WO2019216122A1 - 液晶塗布用基材フィルム、これを含む仮支持体付き光学フィルム、これらを含む偏光板、ならびにこれらの製造方法 - Google Patents
液晶塗布用基材フィルム、これを含む仮支持体付き光学フィルム、これらを含む偏光板、ならびにこれらの製造方法 Download PDFInfo
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- WO2019216122A1 WO2019216122A1 PCT/JP2019/016026 JP2019016026W WO2019216122A1 WO 2019216122 A1 WO2019216122 A1 WO 2019216122A1 JP 2019016026 W JP2019016026 W JP 2019016026W WO 2019216122 A1 WO2019216122 A1 WO 2019216122A1
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- Prior art keywords
- liquid crystal
- film
- temporary support
- layer
- negative resin
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Images
Classifications
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- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- 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
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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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
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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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to a substrate film for applying a liquid crystal, an optical film with a temporary support containing the same, a polarizing plate containing them, and a method for producing them.
- organic EL organic electroluminescence
- a metal material having high light reflectivity is used as the electrode layer constituting the cathode, or a metal plate is separately provided as a light reflecting member. Therefore, a method in which a light reflecting member having a mirror surface is provided on a surface opposite to the light extraction surface has become common.
- the circularly polarizing plate is generally formed by laminating an absorption linear polarizer and a ⁇ / 4 retardation film.
- a circularly polarizing plate as an antireflection film is required not only to have low reflectance but also to have no color in the reflected light (neutral black) and to maintain this low reflectance and neutral black even when viewed from an oblique direction. It has been. In order to exhibit this performance, it is not sufficient that the phase difference at the center wavelength of the ⁇ / 4 retardation film is ⁇ / 4, but chromatic dispersion exhibiting a ⁇ / 4 phase difference in the entire wavelength band of visible light. It is ideal to have (reverse dispersion).
- Nz factor (nx ⁇ nz) / (nx ⁇ ny), which is an index of maintaining performance of ⁇ / 4 phase difference in an oblique field of view, is small.
- nx is the refractive index in the direction x where the refractive index is maximum in the in-plane direction of the film
- ny is the refractive index in the direction y perpendicular to the direction x in the in-plane direction of the film
- nz is the refractive index in the thickness direction of the film.
- JP-A-2004-77719 discloses a rod-like liquid crystal compound that is horizontally aligned on a long transparent support. And a first optically anisotropic layer having a retardation of ⁇ / 2 at a wavelength of 550 nm and a horizontally aligned rod-shaped liquid crystalline compound, and having a retardation of ⁇ / 4 at a wavelength of 550 nm.
- a retardation plate having an optically anisotropic layer is disclosed.
- Japanese Patent Application Laid-Open No. 2005-62669 discloses that a rod-like liquid crystal molecule is uniformly tilted nematically aligned and has a retardation of 80 to 200 nm at a wavelength of 550 nm.
- a phase difference at a wavelength of 550 nm is 200 to 350 nm, and an Nz factor is 0.5 to 2.0, which is obtained by horizontally aligning a certain first optically anisotropic layer and liquid crystalline molecules having positive optical anisotropy.
- a retardation plate having a second optically anisotropic layer which is and a triacetylcellulose film which is a transparent support is disclosed.
- the optical film is usually formed as a laminate of the support and the optically anisotropic layer because the self-supporting property is lowered when the thickness is 20 ⁇ m or less and the handling property is extremely inferior.
- the film thickness of the liquid crystal layer is generally a thin film on the order of several ⁇ m, and therefore, it is formed by applying a liquid crystal compound on a support, aligning, and curing. .
- it is usually used as an optical film integrally with a support.
- Japanese Patent Application Laid-Open No. 2002-196144 (corresponding to US Patent Application Publication No. 2003/0031845) has a peelable temporary support and a liquid crystal layer.
- JP 2008-129121 A discloses a temporary support precursor layer and an optically anisotropic layer precursor layer which is a resin layer. And forming a transfer material having a detachable temporary support and an optically anisotropic layer, laminating the transfer material on the substrate, and then peeling the laminate from the laminate. A method of producing a retardation film for peeling a possible temporary support is disclosed.
- a liquid crystal layer is used as the optically anisotropic layer. Curling occurs in the laminate of the peelable temporary support and the liquid crystal layer, making it difficult to coat two or more liquid crystal layers, and it is difficult to transfer the liquid crystal layer to the transfer target. There is a problem that there is.
- the present invention reduces the curl of the optical film in a state with a temporary support, and enables the optical film to be thinned by peeling the temporary support at the time of use, and the optical film and a member using the optical film
- An object of the present invention is to provide a substrate film for liquid crystal coating that further improves the optical properties of the film.
- It has a laminated structure including a peelable temporary support and a negative resin orientation layer containing a resin having negative retardation and having a slow axis in the plane, and the elastic modulus of the temporary support
- X to Y indicating a range means “X or more and Y or less”.
- the operation and physical properties are measured under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.
- (Meth) acrylate is a general term for acrylate and methacrylate.
- a compound containing (meth) such as (meth) acrylic acid is a general term for a compound having “meta” in the name and a compound not having “meta”.
- One embodiment of the present invention includes a peelable temporary support (hereinafter, also simply referred to as “temporary support”) and a resin having negative retardation, and has a negative axis in a plane.
- a liquid crystal coating base wherein the direction in which the elastic modulus of the temporary support is maximized and the slow axis direction of the negative resin orientation layer are substantially orthogonal to each other. It relates to a material film. According to one embodiment of the present invention, curling of an optical film with a temporary support is reduced, and the optical film can be thinned by peeling the temporary support during use.
- a substrate film for applying a liquid crystal which further improves the optical characteristics of a member using the material.
- FIG. 1 is a schematic diagram showing a preferred example of a substrate film for liquid crystal application according to an embodiment of the present invention.
- FIG. 1A shows a laminated structure
- FIG. 1B shows a relationship between the direction in which the elastic modulus of the peelable temporary support is maximized and the slow axis direction of the negative resin orientation layer.
- 1 is a liquid crystal coating base film
- 2 is a peelable temporary support
- 3 is a negative resin orientation layer
- 4 is the direction in which the elastic modulus of the peelable temporary support is maximized
- 5 represents the slow axis direction of the negative resin alignment layer, respectively.
- the structure of the substrate film for liquid crystal application according to the present invention is not limited to this.
- the inventor presumes the mechanism by which the problem is solved by the above configuration as follows.
- the base film for applying a liquid crystal according to an embodiment of the present invention has a temporary support that can be peeled off. From this, temporary support is possible after bonding to other members such as a polarizer while enabling sufficient handling at the time of production and processing of an optical film with a temporary support using the substrate film for liquid crystal application. By peeling the body, the optical film and a member using the same can be thinned.
- the direction in which the elastic modulus of the temporary support is maximized and the in-plane slow axis direction of the negative resin alignment layer are substantially orthogonal.
- the negative resin alignment layer has the function of aligning the liquid crystal molecules in the main chain alignment direction of the resin molecules since the main chain alignment direction of the resin molecules and the slow axis direction in the plane thereof are orthogonal to each other. Have.
- the direction in which the elastic modulus of the temporary support is maximized and the direction in which the negative resin alignment layer aligns the liquid crystal molecules disposed thereon are substantially parallel.
- the direction where the elastic modulus of the temporary support of the substrate film for liquid crystal application according to one embodiment of the present invention is maximized that is, the direction with the highest resistance to deformation, and the shrinkage force of the liquid crystal layer coated thereon
- the alignment direction (liquid crystal alignment direction) of the liquid crystal molecules, which is the maximum direction coincides.
- the substrate film for liquid crystal coating according to one embodiment of the present invention contains a resin having negative retardation and has a negative resin alignment layer having a slow axis in the plane.
- the negative resin alignment layer has retardation characteristics due to negative retardation development.
- a ⁇ / 4 retardation film is produced using the liquid crystal coating substrate film, when the liquid crystal alignment film and the liquid crystal layer are applied a plurality of times, it is necessary to apply these coatings. Even in the case of only one time, a low Nz factor can be realized.
- the substrate film for liquid crystal application makes it easier to realize a low Nz factor in a ⁇ / 4 retardation film having a liquid crystal layer, and also improves the antireflection performance of a circularly polarizing plate using the same. Make it possible.
- the negative resin alignment layer has appropriate wavelength dispersion, the retardation of the ⁇ / 4 retardation film can be reversed dispersion by combination with the wavelength dispersion of the liquid crystal layer.
- coating implement achieves the improvement of the optical characteristic of the optical film after temporary support peeling, and the member using the same.
- An original film becomes a temporary support body which can be peeled through extending
- the raw film is not particularly limited as long as it can form a peelable temporary support having a direction in which the elastic modulus is maximized by stretching, and a film having a known self-supporting property can be used.
- the temporary support has a function of imparting self-supporting property to the substrate film for liquid crystal application, improving the handling property, and suppressing curling of the liquid crystal layer in the optical film with the temporary support.
- peelable means that an object to be peeled can be peeled without damaging other films or layers included in the laminated structure, and the tensile stress caused by the peeling is the stress at the breaking point of the other films or layers. Means less than.
- thermoplastic resin film As the raw film (temporary support), a resin film is preferably used, and a thermoplastic resin film excellent in optical properties, transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is used. More preferred.
- the thermoplastic resin used for the thermoplastic resin film is not particularly limited.
- These thermoplastic resins may be used individually by 1 type, or may use 2 or more types together.
- the raw film (temporary support) is preferably a resin film insoluble in methylene chloride from the viewpoint of productivity.
- Methylene chloride has a high solubility for various film materials. Therefore, a raw film which is insoluble in methylene chloride when forming a negative resin layer on the raw film, or forming an alignment film, a liquid crystal layer and other optional layers on the base film for liquid crystal application This is because the degree of freedom in selecting these layer forming materials increases.
- “insoluble in methylene chloride” means that the original film shape is approximately maintained when a 100 ⁇ m raw film is immersed in methylene chloride at room temperature for 1 minute.
- the resin constituting the resin film insoluble in methylene chloride is not particularly limited, but is preferably a polyester resin, a polyolefin resin, or a cyclic olefin resin, and more preferably a polyester resin.
- the polyester resin which is a raw material resin for the polyester resin film, can be obtained by polycondensation of an arbitrary dicarboxylic acid component and an arbitrary diol component.
- the dicarboxylic acid component is not particularly limited.
- terephthalic acid isophthalic acid, orthophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, or their salts or
- terephthalic acid or a salt thereof or an anhydride thereof is more preferable.
- the diol component is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, hexamethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, decamethylene glycol, 1, Examples include 3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexadiol, 2,2-bis (4-hydroxyphenyl) propane, and bis (4-hydroxyphenyl) sulfone. be able to. Among these, ethylene glycol and propylene glycol are preferable, and ethylene glycol is more preferable. As the dicarboxylic acid component and the diol component constituting the polyester, these may be used singly or in combination of two or more.
- polyester resins constituting the polyester resin film polyethylene terephthalate (PET) and polyethylene naphthalate are more preferable, and polyethylene terephthalate (PET) is particularly preferable.
- thermoplastic resin used for the raw film (temporary support) cellulose resin, polycarbonate resin, cyclic resin
- Polyolefin resins and (meth) acrylic resins are preferred, polycarbonate resins and (meth) acrylic resins are more preferred, and (meth) acrylic resins are more preferred.
- the (meth) acrylic resin film is not particularly limited, and a known film can be appropriately used.
- a film described in JP-A-2015-214713 can be used.
- the polycarbonate-based resin film is not particularly limited, and a known film can be appropriately used.
- Pure Ace (registered trademark) C110-100 manufactured by Teijin Limited can be used.
- the resin content is preferably 50% by mass or more, preferably 80% by mass or more, and 90% by mass with respect to the total mass of the film. % Or more, more preferably 95% by mass or more (upper limit 100% by mass).
- the raw film may appropriately contain known additive components such as additives used for known optical films such as a polarizing plate protective film and a retardation film. Although it does not restrict
- the raw film may be a commercially available one or may be produced by a known method.
- the production method is not particularly limited, and examples thereof include a film produced by a solution casting method and a film produced by a melt casting method.
- the raw film may be surface-treated.
- the surface treatment is not particularly limited, and examples thereof include plasma treatment, corona treatment, easy adhesion treatment, antistatic treatment, and peeling treatment.
- the release treatment is not particularly limited, and examples thereof include treatment with a release agent such as a silicone release agent, a long-chain alkyl release agent, and a fluorine release agent.
- the raw film may be manufactured through stretching as long as it can have a direction in which the elastic modulus is maximized by the stretching process of the present invention.
- a raw film include a stretched polyester resin.
- a polyester resin film such as polyethylene terephthalate (PET)
- PET polyethylene terephthalate
- a polyester resin is melted, and a non-oriented polyester resin film extruded into a sheet is molded at a temperature equal to or higher than the glass transition temperature.
- the method include a method in which the film is stretched in the longitudinal direction using the difference in the speed of the roll, and then stretched in the transverse direction by a tenter and subjected to heat treatment.
- the raw film (temporary support) is preferably a long film. Since the raw film (temporary support) is a long film, the substrate film for liquid crystal coating, the optical film with the temporary support, the circularly polarizing plate, etc. are also long and have a roll. This is because productivity can be improved.
- long means that it is strip
- the raw film becomes a temporary support having a direction in which the elastic modulus is maximized by the stretching step according to the present invention.
- the temporary support is a long film
- the angle between the long direction (MD direction and vertical direction) and the direction in which the elastic modulus is maximum is 0 ° ⁇ 10 ° (0 ° to 10 °).
- 45 ° ⁇ 5 ° (40 ° to 50 °), more preferably 45 ° ⁇ 4 ° (41 ° to 49 °), 45 ° ⁇ 3 °. (42 to 48 degrees) is particularly preferable, and 45 to ⁇ 2 degrees (43 to 47 degrees).
- the angle formed between the long direction and the direction in which the elastic modulus is maximum is an angle formed by the direction in which the elastic modulus is maximum clockwise or counterclockwise with the long direction as a reference (0 degree).
- the smaller one of the angles is referred to as an angle in the range of 0 to 90 degrees. That is, for example, if it is 135 degrees clockwise with respect to the long direction, it is also 45 degrees counterclockwise. In this case, a value of 45 degrees that is in the range of 0 degrees to 90 degrees is employed. . In addition, for example, if it is 100 degrees clockwise with respect to the long direction, it is also 80 degrees counterclockwise. In this case, a value of 80 degrees within a range of 0 degrees to 90 degrees is employed. .
- the elastic modulus in the direction in which the elastic modulus is maximum is not particularly limited, but is preferably 1 MPa or more and 5 MPa or less.
- the direction in which the elastic modulus is maximized is the separation of the temporary support from the base film for liquid crystal coating and peeling, and from the temporary support after peeling, the long side direction and the longitudinal direction of the liquid crystal coating base film (long It can be obtained by cutting out a plurality of test pieces so that the angle formed with the direction that is the scale direction) is different, and measuring the elastic modulus in the long side direction of these test pieces using Instron's universal testing machine 5966 type it can. Details of the measurement method are described in the examples.
