WO2023053798A1 - 偏光フィルム、画像表示装置及び偏光フィルムの製造方法 - Google Patents
偏光フィルム、画像表示装置及び偏光フィルムの製造方法 Download PDFInfo
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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
- G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—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 comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
- B32B17/1044—Invariable transmission
- B32B17/10449—Wavelength selective transmission
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
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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
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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
- 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
- G02F1/133528—Polarisers
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- 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
- H10K59/8793—Arrangements for polarized light emission
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
- B32B2329/04—Polyvinylalcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- the present invention relates to a polarizing film, an image display device, and a method for manufacturing a polarizing film.
- a polarizing film is, for example, a laminate including a polarizer and a protective film.
- a polarizer can generally be produced by adsorbing a dichroic dye to a hydrophilic polymer film such as a polyvinyl alcohol (PVA) film and uniaxially stretching the film. Iodine is widely used as the dichroic dye from the viewpoint of improving the transmittance and the degree of polarization of the polarizer.
- Patent Document 1 discloses bonding a protective film to a polarizer using an adhesive containing an epoxy compound. Specifically, in Patent Literature 1, the polarizer and the protective film are joined together by curing the applied layer in a state in which the polarizer and the protective film are overlaid with an adhesive applied layer interposed therebetween.
- the iodine contained in the polarizer tends to migrate from the polarizer to the protective film or the adhesive layer for bonding the polarizing film to the image display panel.
- the thickness of the polarizer is small and the concentration of iodine in the polarizer is high, iodine tends to migrate from the polarizer to the protective film or adhesive layer.
- the iodine that has migrated to the protective film or adhesive layer permeates to the outside of the polarizing film through the protective film or adhesive layer.
- the degree of polarization of the polarizing film decreases.
- Conventional polarizing films cannot sufficiently prevent iodine contained in the polarizer from permeating to the outside of the polarizing film in a hot and humid environment.
- an object of the present invention is to provide a polarizing film suitable for sufficiently suppressing transmission of iodine contained in a polarizer to the outside in a hot and humid environment.
- the present inventors newly discovered that the properties of the resin layer included in the polarizing film can be predicted based on the monomers for forming the polymer contained in the resin layer. According to studies by the present inventors, this prediction is particularly reliable for a resin layer containing a polymer having a structural unit derived from a compound containing an epoxy group or a structural unit derived from a compound containing an oxetane group. expensive. Based on this knowledge, the present inventors further studied and completed the present invention.
- the present invention a polarizer containing iodine;
- a polarizing film in which the value of y calculated by the following formula (1) is less than 4.00.
- x 1 is the dispersion term ⁇ D (MPa 1/2 ) in the Hansen solubility parameter of the monomer for forming the polymer
- x2 is the x component (Debye) in the dipole moment of the monomer to form the polymer
- x 3 is the interaction energy (kcal/mol) between the monomer and water molecules to form the polymer
- x 4 is the common logarithm value LogS of the solubility in water at 25° C.
- x5 is the dipole moment (Debye) of the monomer to form the polymer
- x6 is the z component (Debye) in the dipole moment of the monomer to form the polymer
- x7 is the number of hydrogen bond acceptors in the monomer to form the polymer.
- the present invention the above polarizing film; an image display panel; to provide an image display device.
- the present invention A resin layer containing a polymer having at least one selected from the group consisting of a polarizer containing iodine, a structural unit U1 derived from a compound A1 containing an epoxy group, and a structural unit U2 derived from a compound A2 containing an oxetane group.
- a method for producing a polarizing film comprising The manufacturing method is Provided is a method for producing a polarizing film, comprising the step of polymerizing a monomer having a y value of less than 4.00 calculated by the following formula (1) to obtain the polymer.
- x 1 is the dispersion term ⁇ D (MPa 1/2 ) in the Hansen solubility parameter of the monomer
- x2 is the x component (Debye) in the dipole moment of the monomer
- x 3 is the interaction energy (kcal/mol) between the monomer and water molecules
- x 4 is the common logarithm value LogS of the solubility in water at 25° C.
- x 5 is the dipole moment (Debye) of the monomer
- x 6 is the z component (Debye) in the dipole moment of the monomer
- x7 is the number of hydrogen bond acceptors in the monomer.
- a polarizing film suitable for sufficiently suppressing transmission of iodine contained in a polarizer to the outside in a hot and humid environment.
- FIG. 1 is a schematic cross-sectional view of a polarizing film according to one embodiment of the present invention
- FIG. It is a schematic sectional drawing which shows the modification of a polarizing film.
- It is a schematic sectional drawing which shows another modification of a polarizing film.
- It is a schematic sectional drawing which shows another modification of a polarizing film.
- It is a schematic sectional drawing which shows another modification of a polarizing film.
- 1 is a schematic cross-sectional view of an image display device according to an embodiment of the present invention
- FIG. It is the schematic of the polarizing film used for the crack evaluation test.
- the polarizing film according to the first aspect of the present invention is a polarizer containing iodine;
- the value of y calculated by the following formula (1) is less than 4.00.
- x 1 is the dispersion term ⁇ D (MPa 1/2 ) in the Hansen solubility parameter of the monomer for forming the polymer
- x2 is the x component (Debye) in the dipole moment of the monomer to form the polymer
- x 3 is the interaction energy (kcal/mol) between the monomer and water molecules to form the polymer
- x 4 is the common logarithm value LogS of the solubility in water at 25° C.
- x5 is the dipole moment (Debye) of the monomer to form the polymer
- x6 is the z component (Debye) in the dipole moment of the monomer to form the polymer
- x7 is the number of hydrogen bond acceptors in the monomer to form the polymer.
- the value of y is 2.30 or less.
- the polymer in the third aspect of the present invention, for example, in the polarizing film according to the first or second aspect, the polymer includes both the structural unit U1 and the structural unit U2.
- the content of the structural unit U1 and the content of the structural unit U2 is 70% by weight or more.
- the compound A1 contains a ring structure other than an epoxy group.
- the compound A1 contains at least one selected from the group consisting of an aliphatic ring and an aromatic ring. .
- the resin layer contains an acid generator and/or a decomposition product of the acid generator.
- the resin layer is in direct contact with the polarizer.
- the thickness of the resin layer is less than 3 ⁇ m.
- the polarizer has a thickness of 1 ⁇ m or more and less than 7 ⁇ m.
- the polarizer contains polyvinyl alcohol as a main component.
- the polarizing film according to any one of the first to eleventh aspects further comprises a protective film.
- the protective film, the resin layer, and the polarizer are arranged in this order in the stacking direction.
- the protective film has a moisture permeability of 300 g/(m2 ⁇ day) or more.
- the protective film contains triacetyl cellulose as a main component.
- the protective film has a thickness of less than 40 ⁇ m.
- the image display device comprises A polarizing film according to any one of the first to sixteenth aspects; an image display panel; Prepare.
- the method for producing a polarizing film according to the eighteenth aspect of the present invention comprises: A resin layer containing a polymer having at least one selected from the group consisting of a polarizer containing iodine, a structural unit U1 derived from a compound A1 containing an epoxy group, and a structural unit U2 derived from a compound A2 containing an oxetane group. And, a method for producing a polarizing film comprising The manufacturing method is The method includes a step of polymerizing a monomer having a y value of less than 4.00 calculated by the following formula (1) to obtain the polymer.
- x 1 is the dispersion term ⁇ D (MPa 1/2 ) in the Hansen solubility parameter of the monomer
- x2 is the x component (Debye) in the dipole moment of the monomer
- x 3 is the interaction energy (kcal/mol) between the monomer and water molecules
- x 4 is the common logarithm value LogS of the solubility in water at 25° C.
- x 5 is the dipole moment (Debye) of the monomer
- x 6 is the z component (Debye) in the dipole moment of the monomer
- x7 is the number of hydrogen bond acceptors in the monomer.
- the polarizing film 10 of this embodiment includes a polarizer 1 containing iodine and a resin layer 2 containing a polymer P.
- the polymer P contained in the resin layer 2 has at least one selected from the group consisting of the structural unit U1 derived from the compound A1 containing an epoxy group and the structural unit U2 derived from the compound A2 containing an oxetane group.
- the resin layer 2 is located, for example, on the viewing side of the polarizer 1 and is in direct contact with the polarizer 1 .
- the resin layer 2 may be located closer to the image display panel (to be described later) than the polarizer 1 is. In other words, the polarizer 1 may be positioned closer to the viewer than the resin layer 2 is.
- the resin layer 2 is positioned, for example, on the outermost side of the polarizing film 10 .
- film means a member whose thickness is sufficiently smaller than its length and width.
- the polarizing film 10 may further include an adhesive layer 3, a protective film 4 and an adhesive layer 5.
- the protective film 4 is attached to the polarizer 1 via an adhesive layer 3, for example.
- the pressure-sensitive adhesive layer 5 functions, for example, as a member for bonding the polarizing film 10 to an image display panel, which will be described later. Therefore, the pressure-sensitive adhesive layer 5 is positioned, for example, on the outermost side of the polarizing film 10 and closer to the image display panel than the polarizer 1 is. In other words, the polarizer 1 is positioned, for example, on the viewing side of the pressure-sensitive adhesive layer 5 .
- the resin layer 2, the polarizer 1, the adhesive layer 3, the protective film 4, and the adhesive layer 5 are arranged in this order in the stacking direction, for example.
- the value of y calculated by the following formula (1) is less than 4.00.
- y (-3.71) x1 +(-3.94) x2 +(0.299) x3 +(0.226) x4 +(-1.05) x5 +(0.517) x6 +(0.769) x7+ 71.81 (1 )
- x 1 is the dispersion term ⁇ D (MPa 1/2 ) in the Hansen solubility parameters of the monomer M to form the polymer P.
- x 1 can be an index for predicting the interaction that occurs between the polymer P and water molecules or iodine.
- the Hansen solubility parameters are obtained by dividing the solubility parameters introduced by Hildebrand into three components: the dispersion term ⁇ D, the polarization term ⁇ P, and the hydrogen bonding term ⁇ H.
- the dispersion term ⁇ D indicates the energy due to intermolecular dispersion forces. Details of the Hansen Solubility Parameters are disclosed in "Hansen Solubility Parameters; A Users Handbook" (CRC Press, 2007).
- the variance term ⁇ D can be calculated using known software such as HSPiP (version 5). Note that the value of the variance term ⁇ D may differ slightly depending on the software used. However, this error is usually of a size that can be ignored in calculating the value of y.
- the value of x1 can be specified by the following method.
- the dispersion term ⁇ D (MPa 1/2 ) in the Hansen solubility parameters is calculated for each of the plurality of types of monomers M.
- the calculated dispersion term ⁇ D is weighted by the molar ratio of each monomer M to obtain a weighted average.
- the weighted average obtained can be regarded as x1 .
- the value of x 1 is not particularly limited, and is, for example, 15 to 20 (MPa 1/2 ), preferably 16.4 to 18.9 (MPa 1/2 ).
- x 2 is the x component (Debye) in the dipole moment of the monomer M to form the polymer P; x 2 can be an index for predicting the interaction that occurs between the polymer P and water molecules, that is, an index for predicting the degree of hydrophobicity and humidification durability of the polymer P.
- x 2 can be identified, for example, by the following method.
- the monomer M for forming the polymer P is specified.
- the x component in the dipole moment can be calculated.
- Molecular simulation can be performed using known software such as Materials Studio (manufactured by BIOVIA, ver.8.0.0.843) and WebMO (ver.19.0.009e).
- Calculation of the x component in the dipole moment D by molecular simulation can be performed, for example, by the following method.
- a molecular model of the monomer M is created using Materials Studio.
- the force field of COMPASS (Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies) II is employed to optimize the geometry.
- the molecular model of monomer M is processed with WebMO.
- a Gaussian program (Queue: g09) is used to perform structural optimization calculations for the molecular model of the monomer M.
- B3LYP may be used as the functional
- 6-31G(d) may be used as the basis function.
- the x component in the dipole moment D of the monomer M can be calculated.
- the internal coordinates of each atom constituting the monomer M are defined by the Z-matrix format when the molecular simulation is performed.
- the x-, y-, and z-axes for determining the internal coordinates are automatically determined according to the structure of the monomer M.
- x 2 can be specified by the following method. First, for each of the multiple types of monomers M, the x component in the dipole moment is calculated by the method described above. The x component in the calculated dipole moment is weighted by the molar ratio of each monomer M to obtain a weighted average. The weighted average obtained can be taken as x2 . Even when a plurality of types of monomers M are structural isomers of each other, the x component in the calculated dipole moment is weighted by the molar ratio of each structural isomer to perform a weighted average to specify x 2 . can be done. In this embodiment, the value of x 2 is not particularly limited, and is, for example, -1.0 to 1.0 Debye.
