid crystal layer in which nematic liquid crystal molecules having positive refractive index anisotropy are aligned parallel to the substrate plane may be used as a positive a plate having refractive index anisotropy of nx > ny=nz.
In the case of using a thermotropic liquid crystal, a solution containing a liquid crystal compound (liquid crystalline composition) is applied to a substrate, and the liquid crystal molecules are aligned by heating so that the compound contained in the composition becomes a liquid crystal state. When the liquid crystal composition contains a photopolymerizable liquid crystal compound (liquid crystal monomer), alignment of liquid crystal molecules is performed, and then the liquid crystal monomer is cured by irradiation with light, whereby the alignment state is fixed.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2015-7700
Disclosure of Invention
Problems to be solved by the invention
Image display devices such as liquid crystal display devices and organic EL display devices are required to have higher durability, and optical members constituting the image display devices are required to have little change in optical characteristics even when exposed to a high-temperature environment for a long period of time. Patent document 1 describes that by controlling the alignment parameters of the liquid crystal compound, the change in the phase retardation in the high-temperature environment of the aligned liquid crystal film can be reduced.
The optical characteristics of the alignment liquid crystal film may change in a high-temperature environment due to the influence of not only the alignment state of the liquid crystal but also a layer disposed adjacent to the liquid crystal layer. For example, when the parallel alignment liquid crystal layer and the polarizer are bonded via an adhesive layer (pressure-sensitive adhesive layer), there is little change in retardation in a high-temperature environment, whereas a sample in which the parallel alignment liquid crystal layer and the polarizer are bonded via an ultraviolet-curable adhesive tends to be found to have a tendency to rise in retardation in a high-temperature environment.
In view of the above problems, an object of the present invention is to provide an alignment liquid crystal film which has little change in optical characteristics even when exposed to a high-temperature environment for a long period of time and which has excellent heat durability.
Means for solving the problems
The alignment liquid crystal film includes an alignment liquid crystal layer in which liquid crystal molecules are aligned in a predetermined direction. The alignment liquid crystal layer is formed, for example, by applying a liquid crystal composition containing a photopolymerizable liquid crystal monomer onto a support substrate, heating the liquid crystal composition on the support substrate to align the liquid crystal monomer in a liquid crystal state, and polymerizing or crosslinking the liquid crystal monomer by light irradiation. In the alignment liquid crystal layer, the liquid crystal molecules may be aligned in parallel (horizontally aligned). The support substrate for forming the alignment liquid crystal layer may be a resin film.
The alignment liquid crystal film of the present invention includes a resin coating layer in contact with a first main surface of an alignment liquid crystal layer, and an optical layer bonded to the resin coating layer via an adhesive layer. Examples of the optical layer bonded to the alignment liquid crystal layer include a polarizer and a transparent film. The optical layer may be other oriented liquid crystal layers.
The alignment liquid crystal film may be formed by bonding another optical layer to the second main surface of the alignment liquid crystal layer via an adhesive layer. A resin coating layer may be provided on the second main surface of the alignment liquid crystal layer. The alignment liquid crystal film may be formed by bonding another optical layer to the second main surface of the alignment liquid crystal layer via an adhesive layer.
In one embodiment, the alignment liquid crystal film may be a circular polarizer including a polarizer as an optical layer. In an alignment liquid crystal film in which an alignment liquid crystal layer in which liquid crystal molecules are aligned in parallel and a polarizer are laminated, an angle between an alignment direction of the liquid crystal molecules in the alignment liquid crystal layer and an absorption axis direction of the polarizer may be 10 to 80 °.
In one embodiment of the circularly polarizing plate, a resin coating layer is provided on one surface (first main surface) of a parallel alignment liquid crystal layer as a first alignment liquid crystal layer, and a vertical alignment liquid crystal layer as a second alignment liquid crystal layer is provided on the resin coating layer via an adhesive layer. A polarizer or polarizing plate is bonded to the other surface (second main surface) of the parallel alignment liquid crystal layer. The parallel alignment liquid crystal layer may be bonded to the polarizer or polarizer via an adhesive layer in contact with the second major face of the parallel alignment liquid crystal layer.
The resin coating is preferably a non-curable resin layer. The weight average molecular weight of the resin material constituting the resin coating layer is preferably 2 ten thousand or more. The resin material of the resin coating layer includes a non-curable acrylic resin, a non-curable epoxy resin, and the like. The glass transition temperature of the resin coating may be 20 ℃ or higher. The thickness of the resin coating is preferably 0.05 to 3. Mu.m. The resin coating layer may contain an uncured product of a liquid crystal compound constituting the alignment liquid crystal layer.
The resin coating layer is formed by coating a resin solution containing a resin and an organic solvent on the alignment liquid crystal layer. The organic solvent of the resin solution preferably has solubility for the photopolymerizable liquid crystal monomer, and does not dissolve or hardly dissolves the photocurable product of the photopolymerizable liquid crystal monomer. After the resin solution is applied to the surface of the alignment liquid crystal layer, the alignment liquid crystal layer may be heated at 40 to 150 ℃ before the optical layer is bonded.
The thickness of the adhesive layer for bonding the resin coating layer and the optical layer on the alignment liquid crystal layer is preferably 0.01 to 5 μm. The adhesive may be an active energy ray-curable adhesive.
Effects of the invention
The oriented liquid crystal film of the present invention is excellent in heat durability and small in change in retardation even when exposed to a high-temperature environment for a long period of time. Therefore, the optical member is suitable for use as an optical member for image display devices such as liquid crystal display devices and organic EL display devices.
Drawings
Fig. 1 is a cross-sectional view of an alignment liquid crystal film according to an embodiment.
Fig. 2 is a cross-sectional view of a laminate including an alignment liquid crystal layer on a support substrate.
Fig. 3 is an end view of a laminate in which a resin coating layer is formed on an alignment liquid crystal layer.
Fig. 4 is a cross-sectional view of an alignment liquid crystal film according to an embodiment.
Fig. 5 is a cross-sectional view of an oriented liquid crystal film having an adhesive layer.
Fig. 6 is a cross-sectional view of an alignment liquid crystal film according to an embodiment.
Fig. 7 is a cross-sectional view of an alignment liquid crystal film according to an embodiment.
Fig. 8 is a cross-sectional view of an alignment liquid crystal film according to an embodiment.
Fig. 9 is a cross-sectional view of an alignment liquid crystal film according to an embodiment.
Fig. 10 is a cross-sectional view showing an example of a laminated structure of the image display device.
Detailed Description
Fig. 1 is a cross-sectional view showing the structure of an alignment liquid crystal film according to an embodiment. The alignment liquid crystal film 100 includes a resin coating layer 6 in contact with one main surface of the alignment liquid crystal layer 1, and an optical layer 4 bonded to the resin coating layer 6 via an adhesive layer 3.
[ alignment liquid Crystal layer ]
The alignment liquid crystal layer 1 includes liquid crystal molecules aligned in a predetermined direction. For example, the liquid crystal composition containing the liquid crystal compound is applied to the support substrate 8, and the liquid crystal compound is aligned in a predetermined direction, and then the alignment state is fixed, whereby the alignment liquid crystal layer 1 is formed on the support substrate 8 as shown in fig. 2.
Liquid crystalline composition
Examples of the liquid crystal compound include a rod-like liquid crystal compound and a discotic liquid crystal compound. The liquid crystal compound is preferably a rod-like liquid crystal compound from the standpoint of easy parallel alignment by the alignment regulating force of the support substrate. The rod-like liquid crystal compound may be a main chain type liquid crystal or a side chain type liquid crystal. The rod-like liquid crystal compound may be a liquid crystal polymer or a polymer of a polymerizable liquid crystal compound. The liquid crystal compound (monomer) before polymerization may not exhibit liquid crystallinity after polymerization as long as it exhibits liquid crystallinity.
The liquid crystal compound is preferably a thermotropic liquid crystal which exhibits liquid crystallinity by heating. The thermotropic liquid crystal changes with temperature to generate phase transition of crystalline phase, liquid crystal phase and isotropic phase. The liquid crystal compound contained in the liquid crystal composition may be any of nematic liquid crystal, smectic liquid crystal, and cholesteric liquid crystal. Chiral agents may be added to the nematic liquid crystal to impart cholesteric alignment.
Examples of the rod-like liquid crystal compound exhibiting thermal conductivity include: azomethines, azoxynes, cyanobiphenyl, cyanobenzene esters, benzoates, cyclohexane carboxylic acid phenyl esters, cyanophenyl cyclohexanes, cyano-substituted phenyl pyrimidines, alkoxy-substituted phenyl pyrimidines, phenyl dioxanes, diphenylacetylene, alkenyl cyclohexyl benzonitriles, and the like.
Examples of the polymerizable liquid crystal compound include: a polymerizable liquid crystal compound which fixes the alignment state of the rod-like liquid crystal compound using a polymer binder; a polymerizable liquid crystal compound having a polymerizable functional group capable of fixing the alignment state of the liquid crystal compound by polymerization, and the like. Among them, a photopolymerizable liquid crystal compound having a photopolymerizable functional group is preferable.
The photopolymerizable liquid crystal compound (liquid crystal monomer) has a mesogen group in 1 molecule and at least 1 photopolymerizable functional group. The temperature at which the liquid crystal monomer exhibits liquid crystallinity (liquid crystal phase transition temperature) is preferably 40 to 200 ℃, more preferably 50 to 150 ℃, and even more preferably 55 to 100 ℃.