- the phase difference Ro in the in-plane direction represented by the following formula (I) at a wavelength of 550 nm of the temporary support is preferably 0 nm or more and 10 nm or less, and the position in the out-of-plane direction represented by the following formula (II)
- the phase difference Rt is preferably -25 nm or more and 25 nm or less;
- Formula (I): Ro (nx ⁇ ny) ⁇ d
- Formula (II): Rt ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d
- nx is the refractive index in the direction x where the refractive index is maximum in the in-plane direction of the temporary support
- ny is the direction x in the in-plane direction of the temporary support.
- nz is the refractive index in the thickness direction of the temporary support
- d is the film thickness (nm) of the temporary support).
- Ro is preferably 0 nm or more and 5 nm or less
- Rt is more preferably ⁇ 10 nm or more and 10 nm or less
- Ro is more preferably 0 nm or more and 3 nm or less
- Rt is ⁇ 5 nm or more. More preferably, it is 5 nm or less.
- the temporary support is the minimum value from the maximum value of the values measured in the in-plane phase difference Ro represented by the above formula (I) at a wavelength of 550 nm for a total of 9 points of 3 points ⁇ 3 rows every 2 cm.
- the phase difference variation value of the temporary support is preferably 15 nm or less, more preferably 10 nm or less, and further preferably 5 nm or less.
- the Ro and Rt of the temporary support can be measured using an AxoScan manufactured by Axometrics. Details of the measurement method are described in the examples.
- the film thickness of the raw film is not particularly limited, but is preferably 10 to 300 ⁇ m, more preferably 20 to 200 ⁇ m, and further preferably 30 to 100 ⁇ m.
- the film thickness of the temporary support is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, and further preferably 30 to 100 ⁇ m.
- the negative resin layer contains a resin having a negative retardation and stretches the laminate of the above-described raw film and negative resin layer so that the negative resin layer has a slow axis in the plane. It can be set as the negative resin orientation layer which has.
- the negative resin layer is not particularly limited as long as it forms the negative resin alignment layer by the stretching step according to the present invention, and a film containing a resin having a known negative retardation can be used. it can.
- the main chain alignment direction of the resin molecules is orthogonal to the in-plane slow axis direction, and the negative resin alignment layer is the main chain alignment direction (stretching direction) of the resin molecules.
- the negative resin alignment layer has retardation characteristics due to negative retardation development.
- the substrate film for coating a liquid crystal makes it easier to realize reverse dispersion and a low Nz factor in a ⁇ / 4 retardation film having a liquid crystal layer, and antireflection performance of a circularly polarizing plate using the same. It has a function that makes it possible to improve.
- the negative resin alignment layer has a function of improving the optical properties of the optical film produced from the liquid crystal coating substrate film and a member using the same.
- negative retardation development means that birefringence is developed in the direction orthogonal to the stretching direction, that is, the phase difference is developed in the direction orthogonal to the stretching direction.
- the resin having a negative retardation development property is not particularly limited, and examples thereof include a styrene resin, a fluorene resin, and a fumarate ester resin. Among these, a fumaric acid ester-based resin is particularly preferable from the viewpoint of liquid crystal orientation of the liquid crystal layer and negative retardation. These resins having negative retardation can be used singly or in combination of two or more.
- styrenic resin examples include homopolymers of styrene or styrene derivatives; copolymers of styrene or styrene derivatives and other monomers; graft copolymers obtained from styrene or styrene derivatives and other monomers.
- styrene or a homopolymer of a styrene derivative, or a copolymer of styrene or a styrene derivative and another monomer is preferable, and a styrene or a styrene derivative alone A polymer is more preferred.
- homopolymers of styrene or its derivatives include polystyrene, poly ( ⁇ -methylstyrene), poly (o-methylstyrene), poly (p-methylstyrene), poly (p-chlorostyrene), poly (o -Nitrostyrene), poly (p-aminostyrene), poly (p-carboxystyrene), poly (p-phenylstyrene), poly (2,5-dichlorostyrene) and the like.
- copolymers of styrene or styrene derivatives and other monomers include styrene / (meth) acrylonitrile copolymer, styrene / methyl (meth) acrylate copolymer, styrene / ethyl (meth) acrylate copolymer Polymer, styrene / ⁇ -chloroacrylonitrile copolymer, styrene / (meth) butyl acrylate copolymer, styrene / (meth) acrylic acid copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, styrene / Maleic anhydride copolymer, styrene / itaconic acid copolymer, styrene / vinyl carbazole copolymer, styren
- the fluorene resin examples include a polycarbonate having a fluorene skeleton, a polycarbonate copolymer having a fluorene skeleton, a polyester having a fluorene skeleton, a polyester copolymer having a fluorene skeleton, a polyester carbonate having a fluorene skeleton, and a fluorene skeleton.
- Examples thereof include a polyester carbonate-based copolymer, a polyarylate having a fluorene skeleton, and a polyarylate copolymer having a fluorene skeleton.
- These fluorene resins may be used alone or in combination of two or more.
- fumarate-based resin known resins can be used without particular limitation.
- resins described in paragraphs “0018” to “0026” of JP-A-2008-64817, and JP-A-2016-98371 can be used.
- examples thereof include resins described in paragraphs “0024” to “0041” of the publication.
- the fumarate ester resin is preferably a homopolymer of a monomer that provides the following structural unit (1); or a copolymer of a monomer that provides the following structural unit (1) and another monomer.
- X 3 and X 4 each independently represent a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, and * represents a bonding portion with an adjacent structural unit or terminal group.
- the straight-chain alkyl group, branched-chain alkyl group, or cyclic alkyl group represented by X 3 and X 4 is not particularly limited, but examples thereof include straight-chain alkyl groups having 1 to 12 carbon atoms and branched chains having 3 to 12 carbon atoms. Examples thereof include a chain alkyl group and a cyclic alkyl group having 3 to 12 carbon atoms.
- the linear alkyl group having 1 to 12 carbon atoms specifically includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group.
- Examples of the branched alkyl group having 3 to 12 carbon atoms include isopropyl group, isobutyl group, sec-butyl group, and tert-butyl group; examples of the cyclic alkyl group having 3 to 12 carbon atoms include , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
- branched alkyl groups are preferred from the viewpoints of solubility, liquid crystal orientation of the liquid crystal layer, and negative retardation, and isopropyl, isobutyl, sec-butyl, tert-butyl, isopropyl, tert, -A butyl group is more preferable, and an isopropyl group is more preferable.
- X 3 and X 4 may be the same or different, but are preferably the same.
- a structural unit derived from diisopropyl fumarate is particularly preferable.
- These structural units (1) may be contained alone or in a combination of two or more.
- the fumaric acid ester-based resin is more preferably a copolymer of a monomer that provides the structural unit (1) and another monomer from the viewpoint of liquid crystal orientation of the liquid crystal layer and negative retardation.
- a copolymer of a monomer that provides the structural unit (1) and a monomer that provides the following structural unit (2) is more preferable.
- X 1 each independently represents a linear alkyl group, a branched alkyl group, or a cyclic alkyl group
- X 2 each independently represents a linear alkyl group or a branched alkyl group.
- a group, a cyclic alkyl group, an alkoxy group, an aryloxy group, an ester group, a hydroxyl group, a carboxyl group, a halogen atom, or a cyano group a represents an integer of 0 to 5
- * represents an adjacent structural unit or terminal group. Represents the binding part of.
- the straight-chain alkyl group, branched-chain alkyl group, or cyclic alkyl group represented by X 1 is not particularly limited, and examples thereof include a straight-chain alkyl group having 1 to 12 carbon atoms and a branched-chain alkyl group having 3 to 12 carbon atoms. And a cyclic alkyl group having 3 to 12 carbon atoms.
- examples of the linear alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group;
- examples of the branched alkyl group having 3 to 12 include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, etc .
- examples of the cyclic alkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclobutyl group, A cyclopentyl group, a cyclohexyl group, etc. are mentioned.
- X 1 is preferably a linear alkyl group having 1 to 12 carbon atoms, and is preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group. More preferred are a methyl group and an ethyl group, and an ethyl group is particularly preferred.
- the linear alkyl group, branched alkyl group, or cyclic alkyl group represented by X 2 is not particularly limited, and examples thereof include, for example, a linear alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 3 to 12 carbon atoms. And a cyclic alkyl group having 3 to 12 carbon atoms.
- examples of the linear alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group;
- examples of the branched alkyl group having 3 to 12 include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, etc .
- examples of the cyclic alkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclobutyl group, A cyclopentyl group, a cyclohexyl group, etc. are mentioned.
- the alkoxy group represented by X 2 is not particularly limited, and examples thereof include an alkoxy group having 1 to 10 carbon atoms. Specific examples include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.
- ethoxy group isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group are preferable, and ethoxy group An isopropoxy group and a tert-butoxy group are more preferable, and an ethoxy group is more preferable.
- the aryloxy group represented as X 2 is not particularly limited, for example, a phenoxy group, naphthyloxy group, fluorenyl group, and a biphenylyl group and the like.
- ester group represented by X 2 examples include groups represented by the formula: —O—C ( ⁇ O) —R or C ( ⁇ O) —O—R.
- R is an alkyl group or an aromatic group.
- the alkyl group herein is not particularly limited, and examples thereof include a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 3 to 12 carbon atoms.
- examples of the linear alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group;
- examples of the branched alkyl group having 3 to 12 include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, etc .
- examples of the cyclic alkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclobutyl group, A cyclopentyl group, a cyclohexyl group, etc. are mentioned.
- aromatic group examples include aryl groups having 6 to 24 carbon atoms. Specific examples include a phenyl group, a p-tolyl group, a naphthyl group, a biphenyl group, a fluorenyl group, an anthryl group, a pyrenyl group, an azulenyl group, an acenaphthylenyl group, a terphenyl group, and a phenanthryl group.
- halogen atom represented by X 2 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- X 2 is preferably an alkoxy group from the viewpoint of the liquid crystal orientation of the liquid crystal layer and the negative retardation.
- a represents an integer of 0 to 5.
- a is preferably 0 to 3, more preferably 0 to 2, more preferably 0 or 1 from the viewpoints of polymerizability, liquid crystal orientation of the liquid crystal layer, and negative retardation development. Is more preferable, and 1 is particularly preferable.
- the groups represented by X 2 may be the same as or different from each other.
- the position at which X 2 is arranged is not particularly limited, but is preferably a position including at least the 4-position (para-position).
- a structural unit derived from an alkoxycinnamic acid ester is preferable, and a structural unit derived from ethyl 4-methoxycinnamate is particularly preferable.
- the structural unit (2) may be included alone or in combination of two or more.
- the copolymer of the monomer that provides the structural unit (1) and the monomer that provides the structural unit (2) is not particularly limited, but may be a fumaric acid diester / alkoxycinnamic acid ester copolymer.
- a diisopropyl fumarate / 4-methoxyethyl cinnamate copolymer is more preferable.
- the content rate of the structural unit (1) in the copolymer of the monomer which provides the said structural unit (1) and another monomer is not restrict
- the homopolymer of the monomer that provides the structural unit (1) and the terminal of the copolymer of the monomer that provides the structural unit (1) and the other monomer are not particularly limited, It is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms. More preferably, it is particularly preferably a hydrogen atom.
- fumaric acid ester resins may be used alone or in combination of two or more.
- the resin having a negative retardation is a number average in terms of standard polystyrene obtained from an elution curve measured by gel permeation chromatography (GPC) from the viewpoints of solubility, film forming property, and liquid crystal orientation of the liquid crystal layer.
- the molecular weight is preferably 30,000 to 500,000, more preferably 40,000 to 400,000, and even more preferably 50,000 to 300,000.
- the content of the resin having negative retardation in the negative resin layer and the negative resin alignment layer is preferably 50% by mass or more, and 80% by mass or more with respect to the total mass of the layer. Is more preferably 90% by mass or more, and particularly preferably 95% by mass or more (upper limit 100% by mass).
- the negative resin layer and the negative resin alignment layer may appropriately contain known additive components such as additives used for known optical films such as a polarizing plate protective film and a retardation film. Although it does not restrict
- the phase difference Ro in the in-plane direction represented by the following formula (I) at a wavelength of 550 nm of the negative resin alignment layer is preferably more than 0 nm and 300 nm or less, and in the out-of-plane direction represented by the following formula (II).
- the phase difference Rt is preferably ⁇ 300 nm or more and less than 0 nm;
- Formula (I): Ro (nx ⁇ ny) ⁇ d
- Formula (II): Rt ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d
- nx is the refractive index in the direction x where the refractive index is maximum in the in-plane direction of the negative resin alignment layer
- ny is the in-plane direction of the negative resin alignment layer.
- n is the refractive index in the thickness direction of the negative resin alignment layer
- d is the film thickness (nm) of the negative resin alignment layer) .
- the liquid crystal orientation in the main chain orientation direction (stretching direction) of the resin molecules is further increased, and an optical film produced using a base film for liquid crystal coating and The optical characteristics of the member using this are further improved.
- a ⁇ / 4 retardation film having a liquid crystal layer it is easier to realize reverse dispersion and a low Nz factor, and the antireflection performance of a circularly polarizing plate using the same is further improved.
- more appropriate retardation characteristics can be obtained as the entire optical film after the temporary support peeling including the liquid crystal layer.
- Ro is preferably 5 nm or more and 180 nm or less, more preferably 10 nm or more and 150 nm or less, further preferably 30 nm or more and 150 nm or less, and more preferably 50 nm or more and 150 nm or less. Particularly preferred is 130 nm or more and 150 nm or less.
- Rt is more preferably from ⁇ 180 nm to ⁇ 5 nm, more preferably from ⁇ 150 nm to ⁇ 25 nm, even more preferably from ⁇ 150 nm to ⁇ 30 nm, and more preferably from ⁇ 150 nm to ⁇ 50 nm. It is particularly preferred that the thickness be ⁇ 150 nm or more and ⁇ 130 nm or less.
- the negative resin alignment layer has appropriate wavelength dispersion, and in combination with the wavelength dispersion of the liquid crystal layer described later, the optical properties of the used optical film, that is, the optical film after removal of the temporary support can be improved. Can be realized.
- the optical film after removal of the temporary support is a ⁇ / 4 retardation film
- the retardation is inversely dispersed, and a broadband ⁇ / 4 retardation film that gives a uniform retardation to light in a wide wavelength range is obtained. It can be realized and an excellent color can be realized in the circularly polarizing plate.
- the inverse dispersion can be realized by a method of combining two types of birefringence.
- the positive phase difference when the positive phase difference is larger than that (for example, the value of Ro (450 nm) / Ro (550 nm) is greater than 1 and the value of the positive phase difference is Ro (450 nm) / Ro.
- the inverse dispersion can be synthesized by synthesizing (adding together) so as to cancel with a negative phase difference of the opposite sign (greater than (550 nm)).
- the negative resin orientation layer has a negative retardation, when determining the retardation calculated by the above formula (I) as a negative retardation, refraction at the negative retardation is performed.
- a phase difference in which the direction orthogonal to the direction x where the rate is maximum is the direction where the refractive index is maximum is a positive phase difference.