- x 3 is the interaction energy ⁇ E (kcal/mol) between the monomer M and the water molecule for forming the polymer P; x 3 can be an index for predicting the interaction that occurs between the polymer P and water molecules, that is, an index for predicting the degree of hydrophobicity and humidification durability of the polymer P.
- x 3 can be identified, for example, by the following method.
- the monomer M for forming the polymer P is specified.
- a molecular model of the monomer M is created by the method described above for x 2 , and the structure optimization calculation is performed on the molecular model. From this, the potential energy EM (kcal/mol) of the monomer M per molecule is calculated.
- a molecular model of water molecules is created by a similar method, and the structure optimization calculation is performed for the molecular model. From this, the potential energy E H2O (kcal/mol) of water molecule per molecule is calculated.
- a molecular model containing one molecule of monomer M and one molecule of water is created by a similar method.
- a water molecule is arranged near the hydrogen bond acceptor contained in the monomer M.
- a structural optimization calculation is performed on this molecular model to calculate the potential energy E M+H2O (kcal/mol) of the complex of the monomer M and the water molecule.
- the hydrogen bond acceptor means an atom capable of forming a hydrogen bond with a hydrogen atom contained in a water molecule.
- Hydrogen bond acceptors include atoms with relatively high electronegativity such as oxygen atoms and nitrogen atoms.
- the potential energy E M +H2O can be determined by the following method. First, a plurality of molecular models containing one molecule of monomer M and one molecule of water are prepared. The number of molecular models corresponds to the number of hydrogen bond acceptors contained in one monomer M molecule. In multiple molecular models, hydrogen bond acceptors with which water molecules are placed in proximity are different from each other. Next, potential energy is calculated by performing structural optimization calculations for each of the plurality of molecular models. The average value of the obtained calculated values can be regarded as the potential energy E M +H2O .
- x3 can be specified by the following method.
- the interaction energy ⁇ E with water molecules is calculated for each of a plurality of types of monomers M.
- the calculated interaction energy ⁇ E is weighted by the molar ratio of each monomer M to obtain a weighted average.
- the weighted average obtained can be taken as x3 .
- the value of x 3 is not particularly limited and is, for example, -20 to 10 kcal/mol.
- x 4 is the common logarithmic value LogS of the solubility S (g/100 g) of the monomer M in water at 25° C. to form the polymer P; x 4 can be an index for predicting the water solubility of the polymer P, that is, an index for predicting the degree of the polymer P's hydrophobicity and humidification durability.
- the solubility S specifically means the maximum weight (g) of the monomer M that can be dissolved in 100 g of water at 25°C.
- LogS may be calculated using known software such as HSPiP (version 5).
- HSPiP can calculate the solubility of any compound and its common logarithm LogS using a multiple regression equation created based on the measured values of the solubility of many compounds. Solubility and LogS calculated using HSPiP are known to agree well with actual measurements.
- x4 can be identified by the following method. First, LogS is calculated for each of a plurality of types of monomers M. The calculated LogS is weighted by the molar ratio of each monomer M to obtain a weighted average. The weighted average obtained can be taken as x4 .
- the value of x 4 is not particularly limited, and ranges from -5.0 to 10, for example.
- x 5 is the dipole moment (Debye) of the monomer M to form the polymer P; x5 can be an index for predicting the interaction that occurs between the polymer P and water molecules, that is, an index for predicting the degree of hydrophobicity and humidification durability of the polymer P. The closer the value of x5 is to 0, the more hydrophobic the polymer P tends to be. x5 can be calculated by the molecular simulations described above for x2 . Note that the dipole moment is a vector quantity calculated from the x component, the y component, and the z component.
- x5 can be identified by the following method. First, the dipole moment is calculated for each of a plurality of types of monomers M. The calculated dipole moment is weighted by the molar ratio of each monomer M to obtain a weighted average. The weighted average obtained can be taken as x5 . Even when a plurality of types of monomers M are structural isomers of each other, x 5 can be specified by weighting the calculated dipole moments by the molar ratio of each structural isomer and performing a weighted average. In this embodiment, the value of x 5 is not particularly limited, and is, for example, 2.0 to 5.0 Debye.
- x 6 is the z component (Debye) in the dipole moment of the monomer M to form the polymer P; x 6 can be an index for predicting the interaction that occurs between the polymer P and water molecules, that is, an index for predicting the degree of hydrophobicity and humidification durability of the polymer P. The closer the value of x6 is to 0, the more hydrophobic the polymer P tends to be. x 6 can be calculated by the molecular simulations described above for x 2 .
- x 6 can be specified by the following method. First, for each of a plurality of types of monomers M, the z component in the dipole moment is calculated. The z component in the calculated dipole moment is weighted by the molar ratio of each monomer M to obtain a weighted average. The weighted average obtained can be taken as x6 . Even when a plurality of types of monomers M are structural isomers of each other, the z component in the calculated dipole moment is weighted by the molar ratio of each structural isomer and the weighted average is performed to specify x 6 . can be done. In this embodiment, the value of x6 is not particularly limited, and is, for example, -2.0 to 3.0 Debye.
- x7 is the number of hydrogen bond acceptors in monomer M to form polymer P; x7 can be an index for predicting the water solubility of the polymer P, that is, an index for predicting the degree of the polymer P's hydrophobicity and humidification durability.
- a hydrogen bond acceptor means an atom capable of forming a hydrogen bond with a hydrogen atom contained in a water molecule.
- the number of hydrogen bond acceptors may be determined using the molecular simulations described above for x2 .
- x7 can be identified by the following method. First, the number of hydrogen bond acceptors is specified for each of a plurality of types of monomers M. A weighted average is performed on the number of hydrogen bond acceptors identified, weighted by the molar proportion of each monomer M. The weighted average obtained can be taken as x7 . In this embodiment, the value of x7 is not particularly limited, and is, for example, 2.0 to 6.0.
- the value of y calculated by the formula (1) is preferably 3.00 or less, more preferably 2.30 or less, from the viewpoint of sufficiently suppressing the transmission of iodine contained in the polarizer 1 to the outside. Yes, it may be 2.00 or less, or it may be 1.00 or less. However, the smaller the value of y, the higher the viscosity of the monomer M and the solution containing the monomer M, which tends to make it more difficult to produce the resin layer 2 . From the viewpoint that the resin layer 2 can be easily produced, the value of y is, for example, ⁇ 2.00 or more, may be 0 or more, and may be 1.00 or more, or 2.00 or more in some cases. may be
- the value of y calculated by the formula (1) is an index related to the monomer M for forming the polymer P contained in the resin layer 2.
- the value of y is also useful as an index for selecting the resin layer 2 suitable for suppressing the transmission of iodine contained in the polarizer 1 to the outside.
- the polarizer 1 is not particularly limited as long as it contains iodine. One obtained by adsorbing iodine and uniaxially stretching is mentioned.
- the polarizer 1 is preferably composed of a polyvinyl alcohol film and iodine.
- the polarizer 1 contains polyvinyl alcohol as a main component, for example.
- the “main component” means the material contained in the polarizer 1 in the largest amount on a weight basis.
- the thickness of the polarizer 1 is not particularly limited. Especially preferably, it is 10 ⁇ m or less.
- the thickness of the polarizer 1 may be 2 ⁇ m or more, 4 ⁇ m or more, or 5 ⁇ m or more.
- the thickness of the polarizer 1 may be 7 to 12 ⁇ m, optionally 1 ⁇ m or more and less than 7 ⁇ m, particularly 4 to 6 ⁇ m.
- the polarizer 1 having a thickness of 10 ⁇ m or less is sometimes referred to as a thin polarizer. Thin polarizers tend to have less unevenness in thickness and have excellent visibility. Furthermore, thin polarizers have the advantage of being suppressed in dimensional change and excellent in durability.
- the polarizing film 10 can be thinned.
- the polarizer 1 is a thin polarizer, it is necessary to adjust the concentration of iodine in the polarizer 1 to be high so that the polarizing film 10 has a practically sufficient degree of polarization.
- the polarizing film 10 of the present embodiment even when the thickness of the polarizer 1 is small and the concentration of iodine in the polarizer 1 is high, the transmission of iodine from the polarizer 1 to the outside is sufficiently suppressed. can be done.
- the polarizer 1 can be produced by, for example, dyeing a hydrophilic polymer film such as a polyvinyl alcohol-based film by immersing it in an aqueous solution of iodine and stretching it to 3 to 7 times its original length. If necessary, the hydrophilic polymer film may be immersed in an aqueous solution containing boric acid, potassium iodide, or the like. Furthermore, if necessary, the hydrophilic polymer film may be immersed in water and washed with water before dyeing. By washing the hydrophilic polymer film with water, stains and antiblocking agents adhering to the surface can be removed.
- a hydrophilic polymer film such as a polyvinyl alcohol-based film by immersing it in an aqueous solution of iodine and stretching it to 3 to 7 times its original length. If necessary, the hydrophilic polymer film may be immersed in an aqueous solution containing boric acid, potassium iodide, or the like. Furthermore,
- the hydrophilic polymer film When the hydrophilic polymer film is washed with water, the hydrophilic polymer film swells, which has the effect of suppressing uneven dyeing. Stretching of the hydrophilic polymer film may be performed after dyeing with iodine, may be performed while dyeing, or may be performed before dyeing with iodine. The hydrophilic polymer film may be stretched in an aqueous solution containing boric acid, potassium iodide, or the like, or in water.
- a thin polarizer typically, JP-A-51-069644, JP-A-2000-338329, WO 2010/100917, JP-A-2014-59328, JP-A-2012-73563 and the like.
- These thin polarizers are produced by a manufacturing method including a step of stretching a laminate including a polyvinyl alcohol-based resin (PVA-based resin) layer and a stretching resin substrate, and a step of dyeing the obtained stretched film. can.
- PVA-based resin polyvinyl alcohol-based resin
- the PVA-based resin layer is supported by the resin substrate for stretching, defects such as breakage due to stretching are less likely to occur.
- the thin polarizer is manufactured by a manufacturing method including a stretching step in an aqueous boric acid solution among the above manufacturing methods.
- it is preferably produced by a manufacturing method including a step of performing auxiliary stretching in the air before the stretching step in an aqueous boric acid solution.
- a production method including a stretching step in an aqueous boric acid solution is disclosed in WO 2010/100917, JP 2014-59328, JP 2012-73563, and the like.
- a manufacturing method including a step of performing aerial stretching is disclosed in JP-A-2014-59328, JP-A-2012-73563, and the like.
- the resin layer 2 contains a polymer P having at least one selected from the group consisting of the structural unit U1 derived from the compound A1 containing an epoxy group and the structural unit U2 derived from the compound A2 containing an oxetane group.
- a polymer P having at least one selected from the group consisting of the structural unit U1 derived from the compound A1 containing an epoxy group and the structural unit U2 derived from the compound A2 containing an oxetane group.
- Compounds A1 and A2 can be used as monomers M for forming polymers P.
- Compound A1 may be a monofunctional epoxy compound containing one epoxy group, or may be a polyfunctional epoxy compound containing two or more epoxy groups.
- the number of epoxy groups contained in the polyfunctional epoxy compound is not particularly limited, and is, for example, 2 or more, preferably 2-6, more preferably 2-4.
- the compound A1 may not contain a ring structure R other than an epoxy group, but preferably contains it.
- the number of ring structures R contained in compound A1 is, for example, 1 or more, preferably 1-10, and may be 1-6.
- multiple ring structures R may be condensed with each other.
- the epoxy ring and the ring structure R may be condensed.
- fused refers to the state in which two adjacent ring structures share two or more carbon atoms with a covalent bond formed between those carbon atoms. means.
- Compound A1 preferably contains, as ring structure R, at least one selected from the group consisting of an aliphatic ring and an aromatic ring.
- Aliphatic rings are ring structures that have no aromatic character and are composed only of carbon atoms. The number of carbon atoms in the aliphatic ring is not particularly limited, and is, for example, 5-10. Specific examples of the aliphatic ring include cyclopentane ring, cyclohexane ring, cycloheptane ring and the like. Two aliphatic rings may be fused together to form a norbornane ring and the like.
- An aromatic ring is a ring structure having aromatic character. The aromatic ring may consist only of carbon atoms. Aromatic rings are typically benzene rings.
- the ring structure R is not limited to the above-mentioned aliphatic ring and aromatic ring.