Examples of the mesogen group of the liquid crystal monomer include: a cyclic structure such as biphenyl, phenyl benzoate, phenylcyclohexane, azoxyphenyl, azomethine, azoxyphenyl, phenylpyrimidinyl, diphenylethynyl, diphenyl benzoate, dicyclohexyl, cyclohexylphenyl, and terphenyl. The terminal of these cyclic units may have a substituent such as a cyano group, an alkyl group, an alkoxy group, a halogen group, or the like.
Examples of the photopolymerizable functional group include: (meth) acryl, epoxy, vinyl ether, and the like. Among them, a (meth) acryl group is preferable. The photopolymerizable liquid crystal monomer preferably has 2 or more photopolymerizable functional groups in 1 molecule. Since a crosslinked structure is introduced into the liquid crystal layer after photo-curing by using a liquid crystal monomer containing 2 or more photopolymerizable functional groups, durability of the alignment liquid crystal film tends to be improved.
As the photopolymerizable liquid crystal monomer, any suitable liquid crystal monomer may be used. Examples thereof include compounds described in International publication No. 00/37585, U.S. Pat. No. 5211877, U.S. Pat. No. 4388453, international publication No. 93/22397, european patent No. 0261712, german patent No. 19504224, german patent No. 4408171, british patent No. 2280445, japanese patent application publication No. 2017-206460, international publication No. 2014/126113, international publication No. 2016/114348, international publication No. 2014/010325, japanese patent application publication No. 2015-200877, japanese patent application publication No. 2010-31223, international publication No. 2011/050896, japanese patent application publication No. 2011-207765, japanese patent application publication No. 2010-31223, japanese patent application publication No. 2010-270108, international publication No. 2008/119427, japanese patent application publication No. 2008-107767, japanese patent application publication No. 2008-273925, international publication No. 2016/125839, japanese patent application publication No. 2008-392725, and the like. The birefringence appearance and the retardation wavelength dispersion can also be adjusted by selecting the liquid crystal monomer.
The liquid crystal composition may contain a compound for controlling the alignment of the liquid crystal monomer in a specific direction, in addition to the liquid crystal monomer. For example, by including the side chain type liquid crystal polymer in the liquid crystal composition, the liquid crystal compound (monomer) can be vertically aligned. In addition, by adding a chiral agent to the liquid crystal composition, the liquid crystal compound can be aligned in a cholesteric manner.
The liquid crystalline composition may contain a photopolymerization initiator. In the case of curing the liquid crystal monomer by ultraviolet irradiation, the liquid crystal composition preferably contains a photopolymerization initiator (photo radical generator) that generates radicals by light irradiation in order to promote photocuring. Depending on the type of the liquid crystal monomer (type of photopolymerizable functional group), a photocationic generator or a photocationic generator may be used. The photopolymerization initiator is used in an amount of about 0.01 to 10 parts by weight based on 100 parts by weight of the liquid crystal monomer. In addition to the photopolymerization initiator, a sensitizer or the like may be used.
The liquid crystal composition can be prepared by mixing a liquid crystal monomer, and various alignment controlling agents, polymerization initiators, and the like as needed, with a solvent. The solvent is not particularly limited as long as it is a solvent that can dissolve the liquid crystal monomer and does not attack the substrate (or has low aggressiveness), and examples thereof include: halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, and o-dichlorobenzene; phenols such as phenol and p-chlorophenol; aromatic hydrocarbons such as benzene, toluene, xylene, methoxybenzene, and 1, 2-dimethoxybenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, and N-methyl-2-pyrrolidone; ester solvents such as ethyl acetate and butyl acetate; alcohol solvents such as t-butanol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, and 2-methyl-2, 4-pentanediol; amide solvents such as dimethylformamide and dimethylacetamide; nitrile solvents such as acetonitrile and butyronitrile; ether solvents such as diethyl ether, dibutyl ether, and tetrahydrofuran; ethyl cellosolve, butyl cellosolve, and the like. A mixed solvent of 2 or more solvents may be used.
The solid content concentration of the liquid crystal composition is usually about 5 to 60% by weight. The liquid crystal composition may contain additives such as surfactants and leveling agents.
< support substrate >)
Examples of the support substrate 8 coated with the liquid crystal composition include a glass plate, a metal tape, and a resin film substrate. The support substrate has a first main surface and a second main surface, and the liquid crystal composition is applied to the first main surface.
By using the film substrate as the support substrate 8, a series of steps of photo-curing the liquid crystal composition applied to the liquid crystal monomer on the substrate and subsequent heat treatment can be performed by a roll-to-roll method, and thus productivity of the alignment liquid crystal film can be improved. The resin material constituting the film substrate is not particularly limited as long as it is insoluble in the solvent of the liquid crystal composition and has heat resistance at the time of heating for aligning the liquid crystal composition, and examples thereof include: polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefin such as polyethylene and polypropylene; cyclic polyolefin such as norbornene polymer; cellulose polymers such as diacetyl cellulose and triacetyl cellulose; an acrylic polymer; a styrene polymer; polycarbonates, polyamides, polyimides, and the like.
The support substrate 8 may have an orientation capability for orienting the liquid crystal molecules in a prescribed direction. For example, by using a stretched film as a support substrate, liquid crystal molecules can be aligned in parallel along the stretching direction thereof. The stretching ratio of the stretched film may be, for example, about 1.1 to 5 times as high as that capable of exhibiting the orientation ability. The stretched film may be a biaxially stretched film. Even in the case of a biaxially stretched film, if a stretching ratio in the machine direction and a stretching ratio in the transverse direction are different, the liquid crystal molecules can be aligned in a direction having a large stretching ratio. The stretch film may be a bias stretch film. By using the stretched film as the support substrate 8, the liquid crystal molecules can be aligned in a direction that is not parallel to both the longitudinal direction and the transverse direction of the support substrate.
The support substrate 8 may include an alignment film on the first main surface. The alignment film may be appropriately selected depending on the type of liquid crystal compound, the material of the substrate, and the like. As an alignment film for aligning the liquid crystal molecules in parallel in a predetermined direction, a polyimide-based or polyvinyl alcohol-based alignment film is preferably used. In addition, a photo-alignment film may be used. The resin film as the support substrate may be subjected to a rubbing treatment without providing an alignment film.
The support substrate 8 may be provided with an alignment film for vertically aligning the liquid crystal molecules. Examples of the alignment agent for forming the alignment film having a homeotropic alignment property (homeotropic alignment film) include lecithin, stearic acid, cetyltrimethylammonium bromide, octadecylamine hydrochloride, basic chromium carboxylate complex, silane coupling agent, organosilane such as silicone compound, perfluorodimethylcyclohexane, tetrafluoroethylene, polytetrafluoroethylene, and the like.
< formation of aligned liquid Crystal layer on supporting substrate >
In the case where the liquid crystal compound is a thermotropic liquid crystal, the liquid crystal composition is applied to the first main surface of the support substrate 8, and the liquid crystal compound is aligned in a liquid crystal state by heating.
The method of applying the liquid crystal composition to the support substrate 8 is not particularly limited, and spin coating, die coating, roll licking coating, gravure coating, reverse coating, spray coating, bar coating, doctor blade roll coating, air knife blade coating, and the like can be employed. After the solution is applied, the solvent is removed, whereby a liquid crystal composition layer is formed on the support substrate. The thickness of the coating layer is preferably adjusted so that the thickness of the liquid crystal composition layer (the thickness of the alignment liquid crystal film) after the solvent drying becomes about 0.1 to 20 μm.
The liquid crystal compound is aligned by heating the liquid crystal composition layer formed on the support substrate to a liquid crystal phase. Specifically, the liquid crystal composition is applied to a supporting substrate, and then heated to a temperature equal to or higher than the N (nematic) -I (isotropic liquid phase) transition temperature of the liquid crystal composition, whereby the liquid crystal composition is brought into an isotropic liquid state. Thereafter, the nematic phase is developed by slow cooling as necessary. In this case, it is desirable to maintain the temperature at which the liquid crystal phase is temporarily developed, and to grow the liquid crystal phase domains into monodomains. Alternatively, after the liquid crystal composition is applied to the support substrate, the liquid crystal molecules may be aligned in a predetermined direction by maintaining the temperature for a predetermined period of time within a temperature range where the nematic phase appears.
The heating temperature for aligning the liquid crystal compound in a predetermined direction is appropriately selected depending on the type of the liquid crystal composition, and is usually about 40 to 200 ℃. If the heating temperature is too low, the transition to the liquid crystal phase tends to be insufficient, and if the heating temperature is too high, alignment defects may increase. The heating time is adjusted so that the liquid crystal domains sufficiently grow, and is usually about 30 seconds to 30 minutes.
It is preferable that the liquid crystal compound is cooled to a temperature lower than the glass transition temperature after being aligned by heating. The cooling method is not particularly limited, and may be, for example, taking out from a heating atmosphere to room temperature. Forced cooling such as air cooling and water cooling can be performed.
The liquid crystal layer is irradiated with light, whereby photo-curing is performed in a state where the photopolymerizable liquid crystal compound (liquid crystal monomer) has liquid crystal regularity. The irradiation light may be carried out by polymerizing a photopolymerizable liquid crystal compound, and generally ultraviolet light or visible light having a wavelength of 250 to 450nm is used. When the liquid crystal composition contains a photopolymerization initiator, light having a wavelength at which the photopolymerization initiator has sensitivity may be selected. As the irradiation light source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, an LED (Light Emitting Diode ), a black light lamp, a chemical lamp, or the like can be used. In order to promote the photo-curing reaction, it is preferable that the irradiation with light is performed under an inert gas atmosphere such as nitrogen.