- the preferred embodiment of the optical film with a temporary support, which will be described later, manufactured using the substrate film for liquid crystal coating according to one embodiment of the present invention is a negative resin orientation as described in the explanation of the wavelength dispersion.
- the layer has a negative retardation, and the liquid crystal layer has a positive retardation.
- the substrate film for applying a liquid crystal according to an embodiment of the present invention can contribute to canceling the retardation of the liquid crystal layer and increasing the reverse dispersibility.
- a negative resin orientation layer having a slow axis in the direction perpendicular to the orientation direction of the negative resin layer or the main chain orientation direction of the negative resin orientation layer the orientation direction of the negative resin layer or the negative resin orientation layer
- the phase difference produced by both has a positive / negative relationship. Therefore, it is preferable that an optical film with a temporary support, which will be described later, manufactured using the base film for liquid crystal coating according to one embodiment of the present invention, achieves reverse dispersion by synthesizing these retardations.
- a certain wavelength dispersion Ro (450 nm) / Ro (550 nm) is preferably 1 or more, more preferably 1.01 or more, and further preferably 1.05 or more. Within the above range, the optical properties of the optical film after peeling off the temporary support and the member using the same produced using the liquid crystal coating base film are further improved.
- the wavelength dispersion Ro (450 nm) / Ro (550 nm) of the negative resin alignment layer is preferably 1.5 or less, more preferably 1.2 or less, and 1.13 or less. Further preferred. Within the above range, the optical properties of the optical film after peeling off the temporary support and the member using the same produced using the liquid crystal coating base film are further improved. For example, in a ⁇ / 4 retardation film having a liquid crystal layer, it is easier to realize reverse dispersion, and the antireflection performance of a circularly polarizing plate using the same is further improved.
- the direction in which the elastic modulus of the temporary support is maximized and the in-plane slow axis direction of the negative resin alignment layer are substantially orthogonal.
- substantially orthogonal means that the angle formed by the direction in which the elastic modulus of the temporary support is maximum and the slow axis direction in the plane of the negative resin orientation layer is 90 ° ⁇ 10 ° (80 ° or more 90 ° 90 ° ⁇ 5 ° (85 ° to 90 °), more preferably 90 ° ⁇ 4 ° (86 ° to 90 °), 90 ° ⁇ 3 ° It is more preferably (87 degrees or more and 90 degrees or less), particularly preferably 90 degrees ⁇ 2 degrees (88 degrees or more and 90 degrees or less), and 90 degrees ⁇ 1 degree (89 degrees or more and 90 degrees or less).
- the angle between the direction in which the elastic modulus of the temporary support is maximized and the slow axis direction in the plane of the negative resin orientation layer is the direction in which the elastic modulus of the temporary support is maximized.
- a reference (0 degree) it means a smaller angle among the angles formed by the slow axis direction in the plane of the negative resin orientation layer in the clockwise or counterclockwise direction, and an angle in the range of 0 to 90 degrees To do. That is, for example, if it is 135 degrees clockwise with respect to the direction in which the elastic modulus of the temporary support is maximized, it is 45 degrees counterclockwise. In this case, it is within a range of 0 degrees to 90 degrees. A value of 45 degrees is used. In addition, for example, if the degree of elasticity of the temporary support is 100 degrees clockwise with reference to the direction in which the elastic modulus is maximum, it is 80 degrees counterclockwise. A value of 80 degrees is used.
- the angle formed by the long direction (MD direction, vertical direction) and the slow axis direction in the plane of the negative resin alignment layer is 45 degrees ⁇ It is preferably 10 degrees (35 degrees or more and 55 degrees or less), more preferably 45 degrees ⁇ 5 degrees (40 degrees or more and 50 degrees or less), and 45 degrees ⁇ 4 degrees (41 degrees or more and 49 degrees or less). More preferably, it is more preferably 45 ° ⁇ 3 ° (42 ° to 48 °), particularly preferably 45 ° ⁇ 2 ° (43 ° to 47 °), 45 ° ⁇ 1 degree (44 degrees or more and 46 degrees or less) is more particularly preferable, and 45 degrees is most preferable.
- the angle formed between the longitudinal direction and the slow axis direction in the plane of the negative resin orientation layer is negative resin orientation clockwise or counterclockwise with respect to the longitudinal direction as a reference (0 degree).
- the smaller angle among the angles formed by the slow axis direction in the plane of the layer is defined as an angle in the range of 0 degrees to 90 degrees.
- the Ro, Rt, in-plane slow axis direction and wavelength dispersion of the negative resin alignment layer can be measured using AxoScan manufactured by Axometrics.
- the in-plane slow axis direction of the negative resin alignment layer can be obtained by measurement at a wavelength of 550 nm. Details of the measurement method are described in the examples.
- the film thickness of the negative resin layer is not particularly limited, but is preferably 10 to 300 ⁇ m, more preferably 20 to 200 ⁇ m, and further preferably 30 to 100 ⁇ m.
- the film thickness of the negative resin alignment layer is not particularly limited, but is preferably 1 ⁇ m or more, and more preferably 5 ⁇ m or more.
- the liquid crystal orientation in the main chain orientation direction (stretching direction) of the resin molecules is further increased, and is produced using a substrate film for liquid crystal coating, after the temporary support is peeled off.
- the optical characteristics of the optical film and the member using the same are further improved. For example, in a ⁇ / 4 retardation film having a liquid crystal layer, it is easier to realize reverse dispersion and a low Nz factor, and the antireflection performance of a circularly polarizing plate using the same is further improved.
- the film thickness of the negative resin layer is not particularly limited, but is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 15 ⁇ m or less.
- the mechanical moment in the laminate due to the contraction force of the liquid crystal layer generated when the liquid crystal layer is cured is less than or equal to the upper limit, and the mechanical strength of the entire laminate is reduced. Since the balance is more easily maintained, the curl reduction effect of the optical film with a temporary support is further increased.
- a preferable example of the negative resin alignment layer includes one having a film thickness of 1 to 20 ⁇ m.
- a preferable example of the combination of the film thickness with the aforementioned Ro and Rt is a film thickness of 1 ⁇ m. ⁇ 20 ⁇ m or less, Ro is 10 nm or more and 150 nm or less, and Rt is ⁇ 150 nm or more and ⁇ 30 nm or less.
- the base film for liquid crystal coating according to one embodiment of the present invention may have other functional layers as long as the effects of the present invention are not impaired.
- the position of the other functional layer is not particularly limited, and even if disposed on the surface of the temporary support opposite to the negative resin alignment layer, the temporary support of the negative resin alignment layer May be disposed on the opposite side, or may be disposed between the temporary support and the negative resin orientation layer.
- layers generally provided in known optical films such as a polarizing plate, a polarizing plate protective film, and a retardation film can be appropriately selected.
- hard coat layer easy adhesion layer, antiglare layer, antireflection layer, low reflection layer, low reflection antiglare layer, antireflection antiglare layer, antistatic layer, silicone layer, adhesive layer, antifouling layer,
- Examples include a fingerprint-resistant layer, a water-repellent layer, and a blue cut layer.
- Another aspect of the present invention is to form the negative film and the negative resin layer by forming a negative resin layer containing a resin having negative retardation on the raw film.
- Forming a laminate including the step of forming a peelable temporary support having a direction in which the elastic modulus is maximized from the raw film by stretching the laminate, and the negative resin Forming the negative resin orientation layer having a slow axis in-plane from the layer; a direction in which the elastic modulus of the temporary support is maximized; and a slow axis direction in the plane of the negative resin orientation layer
- a stretching step that includes substantially orthogonal to each other, and a method for producing a substrate film for applying a liquid crystal.
- curling of an optical film with a temporary support is reduced, and the optical film can be thinned by peeling the temporary support during use.
- a substrate film for applying a liquid crystal which further improves the optical characteristics of a member using the material.
- the direction in which the elastic modulus of the temporary support is maximized and the slow axis direction in the plane of the negative resin alignment layer are substantially orthogonal.
- a drawing process is included.
- the method can realize the configuration for realizing the curl reduction and the configuration for realizing the improvement of the optical characteristics at a time, thereby reducing the number of steps and improving the productivity. Realized.
- sufficient handling is possible, and the liquid crystal alignment film and the liquid crystal layer Since the number of coating operations can be reduced, the yield is improved and the productivity is improved.
- the manufacturing method includes forming the negative resin layer containing a resin having negative retardation on the raw film, thereby forming the negative film and the negative film.
- the method for forming the negative resin layer is not particularly limited, and known methods such as transfer, coating, and casting are used.
- a negative resin layer may be formed thereon, or the original film and the negative resin layer may be simultaneously formed by co-casting, co-extrusion or the like.
- the method and conditions for preparing, coating and drying the negative resin layer coating solution are not particularly limited, and known methods can be appropriately selected and used.
- the negative resin layer coating liquid can be prepared, for example, by uniformly mixing a resin having negative retardation and other optional components that can be optionally used in a solvent.
- the solvent examples include, but are not limited to, chlorinated solvents such as chloroform and methylene chloride (dichloromethane); aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; methanol, ethanol, isopropanol, n- Alcohol solvents such as butanol and 2-butanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), diethyl ether, methyl acetate, ethyl acetate, amyl acetate, Acetone, methyl ethyl ketone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone,
- chlorinated solvent is preferable, chloroform and methylene chloride are more preferable, and methylene chloride is further preferable. These solvents may be used alone or in combination of two or more.
- the laminating step includes forming a negative resin layer on the raw film by applying a negative resin layer coating liquid containing a resin having negative retardation and methylene chloride.
- the raw film is preferably insoluble in methylene chloride.
- the solid content concentration in the negative resin layer coating solution is not particularly limited, but is preferably 1 to 70% by mass, more preferably 5 to 50% by mass with respect to the total mass of the coating solution. More preferably, it is ⁇ 30% by mass.
- the coating method of the negative resin layer coating liquid is not particularly limited, and can be performed by a known method such as comma coating, die coating, bar coating, roll coating, slit coating, slit reverse coating, reverse roll coating, gravure coating, and the like. it can.
- the drying conditions after coating are not particularly limited, but for example, the drying temperature is preferably 50 to 200 ° C., and the drying time is preferably 30 seconds to 10 minutes.
- the negative resin layer coating solution may be applied directly on the surface of the temporary support, or directly on the surface of another functional layer that can be optionally provided on the temporary support. Also good.
- the laminating step after coating the negative resin layer coating liquid on the support other than the raw film, in a state where it is not completely dried or in a state of the negative resin layer after drying, You may form a laminated body by transcribe
- the manufacturing method which concerns on the other one form of this invention is the peelable temporary support body which has a direction in which an elasticity modulus becomes the maximum by extending
- the stretching step by stretching the laminate, the orientation of the constituent materials in the raw film progresses in the stretching direction, and a temporary support having a direction in which the elastic modulus is maximized is formed.
- the stretching direction is the direction in which the elastic modulus is maximized by orienting the main chain of the polymer (resin) in the stretching direction.
- the resin having a negative retardation in the negative resin layer progresses in the main chain orientation in the stretching direction. Both the orientation directions of the constituent materials of the film are substantially the same in the stretching direction.
- the direction in which the elastic modulus of the temporary support is maximized and the main chain alignment direction of the negative resin alignment layer are substantially parallel.
- a resin having negative retardation develops side chain alignment in a direction substantially perpendicular to the main chain alignment direction, and develops a phase difference in the side chain alignment direction substantially perpendicular to the main chain alignment direction.
- the direction in which the elastic modulus of the temporary support is maximum and the slow axis direction in the plane of the negative resin alignment layer are substantially orthogonal.
- the method for stretching the laminate is not particularly limited, and a method in which a difference in peripheral speed is provided between a plurality of rolls and the roll peripheral speed difference is used between the rolls in the longitudinal direction.
- Fixing with pins, extending the gap between clips and pins in the longitudinal direction (conveying direction), stretching both ends of the web with clips and pins with a tenter, and setting the gap between clips and pins in the width direction (conveying direction) For example, a method of extending and extending in a direction perpendicular to the direction), a method of extending and extending the gap between the clips and pins in the longitudinal direction and the width direction (direction perpendicular to the conveying direction) at the same time can be employed.
- the stretching in the width direction is preferably performed by a tenter.
- the type of tenter may be a pin tenter or a clip tenter.
- driving the clip portion by the linear drive method is preferable because smooth stretching can be performed and the risk of breakage and the like can be reduced.
- a method of stretching in an oblique direction (a direction other than the longitudinal direction and the width direction) using a tenter capable of oblique stretching may be used.
- a known apparatus and method can be employed.
- Known devices and methods are not particularly limited. For example, the devices and methods of paragraphs “0065” to “0106” and paragraphs “0128” to “0147” of International Publication No. 2013/146397 are appropriately adopted. Can do.
- the stretching operation may be performed in multiple stages.
- simultaneous biaxial stretching may be performed or may be performed stepwise.
- stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible.
- Simultaneous biaxial stretching includes stretching in one direction and contracting the other while relaxing the tension.
- the draw ratio in at least one direction is not particularly limited, but is preferably 1.01 to 5 times, more preferably 1.05 to 3 times, and 1.1 to 2 times. Is more preferably 1.15 times or more and 1.8 times or less, particularly preferably 1.2 times or more and 1.5 times or less, and more preferably 1.2 times or more and 1.3 times or less. It is very preferable that it is not more than twice, and it is most preferable that it is not less than 1.2 times and not more than 1.25 times. When the draw ratio is not less than the above lower limit value, the liquid crystal orientation and negative retardation expression of the liquid crystal layer are further improved.
- the liquid crystal orientation and the negative retardation expression of the liquid crystal layer are in a more appropriate range when a predetermined retardation such as a ⁇ / 4 retardation film is to be obtained.
- stretching diagonally draws the longest thing among the diameters which draw the circle
- the stretching temperature is not particularly limited, but is preferably 30 ° C. or higher, and is preferably in the range of ⁇ 50 ° C. to + 100 ° C. with respect to the glass transition point of the raw film to be produced. In certain embodiments, the stretching temperature is more preferably 40 to 280 ° C., further preferably 70 to 200 ° C., and particularly preferably 100 to 180 ° C.
- the angle formed between the long direction (MD direction and longitudinal direction) and the stretching direction is within a range of 0 ° ⁇ 10 ° ( ⁇ 10 ° to 10 °), 45 ° ⁇ It is preferably within a range of 10 degrees (35 degrees to 55 degrees) and within a range of 90 degrees ⁇ 10 degrees (80 degrees to 90 degrees), and within a range of 0 degrees ⁇ 5 degrees ( ⁇ 5 degrees to 5 degrees) Or less), within a range of 45 ° ⁇ 5 ° (40 ° to 50 °), more preferably within a range of 90 ° ⁇ 5 ° (85 ° to 90 °), 45 ° ⁇ 5 ° It is more preferable that it is within the range (40 ° to 50 °), more preferably 45 ° ⁇ 4 ° (41 ° to 49 °), and 45 ° ⁇ 3 ° (42 ° to 48 °).
- the angle formed by the long direction and the extending direction refers to the smaller angle of the angles formed by the extending direction clockwise or counterclockwise with respect to the long direction as a reference (0 degree).
- optical film with temporary support Another embodiment of the present invention relates to an optical film with a temporary support, further having a liquid crystal layer on the negative resin alignment layer of the substrate film for liquid crystal application.