- the ring structure R may be a heterocyclic ring containing a heteroatom such as a nitrogen atom or an oxygen atom.
- compound A1 may contain an oxetane ring as a heterocyclic ring, but preferably does not.
- the compound A1 may further contain functional groups other than the epoxy group.
- Other functional groups include, for example, ether groups, ester groups, and the like.
- Compound A1 may further contain a polar group containing a bond between a hydrogen atom and a heteroatom as another functional group, but preferably does not contain a polar group.
- Polar groups include, for example, hydroxyl groups, carboxyl groups, primary amine groups and secondary amine groups.
- the compound A1 may be an epoxy monomer or an epoxy prepolymer (epoxy resin).
- Compound A1 is preferably an epoxy monomer.
- the molecular weight of the epoxy monomer is not particularly limited, and is, for example, less than 1000, preferably 800 or less, and may be 500 or less.
- the weight average molecular weight of the epoxy prepolymer is not particularly limited, and is, for example, 1,000 to 50,000.
- the compound A1 having an aromatic ring include glycidyl ether compounds (e.g., bisphenol-type epoxy resins) having a structure derived from bisphenols such as bisphenol A, bisphenol F, and bisphenol S; Glycidyl ether compounds having structures derived from other phenols such as hydroxybenzophenone, polyvinylphenol, t-butylphenol; 9,9-bis ⁇ 4-[2-(oxiran-2-ylmethoxy)ethoxy]phenyl ⁇ -9H- Glycidyl ether compounds having a fluorene skeleton such as fluorene, 3′,6′-bis(oxiran-2-ylmethoxy)spiro[fluorene-9,9′-xanthene]; phenol novolak epoxy resin, cresol novolac epoxy resin and hydroxybenzaldehyde phenol A novolac type epoxy resin such as a novolac epoxy resin can be used.
- bisphenol-type epoxy resins having a structure derived from bis
- compound A1 having an aliphatic ring examples include vinylcyclohexene dioxide, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, limonene dioxide, bis(3,4-epoxycyclohexylmethyl ) Epoxy compounds having a cyclohexane skeleton such as adipate; Epoxy compounds having a condensed ring skeleton such as ',2':6,7]naphth[2,3-b]oxirane; and dicyclopentadiene type epoxy resins.
- the compound A1 containing no ring structure R other than an epoxy group examples include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, Glycidyl ether compounds such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and the like.
- the compounds A1 exemplified above may be used singly or in combination of two or more.
- Compound A2 may be a monofunctional oxetane compound containing one oxetane group, or may be a polyfunctional oxetane compound containing two or more oxetane groups.
- the number of oxetane groups contained in the polyfunctional oxetane compound is not particularly limited, and is, for example, 2 or more, preferably 2-6, more preferably 2-4.
- Compound A2 tends to accelerate the reaction for synthesizing polymer P.
- Compound A2 may or may not further contain a ring structure other than an oxetane group.
- ring structures other than the oxetane group include those described above for compound A1.
- Compound A2, for example, does not contain an epoxy group as a ring structure other than an oxetane group.
- the compound A2 may further contain functional groups other than the oxetane group.
- Other functional groups include, for example, ether groups, ester groups, and the like.
- Compound A2 may further contain a polar group as another functional group, but preferably does not contain a polar group.
- the compound A2 may be an oxetane monomer or an oxetane prepolymer (oxetane resin).
- Compound A2 is preferably an oxetane monomer.
- the molecular weight of the oxetane monomer is not particularly limited, and is, for example, less than 1000, preferably 800 or less, and may be 500 or less.
- the weight average molecular weight of the oxetane prepolymer is not particularly limited, and is, for example, 1,000 to 50,000.
- compound A2 include oxetanes such as 3-ethyl-3-hydroxymethyloxetane, bis[(3-ethyl-3-oxetanyl)methyl]ether, and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, 4,4'-(3 oxetane compounds containing a benzene ring such as -ethyloxetan-3-ylmethyloxymethyl)biphenyl;
- the compounds A2 exemplified above may be used singly or in combination of two or more.
- the content of the structural unit U1 derived from the compound A1 is not particularly limited. , 70% by weight or more.
- the polymer P may be substantially composed only of the structural unit U1.
- “consisting essentially of” means excluding other structural units that alter the essential characteristics of the structural unit referred to, for example, 95% by weight or more, or even 99% by weight. It means that the weight % or more is composed of the structural unit.
- a preferred range for the content of the structural unit U1 is, for example, 50% by weight to 90% by weight.
- the content of the structural unit U2 derived from the compound A2 is not particularly limited, and may be, for example, 5 wt% or more, may be 10 wt% or more, or may be 20 wt% or more. , 30% by weight or more, 40% by weight or more, or 50% by weight or more.
- the polymer P may consist substantially only of structural units U2.
- a preferred range for the content of the structural unit U2 is, for example, 10% to 50% by weight.
- the polymer P preferably contains both the structural unit U1 and the structural unit U2.
- the total value of the content of the structural unit U1 and the content of the structural unit U2 is, for example, 50% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more. more preferably 90% by weight or more, particularly preferably 95% by weight or more, particularly preferably 99% by weight or more.
- the polymer P may further contain structural units derived from cationic polymerizable monomers other than compounds A1 and A2. Furthermore, the polymer P may contain a structural unit derived from a radically polymerizable monomer.
- vinyl ether compounds include aliphatic vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether; aromatic vinyl ethers such as phenyl vinyl ether, 2-phenoxyethyl vinyl ether and p-methoxyphenyl vinyl ether; - polyfunctional vinyl ethers such as divinyl ether, triethylene glycol divinyl ether and dipropylene glycol divinyl ether;
- radically polymerizable monomers examples include (meth)acrylic acid esters and styrene compounds.
- (meth)acrylic acid means acrylic acid and/or methacrylic acid.
- (Meth)acrylic acid esters for example, dicyclopentanyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, lauryl (meth)acrylate, 5-(meth)acryloxy-2,6-norbornane carboractone, 3,3,5-trimethylcyclohexyl (meth)acrylate, 4-t-butylphenyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2 -methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 4-biphenyl (meth)acrylate, 1-naphthyl (meth)acrylate , 2-naphthyl (meth)acrylate, 1-anthracen
- styrene compounds include styrene, ⁇ -methylstyrene, vinylbenzyl chloride, butoxystyrene, and vinylpyridine.
- the polymer P preferably contains structural units derived from polyfunctional monomers.
- polyfunctional monomers include the aforementioned polyfunctional epoxy compounds, polyfunctional oxetane compounds, polyfunctional (meth)acrylic acid esters, and polyfunctional vinyl ether compounds.
- the content of the structural unit derived from the polyfunctional monomer in the polymer P is, for example, 20% by weight or more, preferably 40% by weight or more, more preferably 50% by weight or more, and in some cases 70% by weight. or more.
- the upper limit of the content of structural units derived from the polyfunctional monomer is not particularly limited, and is, for example, 95% by weight.
- the polymer P may contain a structural unit derived from a monomer having a polar group, but preferably does not.
- the content of structural units derived from a monomer having a polar group in the polymer P is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less, Particularly preferably, it is 2% by weight or less.
- the resin layer 2 contains, for example, a polymer P as a main component.
- the content of the polymer P in the resin layer 2 is, for example, 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight or more.
- the resin layer 2 preferably consists essentially of the polymer P only.
- the resin layer 2 may contain components other than the polymer P.
- Other components include acid generators, decomposition products of acid generators, antistatic agents, antioxidants, inorganic particles, leveling agents, and the like.
- the resin layer 2 contains, for example, an acid generator and/or a decomposition product of the acid generator as other components.
- the acid generator is typically a photoacid generator that functions as a polymerization initiator for compound A1 and compound A2.
- photoacid generators examples include compounds represented by the following formula (i). L + X ⁇ (i)
- L + is an onium cation.
- Onium cations include sulfonium cations, sulfoxonium cations, phosphonium cations, pyridinium cations, quinolinium cations, isoquinolinium cations, benzoxazolium cations, benzothiazolium cations, furryiodonium cations, thienyliodonium cations, Examples include diaryliodonium cations, preferably sulfonium cations.
- X ⁇ is a counter anion.
- counter anions include PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , SbCl 6 ⁇ , BiCl 5 ⁇ , SnCl 6 ⁇ , ClO 4 ⁇ , dithiocarbamate anions, SCN ⁇ and the like, preferably PF 6 ⁇ . be.
- photoacid generator examples include “Cyracure UVI-6992", “Cyracure UVI-6974” (manufactured by Dow Chemical Japan Co., Ltd.), “ADEKA OPTOMER SP150”, “ADEKA OPTOMER SP152”, “ADEKA OPTOMER SP170”, “ADEKA OPTOMER SP172” (manufactured by ADEKA Corporation), “IRGACURE250” (manufactured by Ciba Specialty Chemicals), “CI-5102", “CI-2855” (manufactured by , Nippon Soda Co., Ltd.), “San-Aid SI-60L”, “San-Aid SI-80L”, “San-Aid SI-100L”, “San-Aid SI-110L”, “San-Aid SI-180L” (manufactured by Sanshin Chemical Co., Ltd.) , “CPI-100P”, “CPI-100A” (manufactured by Sanishin
- the thickness of the resin layer 2 is not particularly limited, and is, for example, 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably less than 3 ⁇ m, and even more preferably less than 2.5 ⁇ m. There is a tendency that the thinner the resin layer 2 is, the less the acid generator used for forming the resin layer 2 can be used. When the amount of the acid generator used is small, even if the resin layer 2 is in direct contact with the polarizer 1, the acid generated from the acid generator is less likely to move from the resin layer 2 to the polarizer 1, thereby preventing deterioration of the polarizer 1. tend to be suppressed. From the viewpoint of sufficiently suppressing transmission of iodine contained in the polarizer 1 to the outside, the thickness of the resin layer 2 is preferably 0.3 ⁇ m or more, and may be 0.5 ⁇ m or more.
- the resin layer 2 may be attached to the polarizer 1 via an adhesive layer or an easy-adhesion layer.
- the adhesive layer for bonding the resin layer 2 to the polarizer 1 include those exemplified for the adhesive layer 3 to be described later.
- the easy-adhesion layer can be formed of, for example, a resin containing a polymer having a polyester skeleton, polyether skeleton, polycarbonate skeleton, polyurethane skeleton, silicone system, polyamide skeleton, polyimide skeleton, polyvinyl alcohol skeleton, or the like. One type or two or more types of polymers may be contained in the resin.
- the easy-adhesion layer may contain an additive.
- Additives include tackifiers, ultraviolet absorbers, antioxidants, stabilizers such as heat-resistant stabilizers, and the like.
- the thickness of the easy-adhesion layer is not particularly limited, but is preferably 0.01 to 5 ⁇ m, more preferably 0.02 to 2 ⁇ m, still more preferably 0.05 to 1 ⁇ m.
- the easy-adhesion layer may be a laminate of a plurality of layers.
- the adhesive layer 3 is a layer containing an adhesive.
- Materials for the adhesive are not particularly limited, and known materials can be used.
- Examples of adhesives contained in the adhesive layer 3 include water-based adhesives and active energy ray-curable adhesives.
- active energy ray-curable adhesive for example, those disclosed in JP-A-2019-147865, JP-A-2016-177248, etc. can be used.
- the thickness of the adhesive layer 3 is not particularly limited. 0.5 to 1.5 ⁇ m. If the thickness of the adhesive layer 3 is too small, the cohesive force of the adhesive layer 3 may be insufficient and the peeling force may be lowered. When the thickness of the adhesive layer 3 is too large, peeling may occur in the adhesive layer 3 when stress is applied to the cross section of the polarizing film 10 . That is, in the polarizing film 10, peeling failure due to impact may occur.
- Protective film 4 is typically a transparent protective film.
- materials for the protective film 4 include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; cellulose polymers such as diacetyl cellulose and triacetyl cellulose; (meth)acrylic polymers such as polymethyl methacrylate; Styrene-based polymers such as styrene copolymers (AS resins); polycarbonate-based polymers; olefin-based polymers such as polyethylene, polypropylene, and ethylene/propylene copolymers; cyclic olefin-based polymers such as polynorbornene; vinyl chloride-based polymers; Amide-based polymers such as aromatic polyamides; imide-based polymers; sulfone-based polymers; polyethersulfone-based polymers; poly
- the protective film 4 preferably contains a polymer that functions as a thermoplastic resin among the above-described polymers.