In the case of photocuring the liquid crystal composition, the liquid crystal compound can be aligned in a predetermined direction by using polarized light in a predetermined direction. As described above, in the case where the liquid crystal compound is aligned by the alignment regulating force of the support substrate 8, the irradiation light may be unpolarized light (natural light).
The irradiation intensity may be appropriately adjusted depending on the composition of the liquid crystal composition, the addition amount of the photopolymerization initiator, and the like. Irradiation energy (cumulative irradiation light quantity) is passed throughUsually 20-10000 mJ/cm 2 About, preferably 50 to 5000mJ/cm 2 More preferably 100 to 800mJ/cm 2 . In order to promote the photo-curing reaction, light irradiation may be performed under heating.
The polymer obtained by photocuring the liquid crystal monomer by irradiation of light is non-liquid crystalline, and no transition of liquid crystal phase, glass phase and crystalline phase occurs due to temperature change. Therefore, the liquid crystal layer which is photo-cured in a state in which the liquid crystal monomer is aligned in a predetermined direction is less likely to undergo a change in molecular alignment due to a temperature change. In addition, since the birefringence of the oriented liquid crystal film is very large compared to a film containing a non-liquid crystal material, the thickness of the optically anisotropic element having a desired retardation can be significantly reduced. The thickness of the alignment liquid crystal film (liquid crystal layer) may be set only in accordance with the retardation value or the like of the object, and is usually about 0.1 to 20. Mu.m, preferably 0.2 to 10. Mu.m, more preferably 0.5 to 7. Mu.m.
The optical characteristics of the alignment liquid crystal layer are not particularly limited. The retardation of the alignment liquid crystal layer in the front direction and the retardation in the thickness direction may be appropriately set according to the application and the like. When the liquid crystal is aligned in parallel, the retardation of the alignment liquid crystal layer is, for example, about 20 to 1000 nm. In the case where the alignment liquid crystal layer is a 1/4 wavelength plate, the front retardation is preferably 100 to 180nm, more preferably 120 to 150nm. In the case where the alignment liquid crystal layer is a 1/2 wavelength plate, the front retardation is preferably 200 to 340nm, more preferably 240 to 300nm.
The retardation value is a measured value at a wavelength of 550nm unless otherwise indicated. The front retardation R (450) at the wavelength 450nm of the oriented liquid crystal layer may be smaller than the front retardation R (550) at the wavelength 550 nm. The front retardation R (650) of the oriented liquid crystal layer at a wavelength of 650nm is larger than R (550) except for R (450) < R (550), and R (550) < R (650) can be satisfied. R (450)/R (550) of the alignment liquid crystal layer may be 0.70 to 0.95, 0.75 to 0.90, or 0.80 to 0.87. R (650)/R (550) of the alignment liquid crystal layer may be 1.05 to 1.30, 1.10 to 1.25, or 1.13 to 1.20. As described above, by selection of the liquid crystal monomer, an alignment liquid crystal layer having a desired wavelength dispersion delayed can be formed.
When the liquid crystal is vertically aligned, the retardation of the alignment liquid crystal layer is substantially 0 (for example, 5nm or less, preferably 3nm or less), and the absolute value of the retardation in the thickness direction is about 30 to 500 nm.
[ resin coating ]
As described above, since the liquid crystal layer after photo-curing does not undergo phase transition even when heated, the thermal stability is superior to that of the uncured alignment liquid crystal layer. However, when the liquid crystal layer after photo-curing is exposed to a high-temperature environment for a long period of time, there is a case where the optical characteristics are changed, and there is room for improvement in the heating durability. In particular, an alignment liquid crystal film obtained by bonding other optical layers to a parallel alignment liquid crystal layer via an adhesive tends to undergo a delayed change under long-term heating, and the heating durability is problematic.
As shown in fig. 3, by providing the resin coating layer 6 on the surface of the alignment liquid crystal layer 1, improvement of the thermal stability of the optical characteristics of the alignment liquid crystal layer can be expected. The resin coating layer 6 is formed by coating a resin solution containing a resin and an organic solvent on the surface of the alignment liquid crystal layer 1.
< resin Material >)
As the resin material of the resin coating layer 6, a non-curable resin is preferable. The non-curable resin is a material capable of forming a resin layer without a curing reaction such as photo-curing or thermal curing after the resin solution is applied. The non-curable resin does not contain a photocurable or thermosetting reactive group, but may have a small amount of reactive groups remaining. For example, the reactive functional group equivalent (mass of the resin containing 1 equivalent of the reactive functional group) is preferably 3000 or more, more preferably 4000 or more, and may be 5000 or more or 6000 or more.
The resin material is preferably high in transparency and less in coloration. Examples of the resin material include polymers such as epoxy resin, silicone resin, acrylic resin, polyurethane, polyamide, polyether, polyvinyl alcohol, polyester, polycarbonate, polyarylate, polyphenylene sulfide, polyether sulfone, polyether ether ketone, polyamide, polyimide, polyolefin, cyclic polyolefin, polystyrene, polyvinyl chloride, and polyvinylidene chloride. Among them, the non-curable acrylic resin and the non-curable epoxy resin are preferable because of high adhesion to the alignment liquid crystal layer 1 and the adhesive layer 3.
The "non-curable acrylic resin" is a polymer obtained by polymerization of (meth) acryl groups of a compound having 1 or more (meth) acryl groups (acrylic monomer) in 1 molecule, and the resin coating layer 6 may be formed without photo-curing or thermal curing after the resin solution is applied to the surface of the alignment liquid crystal layer 1. The non-curable acrylic resin is typically a polymer of alkyl (meth) acrylate, and examples thereof include polymethyl methacrylate, polyethyl methacrylate, and polybutyl methacrylate.
The non-curable acrylic resin may be a copolymer of a plurality of alkyl (meth) acrylates, or a copolymer of an alkyl (meth) acrylate and another monomer.
Examples of the monomer other than the alkyl (meth) acrylate include (meth) acrylic acid, (meth) acrylamide, (meth) acrylonitrile, vinyl monomers, and styrene monomers. The comonomer may contain boron-containing functional groups such as boric acid, boric acid esters, and the like.
The "uncured epoxy resin" is a polymer obtained by polymerization of an epoxy group of a compound (epoxy monomer) having 1 or more epoxy groups in 1 molecule, and the resin coating 6 can be formed without photo-curing or thermosetting after the surface of the alignment liquid crystal layer 1 is coated with a resin solution. Among the non-curable epoxy resins, an epoxy resin having an aromatic ring is preferable.
The resin material may be mixed with 2 or more kinds. From the viewpoint of suppressing the increase in haze of the resin coating layer, it is preferable that 2 or more resin materials have compatibility. The resin material may be a mixture of a non-curable acrylic resin and a non-curable epoxy resin. When the resin material contains an acrylic resin and an epoxy resin, the content ratio of the acrylic resin and the epoxy resin is preferably 95% by weight from the viewpoint of transparency: 5 to 60:40 or 40:60 to 1:99. the weight ratio of the two can be 90:10 to 70:30 or 30: 70-10: 90.
the glass transition temperature of the resin material of the resin coating layer 6 is preferably 20 ℃ or higher, more preferably 30 ℃ or higher, and may be 40 ℃ or higher or 50 ℃ or higher. With respect to a polymer material for interlayer adhesion such as an adhesive, the glass transition temperature is generally set to be lower than room temperature in order to have tackiness. On the other hand, the resin coating layer 6 provided on the surface of the alignment liquid crystal layer has a glass transition temperature higher than room temperature, so that the change in the characteristics in the use environment of the image display device is small, and the change in the optical characteristics of the alignment liquid crystal layer tends to be suppressed. The weight average molecular weight of the resin material is preferably 2 ten thousand or more, more preferably 3 ten thousand or more, from the viewpoint of maintaining the film strength of the resin coating layer 6 from the point of view of not accompanying the curing reaction.
(formation of resin layer)
The organic solvent of the resin solution is not particularly limited as long as it can dissolve the above resin material. The organic solvent is preferably one that does not dissolve the alignment liquid crystal layer. For example, when the alignment liquid crystal layer contains a photo-cured product of a photo-polymerizable liquid crystal monomer, an organic solvent which does not dissolve or hardly dissolves the cured product is preferable. On the other hand, the organic solvent may be one which exhibits solubility to the liquid crystalline compound (monomer) before photocuring. The organic solvent may be 1 solvent or a mixed solvent of 2 or more solvents.
The solid content concentration of the resin solution may be adjusted to a viscosity suitable for coating in a range of about 1 to 50 wt%. From the viewpoint of uniformly forming a resin coating layer having a small thickness, the solid content concentration of the resin solution is preferably 30 wt% or less, more preferably 20 wt% or less, and may be 15 wt% or less or 10 wt% or less.
The method of applying the resin solution to the surface of the alignment liquid crystal layer 1 is not particularly limited, and various application methods can be suitably employed. After the resin solution is applied, heating may be performed in order to remove the organic solvent. The heating temperature is preferably 40℃or higher, more preferably 50℃or higher. When the heating temperature is too high, the heat stability of the alignment liquid crystal film may be lowered due to thermal damage to the substrate, re-alignment of the liquid crystal compound, or the like. Therefore, the heating temperature is preferably 150℃or less, more preferably 130℃or less, and may be 110℃or less or 100℃or less.