- the direction in which the elastic modulus of the temporary support is maximized and the liquid crystal alignment direction of the liquid crystal layer are preferably substantially parallel.
- FIG. 2 is a schematic view showing a preferred example of an optical film with a temporary support according to an embodiment of the present invention.
- FIG. 2A shows a laminated structure
- FIG. 2B shows the relationship between the direction in which the elastic modulus of the peelable temporary support is maximum and the slow axis direction of the negative resin orientation layer.
- 10 is an optical film with a temporary support
- 2 is a removable temporary support
- 3 is a negative resin alignment layer
- 11 is a liquid crystal layer
- 4 is an elastic modulus of a removable temporary support.
- 5 represents the slow axis direction of the negative resin alignment layer
- 12 represents the liquid crystal molecule alignment direction (liquid crystal alignment direction) of the liquid crystal layer.
- the configuration of the optical film with a temporary support according to the present invention is not limited to this.
- the direction in which the elastic modulus of the temporary support is maximized and the liquid crystal alignment direction of the liquid crystal layer are substantially parallel, and the elastic modulus of the temporary support is maximized. That is, the direction with the highest resistance to deformation substantially coincides with the liquid crystal alignment direction which is the maximum direction of contraction force of the liquid crystal layer coated thereon. As a result, the curl of the optical film with the temporary support is reduced.
- the base film for applying a liquid crystal has a temporary support because the direction in which the elastic modulus of the temporary support is maximum and the slow axis direction in the plane of the negative resin orientation layer are substantially orthogonal.
- the in-plane slow axis direction of the negative resin alignment layer and the liquid crystal alignment direction of the liquid crystal layer are substantially orthogonal.
- the negative resin alignment layer expresses a phase difference in a direction substantially perpendicular to the phase difference generated in the liquid crystal alignment direction of the liquid crystal layer
- the optical film in use that is, the optical film after the temporary support is peeled off
- the influence of the axial deviation is very small or does not cause the axial deviation with respect to the slow axis direction in the plane as a whole (generally, the slow axis direction in the plane of the liquid crystal layer).
- the slow axis direction in the plane of the negative resin alignment layer that is, the phase difference expression direction of the negative resin alignment layer is orthogonal to the liquid crystal alignment direction of the liquid crystal layer, that is, the phase difference expression direction of the liquid crystal layer.
- the negative resin alignment layer acts to cancel the phase difference of the liquid crystal layer.
- the value of the wavelength dispersion Ro (450 nm) / Ro (550 nm) of the negative resin alignment layer is more than 1, which is larger than the value of the wavelength dispersion Ro (450 nm) / Ro (550 nm) of the liquid crystal layer.
- the combined phase difference of the two layers will increase the reverse dispersion.
- a negative resin orientation layer reduces the thickness direction phase difference as the whole optical film with a temporary support body by the negative phase difference expression property, and Nz factor is reduced. Thereby, the improvement of the optical characteristic of the optical film after temporary support body peeling is implement
- the film and a linear polarizer or a polarizing plate including the same are used, the slow axis direction in the plane of the film, and linear polarization
- a circularly polarizing plate is manufactured by laminating so that a smaller angle (0 ° or more and 90 ° or less) of the angle formed by the transmission axis direction of the child is 45 ° ⁇ 10 ° (35 ° or more and 55 ° or less). be able to.
- the thickness direction retardation of the optical film after removal of the temporary support is reduced. It can be realized.
- an improvement in the optical properties of the optical film after removal of the temporary support is realized by a combination with the wavelength dispersion of the liquid crystal layer.
- the optical film after removal of the temporary support is a ⁇ / 4 retardation film
- the reverse dispersion of the retardation increases, and a broadband ⁇ / 4 retardation that gives a uniform retardation to light in a wide wavelength range A film is realized, and an excellent color can be realized in a circularly polarizing plate.
- a liquid crystal layer has a function which provides the optical characteristic requested
- the liquid crystal layer is composed of a liquid crystal material containing a liquid crystal compound, and among these, it is preferable to be composed of a cured product of the liquid crystal material.
- the liquid crystal material constituting the liquid crystal layer is not particularly limited, and may include a known liquid crystal compound. Examples of the liquid crystal compound contained in the liquid crystal material include the liquid crystal compounds described in JP-A-2015-155994, International Publication No. 2013/077795, JP2010-528992A, and JP-A-2006-243470.
- liquid crystal compounds having reverse dispersion characteristics described in Japanese Patent No. 4222360, Japanese Patent No. 41868981, International Publication No. 2016/158298, International Publication No. 2016/171041, and the like.
- Specific examples of the liquid crystal compound include, but are not limited to, liquid crystal compounds represented by the following chemical formulas (101) to (114), and a liquid crystal compound according to the chemical formula 4 described in paragraph “0079” of International Publication No.
- the liquid crystal material constituting the liquid crystal layer preferably includes at least one liquid crystal compound having reverse dispersion characteristics, and more preferably includes a liquid crystal compound represented by the following chemical formula (113).
- a commercially available liquid crystal compound may be used, and may be synthesized by a known method. These liquid crystal compounds may be used alone or in combination of two or more.
- the liquid crystal material constituting the liquid crystal layer preferably contains an initiator.
- the initiator may be a thermal polymerization initiator or a photopolymerization initiator, but is preferably a photopolymerization initiator, and more preferably a radical photopolymerization initiator.
- a commercially available polymerization initiator may be used, or may be synthesized by a known method. Although it does not restrict
- the concentration of the initiator in the liquid crystal material is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, with respect to 100 parts by mass of the liquid crystal compound. More preferably, it is 2 parts by mass or more and 10 parts by mass or less.
- the liquid crystal layer can be sufficiently cured, and the shrinkage force during curing is suppressed from being excessive.
- the liquid crystal material may appropriately contain a known additive component such as an additive used for a known liquid crystal layer.
- additive components include catalysts, sensitizers, stabilizers, inhibitors, chain transfer agents, co-reactive monomers, surface active compounds (surfactants), lubricants, wetting agents, dispersants, Examples include hydrophobizing agents, pressure-sensitive adhesives, fluidity improvers, antifoaming agents, deaerators, diluents, reactive diluents, colorants, dyes, pigments or nanoparticles.
- the surfactant is not particularly limited, and examples thereof include fluorine-containing surfactants such as Megafac (registered trademark) F477 manufactured by DIC Corporation.
- co-reactive monomer is not particularly limited, and examples thereof include trimethylolpropane triacrylate.
- Ro is more preferably 130 nm or more and 310 nm or less, particularly preferably 150 nm or more and 310 nm or less, further preferably 170 nm or more and 310 nm or less, and more preferably 250 nm or more and 310 nm or less. Most preferred.
- the optical properties of the used optical film that is, the optical film after peeling the temporary support can be improved by a combination with the wavelength dispersion of the negative resin alignment layer.
- the optical film after removal of the temporary support is a ⁇ / 4 retardation film
- the retardation is inversely dispersed, and a broadband ⁇ / 4 retardation film that gives a uniform retardation to light in a wide wavelength range is obtained. It can be realized and an excellent color can be realized in the circularly polarizing plate.
- the inverse dispersion can be realized by a method of combining two types of birefringence.
- a preferable aspect of the optical film with a temporary support is such that the negative resin alignment layer has a negative retardation and the liquid crystal layer has a positive retardation.
- the substrate film for liquid crystal application can contribute to canceling the phase difference of the liquid crystal layer and improving reverse dispersion.
- the liquid crystal molecules of the liquid crystal layer are aligned in a direction parallel to the stretching direction of the negative resin layer with respect to the negative resin alignment layer having a slow axis in the direction orthogonal to the stretching direction of the negative resin layer
- the phase difference between the two has a positive / negative relationship, and it is preferable that reverse dispersion is realized by combining these phase differences.
- the chromatic dispersion Ro which is the ratio of the phase difference Ro in the in-plane direction represented by the above formula (I) at a wavelength of 450 nm to the phase difference Ro in the in-plane direction represented by the above formula (I) at the wavelength 550 nm of the liquid crystal layer.
- (450 nm) / Ro (550 nm) it is preferable that the following relationship is satisfied. That is, the difference obtained by subtracting the value of the wavelength dispersion Ro (450 nm) / Ro (550 nm) of the negative resin alignment layer from the wavelength dispersion Ro (450 nm) / Ro (550 nm) of the liquid crystal layer is ⁇ 0.3 or more and 0.05 or more.
- the optical properties of the optical film after removal of the temporary support and the members using the optical film are further improved. For example, in a ⁇ / 4 retardation film having a liquid crystal layer, it is easier to realize reverse dispersion, and the antireflection performance of a circularly polarizing plate using the same is further improved.
- the Ro and Rt of the liquid crystal layer can be measured using AxoScan manufactured by Axometrics. Details of the measurement method are described in the examples.
- the direction in which the elastic modulus of the temporary support is maximum and the alignment direction of the liquid crystal molecules in the liquid crystal layer are preferably substantially parallel.
- substantially parallel means that the angle formed between the direction in which the elastic modulus of the temporary support is maximized and the liquid crystal alignment direction of the liquid phase layer is 0 ° ⁇ 10 ° (0 ° to 10 °), It is preferably 0 ° ⁇ 5 ° (0 ° to 5 °), more preferably 0 ° ⁇ 4 ° (0 ° to 4 °), and 0 ° ⁇ 3 ° (0 ° to 3 °).
- the angle formed between the direction in which the elastic modulus of the temporary support is maximized and the liquid crystal alignment direction of the liquid crystal layer is based on the direction in which the elastic modulus of the temporary support is maximized as a reference (0 degree).
- the smaller angle among the angles formed by the liquid crystal alignment direction of the liquid crystal layer in the clockwise or counterclockwise direction, and the angle is in the range of 0 ° to 90 °.
- the angle formed between the long direction (MD direction and vertical direction) and the liquid crystal alignment direction of the liquid crystal layer is 0 degree ⁇ 10 degrees (0 degree or more and 10 degrees). Degrees or less), 45 degrees ⁇ 10 degrees (35 degrees or more and 55 degrees or less), 90 degrees ⁇ 10 degrees (80 degrees or more and 90 degrees or less), preferably 45 degrees ⁇ 10 degrees (35 degrees or more and 55 degrees or less) More preferably 45 ° ⁇ 5 ° (40 ° to 50 °), even more preferably 45 ° ⁇ 4 ° (41 ° to 49 °), 45 ° It is particularly preferably 3 ° (42 ° to 48 °), more preferably 45 ° ⁇ 2 ° (43 ° to 47 °), and 45 ° ⁇ 1 ° (44 ° to 46 °).
- the angle formed between the longitudinal direction and the liquid crystal alignment direction of the liquid crystal layer is an angle formed by the liquid crystal alignment direction of the liquid crystal layer clockwise or counterclockwise with respect to the longitudinal direction as a reference (0 degree).
- the smaller angle is defined as an angle in the range of 0 ° to 90 °.
- the orientation direction of the liquid crystal molecules in the liquid crystal layer can be determined by the following procedure and method.
- a negative resin alignment layer negative resin alignment layer phase difference measurement test piece
- a liquid crystal layer liquid crystal layer phase difference measurement test piece
- Form alone the negative resin orientation layer phase difference measurement test piece and the liquid crystal layer phase difference measurement test piece are overlapped, and the angle between the two is changed variously, and the in-plane slow axis direction in these laminated states Ask for.
- Optical film after temporary support peeling negative resin alignment layer phase measurement test piece, liquid crystal layer phase measurement test piece, negative resin alignment layer phase measurement test piece, and liquid crystal layer phase measurement test
- the in-plane slow axis direction of the laminate with the piece can be obtained by measurement at a wavelength of 550 nm using an AxoScan manufactured by Axometrics. Details of the measurement method are described in the examples. Details of the measurement method are described in the examples.
- the thickness of the liquid crystal layer is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 8 ⁇ m, and further preferably 1 to 5 ⁇ m.
- the liquid crystal layer may be disposed so as to be in contact with the negative resin alignment layer, or may be disposed so as to be in contact with the liquid crystal alignment film described later, or through another functional layer that can be arbitrarily provided on these layers. May be arranged.
- the negative resin alignment layer is such that the main chain alignment direction of the resin molecules is orthogonal to the in-plane slow axis direction, and the main chain alignment direction of the resin molecules (stretched)
- the liquid crystal alignment film has a function of further enhancing the function of aligning the liquid crystal molecules.
- the optical film with a temporary support preferably does not use a liquid crystal alignment film from the viewpoint of productivity.
- the optical film with a temporary support is preferably a liquid crystal alignment film from the viewpoint of optical properties.
- the alignment direction of liquid crystal molecules by the liquid crystal alignment film is substantially parallel to the direction in which the elastic modulus of the temporary support is maximum (0 degree).
- ⁇ 10 degrees direction that is, a direction perpendicular to the slow axis direction in the plane of the negative resin orientation layer (90 degrees ⁇ 10 degrees direction) is preferable.
- the orientation direction of such liquid crystal molecules When the orientation direction of such liquid crystal molecules is used, the effect of suppressing curling of the liquid crystal layer in the optical film with a temporary support is obtained, and the details are unknown, but the liquid crystal orientation ability by the negative resin orientation layer With the combination, the liquid crystal alignment property of the liquid crystal layer is further enhanced as compared with the case of using the liquid crystal alignment film alone.
- the optical properties of the optical film after removal of the temporary support are further improved by using the liquid crystal alignment film.
- the optical film after removal of the temporary support is a ⁇ / 4 retardation film
- ⁇ / 4 The characteristics as a retardation film, particularly the front reflection characteristics, tint, and oblique field reflection characteristics when used as a circularly polarizing plate are further improved.
- the liquid crystal alignment film may be an alignment film that imparts alignment by rubbing or a photo alignment film that imparts alignment by light, and is not particularly limited, and a known liquid crystal alignment film may be used. it can.
- a commercially available liquid crystal alignment film may be used, or may be synthesized or prepared by a known method. Although it does not restrict
- liquid crystal alignment film may be disposed so as to contact the negative resin alignment layer and the liquid crystal layer, or may be disposed so as to contact other functional layers and liquid crystal layers that can be optionally provided thereon.
- a liquid crystal layer is formed on the negative resin alignment layer of the liquid crystal coating base film after the liquid crystal coating base film is manufactured by the method for manufacturing a liquid crystal coating base film. It is related with the manufacturing method of the optical film with a temporary support which further has a liquid crystal layer formation process including forming.
- the method for forming the liquid crystal layer on the negative resin alignment layer of the substrate film for liquid crystal application is not particularly limited, and known methods such as transfer, application, and casting are used.
- the negative resin layer is preferably formed by applying a liquid crystal layer coating liquid from the viewpoint of freedom of material selection and productivity.
- the method and conditions for preparing, applying, drying and curing the liquid crystal layer coating liquid are not particularly limited, and known methods can be appropriately selected and used.
- the liquid crystal layer coating liquid can be prepared, for example, by uniformly mixing, in a solvent, other optional components such as a polymerization initiator in addition to liquid crystal molecules.