- the content of the thermoplastic resin in the protective film 4 is preferably 50 wt% to 100 wt%, more preferably 50 wt% to 99 wt%, still more preferably 60 wt% to 98 wt%, Especially preferred is 70% to 97% by weight. If the content of the thermoplastic resin in the protective film 4 is less than 50% by weight, the functions inherent in the thermoplastic resin, such as high transparency, may not be sufficiently exhibited.
- the protective film 4 preferably contains triacetyl cellulose (TAC) as a main component among the polymers described above.
- TAC triacetyl cellulose
- the protective film 4 may be a polymer film described in JP-A-2001-343529, International Publication No. 01/37007, and the like.
- Materials for this polymer film include, for example, thermoplastic resins having substituted and/or unsubstituted imide groups in side chains, and thermoplastic resins having substituted and/or unsubstituted phenyl groups and nitrile groups in side chains.
- a resin composition containing A specific example of the polymer film is a film formed from a resin composition containing an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer. This film is obtained, for example, by mixing and extruding a resin composition. Since this film has a small retardation and a small photoelastic coefficient, problems such as unevenness due to distortion of the polarizing film 10 can be eliminated. Furthermore, since this film has a low moisture permeability, it has excellent durability in a humid environment.
- the protective film 4 may contain one or more additives.
- additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, and colorants.
- the moisture permeability of the protective film 4 is not particularly limited, and may exceed 150 g/(m 2 ⁇ day), may be 300 g/(m 2 ⁇ day) or more, and may be 500 g/(m 2 ⁇ day). ) or more.
- the resin layer 2 can sufficiently suppress the permeation of iodine contained in the polarizer 1 to the outside.
- the upper limit of the moisture permeability of the protective film 4 is not particularly limited, and is, for example, 5000 g/(m 2 ⁇ day), and may be 1000 g/(m 2 ⁇ day).
- the protective film 4 containing TAC tends to have high moisture permeability.
- the moisture permeability of the protective film 4 can be measured by the following method according to the Japanese Industrial Standard (JIS) Z0208 moisture permeability test (cup method).
- JIS Japanese Industrial Standard
- the protective film 4 is cut into a diameter of 60 mm to prepare a measurement sample.
- a measurement sample is set in a moisture-permeable cup in which about 15 g of calcium chloride is placed.
- This moisture permeable cup is placed in a constant temperature machine set at a temperature of 40° C. and a humidity of 92% RH, and left for 24 hours to conduct a moisture permeability test.
- the moisture permeability of the protective film 4 can be specified.
- the moisture permeability of the protective film 4 may be 150 g/(m 2 ⁇ day) or less. In this case, it is possible to suppress the intrusion of moisture in the air into the polarizing film 10 and suppress the change in the moisture content of the polarizing film 10 . As a result, the polarizing film 10 can be prevented from curling or undergoing dimensional changes during storage.
- materials for forming the protective film 4 with low moisture permeability include polyester-based polymers, polycarbonate-based polymers, arylate-based polymers, amide-based polymers, olefin-based polymers, cyclic olefin-based polymers, (meth)acrylic-based polymers, and these. A mixture of
- the thickness of the protective film 4 is not particularly limited, it is preferably 5 to 100 ⁇ m, more preferably 10 to 60 ⁇ m, and even more preferably 13 to 40 ⁇ m from the viewpoint of strength and handleability.
- the thickness of the protective film 4 may be less than 40 ⁇ m.
- the surface of the protective film 4 may be subjected to easy-adhesion treatment such as corona treatment or plasma treatment in order to improve the adhesion between members.
- An easy-adhesion layer may be arranged on the surface of the protective film 4 .
- the easy-adhesion layer those described above for the resin layer 2 can be used.
- the adhesive layer 5 is a layer containing an adhesive.
- the material of the adhesive is not particularly limited, and for example, (meth)acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyether, fluorine polymer, rubber polymer, etc. may be used as a base polymer. can be done.
- acrylic pressure-sensitive adhesives containing (meth)acrylic polymers have excellent optical transparency, appropriate wettability, cohesiveness, and adhesive properties such as adhesiveness, and are excellent in weather resistance, heat resistance, etc. , suitable for the material of the adhesive layer 5.
- the adhesive layer 5 may be a laminate of multiple layers having different compositions.
- the thickness of the pressure-sensitive adhesive layer 5 is appropriately determined according to the purpose of use, adhesive strength, etc., and is, for example, 1 to 500 ⁇ m, preferably 1 to 200 ⁇ m, more preferably 1 to 100 ⁇ m.
- the thickness of the adhesive layer 5 may be 50 ⁇ m or less.
- the pressure-sensitive adhesive layer 5 may be attached to the separator before the polarizing film 10 is attached to the image display panel.
- the separator can prevent contamination of the pressure-sensitive adhesive layer 5 .
- the separator for example, for thin films such as plastic films, rubber sheets, paper, cloth, non-woven fabrics, nets, foam sheets, metal foils and laminates thereof, silicone-based, long-chain alkyl-based, fluorine-based , Molybdenum sulfide, etc. can be used.
- the polarizing film 10 may further include members other than the members described above.
- the polarizing film 10 may further include, for example, a transparent substrate positioned closer to the viewer than the resin layer 2 is.
- a transparent substrate may be positioned on the outermost side of the polarizing film 10 .
- the transparent substrate is made of glass or polymer, for example. Examples of polymers constituting the transparent substrate include polyethylene terephthalate, polycycloolefin, polycarbonate and the like.
- the thickness of the transparent substrate made of glass is, for example, 0.1 mm to 1 mm.
- the thickness of the transparent substrate made of polymer is, for example, 10 ⁇ m to 200 ⁇ m.
- the transparent substrate is bonded to the resin layer 2 via, for example, an OCA (optical clear adhesive) layer.
- OCA optical clear adhesive
- the OCA layer for example, those described above for the pressure-sensitive adhesive layer 5 can be used.
- the thickness of the OCA layer is preferably 150 ⁇ m or less.
- the polarizing film 10 may further include an optical film such as a reflector, anti-transmission plate, retardation film, viewing angle compensation film, brightness enhancement film, and the like.
- Retardation films include, for example, half-wave plates, quarter-wave plates, and the like.
- the retardation film may be arranged closer to the image display panel than the polarizer 1 (for example, between the adhesive layer 5 and the protective film 4), and closer to the viewer than the polarizer 1. may be placed.
- the polarizing film 10 may further include functional layers such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer, and an antiglare layer.
- the hard coat layer may be arranged on the viewing side of the resin layer 2 .
- the method for producing the polarizing film 10 includes, for example, a step of obtaining a polymer P by polymerizing a monomer M whose y value calculated by the above formula (1) is less than 4.00.
- the polarizing film 10 can be manufactured by the following method. First, the polarizer 1 and the protective film 4 are pasted together with the adhesive layer 3 interposed therebetween. Next, a coating liquid containing the monomer M and a polymerization initiator is prepared.
- the polymerization initiator is typically the acid generator mentioned above for resin layer 2 .
- the content of the polymerization initiator in the coating liquid is, for example, 20% by weight or less, preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, and 0.1 to 5% by weight. %.
- the coating liquid is applied onto the polarizer 1.
- a film (coating film) containing the monomer M and the polymerization initiator can be formed on the polarizer 1 .
- the monomer M is polymerized so that the resin layer 2 is formed from the coating film.
- Polymerization of the monomer M can be carried out by a known method.
- the monomer M can be polymerized by irradiating the coating film with an active energy ray. Active energy rays include, for example, visible light and ultraviolet rays.
- the resin layer 2 produced by polymerizing the monomer M contained in the coating film may be referred to as a cured resin layer.
- the polarizing film 10 is obtained by bonding the adhesive layer 5 to the protective film 4 .
- the resin layer 2 may be produced by the following method. First, the monomer M is polymerized to obtain the polymer P. The obtained polymer P is added to a solvent to prepare a coating liquid. Examples of the solvent include organic solvents capable of dissolving or dispersing the polymer P. Next, a coating film is produced by applying the coating liquid onto the polarizer 1 . The resin layer 2 is obtained by drying the coating film.
- the rate change ⁇ Y1 is, for example, 4 or less, preferably 3 or less, more preferably 2 or less, still more preferably 1.85 or less, particularly preferably 1.5 or less, and particularly preferably 1 or less.
- the change ⁇ Y1 in single transmittance can be measured by the following method. First, the single transmittance Ts1 of the laminate obtained by bonding the polarizing film 10 to the non-alkali glass via the adhesive layer 5 is measured. Next, this laminate is placed in an atmosphere of 65° C. and 90% RH for 8 hours. The single transmittance Ts2 of the laminate after being placed in this atmosphere is measured. A value obtained by subtracting the single transmittance Ts1 from the single transmittance Ts2 is regarded as the single transmittance change ⁇ Y1.
- the single transmittance of the laminated body is the Y value corrected for visual sensitivity using a 2-degree field of view (C light source) of JIS Z8701-1999.
- Single transmittance can be measured using a commercially available spectrophotometer such as DOT-3 manufactured by Murakami Color Research Laboratory.
- the measurement wavelength of single transmittance is 380 to 700 nm (every 10 nm).
- Alkali-free glass is glass that does not substantially contain alkali components (alkali metal oxides). Specifically, the weight ratio of alkali components in the glass is, for example, 1000 ppm or less, and further 500 ppm or less.
- the alkali-free glass is, for example, plate-shaped and has a thickness of 0.5 mm or more.
- the single transmittance Ts1 is not particularly limited, and is, for example, 42% to 46%, preferably 43% or more, and more preferably 44% or more.
- Single transmittance Ts2 is not particularly limited, and is, for example, 42% to 48%, preferably 47% or less, and more preferably 46% or less.
- the single transmittance of the polarizing film 10 is, for example, 20 or less, preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, and particularly preferably 2 or less.
- the change ⁇ Y2 in the transmittance of the single unit was obtained by placing the laminate obtained by bonding the polarizing film 10 to the non-alkali glass via the adhesive layer 5 in an atmosphere of 65° C. and 90% RH for 24 hours.
- the transmittance change ⁇ Y1 can be measured by the same method as described above.
- FIG. 2 is a schematic cross-sectional view of a polarizing film 11 according to a modification.
- the protective film 4 is positioned closer to the viewer than the resin layer 2, and the protective film 4, the resin layer 2, and the polarizer 1 are arranged in the stacking direction. They are in order.
- the polarizing film 11 does not have the adhesive layer 3 .
- the structure of the polarizing film 11 is the same as that of the polarizing film 10 . Therefore, elements common to the polarizing film 10 and the polarizing film 11 are denoted by the same reference numerals, and description thereof may be omitted. That is, the descriptions of the following embodiments are mutually applicable unless technically inconsistent.
- Each of the following embodiments may be combined with each other as long as they are not technically inconsistent.
- the resin layer 2 is in direct contact with each of the polarizer 1 and the protective film 4.
- a polarizer 1 and a protective film 4 are bonded together with a resin layer 2 interposed therebetween.
- other layers such as an adhesive layer and an easy-adhesion layer may be arranged. These members may be bonded together via an adhesive layer or an easy-adhesion layer. Examples of the adhesive layer and the easy-adhesion layer include those described above for the polarizing film 10 .
- the polarizing film 11 may further include a hard coat layer positioned closer to the viewer than the protective film 4 is.
- a hard coat layer may be positioned on the outermost side of the polarizing film 11 .
- the hard coat layer may be positioned between the protective film 4 and the transparent substrate.
- both the protective film 4 and the resin layer 2 are positioned closer to the viewer than the polarizer 1 is.
- This polarizing film 11 tends to further suppress transmission of iodine contained in the polarizer 1 to the outside in a hot and humid environment.
- the polarizing film 11 is attached to non-alkali glass via the adhesive layer 5 and placed in an atmosphere of 85 ° C. and 85% RH for 120 hours, the single transmission of the polarizing film 11
- the rate change ⁇ Y3 is, for example, 2 or less, preferably 1.6 or less, more preferably 1.5 or less, still more preferably 1.3 or less, and may be 1.2 or less. , 1 or less.
- the change ⁇ Y3 in single transmittance can be measured by the following method. First, the single transmittance Ts3 of the laminate obtained by bonding the polarizing film 11 to the non-alkali glass via the adhesive layer 5 is measured. Next, this laminate is placed in an atmosphere of 85° C. and 85% RH for 120 hours. The single transmittance Ts4 of the laminate after being placed in this atmosphere is measured. A value obtained by subtracting the single transmittance Ts3 from the single transmittance Ts4 is regarded as the single transmittance change ⁇ Y3.
- the single transmittance Ts3 is not particularly limited, and is, for example, 42% to 46%, preferably 43% or more, and more preferably 44% or more.