The thickness of the resin coating layer 6 is not particularly limited, but is preferably 3 μm or less, more preferably 2 μm or less, and may be 1 μm or less from the viewpoints of thickness reduction, adhesion, transparency maintenance, and the like. On the other hand, from the viewpoint of encapsulating uncured monomer or the like in the resin coating layer 6 from the dissolved product of the alignment liquid crystal layer 1 and suppressing bleeding, the thickness of the resin coating layer 6 is preferably 0.05 μm or more, more preferably 0.1 μm or more.
The reason for improving the heat durability of the alignment liquid crystal layer by providing the resin coating layer is not yet known, but it is considered that the uncured monomer remaining in the liquid crystal layer after photo-curing, free additives contained in the portion where formation of the three-dimensional network structure is insufficient, and the like are eluted from the organic solvent of the resin solution and taken in the resin coating layer, and therefore removal of substances from the alignment liquid crystal layer that cause a change in retardation due to heating is considered as one cause. Even when uncured material or the like in the alignment liquid crystal layer dissolves into the organic solvent, the dissolved component is collected in the resin coating layer, and therefore contamination due to deposition or the like on the surface of the alignment liquid crystal layer and a decrease in transparency can be prevented. It is considered that the liquid crystal is reoriented and the alignment state is stabilized at the time of heating for removing the organic solvent, and the like also contributes to the improvement of the heating stability.
The resin coating layer 6 and the optical layer 4 provided on the alignment liquid crystal layer 1 are laminated via the adhesive layer 3, thereby obtaining a laminate shown in fig. 1.
[ optical layer ]
The optical layer 4 is not particularly limited, and an optically isotropic or anisotropic film generally used as an optical film can be used without particular limitation. Specific examples of the optical layer 4 include a transparent film such as a retardation film and a polarizer protective film, a polarizer, a viewing angle expanding film, a viewing angle restricting (peeping preventing) film, and a functional film such as a brightness enhancing film. The optical layer 4 may be a single layer or a laminate. The optical layer 4 may be an oriented liquid crystal layer. For example, the optical layer 4 may be a polarizer having a transparent protective film attached to one or both surfaces of the polarizer. When the polarizer has a transparent protective film on one surface, the polarizer may be bonded to the alignment liquid crystal layer, or the transparent protective film may be bonded to the alignment liquid crystal layer.
For example, in a liquid crystal display device, a phase difference plate as an optical compensation film may be disposed between an image display unit (liquid crystal cell) and a polarizer for the purpose of appropriately converting a polarization state of light emitted from the liquid crystal cell to a viewing side to improve viewing angle characteristics. In the organic EL display device, there is a case where a 1/4 wavelength plate is arranged between the cell and the polarizing plate in order to suppress reflection of external light at the metal electrode layer and look like a mirror surface.
[ adhesive layer ]
As described above, by providing the resin coating layer 6 on the surface of the alignment liquid crystal layer 1 and bonding the optical layer 4 thereto via the adhesive layer 3, the heating durability of the alignment liquid crystal layer 1 in the alignment liquid crystal film 100 can be improved.
The material of the adhesive constituting the adhesive layer 3 is not particularly limited as long as it is optically transparent, and examples thereof include: epoxy resins, silicone resins, acrylic resins, polyurethanes, polyamides, polyethers, polyvinyl alcohols, and the like. For the above-mentioned resin coating 6, a non-curable resin is used, and for the adhesive, a curable composition is used. The thickness of the adhesive layer 3 is appropriately set according to the type of adherend, the material of the adhesive, and the like. In the case of using a curable adhesive exhibiting adhesiveness by a crosslinking reaction after application, the thickness of the adhesive layer 3 is preferably 0.01 to 5 μm, more preferably 0.03 to 3 μm.
As the adhesive, various forms such as a water-based adhesive, a solvent-based adhesive, a hot melt adhesive, and an active energy ray-curable adhesive can be used. Among the above, an aqueous adhesive or an active energy ray-curable adhesive is preferable in that the thickness of the adhesive layer can be reduced.
Examples of the aqueous adhesive include water-soluble or water-dispersible polymers such as vinyl polymers, gelatin, vinyl latex, polyurethane, isocyanate, polyester, and epoxy. The adhesive layer formed of such an aqueous adhesive is formed by applying an aqueous solution to a film and drying the film. In the preparation of the aqueous solution, a crosslinking agent, other additives, acid and other catalysts may be optionally blended.
Examples of the crosslinking agent to be blended in the aqueous adhesive include: boric acid, borax; a carboxylic acid compound; alkyl diamines; isocyanates; epoxy; monoaldehydes; dialdehydes; amino-formaldehyde resins; salts of divalent metals or trivalent metals, oxides thereof, and the like.
The active energy ray-curable adhesive is an adhesive that can be subjected to radical polymerization, cationic polymerization or anionic polymerization by irradiation with active energy rays such as electron beams and ultraviolet rays. Among them, a photoradically polymerizable adhesive that initiates radical polymerization by ultraviolet irradiation is preferable from the viewpoint of being curable with low energy.
Examples of the monomer of the radical-polymerizable adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group. Among them, a compound having a (meth) acryloyl group is preferable. As the compound having a (meth) acryloyl group, there may be mentioned: (meth) acrylic acid C 1-20 Alkyl (meth) acrylates such as chain alkyl esters, alicyclic alkyl (meth) acrylates, and polycyclic alkyl (meth) acrylates; (meth) acrylate containing a hydroxyl group; and epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate. The radical polymerizable adhesive may contain a nitrogen-containing monomer such as hydroxyethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, or (meth) acryloylmorpholine. The radical polymerizable adhesive may contain a polyfunctional monomer such as tripropylene glycol diacrylate, 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, cyclic trimethylolpropane formal acrylate, dioxane glycol diacrylate, EO (Ethylene oxide) modified diglycerol tetraacrylate, or the like as a crosslinking component.
The photo-curable adhesive such as a photo-radical polymerizable adhesive preferably contains a photopolymerization initiator. The photopolymerization initiator may be appropriately selected according to the reaction species. For example, in the radical polymerizable adhesive, a photo radical generator that generates radicals by light irradiation is preferably blended as the photopolymerization initiator. Specific examples of the photo radical generator will be described below. The content of the photoradical generator is usually about 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the monomer. In addition, when the radical-polymerizable adhesive is used in the form of an electron beam curable, a photopolymerization initiator is not particularly required. A photosensitizer typified by a carbonyl compound or the like may be added to the radical-polymerizable adhesive as needed. The photosensitizer is used to increase the curing speed and sensitivity obtained by an electron beam. The amount of the photosensitizer used is usually about 0.001 to 10 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the monomer.
The adhesive may contain suitable additives as necessary. Examples of the additives include: silane coupling agents, coupling agents such as titanium coupling agents, adhesion promoters such as ethylene oxide, ultraviolet absorbers, antioxidants, dyes, processing aids, ion capturing agents, antioxidants, tackifiers, fillers, plasticizers, leveling agents, foaming inhibitors, antistatic agents, heat stabilizers, hydrolysis stabilizers, and the like.
The adhesive is applied to either one or both of the surface of the resin coating layer 6 and the surface of the optical layer 4 provided on the alignment liquid crystal layer 1, and then cured, whereby the alignment liquid crystal layer 1 and the optical layer 4 provided with the resin coating layer 6 are laminated via the adhesive layer 3. The curing of the adhesive may be appropriately selected depending on the type of adhesive. For example, the aqueous adhesive may be cured by heating. The active energy ray-curable adhesive is curable by irradiation with active energy rays such as ultraviolet rays.
[ laminated Structure of oriented liquid Crystal films ]
The alignment liquid crystal film 103 in which the resin coating layer 6 is provided on the surface of the alignment liquid crystal layer 1 on the support substrate 8 and the optical layer 4 is bonded to the resin coating layer 6 via the adhesive layer 3 can be used as an optical member as it is. In this case, the support substrate 8 constitutes a part of the alignment liquid crystal film 103. Like the alignment liquid crystal film 100 shown in fig. 1, the support substrate can be peeled from the alignment liquid crystal layer 1. An appropriate adhesive layer 2 may be laminated on the surface of the alignment liquid crystal layer 1 exposed by peeling the support substrate as shown in fig. 5.
In the embodiment shown in fig. 5, the adhesive layer 2 is laminated on the exposed surface of the alignment liquid crystal layer 1 (the substrate surface when the alignment liquid crystal layer is formed) after the supporting substrate 8 is peeled off, but the adhesive layer may be laminated on the air surface side when the alignment liquid crystal layer is formed, and the optical layer may be laminated on the substrate surface side of the alignment liquid crystal layer via the resin coating layer and the adhesive layer.
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 2 is not particularly limited, and those based on an acrylic polymer, a silicone polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine polymer, a rubber polymer, or the like can be appropriately selected and used. Particularly, an adhesive having excellent transparency such as an acrylic adhesive or a rubber adhesive, exhibiting moderate wettability, cohesiveness and adhesiveness, and having excellent weather resistance, heat resistance, and the like is preferable. The thickness of the pressure-sensitive adhesive layer is appropriately set depending on the type of the adherend, and is generally about 5 to 500. Mu.m.
