WO2023286576A1 - 偏光板並びにその偏光板を用いた画像表示装置 - Google Patents
偏光板並びにその偏光板を用いた画像表示装置 Download PDFInfo
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- WO2023286576A1 WO2023286576A1 PCT/JP2022/025483 JP2022025483W WO2023286576A1 WO 2023286576 A1 WO2023286576 A1 WO 2023286576A1 JP 2022025483 W JP2022025483 W JP 2022025483W WO 2023286576 A1 WO2023286576 A1 WO 2023286576A1
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- polarizing plate
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Classifications
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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
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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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
-
- 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
-
- 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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- G—PHYSICS
- G06—COMPUTING OR CALCULATING; COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- 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
Definitions
- the present invention relates to a polarizing plate and an image display device.
- Liquid crystal display devices are widely used not only for liquid crystal televisions, but also for mobile applications such as personal computers and mobile phones, and in-vehicle applications such as car navigation systems.
- a liquid crystal display device has a liquid crystal panel in which polarizing plates are attached to both sides of a liquid crystal cell with an adhesive, and display is performed by controlling light from a backlight with the liquid crystal panel.
- organic EL display devices like liquid crystal display devices, organic EL display devices have also been widely used for mobile applications such as televisions and mobile phones, and in-vehicle applications such as car navigation systems.
- a circular polarizing plate (a polarizing element and a ⁇ /4 plate) is provided on the viewing side surface of the image display panel in order to prevent external light from being reflected by the metal electrode (cathode) and viewed as a mirror surface. ) may be placed.
- Patent Document 1 Japanese Unexamined Patent Application Publication No. 2005-189615
- Patent Document 2 Japanese Patent Application Laid-Open No. 2010-276673 describes that a pot life sufficient for production can be obtained by using an adhesive to which maleic acid is added together with a cross-linking agent.
- polarizing plates are increasingly used in vehicles as components of image display devices such as liquid crystal display devices and organic EL display devices. Compared to mobile applications such as televisions and mobile phones, polarizing plates used in in-vehicle image display devices are often exposed to high-temperature environments. gender) is required.
- a front plate such as a transparent resin plate or glass plate (also referred to as a "window layer" is provided on the viewing side of the image display panel.
- a front plate such as a transparent resin plate or glass plate (also referred to as a "window layer"
- a front panel is provided on the viewing side of the image display panel.
- the space between the polarizing plate and the transparent member arranged on the viewing side surface of the image display panel is a layer other than the air layer and is usually a solid layer (hereinafter sometimes referred to as an "interlayer filler”. ) (hereinafter sometimes referred to as “interlayer filling configuration”).
- the interlayer filler is preferably a material having a refractive index close to that of the polarizing plate or transparent member.
- a pressure-sensitive adhesive or a UV curable adhesive is used for the purpose of suppressing deterioration of visibility due to reflection at the interface and bonding and fixing between each member (for example, Japanese Patent Application Laid-Open No. 11-174417 (See Patent Document 3)).
- the interlayer filling structure is being widely adopted for mobile applications such as mobile phones, which are often used outdoors.
- a front transparent plate is placed on the surface of the image display panel, and the space between the panel and the front transparent plate is filled with an adhesive layer or the like. Adoption of an interlayer filling configuration is being considered.
- JP 2014-102353 A Patent Document 4
- the water content per unit area of the polarizing plate is set to a predetermined amount or less
- the saturated water absorption amount of the transparent protective film adjacent to the polarizing element is It proposes a method of suppressing a decrease in transmittance by setting the amount to a predetermined amount or less.
- the present invention provides a novel polarizing plate having an adhesive layer formed from an adhesive having a sufficient pot life for production and suppressing a decrease in transmittance when exposed to a high-temperature environment, and the polarizing plate.
- An object of the present invention is to provide an image display device using the and an adhesive.
- the present invention provides a polarizing plate and an image display device exemplified below.
- a polarizing plate having a polarizing element in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin layer, and a transparent protective film laminated on at least one surface of the polarizing element, The polarizing element and the transparent protective film are bonded together by an adhesive layer formed from an adhesive containing a first compound, a second compound, and a third compound,
- the first compound is at least one selected from the group consisting of urea, urea derivatives, thiourea, and thiourea derivatives
- the second compound is a dialdehyde
- the polarizing plate, wherein the third compound is a dicarboxylic acid.
- the polarizing plate is used in an image display device, The polarizing plate according to any one of [1] to [7], wherein in the image display device, solid layers are provided in contact with both surfaces of the polarizing plate.
- An image display device comprising the polarizing plate according to claim 1.
- the image display according to [9] further comprising a second adhesive layer laminated on the viewer-side surface of the polarizing plate, and a transparent member laminated on the viewer-side surface of the second adhesive layer. Device.
- the image display device of [10], wherein the transparent member is a glass plate or a transparent resin plate.
- the transparent member is a touch panel.
- the first compound is at least one selected from the group consisting of urea, urea derivatives, thiourea, and thiourea derivatives
- the second compound is a dialdehyde
- the adhesive wherein the third compound is a dicarboxylic acid.
- a polarizing plate which has an adhesive layer formed from an adhesive having a pot life sufficient for production and which suppresses a decrease in transmittance when exposed to a high-temperature environment. becomes possible. Furthermore, by using the polarizing plate according to the present invention, it is possible to provide an image display device in which a decrease in transmittance is suppressed even when exposed to a high-temperature environment.
- a polarizing plate has a polarizing element in which a dichroic dye is adsorbed and oriented in a layer containing a polyvinyl alcohol-based resin, and a transparent protective film.
- the polarizing element and the transparent protective film are bonded together by an adhesive layer formed from an adhesive containing the first compound, the second compound and the third compound.
- the first compound is at least one selected from the group consisting of urea, urea derivatives, thiourea and thiourea derivatives.
- the second compound is a dialdehyde.
- a third compound is a dicarboxylic acid.
- a polarizing plate As a conventional polarizing plate excellent in high-temperature durability, for example, a polarizing plate is known in which a decrease in transmittance is suppressed even when the polarizing plate alone is left in an environment at a temperature of 95°C for 1000 hours.
- a polarizing plate when it is used in an interlayer filling structure, if it is left in an environment at a temperature of 105° C., the transmittance may be remarkably lowered at the central portion of the plane of the polarizing plate.
- the significant decrease in the transmittance of the polarizing plate in a high-temperature environment is due to an interlayer filling structure in which one surface of the polarizing plate is bonded to the image display cell and the other surface is bonded to a transparent member such as a touch panel or front panel. is exposed to a high-temperature environment.
- the polarizing plate according to the present invention can further improve high temperature durability.
- the polarizing plate according to the present invention is incorporated in an image display device having an interlayer filling structure, and can suppress a decrease in transmittance even when exposed to a high temperature environment of, for example, 105°C.
- Such an effect is said to be due to the synergistic action of the first compound, the second compound and the third compound present in the adhesive layer, which suppresses polyenization of the polyvinyl alcohol constituting the polarizing element. guessed.
- Such an effect is exhibited not only when the water content of the polarizing plate is low, but also when the water content of the polarizing plate is high.
- the polarizing plate according to the present invention preferably has at least one of the following characteristics (a) and (b).
- the moisture content of the polarizing element is equal to or higher than the equilibrium moisture content at a temperature of 20° C. and a relative humidity of 30%, and is equal to or lower than the equilibrium moisture content at a temperature of 20° C. and a relative humidity of 70%.