- Single transmittance Ts4 is not particularly limited, and is, for example, 42% to 48%, preferably 47% or less, and more preferably 46% or less.
- the change ⁇ Y4 is, for example, 1.6 or less, preferably 1.5 or less, more preferably 1.4 or less, still more preferably 1.3 or less, and particularly preferably 1.2 or less. be.
- the change ⁇ Y4 in the transmittance of the single unit was obtained by placing the laminate obtained by bonding the polarizing film 11 to the non-alkali glass via the adhesive layer 5 in an atmosphere of 85° C. and 85% RH for 240 hours.
- the transmittance change ⁇ Y3 can be measured by the same method as described above.
- the resin layer 2 may be located closer to the image display panel (to be described later) than the polarizer 1 is. As shown in FIG. 3 , in the polarizing film 12 according to this modified example, the resin layer 2 is located closer to the image display panel than the polarizer 1 is.
- the structure of the polarizing film 12 is the same as that of the polarizing film 10 except for the position of the resin layer 2 .
- the resin layer 2 is positioned, for example, between the polarizer 1 and the adhesive layer 3 and is in direct contact with the polarizer 1 and the adhesive layer 3 respectively.
- another layer such as an adhesive layer or an easy-adhesion layer may be arranged between the resin layer 2 and the polarizer 1.
- the resin layer 2 may be attached to the polarizer 1 via an adhesive layer or an easy-adhesion layer.
- the adhesive layer and the easy-adhesion layer for bonding the resin layer 2 to the polarizer 1 include those described above for the polarizing film 10 .
- the iodine contained in the polarizer 1 moves to the adhesive layer 5 in a hot and humid environment, and passes through the adhesive layer 5 to the polarizing film 12. It is possible to suppress permeation to the outside.
- the polarizing film 10 may further include members other than the members described above.
- the polarizing film 13 according to this modified example further has a protective film (second protective film) 6 in addition to the protective film (first protective film) 4 described above.
- the structure of the polarizing film 13 is the same as that of the polarizing film 10 except for the second protective film 6 .
- the second protective film 6 is positioned closer to the viewer than the polarizer 1 is.
- Polarizer 1 is positioned, for example, between first protective film 4 and second protective film 6 .
- the second protective film 6 is, for example, located on the viewing side of the resin layer 2 and on the outermost side of the polarizing film 13 .
- the second protective film 6 may be positioned between the resin layer 2 and the transparent substrate.
- the second protective film 6 is in direct contact with the resin layer 2, for example.
- the second protective film 6 may be attached to the resin layer 2 via other layers such as an adhesive layer and a hard coat layer. Examples of the adhesive layer for bonding the second protective film 6 to the resin layer 2 include those described above for the adhesive layer 3 .
- the film described above for the first protective film 4 can be used.
- the first protective film 4 and the second protective film 6 may be the same or different.
- the polarizing film 10 may have two or more resin layers 2 .
- the polarizing film 14 according to this modification includes two resin layers 2a and 2b.
- the structure of the polarizing film 14 is the same as that of the polarizing film 10 except for the resin layer 2b.
- the polarizer 1 is positioned between the two resin layers 2a and 2b. Specifically, the resin layer 2b is positioned closer to the image display panel than the polarizer 1 (for example, between the polarizer 1 and the adhesive layer 3).
- the polarizing film 14 tends to further suppress transmission of iodine contained in the polarizer 1 to the outside.
- the resin layer 2b may be in direct contact with the polarizer 1. However, between the resin layer 2b and the polarizer 1, another layer such as an adhesive layer or an easy-adhesion layer may be arranged. For example, the resin layer 2b may be attached to the polarizer 1 via an adhesive layer or an easy-adhesion layer. Examples of the adhesive layer and the easy-adhesion layer for bonding the resin layer 2b to the polarizer 1 include those described above for the polarizing film 10 .
- the image display device 100 of this embodiment includes a polarizing film 10 and an image display panel 20.
- a polarizing film 11, 12, 13 or 14 can also be used instead of the polarizing film 10.
- the polarizing film 10 is attached to the image display panel 20 via the adhesive layer 5, for example.
- the image display panel 20 include an organic EL display panel and a liquid crystal display panel, and the organic EL display panel is preferable.
- the image display device 100 further includes, for example, an illumination system (not shown).
- an illumination system (not shown).
- the polarizing film 10, the image display panel 20, and the lighting system are arranged in this order, and the polarizing film 10 is located on the most visible side.
- the lighting system has, for example, a backlight or a reflector, and irradiates the image display panel 20 with light.
- Example 1 (Preparation of polarizing film A) ⁇ Thin polarizer> First, a laminate was prepared by forming a PVA layer having a thickness of 9 ⁇ m on an amorphous polyethylene terephthalate (PET) substrate. A stretched laminate was produced by subjecting this laminate to auxiliary stretching in the air at a stretching temperature of 130°C. Next, the stretched laminate was dyed with iodine to obtain a colored laminate. Further, the colored laminate was stretched in an aqueous boric acid solution at a stretching temperature of 65° C. to obtain a laminate a in which the amorphous PET substrate and the PVA layer were integrally stretched.
- PET polyethylene terephthalate
- the total draw ratio was 5.94 times and the thickness of the PVA layer was 5 ⁇ m.
- the PVA molecules of the PVA layer formed on the amorphous PET substrate were highly oriented by the above two-stage stretching. Furthermore, the iodine adsorbed by staining was highly oriented in one direction as a polyiodine ion complex.
- the PVA layer included in laminate a functioned as a thin polarizer.
- a resin (imidized MS resin) composed of an imidized methyl methacrylate-styrene copolymer was produced by the method described in Production Example 1 of JP-A-2010-284840.
- 100 parts by weight of the imidized MS resin and 0.62 parts by weight of a triazine-based ultraviolet absorber (trade name: T-712, manufactured by Adeka Co., Ltd.) are mixed at 220° C. to obtain resin pellets. was made.
- the obtained resin pellets were dried in an environment of 100.5 kPa and 100° C. for 12 hours.
- a film having a thickness of 160 ⁇ m was produced by extruding resin pellets from a T-die at a die temperature of 270°C. Further, this film was stretched in the transport direction under an atmosphere of 150° C. to adjust the thickness to 80 ⁇ m.
- a transparent protective film I having a thickness of 40 ⁇ m was obtained by applying an easy-adhesive agent containing a water-based urethane resin to the film and stretching the film in an atmosphere of 150° C. in a direction perpendicular to the transport direction.
- the moisture permeability of this transparent protective film I was 58 g/(m 2 ⁇ day) under the conditions of 40° C. and 92% RH.
- ⁇ Active energy ray-curable adhesive composition 12 parts by weight of hydroxyethyl acrylamide (manufactured by KJ Chemicals, trade name: HEAA), 24 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Toagosei Co., Ltd., trade name: ARONIX M-5700), 12 parts by weight Hydroxypivalic acid neopentyl glycol acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate HPP-A), 38 parts by weight of 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate 1,9ND-A), 10 parts by weight of acrylic oligomer (manufactured by Toagosei Co., Ltd., trade name: ARUFON UP-1190), 3 parts by weight of 2-methyl-1-(4-methylthioph
- visible light emitted from a visible light irradiation device (Light HAMMER10 manufactured by Fusion UV Systems) was used.
- the light source of the visible light irradiation device was a gallium-filled metal halide lamp.
- a V-bulb was used as a bulb in the visible light irradiation device.
- the peak illuminance of light emitted from the visible light irradiation device was 1600 mW/cm 2 .
- the cumulative irradiation amount of light emitted from the visible light irradiation device was 1000 mJ/cm 2 .
- the illuminance of light emitted from the visible light irradiation device was measured using a Sola-Check system manufactured by Solatell.
- the active energy ray-curable adhesive composition in the coating film was cured.
- this laminate was dried with hot air at 70° C. for 3 minutes to obtain a laminate b containing the transparent protective film I, the adhesive layer and the thin polarizer.
- ⁇ Resin layer> 60 parts by weight of 3′,6′-bis(oxiran-2-ylmethoxy)spiro[fluorene-9,9′-xanthene] (manufactured by Taoka Chemical Co., Ltd., trade name: TBIS-RXG), 20 parts by weight of Bis [(3-ethyl-3-oxetanyl) methyl] ether (manufactured by Toagosei Co., Ltd., trade name: OXT-221), 20 parts by weight of 4-t-butylphenyl glycidyl ether (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX-146) and 10 parts by weight of a photoacid generator (manufactured by San-Apro Co., Ltd., trade name: CPI-100P) were mixed and stirred at 25° C. for 1 hour to prepare a coating solution.
- a photoacid generator manufactured by San-Apro
- the amorphous PET substrate adjacent to the PVA layer was removed from the laminate b, and the exposed surface of the PVA layer was subjected to corona treatment.
- an MCD coater manufactured by Fuji Machine Co., Ltd. cell shape: honeycomb, number of gravure roll lines: 250 lines/inch, rotation speed: 160%/line speed
- the above coating solution was applied onto the exposed PVA layer. was coated.
- the thickness of the resulting coating film was 2.0 ⁇ m.
- a COP film (trade name: ZF14, thickness: 25 ⁇ m, manufactured by Nippon Zeon Co., Ltd.) was bonded to the PVA layer using a roll machine. At this time, the coating film and the COP film were brought into contact with each other.
- the line speed of the roll mill was 25 m/min.
- the obtained laminate was irradiated with an active energy ray from the COP film side.
- an active energy ray ultraviolet rays emitted from an irradiation device (Light HAMMER10 manufactured by Fusion UV Systems) were used.
- an H bulb was used as a bulb.
- the peak illuminance of light emitted from the irradiation device was 200 mW/cm 2 .
- the cumulative irradiation amount of light emitted from the irradiation device was 600 mJ/cm 2 .
- the illuminance and cumulative irradiation amount of the emitted light from the irradiation device were measured using a UV radiometer POWER PUCK II manufactured by EIT.
- the monomers in the coating film were polymerized.
- the coating film was cured by the polymerization of the monomer.
- this laminate was dried with hot air at 70° C. for 3 minutes, and then allowed to stand at 25° C. for 24 hours. Thereby, a resin layer was formed.
- a laminate c including the transparent protective film I, the adhesive layer, the thin polarizer and the resin layer was obtained.
- a polarizing film A comprising a resin layer, a polarizer, an adhesive layer, a transparent protective film I and an adhesive layer in this order was obtained.
- the obtained laminate was irradiated with an active energy ray from the thin polarizer side.
- the active energy ray the ultraviolet rays described above for the polarizing film A were used.
- the monomers in the coating film were polymerized.
- the coating film was cured by the polymerization of the monomer.
- this laminate was dried with hot air at 70° C. for 3 minutes, and then allowed to stand at 25° C. for 24 hours. Thereby, a resin layer was formed to obtain a laminate d including the transparent protective film I, the resin layer and the thin polarizer.
- amorphous PET base material adjacent to the PVA layer was removed from the obtained laminate d, and the exposed surface of the PVA layer was subjected to corona treatment.
- a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m was attached to this surface.
- the adhesive layer was composed of an acrylic adhesive.
- a polarizing film B comprising a transparent protective film I, a resin layer, a polarizer and an adhesive layer in this order was obtained.
- a solution (manufactured by DIC, trade name: Unidic 17-806, solid concentration: 80% by weight) was prepared by dissolving an ultraviolet curable resin monomer or oligomer containing urethane acrylate as a main component in butyl acetate. Based on 100 parts by weight of the solid content of this solution, 5 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name: IRGACURE 907), and 0.1 parts by weight of a leveling agent (manufactured by DIC, trade name: GRANDIC PC4100 ) was added.
- cyclopentanone and propylene glycol monomethyl ether were added to the solution at a weight ratio of 45:55 so that the solid content concentration in the solution was adjusted to 36% by weight.
- a coating liquid for forming a hard coat layer was prepared.
- a triacetyl cellulose (TAC) film (trade name: TJ25UL manufactured by Fuji Film Co., Ltd., raw material: triacetyl cellulose-based polymer, thickness: 25 ⁇ m, moisture permeability: 931 g/(m 2 ⁇ day) ) was prepared.
- a coating liquid for forming a hard coat layer was applied onto the transparent protective film to form a coating film.
- the thickness of the coating film was adjusted so that the thickness of the hard coat layer after curing was 7 ⁇ m.
- the coating film was dried at 90° C. for 1 minute, and then irradiated with ultraviolet light having an accumulated light quantity of 300 mJ/cm 2 using a high-pressure mercury lamp.