The lamination of the adhesive layer 2 on the alignment liquid crystal layer 1 is performed by, for example, bonding an adhesive formed in advance in a sheet shape to the surface of the alignment liquid crystal layer 1. After the adhesive composition is applied to the alignment liquid crystal layer 1, drying with a solvent, crosslinking, photo-curing, and the like may be performed to form the adhesive layer 2. In order to improve the adhesion (holding power) between the alignment liquid crystal layer 1 and the adhesive layer 2, the adhesive layer 2 may be laminated after the surface of the alignment liquid crystal layer 1 is subjected to surface treatment such as corona treatment or plasma treatment to form an easy-to-adhere layer.
The separator 9 is preferably temporarily bonded to the surface of the adhesive layer 2. The spacer 9 protects the surface of the adhesive layer 2 during the time from the attachment of the adhesive-carrying optical film to the image display unit 50. As a constituent material of the separator, a plastic film such as an acrylic resin, polyolefin, cyclic polyolefin, polyester, or the like is preferably used. The thickness of the separator is usually about 5 to 200. Mu.m. The surface of the separator is preferably subjected to a mold release treatment. Examples of the release agent include silicone-based materials, fluorine-based materials, long-chain alkyl-based materials, and fatty amide-based materials.
The exposed surface of the alignment liquid crystal layer 1 after the support substrate 8 is peeled off may be laminated with another optical layer via an appropriate adhesive layer or adhesive layer. For example, as shown in fig. 6, another optical layer 5 may be laminated on the alignment liquid crystal layer 1 via an appropriate adhesive layer 7. An adhesive layer (not shown) may be further laminated on the optical layer 5, and the separator may be temporarily bonded to the surface of the adhesive layer.
The support substrate 8 may be peeled off from the alignment liquid crystal layer 1, and the resin solution may be applied to the surface of the alignment liquid crystal layer 1 exposed by the peeling off of the support substrate to form the resin coating layer 16. As shown in fig. 7, the optical layer 5 may be bonded to the resin coating layer 16 provided on the surface of the alignment liquid crystal layer 1 exposed by peeling of the support substrate via the adhesive layer 7.
In fig. 7, the resin coatings 6 and 16 are provided on both sides of the alignment liquid crystal layer 1, but the resin coatings may be provided on only one side of the alignment liquid crystal layer 1. The resin coating 16 may be formed only on the exposed surface (substrate surface when the alignment liquid crystal layer is formed) of the alignment liquid crystal layer 1 (air surface when the alignment liquid crystal layer is formed) of the laminate 101 in which the alignment liquid crystal layer 1 is laminated on the support substrate 8 in an adhered state, by bonding other layers via an adhesive layer or an adhesive layer, and peeling the support substrate 8 from the alignment liquid crystal layer 1.
< circular polarizer >)
The alignment liquid crystal film can be used as an optical film for a display for the purpose of improving visibility and the like. For example, in a liquid crystal display device, a phase difference plate as an optical compensation film may be disposed between an image display unit (liquid crystal cell) and a polarizer in order to appropriately change the polarization state of light emitted from the liquid crystal cell to the viewer side, thereby improving viewing angle characteristics.
In one embodiment, the alignment liquid crystal film is a circular polarizing plate in which a polarizing plate as the optical layer 4 is bonded to a resin coating layer 6 formation surface on the alignment liquid crystal layer 1 via the adhesive layer 3. The circularly polarizing plate may have 2 or more alignment liquid crystal layers.
The polarizer may be formed of only 1 layer of polarizer, and as described above, a transparent protective film may be attached to one or both sides of the polarizer. Examples of the polarizer include: a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene-vinyl acetate copolymer partially saponified film, is obtained by adsorbing a dichroic substance such as iodine or a dichroic dye, and uniaxially stretching the film; and a multi-functional oriented film such as a dehydrated polyvinyl alcohol product and a desalted polyvinyl chloride product.
Among them, a polyvinyl alcohol (PVA) -based polarizer in which a polyvinyl alcohol-based film such as polyvinyl alcohol or partially formalized polyvinyl alcohol adsorbs a dichroic substance such as iodine or a dichroic dye and is oriented in a predetermined direction is preferable from the viewpoint of having a high degree of polarization. For example, a PVA-based polarizer is obtained by subjecting a polyvinyl alcohol film to iodine dyeing and stretching. A PVA-based resin layer may be formed on a resin substrate, and iodine dyeing and stretching may be performed in a laminate state.
In the circular polarizer in which the polarizer and the alignment liquid crystal layer are laminated, it is preferable that at least 1 layer of the alignment liquid crystal layer has liquid crystal molecules aligned in parallel. In the circularly polarizing plate, the alignment direction of the liquid crystal molecules in the aligned liquid crystal layer in which the liquid crystal molecules are aligned in parallel is disposed so as to be neither parallel nor orthogonal to the absorption axis direction of the polarizer.
For example, in the case where the circularly polarizing plate has only 1 layer of aligned liquid crystal layer, the aligned liquid crystal layer 1 is a 1/4 wavelength plate, and the angle between the absorption axis direction of the polarizer and the alignment direction (generally the slow axis direction) of the liquid crystal molecules is set to 45 °. The angle between the absorption axis direction of the polarizer and the alignment direction of the liquid crystal molecules may be 35 to 55 °, 40 to 50 °, or 43 to 47 °.
In a structure in which the polarizing plate 4 and the alignment liquid crystal layer 1, which is a 1/4 wavelength plate, are stacked so that an angle formed by optical axes of both becomes 45 °, an alignment liquid crystal layer in which liquid crystal molecules are aligned perpendicularly (homeotropic alignment) to a substrate surface may be further provided as the optical layer 5. By sequentially stacking the alignment liquid crystal layer 1 functioning as a 1/4 wavelength plate and the vertical alignment liquid crystal layer 5 functioning as a positive C plate on the polarizing plate, a circular polarizing plate capable of shielding reflected light even from external light from an oblique direction can be formed. A vertical alignment liquid crystal layer (positive C plate) and a parallel alignment liquid crystal layer (1/4 wavelength plate as positive a plate) may be sequentially laminated on the polarizing plate.
As shown in fig. 6 and 7, in a circular polarizing plate in which a plurality of alignment liquid crystal layers 1 and 5 are laminated on a polarizing plate 4 as an optical layer, the alignment liquid crystal layers 1 and 5 may be parallel alignment liquid crystal layers. In this case, the alignment liquid crystal layer 1 disposed on the side closer to the polarizing plate 4 is preferably a 1/2 wavelength plate, and the alignment liquid crystal layer 5 disposed on the side farther from the polarizing plate is preferably a 1/4 wavelength plate. In this laminated structure, it is preferable that the angle between the slow axis direction of the 1/2 wavelength plate and the absorption axis direction of the polarizer is 75 ° ± 5 °, and the angle between the slow axis direction of the 1/4 wavelength plate and the absorption axis direction of the polarizer is 15 ° ± 5 °. The circularly polarizing plate having such a laminated structure functions as a circularly polarizing plate in a wide wavelength range of visible light, and therefore, coloring of reflected light can be reduced.
As shown in fig. 8, a circular polarizing plate in which a plurality of alignment liquid crystal layers 1 and 5 are laminated on a polarizing plate 4 may be configured as follows: the resin coating 6 is disposed between the alignment liquid crystal layer 1 and the alignment liquid crystal layer 5, and the resin coating is not disposed between the alignment liquid crystal layer 1 and the polarizing plate 4. For example, as shown in fig. 3, after the resin coating layer 6 is provided on the surface of the alignment liquid crystal layer 1, the alignment liquid crystal layer 5 is bonded to the resin coating layer 6 via the adhesive layer 7, whereby as shown in fig. 9, a laminate (alignment liquid crystal film) 113 is obtained in which the alignment liquid crystal layer is bonded to the resin coating layer 6 formation surface of the alignment liquid crystal layer 1 via the adhesive layer 7. By peeling the support substrate 8 from the laminate, and attaching the polarizing plate 4 via the adhesive layer 12 to the alignment liquid crystal layer 1 exposed by peeling the support substrate, a laminate 107 is obtained in which the resin coating layer 6 is provided on one surface of the alignment liquid crystal layer 1, the alignment liquid crystal layer 5 is laminated thereon via the adhesive layer 7, and the polarizing plate 4 is attached to the other surface of the alignment liquid crystal layer 1 via the adhesive layer 12, as shown in fig. 8.
In one embodiment of the laminate 107, the alignment liquid crystal layer 1 disposed on the side closer to the polarizing plate 4 is a parallel alignment liquid crystal layer that is a 1/4 wavelength plate, and the alignment liquid crystal layer 5 disposed on the side farther from the polarizing plate 4 is a vertical alignment liquid crystal layer that is a positive C plate. In this embodiment, the alignment liquid crystal layer 5 is bonded to the resin coating layer formation surface 6 of the alignment liquid crystal layer 1 via the adhesive layer 7.
The adhesive layer 7 is formed by curing an adhesive that is a curable material, and since the uncured resin coating layer 6 is formed on the alignment liquid crystal layer 1, a change in the front retardation of the alignment liquid crystal layer 1 due to heating is suppressed. The resin coating is not provided on the surface of the alignment liquid crystal layer 1 bonded to the polarizing plate 4, but the alignment liquid crystal layer 1 and the polarizing plate 4 are bonded via the adhesive layer 12 (non-curable material), so that it is difficult to cause a decrease in the heat durability that can be seen when the adhesive layer is directly formed on the alignment liquid crystal layer.