- the water content of the polarizing plate is equal to or higher than the equilibrium water content at a temperature of 20°C and a relative humidity of 30%, and is equal to or lower than the equilibrium water content at a temperature of 20°C and a relative humidity of 70%.
- polarizing element As a polarizing element in which a layer containing a polyvinyl alcohol (hereinafter also referred to as "PVA")-based resin (hereinafter also referred to as a “PVA-based resin layer”) is adsorbed and oriented with a dichroic dye, a known polarizing element is used. can be used.
- a polarizing element a stretched film obtained by dyeing a PVA-based resin film with a dichroic dye and uniaxially stretching the film, or a coating layer formed by coating a coating liquid containing a PVA-based resin on a substrate film.
- PVA-based resin is obtained by saponifying polyvinyl acetate-based resin.
- Polyvinyl acetate-based resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate with other monomers copolymerizable therewith.
- Other copolymerizable monomers include, for example, unsaturated carboxylic acids, olefins such as ethylene, vinyl ethers, unsaturated sulfonic acids and the like.
- the PVA-based resin layer is preferably formed from a PVA-based resin having a boron adsorption rate of 5.70% by mass or more. That is, the PVA-based resin has a boron adsorption rate of 5.70% by mass or more in the raw material stage before being dyed or stretched.
- the transmittance is less likely to decrease even when exposed to a high temperature environment of 105° C., for example.
- the boron adsorption rate of the PVA-based resin is preferably 10% by mass or less.
- the boric acid concentration in the boric acid treatment tank does not have to be high, and the boric acid treatment time can be shortened. of the polarizing element can be easily obtained, and the productivity of the polarizing element can also be improved.
- the boron adsorption rate of the PVA-based resin is 10% by mass or less, an appropriate amount of boron is incorporated into the PVA-based resin layer, and the shrinkage force of the polarizing element can be easily reduced.
- problems such as separation between the polarizing plate and other members such as the front plate are less likely to occur.
- the boron adsorption rate of the PVA-based resin can be measured by the method described in Examples below.
- the boron adsorption rate of PVA-based resin is a property that reflects the spacing between molecular chains and the crystal structure in PVA-based resin.
- a PVA-based resin having a boron adsorption rate of 5.70% by mass or more has a wider spacing between molecular chains than a PVA-based resin having a boron adsorption rate of less than 5.70% by mass, and the crystals of the PVA-based resin are It is thought that there are few. Therefore, it is presumed that boron, first metal ions, and second metal ions are likely to enter the PVA-based resin layer, and polyene formation is likely to be prevented in a high-temperature environment.
- the boron adsorption rate of the PVA-based resin can be obtained, for example, by subjecting the PVA-based resin to pretreatment such as hot water treatment, acid solution treatment, ultrasonic irradiation treatment, and radiation irradiation treatment at the stage before manufacturing the polarizing element.
- pretreatment such as hot water treatment, acid solution treatment, ultrasonic irradiation treatment, and radiation irradiation treatment at the stage before manufacturing the polarizing element.
- the hot water treatment includes, for example, immersion in pure water of 30° C. to 100° C. for 1 second to 90 seconds and drying.
- the acid solution treatment includes, for example, immersion in an aqueous solution of boric acid having a concentration of 10% by mass to 20% by mass for 1 second to 90 seconds, followed by drying.
- ultrasonic treatment for example, ultrasonic waves having a frequency of 20 to 29 kc are applied at an output of 200 W to 500 W for 30 seconds to 10 minutes. Sonication can be performed in a solvent such as water.
- the degree of saponification of the PVA-based resin is preferably 85 mol% or more, more preferably 90 mol% or more, and still more preferably 99 mol% or more and 100 mol% or less.
- the degree of polymerization of the PVA-based resin is, for example, 1000 or more and 10000 or less, preferably 1500 or more and 5000 or less.
- the PVA-based resin may be modified, for example, aldehyde-modified polyvinyl formal, polyvinyl acetal, polyvinyl butyral, or the like.
- the thickness of the polarizing element is preferably 3 ⁇ m or more and 35 ⁇ m or less, more preferably 4 ⁇ m or more and 30 ⁇ m or less, and still more preferably 5 ⁇ m or more and 25 ⁇ m or less.
- the thickness of the polarizing element is 35 ⁇ m or less, it is possible to suppress the influence of the polyene conversion of the PVA-based resin on the deterioration of the optical properties in a high-temperature environment.
- the thickness of the polarizing element is 3 ⁇ m or more, it becomes easy to achieve the desired optical characteristics.
- the polarizing element preferably contains a first compound, a second compound, and a third compound.
- the adhesive layer formed from an adhesive containing the first compound, the second compound, and the third compound, the adhesive layer It is presumed that a portion of the first compound, a portion of the second compound, and a portion of the third compound migrated from the polarizer are contained in the polarizing element.
- the first compound, the second compound and the third compound in the polarizing element may contain those added during the manufacturing process of the polarizing element.
- the transmittance is less likely to decrease even when the polarizing plate is exposed to a high-temperature environment. Further, by providing the adhesive layer containing the first compound, the second compound, and the third compound, it is possible to suppress the deterioration of the degree of polarization even when the polarizing plate is exposed to a high-temperature environment.
- cross leakage light leakage
- the degree of polarization is less likely to decrease even when exposed to a high-temperature environment, making it easier to suppress cross drop-out. It is presumed that the synergistic effect of the first compound, the second compound, and the third compound contained in the polarizing element suppresses polyenization of the PVA-based resin.
- a PVA-based resin layer is added to a treatment solvent containing the first compound and/or the second compound and/or the third compound. or a method of spraying, flowing or dripping the treatment solvent onto the PVA-based resin layer.
- a method of immersing the PVA-based resin layer in a treatment solvent containing all of the first compound, the second compound and the third compound is preferably used.
- Specific examples of the first compound, the second compound, and the third compound include those exemplified as those to be contained in the adhesive described later.
- the step of immersing the PVA-based resin layer in the treatment solvent containing the first compound, the second compound and the third compound is performed simultaneously with the steps of swelling, stretching, dyeing, cross-linking, washing, etc. in the manufacturing method of the polarizing element described below. may be provided separately from these steps.
- the step of adding the first compound, the second compound and the third compound to the PVA-based resin layer is preferably performed after dyeing the PVA-based resin layer with iodine, and more preferably performed simultaneously with the cross-linking step after dyeing. According to such a method, the change in hue is small, and the influence on the optical characteristics of the polarizing element can be reduced.
- both the addition during the production of the polarizing element and the addition to the adhesive may be performed.
- an adhesive containing a first compound, a second compound, and a third compound is used, and at least one of the first compound, the second compound, and the third compound is added during the production of the polarizing element.
- the first compound is at least one selected from the group consisting of urea, urea derivatives, thiourea and thiourea derivatives.
- a 1st compound can be used individually by 1 type or in combination of 2 or more types.
- the first compound may be water-soluble or poorly water-soluble, and either of the first compounds may be used.
- a urea derivative is a compound in which at least one of the four hydrogen atoms in a urea molecule is substituted with a substituent.
- the substituents are not particularly limited, but substituents consisting of carbon, hydrogen and oxygen atoms are preferred.
- urea derivatives include monosubstituted urea such as methylurea, ethylurea, propylurea, butylurea, isobutylurea, N-octadecylurea, 2-hydroxyethylurea, hydroxyurea, acetylurea, allylurea, and 2-propynyl.