- the coating film was cured to form a hard coat layer (HC) having a thickness of 7 ⁇ m, thereby obtaining a transparent protective film II with HC.
- the moisture permeability of the transparent protective film II with HC was 420 g/(m 2 ⁇ day) under the conditions of 40° C. and 92% RH.
- a polarizing film C was produced in the same manner as the polarizing film B, except that a transparent protective film II with HC was used instead of the transparent protective film I.
- the polarizing film C had a hard coat layer, a transparent protective film (TAC film), a resin layer, a polarizer and an adhesive layer in this order.
- Example 2-11 Comparative Example 1-6
- Example 2-11 Comparative Example 1-6
- the monomers contained in the coating liquid for forming the resin layer were changed to the monomers listed in Table 1.
- ⁇ y value calculated by formula (1)> The values of x 1 to x 7 were specified by the method described above for the monomers contained in the coating liquids for forming the resin layers used in Examples and Comparative Examples.
- HSPiP version 5
- Materials Studio manufactured by BIOVIA, ver.8.0.0.843
- WebMO ver.19.0.009e
- ⁇ Crack evaluation> A heat shock test was performed on the polarizing films B and C of Examples and Comparative Examples by the following method. First, a pressure-sensitive adhesive layer was attached to the surface of the transparent protective film I (or the transparent protective film II with HC) of the polarizing film. Next, using a CO 2 laser (manufactured by COMNET, product name: Laser Pro-SPIRIT), the resulting laminate was cut into the shape shown in FIG. Specifically, the measurement sample 15 was produced by cutting a part of a strip-shaped laminate of 50 mm long ⁇ 150 mm wide in a V-shape from one long side of the laminate. At this time, the angle formed by the long side of the laminate before cutting and the cut surface was adjusted to 14°.
- the direction of the absorption axis coincided with the direction in which the short sides extend.
- the irradiation conditions of the CO 2 laser were as follows. ⁇ Irradiation conditions Wavelength: 10.6 ⁇ m Laser output: 30W Oscillation mode: Pulse oscillation Diameter of laser light: 70 ⁇ m Laser irradiation surface: protective film side
- the measurement sample 15 was attached to non-alkali glass with a thickness of 0.5 mm.
- a heat shock test was performed by subjecting the measurement sample 15 to heat shocks of ⁇ 40 to 80° C. 200 times. Each heat shock was performed for 30 minutes. After the heat shock test, it was confirmed whether or not a crack penetrating through the measurement sample 15 occurred in the V-shaped portion (region A in FIG. 7) of the measurement sample 15 .
- the above heat shock test was repeated 10 times, and the case where cracks occurred was rated as x, and the case where cracks did not occur was rated as ⁇ .
- Table 1 shows the evaluation results for each of the produced polarizing films.
- TBIS-RXG 3′,6′-bis(oxiran-2-ylmethoxy)spiro[fluorene-9,9′-xanthene]
- OXT-221 bis [(3-ethyl-3-oxetanyl) methyl] ether (manufactured by Toagosei Co., Ltd., trade name: OXT-221)
- EX-146 4-t-butylphenyl glycidyl ether (manufactured by Nagase ChemteX, trade name: Denacol EX-146)
- jER-834 bisphenol A type epoxy resin (epoxy equivalent 230 to 270 g / eq, manufactured by Mitsubishi Chemical Corporation, trade name: jER-834)
- TBIS-GG 9,9-bis ⁇ 4-[2-(oxiran-2-yl
- the polarizing film of the present invention can be suitably used, for example, for mobile displays such as mobile phones, smart phones, and laptop computers; and vehicle-mounted displays such as car navigation device panels, cluster panels, and mirror displays.
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Abstract
Description
ヨウ素を含む偏光子と、
エポキシ基を含む化合物A1に由来する構造単位U1、及びオキセタン基を含む化合物A2に由来する構造単位U2からなる群より選ばれる少なくとも1つを有する重合体を含む樹脂層と、を備え、
下記式(1)によって算出されるyの値が4.00未満である、偏光フィルムを提供する。
y=(-3.71)x1+(-3.94)x2+(0.299)x3+(0.226)x4+(-1.05)x5+(0.517)x6+(0.769)x7+71.81 (1)
前記式(1)において、x1は、前記重合体を形成するためのモノマーのハンセン溶解度パラメータにおける分散項δD(MPa1/2)であり、
x2は、前記重合体を形成するための前記モノマーの双極子モーメントにおけるx成分(Debye)であり、
x3は、前記重合体を形成するための前記モノマーと水分子との相互作用エネルギー(kcal/mol)であり、
x4は、前記重合体を形成するための前記モノマーの25℃の水に対する溶解度(g/100g)の常用対数値LogSであり、
x5は、前記重合体を形成するための前記モノマーの双極子モーメント(Debye)であり、
x6は、前記重合体を形成するための前記モノマーの双極子モーメントにおけるz成分(Debye)であり、
x7は、前記重合体を形成するための前記モノマーにおける水素結合アクセプターの数である。
上記の偏光フィルムと、
画像表示パネルと、
を備えた、画像表示装置を提供する。
ヨウ素を含む偏光子と、エポキシ基を含む化合物A1に由来する構造単位U1、及びオキセタン基を含む化合物A2に由来する構造単位U2からなる群より選ばれる少なくとも1つを有する重合体を含む樹脂層と、を備えた偏光フィルムの製造方法であって、
前記製造方法は、
下記式(1)によって算出されるyの値が4.00未満であるモノマーを重合させて、前記重合体を得る工程を含む、偏光フィルムの製造方法を提供する。
y=(-3.71)x1+(-3.94)x2+(0.299)x3+(0.226)x4+(-1.05)x5+(0.517)x6+(0.769)x7+71.81 (1)
前記式(1)において、x1は、前記モノマーのハンセン溶解度パラメータにおける分散項δD(MPa1/2)であり、
x2は、前記モノマーの双極子モーメントにおけるx成分(Debye)であり、
x3は、前記モノマーと水分子との相互作用エネルギー(kcal/mol)であり、
x4は、前記モノマーの25℃の水に対する溶解度(g/100g)の常用対数値LogSであり、
x5は、前記モノマーの双極子モーメント(Debye)であり、
x6は、前記モノマーの双極子モーメントにおけるz成分(Debye)であり、
x7は、前記モノマーにおける水素結合アクセプターの数である。
ヨウ素を含む偏光子と、
エポキシ基を含む化合物A1に由来する構造単位U1、及びオキセタン基を含む化合物A2に由来する構造単位U2からなる群より選ばれる少なくとも1つを有する重合体を含む樹脂層と、を備え、
下記式(1)によって算出されるyの値が4.00未満である。
y=(-3.71)x1+(-3.94)x2+(0.299)x3+(0.226)x4+(-1.05)x5+(0.517)x6+(0.769)x7+71.81 (1)
前記式(1)において、x1は、前記重合体を形成するためのモノマーのハンセン溶解度パラメータにおける分散項δD(MPa1/2)であり、
x2は、前記重合体を形成するための前記モノマーの双極子モーメントにおけるx成分(Debye)であり、
x3は、前記重合体を形成するための前記モノマーと水分子との相互作用エネルギー(kcal/mol)であり、
x4は、前記重合体を形成するための前記モノマーの25℃の水に対する溶解度(g/100g)の常用対数値LogSであり、
x5は、前記重合体を形成するための前記モノマーの双極子モーメント(Debye)であり、
x6は、前記重合体を形成するための前記モノマーの双極子モーメントにおけるz成分(Debye)であり、
x7は、前記重合体を形成するための前記モノマーにおける水素結合アクセプターの数である。
第1~第16態様のいずれか1つにかかる偏光フィルムと、
画像表示パネルと、
を備える。
ヨウ素を含む偏光子と、エポキシ基を含む化合物A1に由来する構造単位U1、及びオキセタン基を含む化合物A2に由来する構造単位U2からなる群より選ばれる少なくとも1つを有する重合体を含む樹脂層と、を備えた偏光フィルムの製造方法であって、
前記製造方法は、
下記式(1)によって算出されるyの値が4.00未満であるモノマーを重合させて、前記重合体を得る工程を含む。
y=(-3.71)x1+(-3.94)x2+(0.299)x3+(0.226)x4+(-1.05)x5+(0.517)x6+(0.769)x7+71.81 (1)
前記式(1)において、x1は、前記モノマーのハンセン溶解度パラメータにおける分散項δD(MPa1/2)であり、
x2は、前記モノマーの双極子モーメントにおけるx成分(Debye)であり、
x3は、前記モノマーと水分子との相互作用エネルギー(kcal/mol)であり、
x4は、前記モノマーの25℃の水に対する溶解度(g/100g)の常用対数値LogSであり、
x5は、前記モノマーの双極子モーメント(Debye)であり、
x6は、前記モノマーの双極子モーメントにおけるz成分(Debye)であり、
x7は、前記モノマーにおける水素結合アクセプターの数である。
図1に示すように、本実施形態の偏光フィルム10は、ヨウ素を含む偏光子1と、重合体Pを含む樹脂層2とを備えている。樹脂層2に含まれる重合体Pは、エポキシ基を含む化合物A1に由来する構造単位U1、及びオキセタン基を含む化合物A2に由来する構造単位U2からなる群より選ばれる少なくとも1つを有する。樹脂層2は、例えば、偏光子1よりも視認側に位置し、偏光子1に直接接している。ただし、樹脂層2と偏光子1との間には、本発明の効果を妨げない範囲で、接着剤層、易接着層などの他の層が配置されていてもよい。樹脂層2は、偏光子1よりも後述する画像表示パネル側に位置していてもよい。言い換えると、偏光子1が樹脂層2よりも視認側に位置していてもよい。樹脂層2は、例えば、偏光フィルム10の最も外側に位置している。なお、本明細書において、「フィルム」とは、長さ及び幅に比べて厚さが十分に小さい部材を意味する。