Thus, the laminated body 107 shown in fig. 8 has the following structure: since the non-curable resin coating 6 is provided on the parallel alignment liquid crystal layer 1, and the alignment liquid crystal layer 5 as a positive C plate (optical layer) is bonded thereto via the adhesive layer 7, the change in front retardation is small even when exposed to a high temperature environment for a long period of time, and thus the film is suitable for use as a circularly polarizing plate for a liquid crystal display device, an organic EL display device, or the like. In the laminate 107, the alignment liquid crystal layer 5 as the positive C plate is in contact with the adhesive layer 7, but the front retardation of the positive C plate is substantially 0, so that even when the laminate 107 is exposed to a high temperature environment for a long period of time, the front retardation hardly changes.
[ image display device ]
Fig. 10 is a cross-sectional view showing an example of a laminated structure of the image display device, and an alignment liquid crystal film including an alignment liquid crystal layer 1 is bonded to a surface of an image display unit 50 via an adhesive layer 2. The alignment liquid crystal film may have 2 or more alignment liquid crystal layers. The image display unit 50 includes a liquid crystal unit, an organic EL unit, and the like.
As described above, the alignment liquid crystal film improves the heating durability of the alignment liquid crystal layer by providing the resin coating layer on the surface of the alignment liquid crystal layer. An image display device having an alignment liquid crystal layer with a resin coating layer formed on the surface has little change in retardation of the alignment liquid crystal layer even when exposed to a heating environment for a long period of time, and therefore has little change in visibility and excellent heating durability.
Examples (example)
The present invention will be described in further detail with reference to examples of production of an oriented liquid crystal film, but the present invention is not limited to the examples described below.
[ production of parallel alignment liquid Crystal film ]
Comparative example 1 >
A photopolymerizable liquid crystal compound (Paliocolor LC242 manufactured by BASF) exhibiting a nematic liquid crystal phase was dissolved in cyclopentanone to prepare a solution having a solid content concentration of 30% by weight. To this solution were added a surfactant (BYK-360 manufactured by BYK-Chemie) and a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), to prepare a liquid crystal composition solution. The amounts of the leveling agent and the polymerization initiator to be added were set to 0.01 part by weight and 3 parts by weight, respectively, relative to 100 parts by weight of the photopolymerizable liquid crystal compound.
As a Film base material, a biaxially stretched norbornene-based Film (manufactured by Nippon Denshoku, "Zeonor Film", thickness: 33 μm, front retardation: 135 nm) was used. The liquid crystal composition was applied to the surface of the film substrate by a bar coater so that the thickness of the film substrate after drying became 1. Mu.m, and the film was heated at 100℃for 3 minutes to orient the liquid crystal. After cooling to room temperature, the mixture was irradiated under a nitrogen atmosphere with an accumulated light quantity of 400mJ/cm 2 Ultraviolet rays of (2) are photo-cured to obtain a laminate in which a parallel alignment liquid crystal layer is formed on a film substrate.
Examples 1 to 6 >
The resins shown in table 1 were dissolved in a mixed solvent of cyclopentanone and ethyl acetate so that the solid content concentration became 3 wt%, to prepare resin solutions. After the resin solution was applied to the surface of the alignment liquid crystal layer of the laminate of comparative example 1 with the bar (# 10), the solvent was removed by heating at 85 ℃. In table 1, the acrylic resins of examples 1 to 3 were obtained by the phophyllota synthesis, and the epoxy resins of examples 4 to 6 and comparative example 3 were obtained by mitsubishi chemistry.
Comparative example 2 >
After cyclopentanone was coated on the surface of the alignment liquid crystal layer of the laminate of comparative example 1 using a bar (# 10), the solvent was removed by heating at 85 ℃ for 1 minute.
Comparative example 3 >
A photocurable resin composition (solution) was prepared by dissolving bisphenol A type epoxy resin having an epoxy equivalent of about 190 (Mitsubishi chemical system "jER828" and photo-cationic polymerization initiator (SAN-APRO system "CPI 100P") in a mixed solvent of cyclopentanone and ethyl acetate so that the epoxy resin concentration became 3% by weight, coating the composition on the surface of the oriented liquid crystal layer of the laminate of comparative example 1 with a bar (# 10), heating at 85℃to remove the solvent, and then irradiating ultraviolet rays to photocure the epoxy resin.
[ production of polarizing plate (circular polarizing plate) having oriented liquid Crystal layer ]
A laminate (single-protective polarizer) was prepared in which a PVA polarizer having a thickness of 5 μm was provided on one side of an unstretched norbornene Film (Zeonor Film manufactured by Japan Rumex) having a thickness of 20 μm via a UV-curable adhesive.
Ext> Aext> UVext> curableext> adhesiveext> compositionext> wasext> preparedext> byext> mixingext> 62ext> partsext> byext> weightext> ofext> hydroxyethylext> acrylamideext> (ext> "ext> HEAAext>"ext> manufacturedext> byext> Xinginext>,ext> 25ext> partsext> byext> weightext> ofext> acryloylmorpholineext> (ext> "ext> ACMOext>"ext> manufacturedext> byext> Xinginext>,ext> Inc.ext>)ext>,ext> 7ext> partsext> byext> weightext> ofext> PEGext> 400ext> #ext> diacrylateext> (ext> "ext> Lightext> Acrylateext> 9ext> EGext> -ext> Aext>"ext> manufacturedext> byext> Kyowaext> Chemicalsext>,ext> Inc.ext>)ext>,ext> 3ext> partsext> byext> weightext> ofext> photopolymerizationext> initiatorext> (ext> "ext> Omniradext> 907ext>"ext> manufacturedext> byext> IGMext> resinsext>)ext>,ext> andext> 3ext> partsext> byext> weightext> ofext> 2ext>,ext> 4ext> -ext> diethylthioxanthoneext> (ext> "ext> Kayacureext> DETXext> -ext> Sext>"ext> manufacturedext> byext> Japaneseext> chemicalext>)ext>.ext> The adhesive was applied to the surface of the single protective polarizer to a thickness of about 1 μm, and the surfaces of the laminates of examples 1 to 6 and comparative examples 1 to 3 on the alignment liquid crystal layer side were bonded to the adhesive-applied layer, and then irradiated with a cumulative light amount of 1000mJ/cm 2 The adhesive is cured by ultraviolet rays of (a). In the bonding, the absorption axis direction of the polarizer is aligned with the liquid crystal molecules in the liquid crystal layerThe orientation direction (the slow axis direction of the film substrate) makes an angle of 45 °.
The film base material was peeled off from the alignment liquid crystal film, an acrylic adhesive sheet having a thickness of 15 μm was bonded to the surface of the alignment liquid crystal film, and an alignment liquid crystal layer was bonded to a polarizer of the single protective polarizer via a UV curable adhesive layer, to obtain a polarizer having the acrylic adhesive sheet thereon.
In examples 1 to 6 and comparative example 3, a resin layer having a thickness of about 300nm was formed between the adhesive layer and the alignment liquid crystal layer.
[ evaluation ]
< appearance >
The film surface after the formation of the resin coating (after the surface treatment with cyclopentanone in comparative example 2) was visually observed, and the case where no precipitate was confirmed was noted as OK, and the case where a precipitate was confirmed was noted as NG.
< delay Change >)
An evaluation sample was prepared by bonding the pressure-sensitive adhesive layer of the polarizing plate to a glass plate. After measuring the front retardation at a wavelength of 590nm by a phase difference meter ("KOBRA 21-ADH" manufactured by prince measuring machine), the sample for evaluation was put into an air circulation type constant temperature oven at 85℃for 120 hours. After taking out the sample from the oven, the front retardation was measured again, and the change rate of the retardation before and after the heating test was calculated.
< hue Change >)
The pressure-sensitive adhesive layer of the polarizing plate was bonded to a corning alkali-free glass to prepare an evaluation sample. An aluminum vapor deposited polyester film (DMS-X42 manufactured by Toli advanced film) was disposed under alkali-free glass of the sample for evaluation, and light was irradiated from the polarizer side using a spectrocolorimeter (CM-2600 d manufactured by Konikoku Meida), and the hue (a in Lab color space) of the reflected light was measured by the SCI method * B * Is a value of (2). Then, the sample for evaluation was put into an air circulation type constant temperature oven at 85℃for 120 hours. After taking out the sample from the oven, the hue of the reflected light was measured again on the aluminum vapor deposited polyester film, and the amount of change in the hue of the reflected light before and after the heating test was calculated { (Δa) ＊ ) 2 +(Δb ＊ ) 2 }。
Table 1 shows the evaluation results of the types of resins and the alignment liquid crystal films for forming the resin coatings in examples 1 to 6 and comparative examples 1 to 3.
TABLE 1
In comparative example 1 in which the surface treatment of the alignment liquid crystal layer was not performed, the amount of change in Re before and after the heating test was 3%, whereas in comparative example 2 in which the treatment with cyclopentanone was performed, the change in Re was suppressed, and the change in hue of the reflected light was also suppressed. However, in comparative example 2, the presence of a precipitate on the surface of the alignment liquid crystal layer was confirmed, and an appearance defect was generated.