- Urea cyclohexyl urea, phenyl urea, 3-hydroxyphenyl urea, (4-methoxyphenyl) urea, benzyl urea, benzoyl urea, o-tolyl urea, p-tolyl urea.
- Disubstituted urea 1,1-dimethylurea, 1,3-dimethylurea, 1,1-diethylurea, 1,3-diethylurea, 1,3-bis(hydroxymethyl)urea, 1,3-tert- Butylurea, 1,3-dicyclohexylurea, 1,3-diphenylurea, 1,3-bis(4-methoxyphenyl)urea, 1-acetyl-3-methylurea, 2-imidazolidinone (ethyleneurea), tetrahydro -2-pyrimidinone (propylene urea).
- Tetramethylurea 1,1,3,3-tetraethylurea, 1,1,3,3-tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, 1,3-dimethyl- 2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone.
- a thiourea derivative is a compound in which at least one of four hydrogen atoms in a thiourea molecule is substituted with a substituent.
- the substituents are not particularly limited, but substituents consisting of carbon, hydrogen and oxygen atoms are preferred.
- thiourea derivatives include monosubstituted thiourea such as N-methylthiourea, ethylthiourea, propylthiourea, isopropylthiourea, 1-butylthiourea, cyclohexylthiourea, N-acetylthiourea, N-allylthiourea, (2 -methoxyethyl)thiourea, N-phenylthiourea, (4-methoxyphenyl)thiourea, N-(2-methoxyphenyl)thiourea, N-(1-naphthyl)thiourea, (2-pyridyl)thiourea, Examples include o-tolylthiourea and p-tolylthiourea.
- thiourea Disubstituted thiourea, 1,1-dimethylthiourea, 1,3-dimethylthiourea, 1,1-diethylthiourea, 1,3-diethylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1 ,3-dicyclohexylthiourea, N,N-diphenylthiourea, N,N'-diphenylthiourea, 1,3-di(o-tolyl)thiourea, 1,3-di(p-tolyl)thiourea, 1-benzyl-3-phenylthiourea, 1-methyl-3-phenylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, ethylenethiourea.
- tri-substituted thiourea examples include trimethylthiourea
- examples of tetra-substituted thiourea include tetramethylthiourea and 1,1,3,3-tetraethylthiourea.
- urea derivatives or thiourea derivatives are preferred, and urea derivatives are more preferred.
- urea derivatives mono-substituted urea or di-substituted urea is preferred, and mono-substituted urea is more preferred.
- Disubstituted urea includes 1,1-substituted urea and 1,3-substituted urea, with 1,3-substituted urea being more preferred.
- the second compound is a dialdehyde.
- Dialdehydes include, for example, glyoxal, propanedial (malondialdehyde), butanedial (succinaldehyde), and the like. Glyoxal, which has a simple structure and is highly reactive, is particularly preferred. Although glyoxal may be described below, conventionally known dialdehydes can be used as described above, and the dialdehyde is not limited to glyoxal.
- a third compound is a dicarboxylic acid.
- dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tartaric acid, glutamic acid, malic acid, Maleic acid, fumaric acid, itaconic acid, muconic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyl dicarboxylic acids, 2,5-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenylmethanedicarboxylic acid,
- the polarizing element usually contains potassium ions (also called “first metal ions”), and preferably contains metal ions other than potassium ions (also called “second metal ions”).
- the content of the second metal ion in the polarizing element is preferably 0.05% by mass or more and 10.0% by mass or less, more preferably 0.05% by mass or more and 8.0% by mass or less, and still more preferably It is 0.1 mass % or more and 6.0 mass % or less. If the second metal ion content of the polarizing element exceeds 10.0% by mass, the degree of polarization may decrease in a high-temperature, high-humidity environment.
- the content of the second metal ion is less than 0.05% by mass, the effect of improving the durability in a high-temperature environment may not be sufficient.
- the content of the second metal ions in the polarizing element is calculated as the mass fraction (% by mass) of the metal element with respect to the mass of the polarizing element by, for example, inductively coupled plasma (ICP) emission spectrometry. be able to.
- the metal element is considered to exist in the polarizing element in the form of a metal ion or in a state in which it forms a crosslinked structure with the constituent elements of the polyvinyl alcohol-based resin. is the value of
- the second metal ions are not limited as long as they are metal ions other than potassium ions, and are preferably ions of metals other than alkali metals. , aluminum, copper, manganese, and iron. Among these metal ions, zinc ions are preferred from the viewpoint of adjusting color tone and imparting heat resistance.
- the content of boron in the polarizing element is preferably 2.4% by mass or more.
- the boron content is preferably 3.9% by mass or more and 8.0% by mass or less, more preferably 4.2% by mass or more and 7.0% by mass or less, still more preferably 4.4% by mass or more and 6.0% by mass or more. It is 0% by mass or less.
- the boron content of the polarizing element exceeds 8.0% by mass, the shrinkage force of the polarizing element increases, and the polarizing element is peeled off from other members such as a front plate that are bonded together when incorporated into an image display device. may cause problems such as If the boron content is less than 2.4% by mass, desired optical properties may not be achieved.
- the content of boron in the polarizing element can be calculated as a mass fraction (% by mass) of boron with respect to the mass of the polarizing element by, for example, inductively coupled plasma (ICP) emission spectrometry.
- ICP inductively coupled plasma
- Boron is considered to be present in the polarizing element in a state in which boric acid or a crosslinked structure is formed with the constituent elements of the polyvinyl alcohol-based resin. value.
- the decrease in transmittance is further reduced even when exposed to a high-temperature environment as a component of an image display device having an interlayer filling structure. Suppressed. This is because when the polarizing element has a boron content of 2.4% by mass or more and 8.0% by mass or less, polyene formation is less likely to occur even in a high-temperature environment, and a decrease in transmittance is suppressed. It is assumed that
- the content of potassium ions in the polarizing element is preferably 0.28% by mass or more, more preferably 0.32% by mass or more, from the viewpoint of suppressing deterioration of the optical properties of the polarizing element in a high-temperature environment. It is preferably 0.34% by mass or more, more preferably 0.34% by mass or more, and preferably 0.60% by mass or less, and 0.55% by mass or less from the viewpoint of suppressing hue change in a high-temperature environment. is more preferable, and 0.50% by mass or less is even more preferable.
- the content of potassium ions can be measured in the same manner as the content of the second metal ions, and the content of potassium ions here is the value in terms of potassium atoms.
- the manufacturing method of the polarizing element is not particularly limited, but a method in which a pre-rolled PVA-based resin film is sent out and subjected to stretching, dyeing, cross-linking, etc. (hereinafter referred to as "manufacturing method 1"), A method comprising a step of applying a coating liquid containing a PVA-based resin onto a substrate film to form a PVA-based resin layer as a coating layer, and stretching the obtained laminate (hereinafter referred to as "manufacturing method 2" ) are typical.
- Production method 1 includes a step of uniaxially stretching a PVA-based resin film, a step of dyeing the PVA-based resin film with a dichroic dye such as iodine to adsorb the dichroic dye, and a PVA system to which the dichroic dye is adsorbed. It can be produced through a step of treating the resin film with an aqueous boric acid solution and a step of washing with water after the treatment with the aqueous boric acid solution.
- a dichroic dye such as iodine to adsorb the dichroic dye
- the swelling process is a treatment process in which the PVA-based resin film is immersed in a swelling bath.