- the solvent examples include, but are not limited to, chlorinated solvents such as chloroform and methylene chloride (dichloromethane); aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; methanol, ethanol, isopropanol, n- Alcohol solvents such as butanol and 2-butanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), diethyl ether, methyl acetate, ethyl acetate, amyl acetate, Acetone, methyl ethyl ketone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone,
- the solid content concentration in the liquid crystal layer coating solution is not particularly limited, but is preferably 1 to 70% by weight, more preferably 5 to 50% by weight, based on the total weight of the coating solution. More preferably, it is mass%.
- the application method of the liquid crystal layer coating liquid is not particularly limited, and can be performed by a known method such as comma coating, die coating, bar coating, roll coating, slit coating, slit reverse coating, reverse roll coating, or gravure coating.
- the drying conditions of the liquid crystal coating layer formed by application of the liquid crystal layer coating liquid are not particularly limited.
- the drying temperature is preferably 50 to 110 ° C.
- the drying time is 30 seconds to 10 minutes. Preferably there is.
- the liquid crystal layer by irradiating the liquid crystal coating layer with ionizing radiation such as an electron beam and ultraviolet rays and curing it.
- ionizing radiation such as an electron beam and ultraviolet rays
- those containing ultraviolet rays having a wavelength of 190 to 380 nm are usually emitted.
- an ultraviolet-ray source For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, an electrodeless UV lamp etc. can be used.
- the ultraviolet ray source include an H bulb manufactured by Fusion.
- the irradiation wavelength of ultraviolet rays, illuminance, and light quantity vary depending on the formulation of the liquid crystal material to be used, for example, the addition amount and type of a liquid crystal compound, an initiator, and the like, so that conditions can be appropriately adjusted by those skilled in the art.
- the irradiation energy amount is preferably 50 to 1500 mJ / cm 2 .
- the liquid crystal layer coating liquid may be directly applied on the surface of the negative resin alignment layer or directly on the liquid crystal alignment film, or may be arbitrarily provided on these. You may apply
- the liquid crystal layer is preferably formed so that the direction in which the elastic modulus of the temporary support is maximized and the liquid crystal alignment direction of the liquid crystal layer are substantially parallel.
- the preferred embodiment of the angle formed by the direction in which the elastic modulus of the temporary support is maximized and the liquid crystal alignment direction of the liquid crystal layer is the same as described for the optical film with the temporary support.
- the liquid crystal layer forming step preferably does not include a step of forming a liquid crystal alignment film.
- the negative resin alignment layer of the substrate film for liquid crystal application has a function of aligning liquid crystal molecules in the main chain alignment direction of the resin molecules, and the elastic modulus of the temporary support is maximized.
- the direction and the main chain orientation direction of the negative resin orientation layer are considered to be substantially parallel.
- the liquid crystal alignment direction by the liquid crystal alignment film is substantially parallel to the direction in which the elastic modulus of the temporary support is maximized.
- an optical film with a temporary support having a configuration in which the direction in which the elastic modulus of the temporary support is maximized and the liquid crystal alignment direction of the liquid crystal layer are substantially parallel can be produced.
- the optical film with a temporary support is a ⁇ / 4 retardation film
- the optical film with a temporary support is preferably used for a circularly polarizing plate as described later.
- the circularly polarizing plate includes an optical film with a temporary support and a linear polarizer or a polarizing plate including the same, an in-plane slow axis of the optical film after removal of the temporary support, and a transmission axis of the linear polarizer.
- a linear polarizer or a polarizing plate containing this is a long film as an optical film with a temporary support body and a polarizer or a polarizing plate containing this from a viewpoint of productivity. It is preferable to use a roll to roll method.
- a linear polarizer which is a long film such as a widely used polyvinyl alcohol (PVA) polarizing film has an absorption axis in a direction substantially parallel to the longitudinal direction, and is in the width direction, that is, substantially orthogonal to the longitudinal direction. It is common to have a transmission axis in the direction.
- PVA polyvinyl alcohol
- the lamination by the roll-to-roll method is usually performed by matching the longitudinal direction of the optical film with a temporary support and the polarizer or the polarizing plate including the polarizer.
- the longitudinal direction of the optical film with the temporary support MD direction
- the vertical direction) and the liquid crystal alignment direction of the liquid crystal layer the smaller angle (0 degree or more and 90 degrees or less) is in the range of 45 degrees ⁇ 10 degrees (35 degrees or more and 55 degrees or less).
- the angle formed between the longitudinal direction of the optical film with a temporary support and the main chain alignment direction of the negative resin alignment layer advantageous for realizing the liquid crystal alignment direction is 45 ° ⁇ 10 ° (35 ° 55 degrees or less), which is the same range as above. Since the main chain orientation direction and the slow axis direction in the plane of the negative resin orientation layer are orthogonal, the longitudinal direction of the optical film with the temporary support and the slow direction in the plane of the negative resin orientation layer.
- the angle formed with the phase axis direction is in the range of 135 ° ⁇ 10 ° (125 ° to 145 °), and the smaller angle (0 ° to 90 °) is 45 ° ⁇ 10 ° (35 ° It is preferably within the range of 55 degrees or less.
- the liquid crystal application direction in the liquid crystal layer forming step is usually the same as the long direction of the substrate film for liquid crystal application.
- the liquid crystal application direction in the liquid crystal layer forming step is 45 degrees with respect to the slow axis direction in the plane of the negative resin alignment layer of the base film for liquid crystal application.
- the angle is preferably ⁇ 10 degrees (35 degrees to 55 degrees), more preferably 45 degrees ⁇ 5 degrees (40 degrees to 50 degrees), and 45 degrees ⁇ 4 degrees (41 degrees to 49 degrees).
- the angle formed between the in-plane slow axis direction of the negative resin alignment layer and the liquid crystal application direction is based on the in-plane slow axis direction of the negative resin alignment layer as a reference (0 degree).
- the smaller one of the angles formed by the liquid crystal application direction in the clockwise or counterclockwise direction is defined as an angle within a range of 0 degrees to 90 degrees.
- the optical film with a temporary support and the linear polarizer (polarizer) are optical at a predetermined angle, for example, the transmission axis direction of the polarizer and the temporary support are peeled off.
- the present invention relates to a polarizing plate with a temporary support, which is laminated so that an angle formed with an in-plane slow axis direction is 45 ° ⁇ 10 ° (35 ° to 55 °).
- the optical film after removal of the temporary support and the polarizer have a predetermined angle, for example, the transmission axis direction of the polarizer, and the surface of the optical film after removal of the temporary support.
- the present invention also relates to a polarizing plate laminated so that the angle formed with the slow axis direction is 45 ° ⁇ 10 ° (35 ° to 55 °).
- the optical film with a temporary support and a polarizer After manufacturing an optical film with a temporary support by the method for manufacturing an optical film with a temporary support, the optical film with a temporary support and a polarizer
- the angle for example, the angle formed by the transmission axis direction of the polarizer and the slow axis direction in the plane of the optical film after peeling the temporary support is 45 ° ⁇ 10 ° (35 ° or more and 55 ° or less).
- the present invention relates to a method for producing a polarizing plate with a temporary support, including lamination.
- the angle formed between the transmission axis direction of the polarizer and the in-plane slow axis of the optical film in the state where the temporary support is peeled or the optical support after peeling the temporary support is 45 ° ⁇ 5 ° (40 ° More preferably, it is 45 ° ⁇ 4 ° (41 ° to 49 °), and more preferably 45 ° ⁇ 3 ° (42 ° to 48 °). More preferably, it is 45 ° ⁇ 2 ° (43 ° to 47 °), particularly preferably 45 ° ⁇ 1 ° (44 ° to 46 °), more preferably 45 °. Is most preferred.
- the angle formed between the transmission axis direction of the polarizer and the in-plane slow axis direction of the optical film after the temporary support is peeled or the optical film after the temporary support is peeled is the transmission axis of the polarizer. Smaller than the angle formed by the in-plane slow axis direction of the optical film in the state where the temporary support is peeled clockwise or counterclockwise, or the optical film after the temporary support is peeled off, with the direction as a reference (0 degree) This is the angle in the range of 0 degrees to 90 degrees.
- Another embodiment of the present invention is a method for producing a polarizing plate, comprising producing a circularly polarizing plate with a temporary support by the method for producing a polarizing plate with a temporary support, and then peeling the temporary support.
- the optical film with a temporary support can achieve curl reduction, it is possible to manufacture such a polarizing plate with a temporary support at a high yield.
- the angle formed by the longitudinal direction (MD direction, longitudinal direction) of the optical film with a temporary support and the slow axis direction in the plane of the optical film in a state where the temporary support is peeled off is 45 degrees ⁇ 10.
- the angle formed between the longitudinal direction of the optical film with the temporary support and the in-plane slow axis direction of the optical film in a state where the temporary support is peeled is based on the longitudinal direction of the optical film with the temporary support.
- (0 degree) the smaller one of the angles formed by the optical film in a state where the temporary support is peeled clockwise or counterclockwise is defined, and the angle is in the range of 0 degree or more and 90 degrees or less.
- the polarizing plate with a temporary support is not particularly limited, but preferably has a configuration in which a polarizer is sandwiched between the optical film with a temporary support and a protective film.
- a polarizer is sandwiched between the optical film with a temporary support and a protective film.
- the polarization of the polarizing film with a single-sided protective film having a protective film only on one surface of the polarizer and the optical film with the temporary support. It is preferable to paste the child side surface.
- a protective film may be supplied simultaneously and you may bond continuously.
- a polarizing plate with a temporary support in a long roll state may be obtained by pasting and winding up with an agent (adhesive or pressure-sensitive adhesive).
- an agent adheresive or pressure-sensitive adhesive.
- a polarizer is an element that passes only light having a plane of polarization in a certain direction.
- Examples thereof include a polyvinyl alcohol (PVA) polarizing film.
- the polyvinyl alcohol polarizing film includes those obtained by dyeing iodine on a polyvinyl alcohol film and those obtained by dyeing a dichroic dye.
- the polarizer can be obtained by uniaxially stretching a polyvinyl alcohol-based film and then dyeing, or uniaxially stretching after dyeing a polyvinyl alcohol-based film, and preferably by further performing a durability treatment with a boron compound.
- the film thickness of the linear polarizer is preferably in the range of 0.1 to 30 ⁇ m, and more preferably in the range of 1 to 10 ⁇ m.
- the polyvinyl alcohol-based film include an ethylene unit content of 1 to 4 mol%, a polymerization degree of 2000 to 4000, and a saponification degree of 99 described in JP-A Nos. 2003-248123 and 2003-342322. From 0.0 to 99.99 mol% ethylene-modified polyvinyl alcohol is preferably used.
- the polarizer or the polarizing plate containing the polarizer and the optical film with a temporary support may be bonded by a known adhesive layer (a layer formed from an adhesive or a pressure-sensitive adhesive).
- adhesives include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based adhesives, latex-based adhesives, and water-based polyester resins. it can.
- the adhesive is usually used as an adhesive made of an aqueous solution, and usually contains 0.5 to 60% by weight of a solid content. Further, as the adhesive, a photocurable adhesive such as an ultraviolet curable adhesive or an electron beam curable adhesive may be used.
- an acryl-type adhesive agent etc. can be used.
- the acrylic adhesive known ones can be appropriately employed, and examples thereof include an adhesive described in JP2012-247574A.
- the thickness of the adhesive layer is not particularly limited, but is preferably 0.01 to 20 ⁇ m, more preferably 0.01 to 10 ⁇ m, and further preferably 0.5 to 5 ⁇ m.
- the protective film used for the circularly polarizing plate is not particularly limited, and for example, a thermoplastic resin film having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, and the like is used.
- a thermoplastic resin film having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, and the like is used.
- Specific examples of the thermoplastic resin constituting such a thermoplastic resin film include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, Examples include polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
- the protective film may contain one or more arbitrary appropriate additives.
- the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
- a cellulose resin film is preferable, a cellulose ester film is more preferable, and a triacetyl cellulose film is more preferable.
- the thickness of the protective film is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and further preferably 10 to 70 ⁇ m.
- the film thickness of the circularly polarizing plate (after peeling the temporary support) is not particularly limited, but is preferably 10 ⁇ m or more and 100 ⁇ m or less, and more preferably 20 ⁇ m or more and 70 ⁇ m or less.
- the polarizing plate is not particularly limited, but is preferably applied to a liquid crystal display device or an organic EL display device.
- the polarizing plate is a circularly polarizing plate, the effect of shielding the specular reflection of the metal electrode of the organic EL element can be expressed in a wide wavelength range of visible light by applying to an organic EL display device or the like described later. Particularly preferable from the viewpoint. With such an effect, reflection during observation can be prevented and black expression can be improved.
- Organic EL display device Another embodiment of the present invention relates to an organic EL (organic electroluminescence) display device having the optical film after removal of the temporary support or a polarizing plate including the optical film.
- Another embodiment of the present invention is a method for producing an organic EL display device, comprising producing a polarizing plate by the method for producing a polarizing plate and then bonding the polarizing plate and an organic EL element.
- a method for producing an organic EL display device comprising producing a polarizing plate by the method for producing a polarizing plate and then bonding the polarizing plate and an organic EL element.
- the external light incident on the organic EL display device transmits only the linearly polarized light component through the polarizer.
- the linearly polarized light transmitted through the polarizer is such that the optical film after peeling the temporary support is a ⁇ / 4 retardation film, and the slow axis direction in the plane of the optical film after peeling the temporary support and the polarizer
- the angle with respect to the transmission axis direction is 45 ° ⁇ 10 ° (35 ° or more and 55 ° or less)
- it is circularly polarized by transmitting through the optical film after the temporary support is removed.
- This circularly polarized light is transmitted through the transparent substrate, the transparent electrode, and the organic thin film, then reflected by the metal electrode, and again passes through the organic thin film, the transparent electrode, the transparent substrate, and the optical film after removal of the temporary support to become linearly polarized light. .
- this linearly polarized light is orthogonal to the polarization direction of a polarizer, it cannot permeate
- the organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative and the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Structures having various combinations such as a laminate of such a light emitting layer and an electron injection layer composed of a perylene derivative or the like, or a laminate of these hole injection layer, light emitting layer and electron injection layer are known.
- holes and electrons are injected into the organic light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons excites the phosphor material. Then, light is emitted on the principle that the excited fluorescent material emits light when returning to the ground state.
- the mechanism of recombination in the middle is the same as that of a general diode, and as can be predicted from this, the current and the emission intensity show strong nonlinearity with rectification with respect to the applied voltage.
- At least one of the electrodes needs to be transparent, and is usually formed of a transparent conductor such as indium tin oxide (ITO).
- ITO indium tin oxide
- the electrode is preferably used as the anode.
- metal electrodes such as Mg—Ag and Al—Li are used.
- a negative resin layer coating solution N1 was dissolved in methylene chloride at a solid content of 20% by mass to prepare a negative resin layer coating solution N1.
- a negative resin layer coating solution N1 is applied on the surface of the original film O1 with a comma coater so that the dry film thickness becomes 18 ⁇ m, and then dried, and negatively applied on the surface of the original film O1.
- the resin layer NN1 was formed. In this way, a long laminate L1 in which the raw film O1 and the negative resin layer NN1 were laminated was formed.