In examples 1 to 6 in which the resin coating layer was formed on the alignment liquid crystal layer using the non-curable resin, the Re change and the hue change of the reflected light were suppressed and the appearance was also good as compared with comparative example 1. The resin composition was extracted by dissolving the resin coating surface of example 1 in tetrahydrofuran, and analysis was performed by MALDI-TOF mass spectrometry, and as a result, unreacted liquid crystal monomer was confirmed. From these results, it is considered that by coating the resin solution, uncured material or the like in the alignment liquid crystal layer is extracted and taken into the resin coating layer, which contributes to improvement of the heating durability of the alignment liquid crystal layer.
In comparative example 3 in which UV curing of the resin layer was performed after coating the alignment liquid crystal layer with the photo cation curable resin composition, the front surface Re was lowered after the heat durability test, and the heat durability was insufficient. From these results, it was found that by forming a non-curable resin coating layer on the alignment liquid crystal layer, the heating durability of the alignment liquid crystal layer was improved, and a circularly polarizing plate having little retardation change, and little coloration and color change of reflected light was obtained.
[ example of producing circular polarizing plate having multiple alignment liquid Crystal layers ]
< fabrication of parallel alignment liquid Crystal layer >
55 parts by weight of a compound represented by the formula (I), 25 parts by weight of a compound represented by the formula (II) and 20 parts by weight of a compound represented by the formula (III) were added to 400 parts by weight of cyclopentanone, and after heating to 60℃and stirring and dissolving, the mixture was cooled to room temperature to prepare a solution having a solid content concentration of 20% by weight.
[ chemical formula number 1]
To this solution, 0.2 parts by weight of a surfactant (MEGAFAC F-554, DIC), 3 parts by weight of a photopolymerization initiator (Omnirad 907, IGM Resins) and 0.1 parts by weight of p-methoxyphenol were added to prepare a liquid crystal composition solution.
As the film base material, a film having an alignment film subjected to polishing treatment on a triacetyl cellulose film was used. The liquid crystal composition was spin-coated on an alignment film of a film substrate, and the liquid crystal was aligned by heating at 100℃for 2 minutes. After cooling to room temperature, the mixture was irradiated with a cumulative light amount of 900mJ/cm under a nitrogen atmosphere 2 The ultraviolet ray of (a) was photo-cured to obtain a laminate a in which a parallel alignment liquid crystal layer (thickness: 4 μm) was formed on a film substrate. The front retardation was measured by transferring the alignment liquid crystal layer onto a glass plate, and as a result, the front retardation R (550) at a wavelength of 550nm was 130nm, and the ratio R (450)/R (550) of the front retardation R (550) at a wavelength of 550nm to the front retardation R (450) at a wavelength of 450nm was 0.85.
< fabrication of vertical alignment liquid Crystal layer >
A side chain type liquid crystal polymer having a weight average molecular weight of 5000 represented by the following chemical formula (n=0.35, expressed as a block polymer) was used for convenience: 20 parts by weight of a polymerizable liquid crystal compound exhibiting a nematic liquid crystal phase (BASF "Paliocolor LC 242"): 80 parts by weight and a photopolymerization initiator (made by IGM Resins "Omnirad 907"): 5 parts by weight of the resulting mixture was dissolved in 400 parts by weight of cyclopentanone to prepare a liquid crystal composition.
[ chemical formula number 2]
As a film base material, a biaxially stretched norbornene-based film (ZEONOA film, manufactured by Japanese Rui Weak Co., ltd., thickness: 52 μm, front retardation: 50 nm) was used. The liquid crystal composition was applied to the surface of the film substrate by a bar coater so that the thickness of the film substrate after drying became 1. Mu.m, heated at 80℃for 2 minutes, cooled to room temperature for aligning the liquid crystal, and then irradiated with a nitrogen atmosphere at 700mJ/cm 2 The liquid crystal monomer was photo-cured by ultraviolet rays to obtain a laminate B in which a vertically aligned liquid crystal layer was formed on a film substrate.
< production of adhesive sheet >
92 parts by weight of butyl acrylate, 5 parts by weight of N-acryloylmorpholine, 2.9 parts by weight of acrylic acid, 0.1 part by weight of 2-hydroxyethyl acrylate and 0.1 part by weight of 2,2' -azobisisobutyronitrile as a polymerization initiator were added together with ethyl acetate in a reaction vessel, and reacted at 55℃for 8 hours under a nitrogen gas stream. Then, ethyl acetate was added to the reaction solution to obtain a solution of an acrylic polymer having a weight average molecular weight of 178 ten thousand. To this solution, 0.15 parts by weight of dibenzoyl peroxide (japan oil & fat system "nyer BMT") and 0.6 parts by weight of trimethylolpropane/toluene diisocyanate adduct (easter system "cornate L") were blended as a crosslinking agent with respect to 100 parts by weight of the polymer, to obtain an adhesive composition. The adhesive composition was applied to the release treated surface of a release film (silicone release treated polyethylene terephthalate film), and dried and crosslinked at 150℃to prepare an adhesive sheet having a thickness of 5. Mu.m.
Example 7 >
A resin solution was prepared by dissolving an acrylic polymer having a weight average molecular weight of 80000, which was obtained by copolymerizing methyl methacrylate and 3-methacrylamidophenylboronic acid in a weight ratio of 97:3, in ethyl acetate so that the solid content concentration became 3% by weight. After the resin solution was applied to the surface of the parallel alignment liquid crystal layer of the laminate a with a bar (# 10), the solvent was removed by heating at 85 ℃, and a resin coating layer having a thickness of about 300nm was formed on the surface of the parallel alignment liquid crystal layer, thereby obtaining a laminate D having the parallel alignment liquid crystal layer and the resin coating layer in this order on the film base material.
The UV curable adhesive was applied to a thickness of about 1 μm on the resin coating layer of the laminate D, and the surface of the laminate B on the side of the vertically aligned liquid crystal layer was bonded to the adhesive coating layer, and then the cumulative light amount was 1000mJ/cm 2 The adhesive is cured by ultraviolet rays of (a).
Then, the film base material is peeled off from the surface of the parallel alignment liquid crystal layer, and the surface of the single protective polarizer on the exposed parallel alignment liquid crystal layer is bonded via the adhesive layer. In the lamination, an angle between the absorption axis direction of the polarizer and the alignment direction of the liquid crystal molecules in the parallel alignment liquid crystal layer (rubbing direction of the alignment film of the film base material) was set to 45 °. Then, the film base material was peeled off from the surface of the vertically aligned liquid crystal layer, and the parallel aligned liquid crystal layer was bonded to the polarizer side surface of the single protective polarizer via the adhesive layer, to obtain a laminate (circularly polarizing plate) having the vertically aligned liquid crystal layer bonded thereto via the resin coating layer and the adhesive layer.
Comparative example 4 >
In the same manner as in example 7, a resin coating layer having a thickness of about 300nm was formed on the surface of the parallel alignment liquid crystal layer, to obtain a laminate D. The polarizer-side surface of the single-protective polarizer was bonded to the resin coating layer of the laminate D via the adhesive layer. In the lamination, an angle between the absorption axis direction of the polarizer and the alignment direction of the liquid crystal molecules in the parallel alignment liquid crystal layer (rubbing direction of the alignment film of the film base material) was set to 45 °.
Then, the film base material was peeled off from the surface of the parallel alignment liquid crystal layer, the UV curable adhesive was applied to the exposed parallel alignment liquid crystal layer at a thickness of about 1 μm, and the surface of the laminate B on the side of the vertical alignment liquid crystal layer was bonded to the adhesive coating layer, and then the cumulative light amount was irradiated at 1000mJ/cm 2 The adhesive is cured by ultraviolet rays of (a). Then, the film base material is peeled off from the surface of the homeotropically aligned liquid crystal layer, and the surface of the single protective polarizer on the polarizer side is adhered thereto via adhesionThe mixture layer was laminated with the resin coating layer and the parallel alignment liquid crystal layer to obtain a laminate (circularly polarizing plate) in which the perpendicular alignment liquid crystal layer was laminated on the parallel alignment liquid crystal layer via the adhesive layer.
Example 8 >
Instead of the acrylic polymer solution, a solution of 85 weight ratio: 15A methyl ethyl ketone solution containing an acrylic polymer and an epoxy resin (Mitsubishi chemical corporation "jER YX7200B 35") in a solid content concentration of 3% by weight. Except for this, a resin coating layer having a thickness of about 300nm was formed on the surface of the parallel alignment liquid crystal layer in the same manner as in example 7. Thereafter, in the same manner as in example 7, a parallel alignment liquid crystal layer was bonded to the polarizer side surface of the single protective polarizer via an adhesive layer, and a laminate (circular polarizer) having a vertical alignment liquid crystal layer bonded thereto via a resin coating layer and an adhesive layer was obtained.
Example 9 >
A circularly polarizing plate was produced in the same manner as in example 8, except that the thickness of the resin coating layer was changed to about 600 nm.
Comparative example 5 >
In the same manner as in example 8, a resin coating layer having a thickness of about 300nm was formed on the surface of the parallel alignment liquid crystal layer using a mixed resin solution of an acrylic polymer and an epoxy resin. Thereafter, in the same manner as in comparative example 4, a laminate of the resin coating layer and the parallel alignment liquid crystal layer was bonded to the polarizer side surface of the single protective polarizer via the adhesive layer, and a laminate (circular polarizer) in which the vertical alignment liquid crystal layer was bonded to the parallel alignment liquid crystal layer via the adhesive layer was obtained.