- the swelling step can remove stains, blocking agents, and the like on the surface of the PVA-based resin film, and swelling the PVA-based resin film can suppress uneven dyeing.
- a medium containing water as a main component such as water, distilled water, or pure water, is usually used for the swelling bath.
- Surfactants, alcohols and the like may be appropriately added to the swelling bath according to conventional methods.
- Potassium iodide may be used in the swelling bath from the viewpoint of controlling the potassium content of the polarizing element. In this case, the concentration of potassium iodide in the swelling bath should be 1.5% by mass or less. It is preferably 1.0% by mass or less, more preferably 0.5% by mass or less.
- the temperature of the swelling bath is preferably 10°C or higher and 60°C or lower, more preferably 15°C or higher and 45°C or lower, and even more preferably 18°C or higher and 30°C or lower.
- the immersion time in the swelling bath cannot be unconditionally determined because the degree of swelling of the PVA-based resin film is affected by the temperature of the swelling bath. and more preferably 20 seconds or more and 100 seconds or less.
- the swelling step may be performed only once, or may be performed multiple times as necessary.
- the dyeing process is a treatment process in which the PVA-based resin film is immersed in a dyeing bath (iodine solution), and a dichroic dye such as iodine can be adsorbed and oriented on the PVA-based resin film.
- iodine solution is usually preferably an aqueous iodine solution containing iodine and iodide as a dissolution aid.
- iodides examples include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. mentioned. Among these, potassium iodide is preferable from the viewpoint of controlling the content of potassium in the polarizing element.
- the concentration of iodine in the dyeing bath is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.02% by mass or more and 0.5% by mass or less.
- the concentration of iodide in the dyeing bath is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and 0.1% by mass or more and 3 % by mass or less is more preferable.
- the temperature of the dyeing bath is preferably 10°C or higher and 50°C or lower, more preferably 15°C or higher and 45°C or lower, and even more preferably 18°C or higher and 30°C or lower.
- the immersion time in the dyeing bath cannot be unconditionally determined because the degree of dyeing of the PVA-based resin film is affected by the temperature of the dyeing bath, but it is preferably 10 seconds or more and 300 seconds or less, and 20 seconds or more and 240 seconds or less. is more preferable.
- the dyeing step may be performed only once, or may be performed multiple times as necessary.
- the cross-linking step is a treatment step in which the PVA-based resin film dyed in the dyeing step is immersed in a treatment bath (cross-linking bath) containing a boron compound.
- a treatment bath containing a boron compound.
- Molecules or dye molecules can adsorb to the crosslinked structures.
- Boron compounds include, for example, boric acid, borates, and borax.
- the cross-linking bath is generally an aqueous solution, but may be a mixed solution of an organic solvent miscible with water and water.
- the cross-linking bath preferably contains potassium iodide from the viewpoint of controlling the potassium content in the polarizing element.
- the concentration of the boron compound in the cross-linking bath is preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, and 2% by mass or more and 5% by mass or less. It is more preferable to have When potassium iodide is used in the cross-linking bath, the concentration of potassium iodide in the cross-linking bath is preferably 1% by mass or more and 15% by mass or less, and is preferably 1.5% by mass or more and 10% by mass or less. More preferably, it is 2% by mass or more and 5% by mass or less.
- the temperature of the cross-linking bath is preferably 20°C or higher and 70°C or lower, more preferably 30°C or higher and 60°C or lower.
- the immersion time in the cross-linking bath cannot be unconditionally determined because the degree of cross-linking of the PVA-based resin film is affected by the temperature of the cross-linking bath, but it is preferably 5 seconds or more and 300 seconds or less, and 10 seconds or more and 200 seconds or less. is more preferable.
- the cross-linking step may be performed only once, or may be performed multiple times as necessary.
- the stretching step is a processing step of stretching the PVA-based resin film in at least one direction to a predetermined magnification.
- a PVA-based resin film is uniaxially stretched in the transport direction (longitudinal direction).
- the stretching method is not particularly limited, and both wet stretching and dry stretching can be employed.
- the stretching step may be performed only once, or may be performed multiple times as necessary.
- the stretching step may be performed at any stage in the production of the polarizing element.
- the stretching bath preferably contains potassium iodide from the viewpoint of controlling the potassium content in the polarizing element.
- concentration of potassium iodide in the drawing bath is preferably 1% by mass or more and 15% by mass or less, more preferably 2% by mass or more and 10% by mass or less. , 3% by mass or more and 6% by mass or less.
- the treatment bath (stretching bath) may contain a boron compound from the viewpoint of suppressing film breakage during stretching.
- the concentration of the boron compound in the drawing bath is preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, and 2% by mass. It is more preferable to be 5% by mass or less.
- the temperature of the drawing bath is preferably 25 to 80°C, more preferably 40 to 80°C, even more preferably 50 to 75°C, and particularly preferably 65 to 75°C.
- the immersion time in the stretching bath cannot be unconditionally determined because the degree of stretching of the PVA-based resin film is affected by the temperature of the stretching bath. is more preferable.
- the stretching treatment in the wet stretching method may be performed together with one or more of the swelling process, dyeing process, cross-linking process and washing process.
- Examples of the dry drawing method include a roll-to-roll drawing method, a heating roll drawing method, a compression drawing method, and the like.
- the dry stretching method may be applied together with the drying process.
- the total draw ratio (cumulative draw ratio) applied to the polyvinyl alcohol resin film can be appropriately set according to the purpose, but is preferably 2 to 7 times, and 3 to 6.8 times. more preferably 3.5 times or more and 6.5 times or less.
- the washing process is a treatment process in which the polyvinyl alcohol-based resin film is immersed in a washing bath, and foreign substances remaining on the surface of the polyvinyl alcohol-based resin film can be removed.
- a medium containing water as a main component such as water, distilled water, or pure water, is usually used.
- potassium iodide in the cleaning bath.
- the concentration of potassium iodide in the cleaning bath is 1% by mass or more and 10% by mass. is preferably 1.5% by mass or more and 4% by mass or less, more preferably 1.8% by mass or more and 3.8% by mass or less.
- the temperature of the washing bath is preferably 5°C or higher and 50°C or lower, more preferably 10°C or higher and 40°C or lower, and even more preferably 15°C or higher and 30°C or lower.
- the immersion time in the cleaning bath cannot be unconditionally determined because the degree of cleaning of the PVA-based resin film is affected by the temperature of the cleaning bath. and more preferably 3 seconds or more and 20 seconds or less.
- the washing step may be performed only once, or may be performed multiple times as necessary.
- the metal ion treatment step is performed by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing a metal salt of the second metal ion.
- the second metal ion is incorporated into the polyvinyl alcohol-based resin film by the metal ion treatment step.
- the second metal ions are not limited as long as they are metal ions other than potassium ions, and are preferably ions of metals other than alkali metals. , aluminum, copper, manganese, and iron. Among these metal ions, zinc ions are preferred from the viewpoint of adjusting color tone and imparting heat resistance.
- Zinc salts include zinc halides such as zinc chloride and zinc iodide, zinc sulfate, zinc acetate, and the like.
- a metal salt solution is used in the metal ion treatment process.
- Immersion treatment in a zinc-containing solution will be described below as a typical example of using a zinc salt aqueous solution among the metal ion treatment steps.
- the zinc ion concentration in the zinc salt aqueous solution is in the range of 0.1 to 10% by mass, preferably 0.3 to 7% by mass.