y=(-3.71)x1+(-3.94)x2+(0.299)x3+(0.226)x4+(-1.05)x5+(0.517)x6+(0.769)x7+71.81 (1)
x3(ΔE)=EM+H2O-(EM+EH2O)
偏光子1は、ヨウ素を含む限り、特に限定されず、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルムなどの親水性高分子フィルムに、ヨウ素を吸着させて一軸延伸したものが挙げられる。偏光子1は、ポリビニルアルコール系フィルム及びヨウ素から構成されていることが好ましい。偏光子1は、例えば、ポリビニルアルコールを主成分として含む。本明細書において、「主成分」は、偏光子1に重量基準で最も多く含まれる材料を意味する。
上述のとおり、樹脂層2は、エポキシ基を含む化合物A1に由来する構造単位U1、及びオキセタン基を含む化合物A2に由来する構造単位U2からなる群より選ばれる少なくとも1つを有する重合体Pを含む。化合物A1及びA2は、重合体Pを形成するためのモノマーMとして用いることができる。
L+X- (i)
接着剤層3は、接着剤を含む層である。接着剤の材料は、特に限定されず、公知の材料を用いることができる。接着剤層3に含まれる接着剤としては、例えば、水系接着剤及び活性エネルギー線硬化型接着剤が挙げられる。活性エネルギー線硬化型接着剤としては、例えば、特開2019-147865号、特開2016-177248号などに開示されたものを用いることができる。
保護フィルム4としては、透明性、機械的強度、熱安定性、水分遮断性、等方性などに優れるものが好ましい。保護フィルム4は、典型的には、透明保護フィルムである。保護フィルム4の材料としては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル系ポリマー;ジアセチルセルロース、トリアセチルセルロースなどのセルロース系ポリマー;ポリメチルメタクリレートなどの(メタ)アクリル系ポリマー;ポリスチレン、アクリロニトリル・スチレン共重合体(AS樹脂)などのスチレン系ポリマー;ポリカーボネート系ポリマー;ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体などのオレフィン系ポリマー;ポリノルボルネンなどの環状オレフィン系ポリマー;塩化ビニル系ポリマー;ナイロン、芳香族ポリアミドなどのアミド系ポリマー;イミド系ポリマー;スルホン系ポリマー;ポリエーテルスルホン系ポリマー;ポリエーテルエーテルケトン系ポリマー;ポリフェニレンスルフィド系ポリマー;ビニルアルコール系ポリマー;塩化ビニリデン系ポリマー;ビニルブチラール系ポリマー;アリレート系ポリマー;ポリオキシメチレン系ポリマー;エポキシ系ポリマー;これらのポリマーの混合物などが挙げられる。
粘着剤層5は、粘着剤を含む層である。粘着剤の材料は、特に限定されず、例えば、(メタ)アクリル系ポリマー、シリコーン系ポリマー、ポリエステル、ポリウレタン、ポリアミド、ポリエーテル、フッ素系ポリマー、ゴム系ポリマーなどをベースポリマーとして含むものを用いることができる。特に、(メタ)アクリル系ポリマーを含むアクリル系粘着剤は、光学的透明性に優れ、適切な濡れ性、凝集性、接着性などの粘着特性を有し、耐候性、耐熱性等に優れるため、粘着剤層5の材料に適している。
偏光フィルム10は、上述した部材以外の他の部材をさらに備えていてもよい。偏光フィルム10は、例えば、樹脂層2よりも視認側に位置する透明基板をさらに備えていてもよい。透明基板が偏光フィルム10の最も外側に位置していてもよい。透明基板は、例えば、ガラス又はポリマーで構成されている。透明基板を構成するポリマーとしては、例えば、ポリエチレンテレフタレート、ポリシクロオレフィン、ポリカーボネートなどが挙げられる。ガラスで構成された透明基板の厚さは、例えば、0.1mm~1mmである。ポリマーで構成された透明基板の厚さは、例えば、10μm~200μmである。
偏光フィルム10の製造方法は、例えば、上記の式(1)によって算出されるyの値が4.00未満であるモノマーMを重合させて、重合体Pを得る工程を含む。詳細には、偏光フィルム10は、次の方法によって製造できる。まず、接着剤層3を介して、偏光子1と保護フィルム4とを貼り合わせる。次に、上記のモノマーMと、重合開始剤とを含む塗布液を準備する。重合開始剤は、典型的には、樹脂層2について上述した酸発生剤である。
本実施形態の偏光フィルム10では、高温多湿環境下において、偏光子1に含まれるヨウ素の外部への透過が十分に抑制される。すなわち、高温多湿環境下において、偏光子1におけるヨウ素の濃度がほとんど変化しない。偏光子1におけるヨウ素の濃度の変化は、例えば、偏光フィルム10の単体透過率の変化から読み取ることができる。一例として、粘着剤層5を介して偏光フィルム10を無アルカリガラスに貼り合わせた状態で、偏光フィルム10を65℃90%RHの雰囲気下に8時間置いた場合に、偏光フィルム10の単体透過率の変化ΔY1は、例えば4以下であり、好ましくは3以下であり、より好ましくは2以下であり、さらに好ましくは1.85以下であり、特に好ましくは1.5以下であり、とりわけ好ましくは1以下である。
図2は、変形例にかかる偏光フィルム11の概略断面図である。図2に示すように、本変形例の偏光フィルム11において、保護フィルム4は、樹脂層2よりも視認側に位置しており、保護フィルム4、樹脂層2及び偏光子1が積層方向にこの順で並んでいる。偏光フィルム11は、接着剤層3を備えていない。以上を除き、偏光フィルム11の構造は、偏光フィルム10の構造と同じである。したがって、偏光フィルム10と偏光フィルム11とで共通する要素には同じ参照符号を付し、それらの説明を省略することがある。すなわち、以下の各実施形態に関する説明は、技術的に矛盾しない限り、相互に適用される。以下の各実施形態は、技術的に矛盾しない限り、相互に組み合わされてもよい。
偏光フィルム10において、樹脂層2は、偏光子1よりも後述する画像表示パネル側に位置していてもよい。図3に示すとおり、本変形例にかかる偏光フィルム12において、樹脂層2は、偏光子1よりも画像表示パネル側に位置する。樹脂層2の位置を除き、偏光フィルム12の構造は、偏光フィルム10の構造と同じである。
偏光フィルム10は、上述した部材以外の他の部材をさらに備えていてもよい。図4に示すとおり、本変形例にかかる偏光フィルム13は、上述した保護フィルム(第1保護フィルム)4とともに、保護フィルム(第2保護フィルム)6をさらに有している。第2保護フィルム6を除き、偏光フィルム13の構造は、偏光フィルム10の構造と同じである。
偏光フィルム10は、2つ以上の樹脂層2を備えていてもよい。図5に示すとおり、本変形例にかかる偏光フィルム14は、2つの樹脂層2a及び2bを備えている。樹脂層2bを除き、偏光フィルム14の構造は、偏光フィルム10の構造と同じである。
図6に示すように、本実施形態の画像表示装置100は、偏光フィルム10及び画像表示パネル20を備える。画像表示装置100では、偏光フィルム10に代えて、偏光フィルム11、12、13又は14も使用可能である。画像表示装置100において、偏光フィルム10は、例えば、粘着剤層5を介して画像表示パネル20に貼り合わされている。画像表示パネル20としては、有機EL表示パネル、液晶表示パネルなどが挙げられ、好ましくは有機EL表示パネルである。
(偏光フィルムAの作製)
<薄型偏光子>
まず、非晶性ポリエチレンテレフタラート(PET)基材に、厚さ9μmのPVA層が製膜された積層体を準備した。この積層体について、延伸温度130℃で空中補助延伸を行うことによって延伸積層体を作製した。次に、ヨウ素を用いて、延伸積層体を染色し、着色積層体を得た。さらに、着色積層体について、ホウ酸水溶液中、延伸温度65度で延伸することによって、非晶性PET基材とPVA層とが一体に延伸された積層体aを得た。積層体aにおいて、総延伸倍率は5.94倍であり、PVA層の厚さは5μmであった。上記の2段延伸によって、非晶性PET基材に製膜されたPVA層のPVA分子は、高次に配向された。さらに、染色によって吸着されたヨウ素は、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。積層体aに含まれるPVA層は、薄型偏光子として機能した。
まず、特開2010-284840号公報の製造例1に記載された方法によって、イミド化されたメタクリル酸メチル-スチレン共重合体から構成された樹脂(イミド化MS樹脂)を作製した。次に、2軸混練機を用いて、イミド化MS樹脂100重量部及びトリアジン系紫外線吸収剤(アデカ社製、商品名:T-712)0.62重量部を220℃で混合し、樹脂ペレットを作製した。得られた樹脂ペレットは、100.5kPa、100℃の環境下で12時間乾燥させた。次に、単軸の押出機を用いて、ダイス温度270℃でTダイから樹脂ペレットを押し出すことによって、厚さ160μmのフィルムを作製した。さらに、このフィルムについて、その搬送方向に150℃の雰囲気下で延伸し、厚さを80μmに調節した。次に、水性ウレタン樹脂を含む易接着剤をフィルムに塗布した後に、搬送方向と直交する方向に150℃の雰囲気下でフィルムを延伸することによって、厚さ40μmの透明保護フィルムIを得た。この透明保護フィルムIの透湿度は、40℃92%RHの条件下で58g/(m2・day)であった。
12重量部のヒドロキシエチルアクリルアミド(KJケミカルズ社製、商品名:HEAA)、24重量部の2-ヒドロキシ-3-フェノキシプロピルアクリレート(東亞合成社製、商品名:ARONIX M-5700)、12重量部のヒドロキシピバリン酸ネオペンチルグリコールアクリル酸付加物(共栄社化学社製、商品名:ライトアクリレートHPP-A)、38重量部の1,9-ノナンジオールジアクリレート(共栄社化学社製、商品名:ライトアクリレート1,9ND-A)、10重量部のアクリルオリゴマー(東亞合成社製、商品名:ARUFON UP-1190)、3重量部の2-メチル-1-(4-メチルチオフェニル)-2-モルホリノプロパン-1-オン(IGM Resins社製、商品名:OMNIRAD 907)及び2重量部の2,4-ジエチルチオキサントン(日本化薬社製、商品名:KAYACURE DETX-S)を混合し、3時間撹拌することにより、活性エネルギー線硬化型接着剤組成物を得た。
富士機械社製のMCDコーター(セル形状:ハニカム、グラビアロール線数:1000本/inch、回転速度140%/対ライン速)を用いて、活性エネルギー線硬化型接着剤組成物を透明保護フィルムIの貼合面に塗工した。得られた塗膜の厚さは、0.7μmであった。次に、ロール機を用いて、透明保護フィルムIとPVA層を含む積層体aとを貼り合わせた。このとき、塗膜とPVA層とを接触させた。ロール機のライン速度は、25m/minであった。次に、得られた積層体について、透明保護フィルム側から活性エネルギー線を照射した。活性エネルギー線としては、可視光線照射装置(Fusion UV Systems社製Light HAMMER10)から出射された可視光線を用いた。可視光線照射装置の光源は、ガリウム封入メタルハライドランプであった。可視光線照射装置では、バルブとしてVバルブを用いた。可視光線照射装置からの出射光のピーク照度は、1600mW/cm2であった。波長380nm~440nmの範囲において、可視光線照射装置からの出射光の積算照射量は、1000mJ/cm2であった。可視光線照射装置からの出射光の照度は、Solatell社製のSola-Checkシステムを用いて測定した。積層体に活性エネルギー線を照射することによって、塗膜中の活性エネルギー線硬化型接着剤組成物が硬化した。次に、この積層体について、70℃で3分間熱風乾燥を行うことによって、透明保護フィルムI、接着剤層及び薄型偏光子を含む積層体bを得た。
まず、60重量部の3’,6’-ビス(オキシラン-2-イルメトキシ)スピロ[フルオレン-9,9’-キサンテン](田岡化学工業社製、商品名:TBIS-RXG)、20重量部のビス[(3-エチル-3-オキセタニル)メチル]エーテル(東亞合成社製、商品名:OXT-221)、20重量部の4-t-ブチルフェニルグリシジルエーテル(ナガセケムテックス社製、商品名:デナコール EX-146)、及び10重量部の光酸発生剤(サンアプロ社製、商品名:CPI-100P)を混合し、25℃で1時間攪拌することにより塗布液を作製した。
まず、上記の透明保護フィルムIの貼合面に対して、コロナ処理を行った。次に、富士機械社製のMCDコーター(セル形状:ハニカム、グラビアロール線数:250本/inch、回転速度160%/対ライン速)を用いて、透明保護フィルムIの貼合面に上記の塗布液を塗工した。得られた塗膜の厚さは、2.0μmであった。次に、ロール機を用いて、透明保護フィルムIとPVA層を含む積層体aとを貼り合わせた。このとき、塗膜とPVA層とを接触させた。ロール機のライン速度は、25m/minであった。次に、得られた積層体について、薄型偏光子側から活性エネルギー線を照射した。活性エネルギー線としては、偏光フィルムAについて上述した紫外線を用いた。積層体に活性エネルギー線を照射することによって、塗膜中のモノマーが重合した。モノマーが重合することによって塗膜が硬化した。次に、この積層体について、70℃で3分間熱風乾燥を行い、さらに、25℃で24時間静置した。これにより、樹脂層が形成され、透明保護フィルムI、樹脂層及び薄型偏光子を含む積層体dを得た。
<ハードコート層付き透明保護フィルム>
まず、ウレタンアクリレートを主成分として含む紫外線硬化型樹脂モノマー又はオリゴマーを酢酸ブチルに溶解させた溶液(DIC社製、商品名:ユニディック17-806、固形分濃度:80重量%)を準備した。この溶液の固形分100重量部に対して、5重量部の光重合開始剤(BASF社製、商品名:IRGACURE907)、及び0.1重量部のレベリング剤(DIC社製、商品名:GRANDIC PC4100)を添加した。さらに、溶液中の固形分濃度が36重量%に調整されるように、シクロペンタノンとプロピレングリコールモノメチルエーテルを重量比45:55で溶液に添加した。これにより、ハードコート層を形成するための塗布液を作製した。
樹脂層を形成するための塗布液に含まれるモノマーを表1に記載されたモノマーに変更したことを除き、実施例1と同じ方法によって、実施例2-11、比較例1-6のそれぞれについて、偏光フィルムA-Cを作製した。