[ evaluation ]
On the surfaces of the circularly polarizing plates of examples 7 to 9 and comparative examples 4 and 5 on the side of the vertically aligned liquid crystal layer, an acrylic pressure-sensitive adhesive sheet having a thickness of 15 μm was bonded, and the pressure-sensitive adhesive sheet was bonded to a glass plate to prepare a sample for evaluation. After measuring the front retardation (initial value) at a wavelength of 590nm by a phase difference meter (KOBRA 21-ADH manufactured by prince measuring machine), the sample for evaluation was put into an air circulation type constant temperature oven at 85℃and the front retardation was measured after 120 hours, 240 hours and 500 hours, and the rate of change from the initial value was calculated.
Table 2 shows the laminated structure of the circularly polarizing plates of examples 7 to 9 and comparative examples 4 and 5, the polymer type and thickness of the resin coating, and the change rate of the front retardation in the heat durability test (after 120 hours, after 240 hours, and after 500 hours).
TABLE 2
In comparative examples 4 and 5 in which an adhesive layer was provided in contact with a parallel alignment layer and a vertical alignment liquid crystal layer was bonded, a reduction in front retardation of 1% or more was observed by a 120-hour heating test, whereas in examples 7 to 9 in which a resin coating layer was provided on a parallel alignment liquid crystal layer and a vertical alignment liquid crystal layer was bonded thereto via an adhesive layer, the change in front retardation due to a heating durability test was suppressed.
From these results, it is clear that by providing the resin coating layer so that the parallel alignment liquid crystal layer is not in contact with the cured adhesive layer, the heating durability of the alignment liquid crystal layer is improved and the change in retardation is suppressed. As is clear from the comparison between example 8 and example 9, when the thickness of the resin coating layer is large, the heating durability tends to be improved (the retardation change is suppressed).
[ description of reference numerals ]
1. Alignment liquid crystal layer
6. Resin coating
8. Support substrate
4. Optical layer (polarizing plate)
5. Optical layer (oriented liquid crystal layer)
3,7 adhesive layer
2, 12 adhesive layer
9. Partition board
50. And an image display unit.
Claims (23)
1. An oriented liquid crystal film comprising: a first alignment liquid crystal layer in which liquid crystal molecules are aligned; a resin coating layer in contact with a first main surface of the first alignment liquid crystal layer; and an optical layer bonded to the resin coating layer via an adhesive layer, wherein the resin coating layer is a non-curable resin layer.
2. The oriented liquid crystal film according to claim 1, wherein the glass transition temperature of the resin coating layer is 20 ℃ or higher.
3. The oriented liquid crystal film according to claim 1 or 2, wherein the adhesive layer has a thickness of 0.01 to 5 μm.
4. The oriented liquid crystal film according to any one of claims 1 to 3, wherein the adhesive constituting the adhesive layer is an active energy ray-curable adhesive.
5. The oriented liquid crystal film according to any one of claims 1 to 4, wherein the optical layer is a polarizer, a transparent film or other oriented liquid crystal layer.
6. The oriented liquid crystal film according to any one of claims 1 to 5, wherein the thickness of the resin coating layer is 0.05 to 3 μm.
7. The oriented liquid crystal film according to any one of claims 1 to 6, wherein a weight average molecular weight of a resin material constituting the resin coating layer is 2 ten thousand or more.
8. The oriented liquid crystal film according to any one of claims 1 to 7, wherein the resin coating layer comprises a non-curable acrylic resin or a non-curable epoxy resin.
9. The oriented liquid crystal film according to any one of claims 1 to 8, wherein an uncured product of a liquid crystal compound constituting the first oriented liquid crystal layer is contained in the resin coating layer.
10. The oriented liquid crystal film according to any one of claims 1 to 9, wherein an adhesive layer is provided on the second main surface side of the first oriented liquid crystal layer.
11. The oriented liquid crystal film according to any one of claims 1 to 10, wherein in the first oriented liquid crystal layer, liquid crystal molecules are oriented in parallel.
12. The oriented liquid crystal film according to claim 11, wherein the optical layer comprises a polarizer, and an angle formed between an orientation direction of liquid crystal molecules in the first oriented liquid crystal layer and an absorption axis direction of the polarizer is 10 to 80 °.
13. The alignment liquid crystal film according to claim 11 or 12, wherein the optical layer is a second alignment liquid crystal layer in which liquid crystal molecules are vertically aligned, and a polarizing plate is bonded to the second main surface side of the first alignment liquid crystal layer.
14. The oriented liquid crystal film according to claim 13, wherein the first oriented liquid crystal layer and the polarizing plate are bonded via an adhesive layer.
15. The oriented liquid crystal film of claim 14, wherein the adhesive layer is in contact with the second major face of the first oriented liquid crystal layer.
16. An image display device comprising an image display unit and the alignment liquid crystal film according to any one of claims 1 to 15 disposed on the image display unit.
17. A method for producing an alignment liquid crystal film according to any one of claims 1 to 15, wherein a resin solution containing a resin and an organic solvent is applied to a first main surface of the first alignment liquid crystal layer to form the resin coating layer; and bonding the resin coating layer and the optical layer via an adhesive.
18. The method for producing an oriented liquid crystal film according to claim 17, wherein the resin solution is applied and then heated at 40 to 150 ℃ before the optical layer is bonded.
19. The method for producing an alignment liquid crystal film according to claim 17 or 18, wherein the first alignment liquid crystal layer is formed by applying a liquid crystal composition containing a photopolymerizable liquid crystal monomer onto a support substrate, heating the liquid crystal composition on the support substrate to align the liquid crystal monomer in a liquid crystal state, and polymerizing or crosslinking the liquid crystal monomer by light irradiation.
20. The method for producing an oriented liquid crystal film according to claim 19, wherein the supporting substrate is a resin film.
21. The method for producing an oriented liquid crystal film according to claim 19 or 20, wherein the resin solution is applied to a surface of the first oriented liquid crystal layer which is not in contact with the support substrate in a state where the first oriented liquid crystal layer is provided on the support substrate.
22. The method for producing an oriented liquid crystal film according to claim 19 or 20, wherein the supporting substrate is peeled off from the first oriented liquid crystal layer, and the resin solution is applied to the surface of the first oriented liquid crystal layer exposed by peeling off the supporting substrate.
23. The method for producing an oriented liquid crystal film according to any one of claims 17 to 22, wherein the organic solvent of the resin solution has solubility for the photopolymerizable liquid crystal monomer and does not dissolve or hardly dissolves a photocurable product of the photopolymerizable liquid crystal monomer.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020144989 | 2020-08-28 | ||
| JP2020-144989 | 2020-08-28 | ||
| JP2021091403A JP2022039954A (en) | 2020-08-28 | 2021-05-31 | Aligned liquid crystal film, method of manufacturing the same, and image display device |
| JP2021-091403 | 2021-05-31 | ||
| PCT/JP2021/030220 WO2022044925A1 (en) | 2020-08-28 | 2021-08-18 | Alignment liquid crystal film, method for manufacturing same, and image display device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116261681A true CN116261681A (en) | 2023-06-13 |
Family
ID=76920381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180053493.3A Pending CN116261681A (en) | 2020-08-28 | 2021-08-18 | Oriented liquid crystal film, method for producing the same, and image display device |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP6906670B1 (en) |
| KR (1) | KR20230056711A (en) |
| CN (1) | CN116261681A (en) |
| TW (1) | TW202208895A (en) |
| WO (1) | WO2022044925A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4066318B2 (en) * | 2001-02-23 | 2008-03-26 | 日本化薬株式会社 | Retardation film comprising UV-curable resin composition for alignment film and polymer film having liquid crystal compound |
| JP6318481B2 (en) | 2013-06-25 | 2018-05-09 | 大日本印刷株式会社 | Method for producing optical film transfer body, method for producing optical film |
| JP2016139566A (en) * | 2015-01-28 | 2016-08-04 | Ｊｘエネルギー株式会社 | Organic electroluminescence display device |
| KR102641042B1 (en) * | 2015-07-24 | 2024-02-26 | 스미또모 가가꾸 가부시끼가이샤 | Laminated body, circularly polarizing plate including laminated body, display device including laminated body |
| TWI719177B (en) * | 2016-03-30 | 2021-02-21 | 日商日本瑞翁股份有限公司 | Optically anisotropic laminated body, circular polarizing plate and image display device |
| JP6632479B2 (en) * | 2016-05-31 | 2020-01-22 | 富士フイルム株式会社 | Half mirror and mirror with image display function |
-
2020
- 2020-09-16 TW TW109131839A patent/TW202208895A/en unknown
- 2020-09-25 JP JP2020160923A patent/JP6906670B1/en active Active
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2021
- 2021-05-31 JP JP2021091403A patent/JP2022039954A/en active Pending
- 2021-08-18 WO PCT/JP2021/030220 patent/WO2022044925A1/en active Application Filing
- 2021-08-18 CN CN202180053493.3A patent/CN116261681A/en active Pending
- 2021-08-18 KR KR1020237009245A patent/KR20230056711A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022044925A1 (en) | 2022-03-03 |
| TW202208895A (en) | 2022-03-01 |
| JP2022039873A (en) | 2022-03-10 |
| JP2022039954A (en) | 2022-03-10 |
| JP6906670B1 (en) | 2021-07-21 |
| KR20230056711A (en) | 2023-04-27 |
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