- the zinc salt solution it is preferable to use an aqueous solution containing potassium ions and iodine ions with potassium iodide or the like, since it is easy to impregnate with zinc ions.
- the concentration of potassium iodide in the zinc salt solution is preferably 0.1-10 mass %, more preferably 0.2-5 mass %.
- the temperature of the zinc salt solution is usually 15-85°C, preferably 25-70°C.
- the immersion time is usually in the range of 1 to 120 seconds, preferably 3 to 90 seconds.
- the zinc content in the polyvinyl alcohol resin film can be adjusted by adjusting the conditions such as the concentration of the zinc salt solution, the immersion temperature of the polyvinyl alcohol resin film in the zinc salt solution, and the immersion time. Adjust so that it falls within the above range. There are no particular restrictions on when the immersion treatment in the zinc-containing solution is performed.
- the immersion treatment in the zinc-containing liquid may be performed alone, or a zinc salt may coexist in the dyeing bath, the cross-linking bath, and the stretching bath, and at least one step of the dyeing step, the cross-linking step, and the stretching step may be performed. You can go at the same time.
- the drying process is a process of drying the PVA-based resin film washed in the washing process to obtain a polarizing element. Drying is performed by any appropriate method, such as natural drying, air drying, and heat drying.
- Production method 2 includes a step of applying a coating liquid containing a PVA-based resin onto a substrate film, a step of uniaxially stretching the obtained laminated film, and a PVA-based resin layer of the uniaxially stretched laminated film with a dichroic dye. It can be produced through a step of dyeing to adsorb a polarizing element, a step of treating a film on which a dichroic dye is adsorbed with an aqueous boric acid solution, and a step of washing with water after treatment with an aqueous boric acid solution.
- the base film used to form the polarizing element may be used as a protective layer for the polarizing element. If necessary, the base film may be peeled off from the polarizing element.
- the transparent protective film (hereinafter also simply referred to as "protective film") used in this embodiment is attached to at least one surface of the polarizing element via an adhesive layer.
- the transparent protective film is laminated on one side or both sides of the polarizing element, preferably on both sides.
- the protective film may have other optical functions at the same time, and may be formed into a laminated structure in which multiple layers are laminated.
- the film thickness of the protective film is preferably thin from the viewpoint of optical properties, but if it is too thin, the strength will decrease and the workability will be poor.
- a suitable film thickness is 5 ⁇ m or more and 100 ⁇ m or less, preferably 10 ⁇ m or more and 80 ⁇ m or less, and more preferably 15 ⁇ m or more and 70 ⁇ m or less.
- a film such as a cellulose acylate film, a polycarbonate resin film, a cycloolefin resin film such as norbornene, a (meth)acrylic polymer film, or a polyester resin film such as polyethylene terephthalate is used.
- a water-based adhesive such as PVA is used to attach protective films to both sides of the polarizing element
- the protective film on at least one side is either a cellulose acylate film or a (meth)acrylic polymer film in terms of moisture permeability.
- a cellulose acylate film is preferred.
- At least one protective film may have a retardation function for the purpose of viewing angle compensation.
- the protective film itself may have a retardation function, may have a separate retardation layer, or may be a combination of both.
- a film having a retardation function may be directly bonded to the polarizing element via an adhesive, but may be bonded via a pressure-sensitive adhesive or adhesive via another protective film bonded to the polarizing element. configuration may be used.
- the adhesive layer for bonding the protective film to the polarizing element is formed from the following adhesives.
- the adhesive contains a first compound, a second compound and a third compound.
- the adhesive is not limited and may be a water-based adhesive, a solvent-based adhesive, an active energy ray-curable adhesive, or the like, but is preferably a water-based adhesive and preferably contains a PVA-based resin.
- the thickness of the adhesive when applied can be set to any value, for example, it can be set so that an adhesive layer having a desired thickness is obtained after curing or after heating (drying).
- the thickness of the adhesive layer composed of the adhesive is preferably 0.01 ⁇ m or more and 7 ⁇ m or less, more preferably 0.01 ⁇ m or more and 5 ⁇ m or less, still more preferably 0.01 ⁇ m or more and 2 ⁇ m or less, and most preferably. is 0.01 ⁇ m or more and 1 ⁇ m or less.
- the content of the third compound is, for example, 0.01 parts by mass or more and 400 parts by mass or less, preferably 0, with respect to 100 parts by mass of the PVA-based resin. 0.05 parts by mass or more and 50 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less. If it is less than 0.01 parts by mass, the effect of improving the pot life may not be sufficient, or the effect of suppressing polyene conversion of the polarizing element in a high-temperature environment may not be sufficient. On the other hand, if it exceeds 400 parts by mass, the third compound may precipitate after the polarizing plate is produced.
- the content of the first compound is preferably 0.1 parts by mass or more and 400 parts by mass or less, more preferably 100 parts by mass of the PVA-based resin. is 1 part by mass or more and 200 parts by mass or less, more preferably 3 parts by mass or more and 100 parts by mass or less. If it is less than 0.1 part by mass, the effect of suppressing polyenization of the polarizing element in a high-temperature environment may not be sufficient. On the other hand, if it exceeds 400 parts by mass, the first compound may precipitate after the polarizing plate is produced, resulting in an increase in haze.
- the content of the second compound is preferably 1 part by mass or more and 60 parts by mass or less, more preferably 1 part by mass or more, with respect to 100 parts by mass of the PVA-based resin. .5 parts by mass or more and 50 parts by mass or less, more preferably 2 parts by mass or more and 45 parts by mass or less. If it is less than 1 part by mass, the effect of improving water resistance may not be sufficient. On the other hand, if it exceeds 60 parts by mass, the liquid preparation stability of the adhesive may deteriorate.
- the content of the dialdehyde, which is the second compound is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, relative to 1 part by mass of the urea-based compound, which is the first compound, More preferably, it is 10 parts by mass or less, and although the lower limit is not limited, it is, for example, 0.03 parts by mass or more.
- the content ratio of the urea-based compound and the dialdehyde in the adhesive is within the above range, it becomes easy to achieve both the effect of improving the high-temperature durability due to the urea-based compound and the effect of improving the adhesiveness due to the dialdehyde.
- the water resistance improvement effect is obtained due to the adhesiveness improvement effect of the dialdehyde. If the dialdehyde content exceeds 20 parts by mass with respect to 1 part by mass of the urea-based compound, the urea-based compound may not sufficiently exhibit the effect of improving high-temperature durability. It can be considered that the content ratio of the urea-based compound and dialdehyde in the adhesive is the same as the content ratio of the urea-based compound and dialdehyde in the adhesive layer.
- the content of the dicarboxylic acid, which is the third compound is preferably 0.001 parts by mass or more and 100 parts by mass or less, preferably 0.01 part by mass, relative to 1 part by mass of the dialdehyde, which is the second compound. It is more than 80 parts by mass and less than 80 parts by mass. If it is less than 0.001 part by mass, the effect of improving the pot life may not be sufficient. On the other hand, if it exceeds 100 parts by mass, the third compound may precipitate after the polarizing plate is produced.
- the polarizing element to be bonded contains the first compound, the second compound, and the third compound.
- the amounts of these compounds contained in the adhesive may be appropriately adjusted depending on whether or not they are contained.
- the adhesive layer on one side of the adhesive layers on both sides of the polarizing element contains the first compound, the second compound, and the third compound. It may be a layer containing a compound, but it is preferable that both adhesive layers are layers containing a first compound, a second compound and a third compound.