- Laminate L2 In the formation of the laminate L1, the negative resin layer coating liquid N1 was applied so that the dry film thickness was 11 ⁇ m, and then dried to form a negative resin layer on the surface of the raw film O1. In the same manner, a long laminate L2 in which the raw film O1 and the negative resin layer NN2 were laminated was formed.
- a negative resin layer coating solution N2 was prepared in the same manner except that polyisopropyl difumarate was changed to the fumarate diester / alkoxycinnamic acid ester copolymer.
- a negative resin layer NN4 was formed on the surface of the anti-film O1. In this way, a long laminate L4 in which the raw film O1 and the negative resin layer NN4 were laminated was formed.
- Laminate L5 In the formation of the laminate L1, a negative resin layer coating liquid N3 was prepared in the same manner except that polyisopropyl difumarate was changed to polystyrene having a weight average molecular weight of 50,000, which is a negative resin, and a raw film O1 A negative resin layer NN5 was formed on the surface. In this way, a long laminate L5 in which the raw film O1 and the negative resin layer NN5 were laminated was formed.
- Laminate L6 In the formation of the laminate L1, a positive resin is obtained in the same manner except that diisopropyl polyfumarate is changed to a cyclic olefin resin (COP) (product name: Arton (registered trademark) G7810 manufactured by JSR Corporation) which is a positive resin. A layer coating solution P1 was prepared, and a positive resin layer PN1 was formed on the surface of the raw film O1. In this way, a long laminate L6 in which the raw film O1 and the positive resin layer PN1 were laminated was formed.
- COP cyclic olefin resin
- the film thickness of the negative resin alignment layer formed from the negative resin layer or the positive resin alignment layer formed from the positive resin layer was set to the values shown in Table 2 below.
- the rail pattern is adjusted so that the path difference between the outer rail and the inner rail is substantially equal to the film width at the outlet of the stretching machine, and the stretching ratio is 1 for stretching at L1, L2, and L4-6 at a stretching temperature of 180 ° C. .2 times, L3 stretching is 1.4 times, and the longitudinal direction (MD direction, longitudinal direction) and the angle formed by the stretching direction (stretching angle) are 45 degrees, and the liquid crystal coating is performed obliquely.
- Substrate films B1 to B6 were produced.
- negative resin alignment layers NA1 to NA5 are formed from the negative resin layers NN1 to NN, a positive resin alignment layer PA1 is formed from the positive resin layer PN1, and the temporary support S1 is formed from the raw film O1.
- substrate films B1 to B6 for applying a liquid crystal were respectively produced.
- the temporary supports S1 and S2 could be peeled from the negative resin alignment layers NA1 to NA5 or the positive resin alignment layer PA1, respectively.
- the film thickness of the temporary support S1 was 83 ⁇ m
- the film thickness of the temporary support S2 was 71 ⁇ m.
- the laminate L1 obtained above is stretched at a stretching temperature of 180 ° C., a stretching ratio of 1.3 times, a longitudinal direction (MD direction, longitudinal direction), and a stretching direction by an MD stretching machine using a difference in peripheral speed of the roll.
- the base film B7 for liquid crystal application was manufactured by performing longitudinal stretching (longitudinal stretching, MD stretching) with the angle (stretching angle) formed by
- the negative resin alignment layer NA6 is formed from the negative resin layer NN1, and the temporary support S3 is formed from the raw film O1, whereby the liquid crystal coating base film B7 is manufactured. It was. Moreover, temporary support body S3 was peelable between negative resin orientation layer NA6. Here, the film thickness of the temporary support S3 was 83 ⁇ m.
- the obtained liquid crystal layer coating liquid LC1 was applied to the liquid crystal coating substrate films B1 to 5 and 7 thus produced to form a liquid crystal coating layer and dried at 65 ° C. for 5 minutes. . Thereafter, ultraviolet rays of 380 mJ / cm 2 were irradiated with a Fusion H bulb, the liquid crystal coating layer was cured to form a liquid crystal layer, and optical films 1 to 5 and 10 with a temporary support were produced.
- the coating thickness of the liquid crystal coating layer is such that a liquid crystal alignment film is provided on glass in the same manner as in the production of the optical film 6 with the temporary support described below, and then the liquid crystal coating layer is formed on the alignment film.
- the liquid crystal layer formed by coating and drying by the above method was set as a condition so that the retardation values shown in Table 1 below were obtained. A method for measuring the retardation of the liquid crystal layer will be described later.
- a liquid crystal layer coating solution was obtained in the same manner as in the production of the substrate films for liquid crystal coating 1 to 5 and 10.
- the liquid crystal alignment direction is the direction in which the elastic modulus of the temporary support is maximized.
- the rubbing process was performed so as to be parallel to (0 degree).
- the liquid crystal aligning film was formed on the base film B1 for liquid crystal application before the application of the liquid crystal layer coating liquid.
- the obtained liquid crystal layer coating liquid LC1 was applied onto the liquid crystal alignment film on the liquid crystal coating base film B1 produced to form a liquid crystal coating layer, and dried at 65 ° C. for 5 minutes. . Thereafter, an ultraviolet ray of 380 mJ / cm 2 was irradiated with an H bulb manufactured by Fusion to cure the liquid crystal coating layer to form a liquid crystal layer, thereby producing an optical film 6 with a temporary support.
- a liquid crystal alignment film and a liquid crystal layer are formed in the same manner as in the production of the base film 6 for liquid crystal coating, except that the liquid crystal layer coating liquid LC1 is changed to the liquid crystal layer coating liquid LC2.
- Film 8 was produced.
- the base film for liquid crystal application B1 is changed to the base film for liquid crystal application B6, and the rubbing treatment of the alignment film is changed so that the liquid crystal alignment direction is orthogonal to the direction in which the elastic modulus of the temporary support is maximum.
- the liquid crystal alignment film and the liquid crystal layer were formed in the same manner as in the manufacture of the substrate film 8 for liquid crystal application, and the optical film 9 with a temporary support was manufactured.
- PVA molecules in the PVA layer are highly oriented, and iodine adsorbed by dyeing constitutes a highly functional polarizer oriented in one direction as a polyiodine ion complex.
- An optical film laminate including a PVA layer having a thickness of 4 ⁇ m could be produced.
- the amorphous PET substrate was peeled off, A polarizing plate with a single-sided protective film using a thin polarizer (thin single-sided polarizing plate) was produced.
- the obtained acrylic pressure-sensitive adhesive solution is uniformly coated on the surface of a polyethylene terephthalate film (separator film) treated with a silicone-based release agent with a fountain coater, and then for 2 minutes in a 155 ° C air circulation type thermostatic oven. It dried and formed the 20-micrometer-thick adhesive layer on the surface of a separator film. Next, the pressure-sensitive adhesive layer formed on the separator film was transferred to the polarizer side of the thin single-sided polarizing plate formed above to produce a pressure-sensitive adhesive polarizing plate.
- the separator film of the obtained pressure-sensitive adhesive polarizing plate was peeled, and the optical films 1 to 9 with the temporary support produced above were peeled from each other so that the liquid crystal layer and the pressure-sensitive adhesive layer were in contact with each other. Bonding was performed by a roll-to-roll method so as to match. Next, after the adhesion, the temporary support was peeled off to produce circularly polarizing plates using the optical films 1 to 9 with the temporary support.
- an adhesion type polarizing plate is cut out as a square test piece so that a longitudinal direction and the direction of one side may become parallel, and the optical film 10 with a temporary support body was cut out as a square test piece of the same size so that the direction at 45 degrees with respect to the longitudinal direction would be the direction of one side.
- the separator film of the test piece of the pressure-sensitive adhesive polarizing plate is peeled, and the test piece of the optical film 10 with the temporary support is made to contact the liquid crystal layer and the pressure-sensitive adhesive layer so that the sides coincide with each other. Pasted.
- a circularly polarizing plate using the optical film 10 with a temporary support was manufactured by peeling the temporary support after bonding.
- the temporary support is separated from the negative resin alignment layer or the positive resin alignment layer of the produced substrate film for liquid crystal coating or peeled, and from the temporary support after peeling, the short side direction is 1 cm ⁇ the long side direction is 10 cm.
- the test piece was cut out and the elastic modulus in the long side direction was measured using a universal testing machine 5966 type manufactured by Instron.
- the test piece was cut out at an angle of 45 degrees so that the angle formed between the long side direction of the test piece and the direction that was the longitudinal direction of the liquid crystal coating base film was 0 to 135 degrees (ie, Test pieces having long side directions of 0 °, 45 °, 90 °, and 135 ° with respect to the longitudinal direction of the liquid crystal coating base film were cut out), and the elastic modulus of these test pieces was measured. Next, from the result of the elastic modulus of these test pieces, the direction in which the elastic modulus was maximized was roughly determined.
- the cut angle around the direction where the approximate elastic modulus obtained above is maximized is incremented by 5 degrees, and the test piece is cut again within a range of ⁇ 20 degrees in the direction where the elastic modulus is maximum (ie, approximately The direction in which the elastic modulus is maximum, the direction in which the elastic modulus is maximum ⁇ 5 degrees, the direction in which the elastic modulus is maximum ⁇ 10 degrees, the direction in which the elastic modulus is maximum ⁇ 15 degrees, and the elastic modulus A test piece having a maximum direction ⁇ 20 degrees was cut out), and the direction in which the elastic modulus of the temporary support was maximized was determined.
- the direction in which the elastic modulus of the temporary support is maximized in increments of 5 degrees is determined.
- the elastic modulus of the temporary support is maximized at a smaller angle, for example, in increments of 1 degree. Experiments may be performed to determine the direction.
- a liquid crystal alignment film was formed on the glass substrate in the same manner as the liquid crystal layer of the optical film 6 with a temporary support, except that the rubbing direction was a specific direction. Next, a liquid crystal layer corresponding to each of the optical films 1 to 10 with the temporary support is formed on the liquid crystal alignment film, and each liquid crystal layer corresponding to these optical films with the temporary support is used for phase difference measurement. A test piece was formed.
- the in-plane slow axis direction in the laminated state of the negative resin alignment layer or the positive resin alignment layer retardation measurement specimen and each liquid crystal layer retardation measurement specimen is the position of the liquid crystal layer. It measured using the wavelength of 550 nm by AxoScan by Axometrics similarly to the measurement of a phase difference.
- the in-plane slow axis direction in these laminated states and the in-plane slow axis direction of the optical film after removal of the corresponding temporary support were determined.
- the orientation direction of the liquid crystal molecules of the liquid crystal layer was determined from the angle formed between the negative resin alignment layer or the positive resin alignment layer evaluation test piece and each liquid crystal layer retardation measurement test piece.
- the stretching angle and the angle 1 are parallel in the liquid crystal coating base materials B1 to B7, and in the liquid crystal coating base materials B1 to 5 and B7, the stretching angle and the angle 3 are orthogonal to each other. In the base material B6, the stretching angle and the angle 3 were parallel.
- the optical films 1 to 6, 8 and 10 with temporary supports produced using the base films B1 to 5 and 7 for liquid crystal coating according to the present invention are excellent in curling and circularly polarized. Even when used as a plate, it was confirmed that the front reflection characteristics, tint and oblique field reflection characteristics were also excellent.
- the optical films 7 and 9 with the temporary support produced using the substrate film B6 for liquid crystal application according to the present invention are more curled, compared with the optical films 1 to 6, 8 and 10 with the temporary support. It was confirmed that it was inferior to all of the front reflection characteristics, tint and oblique field reflection characteristics when used as a circularly polarizing plate.
- the negative film thickness is set to 18 ⁇ m with a comma coater on the surface of the raw film O1. After the resin layer coating solution N1 was applied, it was partially dried, and the negative resin layer NN1 was peeled from the raw film O1 before the solvent was completely dried.
- the temporary support S8 is formed from the raw film O2
- the negative resin alignment layer NA7 is formed from the negative resin layer NN1
- the film thickness of the temporary support S8 is 103 ⁇ m
- the negative retardation alignment layer NA7 was 15 ⁇ m.
- a circularly polarizing plate was prepared in the same manner as in the production of the circularly polarizing plate using the optical film 1 with a temporary support except that the optical films 11 and 12 with a temporary support were used in place of the optical film 1 with a temporary support. Manufactured. Next, for these circularly polarizing plates, the front reflection characteristics, color, and oblique viewing characteristics were evaluated in the same manner as described above, and the same results as the circularly polarizing plate using the optical film 1 with a temporary support were obtained. .
- Phase difference fluctuation value About the manufactured substrate films B8 and B9 for liquid crystal application, the temporary support was separated and peeled, and a test piece was cut out from the peeled temporary support, and 3 points ⁇ 3 every 2 cm using AxoScan manufactured by Axometrics. A total of 9 points in each row were measured. The reference wavelength of Ro was 550 nm. Next, for each film, the difference obtained by subtracting the minimum value from the maximum value of these measured values was calculated as the phase difference fluctuation value. These results are shown in Table 4 below.
- the optical films 11 and 12 with a temporary support produced using the substrate films for liquid crystal coating B8 and B9 according to the present invention have small phase difference variation values and excellent quality assurance suitability. was confirmed.
- 1 substrate film for liquid crystal coating 2 temporary support that can be peeled, 3 negative resin orientation layer, 4 direction in which the elastic modulus of the peelable temporary support is maximized, 5 In-plane slow axis direction of negative resin orientation layer, 10 Optical film with temporary support, 11 Liquid crystal layer, 12 Orientation direction of liquid crystal molecules in the liquid crystal layer.