実施例及び比較例で用いられた樹脂層を形成するための塗布液に含まれるモノマーについて、上述した方法によってx1~x7の値を特定した。なお、モノマーのハンセン溶解度パラメータにおける分散項δD(MPa1/2)、及び、モノマーの25℃の水に対する溶解度S(g/100g)の常用対数値LogSは、HSPiP(version5)を用いて算出した。モノマーの双極子モーメントなどを算出するための分子シミュレーションは、Materials Studio(BIOVIA社製、ver.8.0.0.843)及びWebMO(ver.19.0.009e)を利用した。さらに、x1~x7の値を用いて、式(1)に基づいて、yの値を算出した。
実施例及び比較例の偏光フィルムAについて、以下の方法によって、単体透過率の変化ΔY1を測定した。まず、粘着剤層を介して、偏光フィルムAを無アルカリガラスに貼り合わせた。得られた積層体について、単体透過率Ts1を測定した。単体透過率Ts1は、積分球付き分光透過率測定器(村上色彩技術研究所製のDot-3c)を用いて測定した。次に、この積層体を65℃90%RHの雰囲気下に8時間置いた。この雰囲気下に置いた後の積層体について、上記の分光透過率測定器を用いて、単体透過率Ts2を測定した。単体透過率Ts2から単体透過率Ts1を差し引くことによって、単体透過率の変化ΔY1を算出した。
粘着剤層を介して偏光フィルムAを無アルカリガラスに貼り合わせることによって得られた積層体を65℃90%RHの雰囲気下に24時間置いたことを除き、単体透過率の変化ΔY1について上述した方法と同じ方法によって、単体透過率の変化ΔY2を測定した。
実施例及び比較例の偏光フィルムB及びCについて、以下の方法によって、単体透過率の変化ΔY3を測定した。まず、粘着剤層を介して、偏光フィルムB及びCを無アルカリガラスに貼り合わせた。得られた積層体について、単体透過率Ts3を測定した。単体透過率Ts3は、積分球付き分光透過率測定器(村上色彩技術研究所製のDot-3c)を用いて測定した。次に、この積層体を85℃85%RHの雰囲気下に120時間置いた。この雰囲気下に置いた後の積層体について、上記の分光透過率測定器を用いて、単体透過率Ts4を測定した。単体透過率Ts4から単体透過率Ts3を差し引くことによって、単体透過率の変化ΔY3を算出した。
粘着剤層を介して偏光フィルムBを無アルカリガラスに貼り合わせることによって得られた積層体を85℃85%RHの雰囲気下に240時間置いたことを除き、単体透過率の変化ΔY3について上述した方法と同じ方法によって、単体透過率の変化ΔY4を測定した。
実施例及び比較例の偏光フィルムB及びCについて、以下の方法によって、ヒートショック試験を行った。まず、偏光フィルムの透明保護フィルムI(又はHC付き透明保護フィルムII)の表面に粘着剤層を貼り合わせた。次に、CO2レーザー(コムネット社製、製品名:Laser Pro-SPIRIT)を用いて、得られた積層体を図7に示す形状に裁断し、測定サンプル15を作製した。詳細には、測定サンプル15は、縦50mm×横150mmの短冊状の積層体について、一方の長辺側からV字状に当該積層体の一部を切り取ることによって作製した。このとき、切断前の積層体の長辺と、切断面とのなす角度を14°に調整した。なお、短冊状の積層体において、吸収軸方向は、短辺が延びる方向に一致していた。CO2レーザーの照射条件は、以下のとおりであった。
・照射条件
波長:10.6μm
レーザー出力:30W
発振モード:パルス発振
レーザー光の直径:70μm
レーザー照射面:保護フィルム側
TBIS-RXG:3’,6’-ビス(オキシラン-2-イルメトキシ)スピロ[フルオレン-9,9’-キサンテン](田岡化学工業社製、商品名:TBIS-RXG)
OXT-221:ビス[(3-エチル-3-オキセタニル)メチル]エーテル(東亞合成社製、商品名:OXT-221)
EX-146:4-t-ブチルフェニルグリシジルエーテル(ナガセケムテックス社製、商品名:デナコール EX-146)
jER-834:ビスフェノールA型エポキシ樹脂(エポキシ当量230~270g/eq、三菱ケミカル社製、商品名:jER-834)
TBIS-GG:9,9-ビス{4-[2-(オキシラン-2-イルメトキシ)エトキシ]フェニル}-9H-フルオレン(田岡化学工業社製、商品名:TBIS-GG)
THI-DE:ビシクロノナジエンジエポキシド(ENEOS社製、商品名:THI-DE)
ED-505:トリメチロールプロパントリグリシジルエーテル(ADEKA社製、商品名:アデカグリシロールED-505)
EP-4088S:ジシクロペンタジエン型エポキシ樹脂(ADEKA社製、商品名:EP-4088S)
BATG:2,2-ビス(3-グリシジル-4-グリシジルオキシフェニル)プロパン(昭和電工社製、商品名:ショウフリーBATG)
OXBP:4,4’-(3-エチルオキセタン-3-イルメチルオキシメチル)ビフェニル(宇部興産社製、商品名:ETERNACOLL-OXBP)
DE-102:ノルボルナン環を有するエポキシ化合物(ENEOS社製、商品名:DE-102)
DE-103:トリシクロペンタジエンジエポキシド(ENEOS社製、商品名:DE-103)
ED-523T:ネオペンチルグリコールジグリシジルエーテル(ADEKA社製、商品名:アデカグリシロールED-523T)
EX-313:グリセロールポリグリシジルエーテル(ナガセケムテックス社製、商品名:デナコール EX-313)
EX-212:1,6-ヘキサンジオールジグリシジルエーテル(ナガセケムテックス社製、商品名:デナコール EX-212)
EX-832:ポリエチレングリコールジグリシジルエーテル(エポキシ当量284g/eq、ナガセケムテックス社製、商品名:デナコール EX-832)
EX-821:ポリエチレングリコールジグリシジルエーテル(エポキシ当量185g/eq、ナガセケムテックス社製、商品名:デナコール EX-821)
Claims (18)
- ヨウ素を含む偏光子と、
エポキシ基を含む化合物A1に由来する構造単位U1、及びオキセタン基を含む化合物A2に由来する構造単位U2からなる群より選ばれる少なくとも1つを有する重合体を含む樹脂層と、を備え、
下記式(1)によって算出されるyの値が4.00未満である、偏光フィルム。
y=(-3.71)x1+(-3.94)x2+(0.299)x3+(0.226)x4+(-1.05)x5+(0.517)x6+(0.769)x7+71.81 (1)
前記式(1)において、x1は、前記重合体を形成するためのモノマーのハンセン溶解度パラメータにおける分散項δD(MPa1/2)であり、
x2は、前記重合体を形成するための前記モノマーの双極子モーメントにおけるx成分(Debye)であり、
x3は、前記重合体を形成するための前記モノマーと水分子との相互作用エネルギー(kcal/mol)であり、
x4は、前記重合体を形成するための前記モノマーの25℃の水に対する溶解度(g/100g)の常用対数値LogSであり、
x5は、前記重合体を形成するための前記モノマーの双極子モーメント(Debye)であり、
x6は、前記重合体を形成するための前記モノマーの双極子モーメントにおけるz成分(Debye)であり、
x7は、前記重合体を形成するための前記モノマーにおける水素結合アクセプターの数である。 - 前記yの値が2.30以下である、請求項1に記載の偏光フィルム。
- 前記重合体は、前記構造単位U1及び前記構造単位U2の両方を含む、請求項1に記載の偏光フィルム。
- 前記重合体において、前記構造単位U1の含有率と、前記構造単位U2の含有率との合計値が70重量%以上である、請求項1に記載の偏光フィルム。
- 前記化合物A1は、エポキシ基以外の環構造を含む、請求項1に記載の偏光フィルム。
- 前記化合物A1は、脂肪族環及び芳香族環からなる群より選ばれる少なくとも1つを含む、請求項1に記載の偏光フィルム。
- 前記樹脂層は、酸発生剤及び/又は酸発生剤の分解物を含む、請求項1に記載の偏光フィルム。
- 前記樹脂層は、前記偏光子に直接接している、請求項1に記載の偏光フィルム。
- 前記樹脂層の厚さが3μm未満である、請求項1に記載の偏光フィルム。
- 前記偏光子の厚さが1μm以上7μm未満である、請求項1に記載の偏光フィルム。
- 前記偏光子は、ポリビニルアルコールを主成分として含む、請求項1に記載の偏光フィルム。
- 保護フィルムをさらに備えた、請求項1に記載の偏光フィルム。
- 前記保護フィルム、前記樹脂層及び前記偏光子が積層方向にこの順で並んでいる、請求項12に記載の偏光フィルム。
- 前記保護フィルムの透湿度が300g/(m2・day)以上である、請求項12に記載の偏光フィルム。
- 前記保護フィルムがトリアセチルセルロースを主成分として含む、請求項12に記載の偏光フィルム。
- 前記保護フィルムの厚さが40μm未満である、請求項12に記載の偏光フィルム。
- 請求項1~16のいずれか1項に記載の偏光フィルムと、
画像表示パネルと、
を備えた、画像表示装置。 - ヨウ素を含む偏光子と、エポキシ基を含む化合物A1に由来する構造単位U1、及びオキセタン基を含む化合物A2に由来する構造単位U2からなる群より選ばれる少なくとも1つを有する重合体を含む樹脂層と、を備えた偏光フィルムの製造方法であって、
前記製造方法は、
下記式(1)によって算出されるyの値が4.00未満であるモノマーを重合させて、前記重合体を得る工程を含む、偏光フィルムの製造方法。
y=(-3.71)x1+(-3.94)x2+(0.299)x3+(0.226)x4+(-1.05)x5+(0.517)x6+(0.769)x7+71.81 (1)
前記式(1)において、x1は、前記モノマーのハンセン溶解度パラメータにおける分散項δD(MPa1/2)であり、
x2は、前記モノマーの双極子モーメントにおけるx成分(Debye)であり、
x3は、前記モノマーと水分子との相互作用エネルギー(kcal/mol)であり、
x4は、前記モノマーの25℃の水に対する溶解度(g/100g)の常用対数値LogSであり、
x5は、前記モノマーの双極子モーメント(Debye)であり、
x6は、前記モノマーの双極子モーメントにおけるz成分(Debye)であり、
x7は、前記モノマーにおける水素結合アクセプターの数である。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160154436A1 (en) * | 2014-11-28 | 2016-06-02 | Samsung Sdi Co., Ltd. | Composition for window film, flexible window film manufactured using the same and flexible display including the same |
| WO2018025714A1 (ja) * | 2016-08-03 | 2018-02-08 | 住友化学株式会社 | 積層フィルム |
| WO2018025716A1 (ja) * | 2016-08-03 | 2018-02-08 | 住友化学株式会社 | 積層フィルム |
| WO2018147284A1 (ja) * | 2017-02-08 | 2018-08-16 | 日東電工株式会社 | 偏光フィルム用接着剤組成物、偏光フィルム、光学フィルムおよび画像表示装置 |
| WO2019058778A1 (ja) * | 2017-09-21 | 2019-03-28 | 日東電工株式会社 | 積層光学フィルムおよびその製造方法、ならびに画像表示装置 |
| WO2020196625A1 (ja) * | 2019-03-28 | 2020-10-01 | 日東電工株式会社 | 偏光フィルムの製造方法 |
| WO2021065107A1 (ja) * | 2019-09-30 | 2021-04-08 | 日東電工株式会社 | 位相差層付偏光板、および、それを用いた画像表示装置 |
| WO2021192615A1 (ja) * | 2020-03-27 | 2021-09-30 | 日東電工株式会社 | 偏光フィルム、画像表示装置及び偏光フィルムの製造方法 |
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| JP5677883B2 (ja) | 2011-03-29 | 2015-02-25 | 住友化学株式会社 | 光硬化性接着剤、偏光板および積層光学部材 |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160154436A1 (en) * | 2014-11-28 | 2016-06-02 | Samsung Sdi Co., Ltd. | Composition for window film, flexible window film manufactured using the same and flexible display including the same |
| WO2018025714A1 (ja) * | 2016-08-03 | 2018-02-08 | 住友化学株式会社 | 積層フィルム |
| WO2018025716A1 (ja) * | 2016-08-03 | 2018-02-08 | 住友化学株式会社 | 積層フィルム |
| WO2018147284A1 (ja) * | 2017-02-08 | 2018-08-16 | 日東電工株式会社 | 偏光フィルム用接着剤組成物、偏光フィルム、光学フィルムおよび画像表示装置 |
| WO2019058778A1 (ja) * | 2017-09-21 | 2019-03-28 | 日東電工株式会社 | 積層光学フィルムおよびその製造方法、ならびに画像表示装置 |
| WO2020196625A1 (ja) * | 2019-03-28 | 2020-10-01 | 日東電工株式会社 | 偏光フィルムの製造方法 |
| WO2021065107A1 (ja) * | 2019-09-30 | 2021-04-08 | 日東電工株式会社 | 位相差層付偏光板、および、それを用いた画像表示装置 |
| WO2021192615A1 (ja) * | 2020-03-27 | 2021-09-30 | 日東電工株式会社 | 偏光フィルム、画像表示装置及び偏光フィルムの製造方法 |
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