- polarizing plates having a transparent protective film on only one side of the polarizing element have been developed. Also in this configuration, the transparent protective film is laminated via the adhesive layer containing the first compound, the second compound and the third compound.
- a method for producing such a polarizing plate having a transparent protective film only on one side of the polarizing element first, a polarizing plate is produced by laminating transparent protective films on both sides via an adhesive layer, and then one transparent protective film is prepared. can be considered.
- only one of the adhesive layers may contain the first compound, the second compound and the third compound, but both adhesive layers may contain the first compound.
- the adhesive layer on the side of the film that is not peeled preferably contains the first compound, the second compound and the third compound.
- water-based adhesive As the water-based adhesive, any suitable water-based adhesive may be employed, but preferably a water-based adhesive containing PVA-based resin (PVA-based adhesive) is used.
- the average degree of polymerization of the PVA-based resin contained in the water-based adhesive is preferably 100 or more and 5500 or less, more preferably 1000 or more and 4500 or less, from the viewpoint of adhesiveness.
- the average degree of saponification is preferably 85 mol % or more and 100 mol % or less, more preferably 90 mol % or more and 100 mol % or less, from the viewpoint of adhesion.
- the PVA-based resin contained in the water-based adhesive one containing an acetoacetyl group is preferable, because it has excellent adhesion between the PVA-based resin layer and the protective film and is excellent in durability.
- An acetoacetyl group-containing PVA-based resin can be obtained, for example, by reacting a PVA-based resin with diketene by any method.
- the acetoacetyl group modification degree of the acetoacetyl group-containing PVA resin is typically 0.1 mol % or more, preferably 0.1 mol % or more and 20 mol % or less.
- the resin concentration of the water-based adhesive is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less.
- the second compound, the dialdehyde can act as a cross-linking agent.
- the water-based adhesive can also contain a cross-linking agent other than the second compound.
- a known cross-linking agent can be used as the cross-linking agent.
- Examples of cross-linking agents include water-soluble epoxy compounds and isocyanates.
- the crosslinking agent is preferably either glyoxylate or methylolmelamine, more preferably glyoxylate.
- the water-based adhesive can also contain organic solvents.
- the organic solvent is preferably alcohols because it is miscible with water, and among alcohols, methanol or ethanol is more preferable.
- the concentration of methanol in the water-based adhesive is preferably 10% by mass or more and 70% by mass or less, more preferably 15% by mass or more and 60% by mass or less, and still more preferably 20% by mass or more and 60% by mass or less.
- concentration of methanol is 10% by mass or more, it becomes easier to suppress polyene formation of the PVA-based resin in a high-temperature environment. Further, when the content of methanol is 70% by mass or less, deterioration of hue can be suppressed.
- urea derivatives have low solubility in water, but some have sufficient solubility in alcohol.
- the urea-based compound is dissolved in alcohol to prepare an alcohol solution of the urea-based compound, and then the alcohol solution of the urea-based compound is added to the PVA aqueous solution to prepare the adhesive. be.
- Active energy ray-curable adhesives are adhesives that are cured by irradiation with active energy rays such as ultraviolet rays.
- adhesives containing a polymerizable compound and a photopolymerization initiator adhesives containing a photoreactive resin , an adhesive containing a binder resin and a photoreactive cross-linking agent, and the like.
- the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers, and photocurable urethane monomers, and oligomers derived from these monomers.
- the photopolymerization initiator include compounds containing substances that generate active species such as neutral radicals, anion radicals, and cation radicals upon irradiation with active energy rays such as ultraviolet rays.
- the first compound, the second compound, and the third compound are not limited to being contained in the adhesive layer as described above, and from the viewpoint of improving the high-temperature durability of the polarizing plate, may be contained in other layers.
- a cured layer may be laminated on the opposite side of the polarizing element from the transparent protective film, from the viewpoint of improving physical strength. It may be a layer containing two compounds and a third compound.
- the thickness of the layer containing the first compound, the second compound, and the third compound is preferably 0.1 ⁇ m or more and 20 ⁇ m or less, more preferably 0.5 ⁇ m or more and 15 ⁇ m or less, and still more preferably 1 ⁇ m or more and 10 ⁇ m or less. .
- the polarizing plate of the present embodiment is used in various image display devices such as liquid crystal display devices and organic EL display devices.
- image display devices such as liquid crystal display devices and organic EL display devices.
- the transmittance is reduced in a high temperature environment. tends to decrease.
- the image display device using the polarizing plate of this embodiment even with the interlayer filling structure, it is possible to suppress the decrease in the transmittance of the polarizing plate in a high-temperature environment.
- an image display device a configuration having an image display cell, a first adhesive layer laminated on the viewer side surface of the image display cell, and a polarizing plate laminated on the viewer side surface of the first adhesive layer is exemplified. be done.
- Such an image display device may further have a second pressure-sensitive adhesive layer laminated on the viewer-side surface of the polarizing plate, and a transparent member laminated on the viewer-side surface of the second pressure-sensitive adhesive layer.
- the transparent member is arranged on the viewing side of the image display device, the polarizing plate and the image display cell are bonded together by the first adhesive layer, and the polarizing plate and the transparent member are the second adhesive layer.
- first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be simply referred to as "pressure-sensitive adhesive layer".
- the member used for bonding the polarizing plate and the image display cell and the member used for bonding the polarizing plate and the transparent member are not limited to the pressure-sensitive adhesive layer, and may be an adhesive layer. good too.
- image display cells include liquid crystal cells and organic EL cells.
- Liquid crystal cells include reflective liquid crystal cells that use external light, transmissive liquid crystal cells that use light from a light source such as a backlight, and transflective liquid crystal cells that use both external light and light from a light source. Any liquid crystal cell may be used.
- the image display device liquid crystal display device
- the image display device has a polarizing plate arranged on the opposite side of the image display cell (liquid crystal cell) from the viewing side, and a light source is further arranged. be done. It is preferable that the polarizing plate on the light source side and the liquid crystal cell are bonded together via an appropriate pressure-sensitive adhesive layer.
- any type such as VA mode, IPS mode, TN mode, STN mode, or bend orientation ( ⁇ type) can be used.
- the organic EL cell one having a light emitter (organic electroluminescence light emitter) formed by sequentially laminating a transparent electrode, an organic light emitting layer and a metal electrode on a transparent substrate is preferably used.
- the organic light-emitting layer is a laminate of various organic thin films.
- Various layer structures can be adopted, such as a laminate of an electron injection layer composed of a layer and a perylene derivative or the like, or a laminate of a hole injection layer, a light emitting layer and an electron injection layer.
- An adhesive layer is preferably used for bonding the image display cell and the polarizing plate.
- a method of bonding a polarizing plate with an adhesive layer provided on one surface of the polarizing plate to the image display cell is preferable from the viewpoint of workability and the like.
- Attachment of the pressure-sensitive adhesive layer to the polarizing plate can be performed by an appropriate method.
- a base polymer or its composition is dissolved or dispersed in a suitable solvent such as toluene or ethyl acetate alone or in a mixture to prepare a pressure-sensitive adhesive solution of 10% by mass or more and 40% by mass or less.
- a method of directly applying it on a polarizing plate by an appropriate spreading method such as a casting method or a coating method, a method of forming an adhesive layer on a separator and transferring it to the polarizing plate, and the like.