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Abstract
Description
前記積層体を延伸することによって、前記原反フィルムから弾性率が最大となる方向を有する、剥離可能な仮支持体を形成することと、前記負の樹脂層から面内に遅相軸を有する負の樹脂配向層を形成することと、前記仮支持体の弾性率が最大となる方向と、前記負の樹脂配向層の面内の遅相軸方向と、を略直交とすることと、を有する延伸工程と、を含む、液晶塗布用基材フィルムの製造方法。
本発明の一形態は、剥離可能な仮支持体(以下、単に「仮支持体」とも称する。)と、負の位相差発現性を有する樹脂を含有し、面内に遅相軸を有する負の樹脂配向層と、を含む積層構造を有し、前記仮支持体の弾性率が最大となる方向と、前記負の樹脂配向層の遅相軸方向とが略直交である、液晶塗布用基材フィルムに関する。本発明の一形態によれば、仮支持体付きの状態での光学フィルムのカールを低減するとともに、使用時に仮支持体を剥離することで光学フィルムの薄膜化を可能とし、当該光学フィルムおよびこれを用いた部材の光学特性をより向上させる液晶塗布用基材フィルムが提供される。
原反フィルムは、当該原反フィルムおよび負の樹脂層を含む積層体を延伸することを経て剥離可能な仮支持体となる。原反フィルムは、延伸によって、弾性率が最大となる方向を有する、剥離可能な仮支持体を形成できるものであれば特に制限されず、公知の自己支持性を有するフィルムを用いることができる。
式(I):Ro=(nx-ny)×d
式(II):Rt={(nx+ny)/2-nz}×d
(式(I)および(II)において、nxは、仮支持体の面内方向において屈折率が最大となる方向xにおける屈折率であり、nyは、仮支持体の面内方向において前記方向xと直交する方向yにおける屈折率であり、nzは、仮支持体の厚み方向における屈折率であり、dは、仮支持体の膜厚(nm)である)。
負の樹脂層は、負の位相差発現性を有する樹脂を含有し、上述した原反フィルムおよび負の樹脂層の積層体を延伸することによって、負の樹脂層を、面内に遅相軸を有する負の樹脂配向層とすることができる。負の樹脂層は、本発明に係る延伸工程によって、負の樹脂配向層を形成するものであれば特に制限されず、公知の負の位相差発現性を有する樹脂を含有するフィルムを用いることができる。
式(I):Ro=(nx-ny)×d
式(II):Rt={(nx+ny)/2-nz}×d
(式(I)および(II)において、nxは、負の樹脂配向層の面内方向において屈折率が最大となる方向xにおける屈折率であり、nyは、負の樹脂配向層の面内方向において前記方向xと直交する方向yにおける屈折率であり、nzは、負の樹脂配向層の厚み方向における屈折率であり、dは、負の樹脂配向層層の膜厚(nm)である)。
本発明の一形態に係る液晶塗布用基材フィルムは、本発明の効果を損なわない限り、他の機能層を有していてもよい。なお、本発明では、他の機能層の位置は特に制限されず、仮支持体の負の樹脂配向層とは反対側の面側に配置されても、負の樹脂配向層の仮支持体とは反対側に配置されても、また仮支持体と負の樹脂配向層との間に配置されてもよい。他の機能層としては、偏光板や、偏光板保護フィルム、位相差フィルム等の公知の光学フィルムにおいて一般的に設けられる層を適宜選択することができる。例えば、ハードコート層、易接着層、防眩層、反射防止層、低反射層、低反射防眩層、反射防止防眩層、帯電防止層、シリコーン層、粘接着層、防汚層、耐指紋層、撥水層、およびブルーカット層等が挙げられる。
本発明の他の一形態は、原反フィルム上に、負の位相差発現性を有する樹脂を含有する負の樹脂層を形成することによって、前記原反フィルムと、前記負の樹脂層とを含む積層体を形成する積層工程と、前記積層体を延伸することによって、前記原反フィルムから弾性率が最大となる方向を有する、剥離可能な仮支持体を形成することと、前記負の樹脂層から面内に遅相軸を有する前記負の樹脂配向層を形成することと、前記仮支持体の弾性率が最大となる方向と、前記負の樹脂配向層の面内の遅相軸方向と、を略直交とすることと、を含む延伸工程と、を含む、液晶塗布用基材フィルムの製造方法に関する。本発明の一形態によれば、仮支持体付きの状態での光学フィルムのカールを低減するとともに、使用時に仮支持体を剥離することで光学フィルムの薄膜化を可能とし、当該光学フィルムおよびこれを用いた部材の光学特性をより向上させる液晶塗布用基材フィルムが提供される。
本発明の他の一形態に係る製造方法は、原反フィルム上に、負の位相差発現性を有する樹脂を含有する負の樹脂層を形成することによって、前記原反フィルムと、前記負の樹脂層とを含む積層体を形成する積層工程を含む。
本発明の他の一形態に係る製造方法は、原反フィルムと、負の樹脂層とを含む積層体を延伸することによって、弾性率が最大となる方向を有する、剥離可能な仮支持体を形成することと、面内に遅相軸を有する負の樹脂配向層を形成することと、仮支持体の弾性率が最大となる方向と、負の樹脂配向層の面内の遅相軸方向と、を略直交とすることと、を有する延伸工程を含む。
[仮支持体付き光学フィルム]
本発明の他の一形態は、上記液晶塗布用基材フィルムの前記負の樹脂配向層上に液晶層をさらに有する、仮支持体付き光学フィルムに関する。また、本発明の一形態に係る仮支持体付き光学フィルムは、仮支持体の弾性率が最大となる方向と、前記液晶層の液晶配向方向とが略平行であることが好ましい。
液晶層は、仮支持体付き光学フィルムに対して、仮支持体剥離後の光学フィルムとして要求される光学特性を付与する機能を有する。特に、負の樹脂配向層との組み合わせによって、所望の光学特性を達成することが好ましい。
式(I):Ro=(nx-ny)×d
(式(I)において、nxは、液晶層の面内方向において屈折率が最大となる方向xにおける屈折率であり、nyは、液晶層の面内方向において前記方向xと直交する方向yにおける屈折率であり、dは、液晶層の膜厚(nm)である)。
上記液晶塗布用基材フィルムにおいて、負の樹脂配向層は、樹脂の分子の主鎖配向方向とその面内の遅相軸方向とが直交しており、樹脂の分子の主鎖配向方向(延伸方向)に液晶分子を配向させる機能を有するが、液晶配向膜は、この液晶分子を配向させる機能をより高める機能を有する。
本発明の他の一形態は、上記液晶塗布用基材フィルムの製造方法によって前記液晶塗布用基材フィルムを製造した後、前記液晶塗布用基材フィルムの前記負の樹脂配向層上に液晶層を形成することを含む、液晶層形成工程をさらに有する、仮支持体付き光学フィルムの製造方法に関する。
上記液晶塗布用基材フィルムの負の樹脂配向層上に液晶層を形成する方法としては、特に制限されず、転写や塗布、流延等の公知の方法が用いられる。また、これらの中でも、材料選択の自由度や生産性の観点から、負の樹脂層は、液晶層塗工液を塗布することによって形成することが好ましい。液晶層塗工液の調製、塗布、乾燥、硬化の方法、条件としては、特に制限されず、公知の方法を適宜選択して用いることができる。液晶層塗工液は、例えば、液晶分子に加え、重合開始剤等の任意に用いられうる他の添加成分を、溶媒中で均質に混合することが調製することができる。
[偏光板およびその製造方法]
本発明の他の一形態は、仮支持体付き光学フィルムと、直線偏光子(偏光子)とが、所定の角度、例えば、偏光子の透過軸方向と、仮支持体を剥離した状態における光学フィルムの面内の遅相軸方向とのなす角度が45度±10度(35度以上55度以下)となるよう積層された、仮支持体付き偏光板に関する。また、本発明のその他の一形態は、仮支持体剥離後の光学フィルムと、偏光子とが、所定の角度、例えば、偏光子の透過軸方向と、仮支持体剥離後の光学フィルムの面内の遅相軸方向とのなす角度が45度±10度(35度以上55度以下)となるよう積層された偏光板にも関する。また、本発明の他の一形態は、上記の仮支持体付き光学フィルムの製造方法によって仮支持体付き光学フィルムを製造した後、当該仮支持体付き光学フィルムと、偏光子とを、所定の角度、例えば、偏光子の透過軸方向と、仮支持体剥離後の光学フィルムの面内の遅相軸方向とのなす角度とが45度±10度(35度以上55度以下)となるよう積層することを含む、仮支持体付き偏光板の製造方法に関する。これらの偏光板は、円偏光板として好ましく用いることができる。この際、偏光子の透過軸方向と、仮支持体を剥離した状態における光学フィルムまたは仮支持体剥離後の光学フィルムの面内の遅相軸とのなす角度は、45度±5度(40度以上50度以下)であることがより好ましく、45度±4度(41度以上49度以下)であることがさらに好ましく、45度±3度(42度以上48度以下)であることがよりさらに好ましく、45度±2度(43度以上47度以下)であることが特に好ましく、45度±1度(44度以上46度以下)であることがさらに特に好ましく、45度であることが最も好ましい。ここで、偏光子の透過軸方向と、仮支持体を剥離した状態における光学フィルムまたは仮支持体剥離後の光学フィルムの面内の遅相軸方向とのなす角度とは、偏光子の透過軸方向を基準(0度)として、時計回りまたは反時計回りに仮支持体を剥離した状態における光学フィルムまたは仮支持体剥離後の光学フィルムの面内の遅相軸方向がなす角度のうちより小さい方の角度をいい、0度以上90度以下の範囲内の角度とする。
本発明のその他の一形態は、上記仮支持体剥離後の光学フィルム、またはこれを含む偏光板を有する、有機EL(有機エレクトロルミネッセンス)表示装置に関する。また、本発明のその他の一形態は、上記の偏光板の製造方法によって偏光板を製造した後、当該偏光板と、有機EL素子とを貼合することを含む、有機EL表示装置の製造方法に関する。
ポリエチレンテレフタレートからなる樹脂ペレット(固有粘度0.65dl/g)を回転式真空乾燥機に投入し、150℃で8時間乾燥した後、押出機にて285℃で溶融混練した。コートハンガーダイスリットから二軸延伸後の膜厚が100μmになるように50℃の回転冷却ドラムの上に押出し、冷却後ドラムから剥離し、95℃で縦方向に2倍延伸し、さらに95℃で横方向に2倍延伸し、220℃で熱固定した。その後冷却して巻き取り、ポリエチレンテレフタレートからなる長尺の原反フィルムO1を得た。
[積層体L1の形成]
特開2016-98371号公報の段落「0081」の合成例3に記載の方法によって、数平均分子量は118,000である、ポリフマル酸ジイソプロピル(フマル酸ジイソプロピル単独重合体)を合成した。また、ポリフマル酸ジイソプロピルは負の位相差発現性を有する樹脂であることを確認した。
上記積層体L1の形成において、乾燥膜厚が11μmとなるよう負の樹脂層塗工液N1を塗布した後、乾燥をして、原反フィルムO1の表面上に負の樹脂層を形成した以外は同様にして、原反フィルムO1と、負の樹脂層NN2とが積層された長尺の積層体L2を形成した。
上記積層体L1の形成において、乾燥膜厚が28μmとなるよう負の樹脂層塗工液N1を塗布した後、乾燥をして、原反フィルムO1の表面上に負の樹脂層を形成した以外は同様にして、原反フィルムO1と、負の樹脂層NN3とが積層された長尺の積層体L3を形成した。
特開2016-98371号公報の段落「0071」の実施例3に記載の方法によって、数平均分子量は51,000であり、共重合体組成はフマル酸ジイソプロピル残基単位/4-メトキシケイ皮酸エチル残基単位=61/39(モル%)である、フマル酸ジエステル/アルコキシケイ皮酸エステル共重合体を合成した。また、フマル酸ジエステル/アルコキシケイ皮酸エステル共重合体は負の位相差発現性を有する樹脂であることを確認した。
上記積層体L1の形成において、ポリフマル酸ジイソプロピルを負の樹脂である重量平均分子量50,000のポリスチレンに変更した以外は同様にして、負の樹脂層塗工液N3を調製し、原反フィルムO1の表面上に負の樹脂層NN5を形成した。このようにして、原反フィルムO1と、負の樹脂層NN5とが積層された長尺の積層体L5を形成した。
上記積層体L1の形成において、ポリフマル酸ジイソプロピルを正の樹脂である環状オレフィン系樹脂(COP)(JSR株式会社製 製品名Arton(登録商標)G7810)に変更した以外は同様にして、正の樹脂層塗工液P1を調製し、原反フィルムO1の表面上に正の樹脂層PN1を形成した。このようにして、原反フィルムO1と、正の樹脂層PN1とが積層された長尺の積層体L6を形成した。
[液晶塗布用基材フィルムB1~6の製造]
上記にて得られた積層体L1~6を、国際公開第2013/146397号の図6および図7に記載の斜め延伸装置を用いて、国際公開第2013/146397号の実施例2に記載の方法を参照して延伸し、液晶塗布用基材フィルムB1~6を製造した。
上記にて得られた積層体L1を、ロール周速差を利用したMD延伸機によって、延伸温度180℃で、延伸倍率1.3倍、長尺方向(MD方向、縦方向)と、延伸方向のなす角度(延伸角度)を0度として長手方向延伸(縦延伸、MD延伸)を行うことで、液晶塗布用基材フィルムB7を製造した。
[仮支持体付き光学フィルム1~5および10の製造]
上記化学式(113)で表される液晶化合物、上記化学式(114)で表される液晶化合物、および上記化学式(116)で表される液晶化合物、ならびにIrgacure(登録商標)184(BASFジャパン株式会社製)を5:3:2:0.5の配合質量比で、トルエン/シクロヘキサノンの7:3(質量比)の混合溶剤に溶解させ、固形分濃度が25質量%である液晶層塗工液LC1を得た。
上記液晶塗布用基材フィルム1~5および10の製造と同様にして液晶層塗工液を得た。
液晶塗布用基材フィルムB1を液晶塗布用基材フィルムB6に変更し、液晶配向膜のラビング処理を、液晶配向方向が仮支持体の弾性率が最大となる方向と直交方向(90度)になるように変更して行った以外は、液晶塗布用基材フィルム6の製造と同様にして、液晶配向膜および液晶層を形成し、仮支持体付き光学フィルム7を製造した。
重合性液晶化合物LC242(BASF社製)、トリメチロールプロパントリアクリレート(新中村化学工業株式会社製)、光重合開始剤であるIrgacure(登録商標)379(BASFジャパン株式会社製)、およびフッ素を含む界面活性剤であるメガファック(登録商標)F477(DIC株式会社製)を75:5:3:0.1の配合質量比で、トルエン/シクロヘキサノンの7:3(質量比)の混合溶剤に溶解させ、固形分濃度が25%である液晶層塗工液LC2を得た。
液晶塗布用基材フィルムB1を液晶塗布用基材フィルムB6に変更し、配向膜のラビング処理を、液晶配向方向が仮支持体の弾性率が最大となる方向と直交方向になるように変更して行った以外は、液晶塗布用基材フィルム8の製造と同様にして、液晶配向膜および液晶層を形成し、仮支持体付き光学フィルム9を製造した。
(片面保護フィルム付き偏光板の形成)
非晶性ポリエチレンテレフタレート(PET)基材に9μm厚のポリビニルアルコール(PVA)層が製膜された積層体を、延伸温度130℃の空中補助延伸によって延伸積層体を生成した。次に、延伸積層体を染色して着色積層体を生成し、得られた着色積層体を延伸温度65℃のホウ酸水中延伸によって、総延伸倍率が5.94倍になるように非晶性PET基材と一体に延伸した。このようにして、4μm厚のPVA層を含む光学フィルム積層体を生成した。このような2段延伸によって、PVA層中のPVA分子が高次に配向され、染色によって吸着されたヨウ素がポリヨウ素イオン錯体として一方向に高次に配向された高機能偏光子を構成する、厚さ4μmのPVA層を含む光学フィルム積層体を生成することができた。さらに、当該光学フィルム積層体の偏光子の表面にポリビニルアルコール系接着剤を塗布しながら、けん化処理した40μm厚のトリアセチルセルロースフィルムを貼合した後、非晶性PET基材を剥離して、薄型偏光子を用いた片面保護フィルム付き偏光板(薄型片面偏光板)を作製した。