- the pressure-sensitive adhesive layer may consist of one layer or two or more layers, but preferably consists of one layer.
- the adhesive layer can be composed of an adhesive composition containing (meth)acrylic resin, rubber resin, urethane resin, ester resin, silicone resin, or polyvinyl ether resin as a main component. Among them, a pressure-sensitive adhesive composition using a (meth)acrylic resin as a base polymer, which is excellent in transparency, weather resistance, heat resistance, etc., is preferable.
- the adhesive composition may be active energy ray-curable or heat-curable.
- the (meth)acrylic resin (base polymer) used in the adhesive composition includes butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like. Polymers or copolymers containing one or more of the (meth)acrylic acid esters as monomers are preferably used.
- the base polymer is copolymerized with a polar monomer.
- Polar monomers include (meth)acrylic acid compounds, 2-hydroxypropyl (meth)acrylate compounds, hydroxyethyl (meth)acrylate compounds, (meth)acrylamide compounds, and N,N-dimethylaminoethyl (meth)acrylate compounds. , glycidyl (meth)acrylate compounds, and other monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, and the like.
- the adhesive composition may contain only the above base polymer, but usually further contains a cross-linking agent.
- a cross-linking agent a metal ion having a valence of 2 or more and forming a carboxylic acid metal salt with a carboxyl group, a polyamine compound forming an amide bond with a carboxyl group, and a carboxyl group
- examples include polyepoxy compounds or polyols that form ester bonds with and polyisocyanate compounds that form amide bonds with carboxyl groups. Among them, polyisocyanate compounds are preferred.
- the active energy ray-curable pressure-sensitive adhesive composition has the property of being cured by being irradiated with an active energy ray such as an ultraviolet ray or an electron beam. It has the property that it can be adhered to an adherend and can be cured by irradiation with active energy rays to adjust the adhesion force.
- the active energy ray-curable pressure-sensitive adhesive composition is preferably UV-curable.
- the active energy ray-curable pressure-sensitive adhesive composition further contains an active energy ray-polymerizable compound in addition to the base polymer and the cross-linking agent. If necessary, a photopolymerization initiator, a photosensitizer, etc. may be contained.
- the adhesive composition contains fine particles for imparting light scattering properties, beads (resin beads, glass beads, etc.), glass fibers, resins other than base polymers, tackifiers, fillers (metal powders and other inorganic powders). etc.), antioxidants, ultraviolet absorbers, dyes, pigments, colorants, antifoaming agents, corrosion inhibitors, photopolymerization initiators, and other additives.
- the pressure-sensitive adhesive layer can be formed by applying an organic solvent-diluted solution of the above pressure-sensitive adhesive composition onto the surface of a substrate film, an image display cell or a polarizing plate, and drying.
- the base film is generally a thermoplastic resin film, and a typical example thereof is a release-treated separate film.
- the separate film can be, for example, a film made of a resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyalate, etc., and the surface on which the pressure-sensitive adhesive layer is formed is subjected to release treatment such as silicone treatment.
- a pressure-sensitive adhesive composition may be directly applied to the release-treated surface of the separate film to form a pressure-sensitive adhesive layer, and this pressure-sensitive adhesive layer with a separate film may be laminated on the surface of the polarizer.
- a pressure-sensitive adhesive layer may be formed by directly coating the pressure-sensitive adhesive composition on the surface of the polarizing plate, and a separate film may be laminated on the outer surface of the pressure-sensitive adhesive layer.
- the bonding surface of the polarizing plate and/or the bonding surface of the pressure-sensitive adhesive layer is provided on the surface of the polarizing plate, it is preferable to subject the bonding surface of the polarizing plate and/or the bonding surface of the pressure-sensitive adhesive layer to surface activation treatment such as plasma treatment and corona treatment. Treatment is more preferred.
- a pressure-sensitive adhesive composition is applied onto the second separate film to form a pressure-sensitive adhesive layer, a separate film is laminated on the formed pressure-sensitive adhesive layer to prepare a pressure-sensitive adhesive sheet, and from this pressure-sensitive adhesive sheet the second After peeling off the separate film, the pressure-sensitive adhesive layer with the separate film may be laminated on the polarizing plate.
- the second separate film is weaker in adhesion to the pressure-sensitive adhesive layer than the separate film and easy to peel off.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, it is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 3 ⁇ m or more and 50 ⁇ m or less, and may be 20 ⁇ m or more.
- a transparent plate (window layer), a touch panel, and the like are examples of the transparent member arranged on the viewing side of the image display device.
- a transparent plate having appropriate mechanical strength and thickness is used.
- examples of such a transparent plate include a transparent resin plate such as a polyimide resin, acrylic resin, or polycarbonate resin, or a glass plate.
- a functional layer such as an antireflection layer may be laminated on the visible side of the transparent plate.
- a hard coat layer for increasing physical strength and a low moisture permeable layer for decreasing moisture permeability may be laminated.
- touch panel various types of touch panels such as resistive type, capacitive type, optical type, and ultrasonic type, and glass plates and transparent resin plates having a touch sensor function are used.
- capacitive touch panel is used as the transparent member, it is preferable to provide a transparent plate made of glass or a transparent resin plate on the viewing side of the touch panel.
- a pressure-sensitive adhesive or an active energy ray-curable adhesive is preferably used for bonding the polarizing plate and the transparent member.
- the attachment of the adhesive can be performed by any appropriate method.
- a specific attachment method includes, for example, the method of attaching the pressure-sensitive adhesive layer used in bonding the image display cell and the polarizing plate described above.
- a dam material is provided so as to surround the periphery of the image display panel for the purpose of preventing spreading of the adhesive solution before curing, and a transparent member is placed on the dam material.
- a method of injecting an adhesive solution is preferably used. After injection of the adhesive solution, alignment and defoaming are performed as necessary, and then curing is performed by irradiating active energy rays.
- Nitric acid was added to the precisely weighed polarizing element, and acid decomposition was performed using a microwave sample pretreatment device (ETHOS D) manufactured by Milestone General to obtain a solution as a measurement solution.
- the zinc ion content was calculated by quantifying the zinc concentration of the measurement solution with an ICP emission spectrometer (5110 ICP-OES) manufactured by Agilent Technologies, and calculating the zinc mass with respect to the polarizing element mass.
- the resulting aqueous solution was titrated with a 1 mol/L sodium hydroxide aqueous solution, and the boron content of the PVA-based resin film was calculated by comparing the amount of the sodium hydroxide aqueous solution required for neutralization with the calibration curve. .
- the boron content of the PVA-based resin film thus obtained was used as the boron adsorption rate of the PVA-based resin film.
- PVA solution for adhesive 50 g of a modified PVA resin containing an acetoacetyl group (manufactured by Mitsubishi Chemical Corporation: Gohsenex Z-410) is dissolved in 950 g of pure water, heated at 90° C. for 2 hours, and then cooled to room temperature to obtain a PVA solution for adhesives. Obtained.
- the polarizing plates 1 to 3 obtained above were stored at a temperature of 20° C. and a relative humidity of 30%, 35%, 40%, 45%, 50% or 55% for 72 hours. Moisture content was measured using the Karl Fischer method at 66, 69 and 72 hours of storage. Under any humidity conditions, the moisture content did not change after storage for 66 hours, 69 hours, and 72 hours. Therefore, it can be considered that the water content of the polarizing plates 1 to 3 is the same as the equilibrium water content of the 72-hour storage environment used in this experimental example.