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート82質量部、ベンジルアクリレート15質量部、4-ヒドロキシブチルアクリレート3質量部を含有するモノマー混合物を仕込んだ。さらに、前記モノマー混合物(固形分)100質量部に対して、重合開始剤として2,2’-アゾビスイソブチロニトリル0.1質量部を酢酸エチルと共に仕込み、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を60℃付近に保って7時間重合反応を行った。その後、得られた反応液に、酢酸エチルを加えて、固形分濃度30質量%に調整した、重量平均分子量100万のアクリル系ポリマー(A-1)の溶液を調製した。
上記得られたアクリル系粘着剤溶液を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(セパレータフィルム)の表面に、ファウンテンコーターで均一に塗工し、155℃の空気循環式恒温オーブンで2分間乾燥し、セパレータフィルムの表面に厚さ20μmの粘着剤層を形成した。次いで、上記で形成した薄型片面偏光板の偏光子の側に、セパレータフィルム上に形成した粘着剤層を転写して、粘着型偏光板を作製した。
上記得られた粘着型偏光板のセパレータフィルムを剥離し、これに対して上記製造した仮支持体付き光学フィルム1~9を、液晶層と粘着層とが接するように、また互いに長尺方向が一致するようにロールtoロール法によって接着した。次いで、接着後に仮支持体を剥離することで、仮支持体付き光学フィルム1~9を用いて円偏光板をそれぞれ製造した。
[仮支持体の弾性率最大方向]
上記製造した液晶塗布用基材フィルムの負の樹脂配向層または正の樹脂配向層から仮支持体を分離して剥離し、剥離後の仮支持体から、短辺方向1cm×長辺方向10cmの試験片を切り出し、インストロン社製 万能試験機5966型を用いて長辺方向の弾性率を測定した。ここで、試験片の長辺方向と、液晶塗布用基材フィルムの長手方向であった方向とのなす角度が0度~135度となるよう45度刻みの角度で試験片を切り出し(すなわち、長辺方向が液晶塗布用基材フィルムの長手方向に対して0度、45度、90度および135度となる試験片を切り出し)、これらの試験片の弾性率を測定した。次いで、これらの試験片の弾性率の結果より、弾性率が最大となる方向を粗々求めた。
上記製造した液晶塗布用基材フィルムの負の樹脂配向層または正の樹脂配向層から仮支持体を分離して剥離し、負の樹脂配向層または正の樹脂配向層から試験片(負の樹脂配向層または正の樹脂配向層位相差測定用試験片)を切り出し、Axometrics社製 AxoScanを用いて、フィルムのRo、Rt、面内の遅相軸方向、波長分散を求めた。Ro、Rtの基準波長は550nmとし、波長分散はRo(450nm)/Ro(550nm)と定義した。また、負の樹脂配向層または正の樹脂配向層の面内の遅相軸方向は、Axometrics社製 AxoScanを用いた550nmにおけるRoの測定時に得られた値を使用した。これらの結果を表2に示す。
ガラス基板上に、ラビング方向を特定の一方向とした以外は上記仮支持体付き光学フィルム6の液晶層の形成と同様にして液晶配向膜を形成した。次いで、当該液晶配向膜上に上記仮支持体付き光学フィルム1~10と同様にしてそれぞれに対応する液晶層を形成し、これらの仮支持体付き光学フィルムに対応する各液晶層位相差測定用試験片を形成した。
[仮支持体剥離後の光学フィルムの面内の遅相軸方向]
上記各仮支持体付き光学フィルムから仮支持体を剥離し、上記の液晶層の位相差の測定と同様にして、Axometrics社製 AxoScanにより550nmの波長を用いて、仮支持体剥離後の光学フィルムの面内の遅相軸方向を測定した。
上記負の樹脂配向層および正の樹脂配向層の位相差および面内の遅相軸方向の測定と同様にして、仮支持体付き光学フィルムに対応する負の樹脂配向層または正の樹脂配向層位相差測定用試験片を切り出した。また、上記の液晶層の位相差の測定と同様にして、仮支持体付き光学フィルムに対応する各液晶層位相差測定用試験片を切り出した。次いで、仮支持体付き光学フィルムに対応する組み合わせとして、負の樹脂配向層または正の樹脂配向層位相差測定用試験片と、各液晶層位相差測定用試験片とを重ね、両者のなす角度を様々に変化させて、これらの積層状態における面内の遅相軸方向を測定した。ここで、負の樹脂配向層または正の樹脂配向層位相差測定用試験片と各液晶層位相差測定用試験片との積層状態における面内の遅相軸方向は、上記の液晶層の位相差の測定と同様にして、Axometrics社製 AxoScanにより550nmの波長を用いて測定した。そして、負の樹脂配向層または正の樹脂配向層位相差測定用試験片と、各液晶層位相差測定用試験片との負の樹脂配向層または正の樹脂配向層の面内の遅相軸方向を同一方向とした際に、これらの積層状態における面内の遅相軸方向と、対応する仮支持体剥離後の光学フィルムの面内の遅相軸方向とが一致する状態を求めた。このときの負の樹脂配向層または正の樹脂配向層評価用試験片と、各液晶層位相差測定用試験片とのなす角度から、液晶層の液晶分子の配向方向を求めた。
上記製造した仮支持体付き光学フィルムをA4サイズに切り出し、仮支持体側を下向きにした状態で水平面に置き、四隅の水平面からの高さの平均値を求めることで、カールを評価した。高さの平均値が小さいほど望ましい特性を表すものとし、◎、○および△が良好な特性を表すものとする。これらの結果を表3に示す;
◎:四隅の水平面からの高さの平均値0mm以上1mm未満である、
○:四隅の水平面からの高さの平均値1mm以上2mm未満である、
△:四隅の水平面からの高さの平均値2mm以上4mm未満である、
×:四隅の水平面からの高さの平均値4mm以上である。
上記製造した円偏光板の光学フィルム側(トリアセチルセルロースフィルムとは反対側)と、鏡面を有するアルミニウム反射板の鏡面側とを、市販の感圧性粘着フィルムを介して接着し、太陽光下、円偏光板側の正面から見た反射板からの反射光を下記基準に従い目視評価した。反射光が少ないほど望ましい特性を表すものとし、◎、○および△が良好な特性を表すものとする。これらの結果を表3に示す;
◎:反射光を全く感じない、
○:反射光をほとんど感じない、
△:反射光をやや感じる、
×:円偏光板を貼合しないアルミニウム反射板のみの状態と同程度の反射光を感じる。
上記円偏光板の反射率の評価において、正面から見た円偏光板の色味を下記基準に従い目視評価した。黒色に近いほど望ましい特性を表すものとし、◎、○および△が良好な特性を表すものとする。これらの結果を表3に示す;
◎:全く色味のない黒色であった、
○:やや青みを感じるが、全体として黒色と認識できる、
△:やや赤みを感じるが、全体として黒色と認識できる、
×:強い有彩色の色味(青み、赤み等)を感じ、全体として黒色とは認識できない。
上記円偏光板の正面反射特性の評価において、円偏光板側の正面法線に対し45度の倒れ角方向から見た反射板からの反射光を測定した以外は同様にして、反射光を下記基準に従い目視評価した。反射光が少ないほど望ましい特性を表すものとし、◎、○および△が良好な特性を表すものとする。これらの結果を表3に示す;
◎:反射光を全く感じない、
○:反射光をほとんど感じない、
△:反射光をやや感じる、
×:円偏光板を貼合しないアルミニウム反射板のみの状態と同程度の反射光を感じる。
[仮支持体付き光学フィルム11の製造]
上記仮支持体付き光学フィルム1の製造において、液晶塗布用基材フィルムB1の製造過程における積層体L1の形成に際して、原反フィルムO1の表面上にコンマコーターで乾燥膜厚が18μmとなるよう負の樹脂層塗工液N1を塗布した後、部分的に乾燥をし、溶媒が完全に乾く前に原反フィルムO1から負の樹脂層NN1を剥離した。次いで、長尺の(メタ)アクリル樹脂系フィルムである特開2015-214713号公報の実施例1に記載の未延伸フィルム(125μm)(原反フィルムO2)に転写した後、負の樹脂層NN1を完全に乾燥させて、長尺の積層体L8を形成した。
長尺のアクリル樹脂フィルム(原反フィルムO2)に代えて長尺のポリカーボネート(PC)フィルムである帝人株式会社製 ピュアエース(登録商標)C110-100(原反フィルムO3)を使用し、延伸温度を140℃から170℃へと変更した以外は液晶塗布用基材フィルムB8および仮支持体付き光学フィルム11の製造と同様にして、液晶塗布用基材フィルムB9を製造し、仮支持体付き光学フィルム12を製造した。ここで、原反フィルムO3から仮支持体S9が形成され、負の樹脂層NN1から負の樹脂配向層NA8が形成され、仮支持体S9の膜厚は83μm、負の位相差配向層NA8の膜厚は15μmであった。
[液晶塗布用基材フィルムおよび仮支持体付き光学フィルムの評価]
上記と同様に、液晶塗布用基材フィルムB8およびB9について、仮支持体の弾性率最大方向、ならびに負の樹脂配向層の位相差および面内の遅相軸方向をそれぞれ測定したところ、液晶塗布用基材フィルムB1と同様の結果が得られた。また、上記と同様に、仮支持体付き光学フィルム11および12について液晶層の位相差、液晶層の液晶分子の配向方向、カールを測定したところ、仮支持体付き光学フィルム1と同様の結果が得られた。
仮支持体付き光学フィルム1に代えて仮支持体付き光学フィルム11および12をそれぞれ使用した以外は、仮支持体付き光学フィルム1を使用した円偏光板の製造と同様にして、円偏光板を製造した。次いで、これらの円偏光板について、上記と同様に正面反射特性、色味、および斜め視野特性を評価したところ、仮支持体付き光学フィルム1を使用した円偏光板と同様の結果が得られた。
上記製造した液晶塗布用基材フィルムB8およびB9について、仮支持体を分離して剥離し、剥離した仮支持体から試験片を切り出し、Axometrics社製 AxoScanを用いて、2cmおきに3点×3列の計9点をそれぞれ測定した。Roの基準波長は550nmとした。次いで、各フィルムについて、これらの測定値の最大値から最小値を差し引いた差分を位相差変動値として算出した。これらの結果を下記表4に示す。
仮支持体付き光学フィルム11および12をそれぞれクロスニコル下にて目視観察し、液晶層の塗布欠陥有無の確認のし易さを下記基準に従って評価した。これらの結果を下記表4に示す;
○:液晶層の塗布欠陥の有無の観察を容易に行うことができる、
△:液晶層の塗布欠陥を注意して探すことでその有無を確認することができる。
2 剥離可能な仮支持体、
3 負の樹脂配向層、
4 剥離可能な仮支持体の弾性率が最大となる方向、
5 負の樹脂配向層の面内の遅相軸方向、
10 仮支持体付き光学フィルム、
11 液晶層、
12 液晶層の液晶分子の配向方向。
Claims (15)
- 原反フィルム上に、負の位相差発現性を有する樹脂を含有する負の樹脂層を形成することによって、前記原反フィルムと、前記負の樹脂層とを含む積層体を形成する積層工程と、
前記積層体を延伸することによって、前記原反フィルムから弾性率が最大となる方向を有する、剥離可能な仮支持体を形成することと、前記負の樹脂層から面内に遅相軸を有する負の樹脂配向層を形成することと、前記仮支持体の弾性率が最大となる方向と、前記負の樹脂配向層の面内の遅相軸方向と、を略直交とすることと、を含む延伸工程と、
を有する、液晶塗布用基材フィルムの製造方法。 - 前記積層工程は、前記原反フィルム上に、前記負の位相差発現性を有する樹脂と、メチレンクロライドとを含む負の樹脂層塗工液を塗布することによって前記負の樹脂層を形成することを含み、前記原反フィルムは、メチレンクロライドに不溶である、請求項1に記載の液晶塗布用基材フィルムの製造方法。
- 剥離可能な仮支持体と、負の位相差発現性を有する樹脂を含有する、面内に遅相軸を有する負の樹脂配向層とを含む積層構造を有し、前記仮支持体の弾性率が最大となる方向と、前記負の樹脂配向層の面内の遅相軸方向とが略直交である、液晶塗布用基材フィルム。
- 前記負の樹脂配向層の膜厚は、1μm以上20μm以下であり、且つ、波長550nmにおける下記式(I)で表される面内方向の位相差Roは、10nm以上150nm以下であり、下記式(II)で表される面外方向の位相差Rtは、-150nm以上-30nm以下である、請求項3に記載の液晶塗布用基材フィルム;
式(I):Ro=(nx-ny)×d
式(II):Rt={(nx+ny)/2-nz}×d
(式(I)および(II)において、nxは、前記負の樹脂配向層の面内方向において屈折率が最大となる方向xにおける屈折率であり、nyは、前記負の樹脂配向層の面内方向において前記方向xと直交する方向yにおける屈折率であり、nzは、前記負の樹脂配向層の厚み方向における屈折率であり、dは、前記負の樹脂配向層の膜厚(nm)である)。 - 長尺フィルムであり、長尺方向と、前記負の樹脂配向層の面内の遅相軸方向とのなす角度が35度以上55度以下である、請求項3または4に記載の液晶塗布用基材フィルム。
- 前記仮支持体の位相差変動値は、10nm以下である、請求項3~5のいずれか1項に記載の液晶塗布用基材フィルム。
- 請求項1または2に記載の製造方法によって前記液晶塗布用基材フィルムを製造した後、
前記液晶塗布用基材フィルムの前記負の樹脂配向層上に液晶層を形成することを含む、液晶層形成工程をさらに有する、仮支持体付き光学フィルムの製造方法。 - 前記仮支持体の弾性率が最大となる方向と、前記液晶層の液晶配向方向とを略平行とすることを含む、請求項7に記載の仮支持体付き光学フィルムの製造方法。
- 前記液晶層形成工程は、液晶配向膜を形成する段階を含まない、請求項7または8に記載の仮支持体付き光学フィルムの製造方法。
- 前記液晶層形成工程における液晶塗布方向は、前記負の樹脂配向層の面内の遅相軸方向に対して35度以上55度以下の角度をなす、請求項7~9のいずれか1項に記載の仮支持体付き光学フィルムの製造方法。
- 請求項7~10のいずれか1項に記載の製造方法で仮支持体付き光学フィルムを製造した後、前記仮支持体付き光学フィルムと、偏光子とを、前記偏光子の透過軸方向と、仮支持体を剥離した状態における光学フィルムの面内の遅相軸方向とのなす角度が35度以上55度以下となるように積層することを含む、仮支持体付き偏光板の製造方法。
- 請求項11に記載の製造方法で仮支持体付き偏光板を製造した後、仮支持体を剥離することを含む、偏光板の製造方法。
- 請求項12に記載の製造方法で偏光板を製造した後、前記偏光板と、有機エレクトロルミネッセンス素子とを貼合することを含む、有機エレクトロルミネッセンス表示装置の製造方法。
- 請求項3~6のいずれか1項に記載の液晶塗布用基材フィルムに含まれる前記負の樹脂配向層上に液晶層をさらに有し、前記仮支持体の弾性率が最大となる方向と、前記液晶層の液晶配向方向とが略平行である、仮支持体付き光学フィルム。
- 請求項14に記載の仮支持体付き光学フィルムと、偏光子とが、前記偏光子の透過軸方向と、仮支持体を剥離した状態における光学フィルムの面内の遅相軸方向とのなす角度が35度以上55度以下で積層された、仮支持体付き偏光板。
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