- the water content of the polarizing plate reaches equilibrium in a certain storage environment, it can be considered that the water content of the polarizing element in the polarizing plate also reaches equilibrium in that storage environment. Also, when the water content of the polarizing element in the polarizing plate reaches equilibrium in a certain storage environment, it can be considered that the water content of the polarizing plate also reaches equilibrium in that storage environment.
- the polarizing plates 1 to 3 are stored for 72 hours at a temperature of 20°C and a relative humidity of 55% so that the water content of the polarizing plates 1 to 3 becomes an equilibrium water content of 55% at 20°C. It was adjusted.
- Table 2 shows the results obtained.
- the distance from the edge of the sample to the edge of the polarizing element is 1 mm or less: A The distance from the edge of the sample to the edge of the polarizing element is more than 1 mm and 3 mm or less: B The distance from the edge of the sample to the edge of the polarizing element is greater than 3 mm: C
- the polarizing plate containing the first compound (urea), the second compound (glyoxal), and the third compound (maleic acid) in the adhesive can be used in a high temperature environment of 105 ° C. compared to the polarizing plate without urea in the adhesive. It can be seen that the transmittance does not easily decrease even when exposed to the bottom, and the high temperature durability is excellent. Further, it can be seen that any adhesive has excellent water resistance and a sufficient pot life in terms of productivity even in the case of a polarizing plate prepared by using it after storage for 3 days.
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Abstract
Description
〔1〕 ポリビニルアルコール系樹脂層に二色性色素を吸着配向させた偏光素子と、前記偏光素子の少なくとも一方の面に積層された透明保護フィルムと、を有する偏光板であって、
前記偏光素子と前記透明保護フィルムとは、第1化合物、第2化合物、及び第3化合物を含有する接着剤から形成される接着剤層によって貼合されており、
前記第1化合物は、尿素、尿素誘導体、チオ尿素、及びチオ尿素誘導体からなる群より選択される少なくとも1種であり、
前記第2化合物は、ジアルデヒドであり、
前記第3化合物は、ジカルボン酸である、偏光板。
〔2〕 前記接着剤は、ポリビニルアルコール系樹脂を含む、〔1〕に記載の偏光板。
〔3〕 前記接着剤において、前記第3化合物の含有量が、前記ポリビニルアルコール系樹脂100質量部に対して0.01質量部以上400質量部以下である、〔2〕に記載の偏光板。
〔4〕 前記接着剤において、前記第1化合物の含有量が、前記ポリビニルアルコール系樹脂100質量部に対して0.1質量部以上400質量部以下である、〔2〕または〔3〕に記載の偏光板。
〔5〕 前記接着剤において、前記第2化合物の含有量が、前記第1化合物1質量部に対して0.03質量部以上20質量部以下である、〔2〕~〔4〕のいずれか1項に記載の偏光板。
〔6〕 前記ジアルデヒドはグリオキサールである、〔1〕~〔5〕のいずれか1項に記載の偏光板。
〔7〕 前記接着剤層は、厚みが0.01μm以上7μm以下である、〔1〕~〔6〕のいずれか1項に記載の偏光板。
〔8〕 前記偏光板は画像表示装置に用いられ、
前記画像表示装置において、前記偏光板の両面には固体層が接して設けられている、〔1〕~〔7〕のいずれか1項に記載の偏光板。
〔9〕 画像表示セルと、前記画像表示セルの視認側表面に積層された第1粘着剤層と、前記第1粘着剤層の視認側表面に積層された〔1〕~〔8〕のいずれか1項に記載の偏光板と、を有する画像表示装置。
〔10〕 前記偏光板の視認側表面に積層された第2粘着剤層と、前記第2粘着剤層の視認側表面に積層された透明部材と、をさらに有する〔9〕に記載の画像表示装置。
〔11〕 前記透明部材がガラス板又は透明樹脂板である、〔10〕に記載の画像表示装置。
〔12〕 前記透明部材がタッチパネルである、〔10〕に記載の画像表示装置。
〔13〕 第1化合物、第2化合物、及び第3化合物を含有し、
前記第1化合物は、尿素、尿素誘導体、チオ尿素、及びチオ尿素誘導体からなる群より選択される少なくとも1種であり、
前記第2化合物は、ジアルデヒドであり、
前記第3化合物は、ジカルボン酸である、接着剤。
本発明の実施形態に係る偏光板は、ポリビニルアルコール系樹脂を含む層に二色性色素を吸着配向させた偏光素子と、透明保護フィルムと、を有する。偏光素子と透明保護フィルムとは、第1化合物、第2化合物、及び第3化合物を含有する接着剤から形成される接着剤層によって貼合されている。
(a)偏光素子の含水率が、温度20℃相対湿度30%の平衡含水率以上、かつ温度20℃相対湿度70%の平衡含水率以下である。
(b)偏光板の含水率が、温度20℃相対湿度30%の平衡含水率以上、かつ温度20℃相対湿度70%の平衡含水率以下である。
ポリビニルアルコール(以下、「PVA」とも称す。)系樹脂を含む層(以下、「PVA系樹脂層」とも称す。)に二色性色素を吸着配向させた偏光素子としては、周知の偏光素子を用いることができる。偏光素子としては、PVA系樹脂フィルムを二色性色素で染色し、一軸延伸することによって得られる延伸フィルムや、基材フィルム上にPVA系樹脂を含む塗布液を塗布して形成した塗布層を有する積層フィルムを用いて、塗布層を二色性色素で染色し、積層フィルムを一軸延伸することによって得られる延伸層が挙げられる。延伸は二色性色素で染色した後に行ってもよいし、染色しながら延伸してもよいし、延伸してから染色してもよい。
第1化合物は、尿素、尿素誘導体、チオ尿素及びチオ尿素誘導体からなる群より選択される少なくとも1種である。第1化合物は、1種を単独でまたは2種以上を組み合わせて用いることができる。第1化合物には水溶性のものと難水溶性のものがあるが、どちらの第1化合物も使用することができる。難水溶性の第1化合物を水溶性接着剤に用いる場合は、接着剤層を形成後、ヘイズ上昇などが起きないように分散方法を工夫することが好ましい。
尿素誘導体は、尿素分子の4つの水素原子の少なくとも1つが、置換基に置換された化合物である。この場合、置換基に特に制限はないが、炭素原子、水素原子および酸素原子よりなる置換基であることが好ましい。
チオ尿素誘導体は、チオ尿素分子の4つの水素原子の少なくとも1つが、置換基に置換された化合物である。この場合、置換基に特に制限はないが、炭素原子、水素原子および酸素原子よりなる置換基であることが好ましい。
第2化合物は、ジアルデヒドである。ジアルデヒドとしては、例えば、グリオキサール、プロパンジアール(マロンジアルデヒド)、ブタンジアール(スクシンアルデヒド)などが挙げられる。特に、構造が簡潔で反応性に富むグリオキサールが好ましい。以下、グリオキサールについて説明する場合があるが、ジアルデヒドとしては、上述のように従来公知のものを用いることが可能であり、グリオキサールに限定するものでない。
第3化合物は、ジカルボン酸である。ジカルボン酸としては、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸、酒石酸、グルタミン酸、リンゴ酸、マレイン酸、フマル酸、イタコン酸、ムコン酸、1,4-シクロヘキサンジカルボン酸、1,4-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、2,7-ナフタレンジカルボン酸、4,4’-ビフェニルジカルボン酸、2,5-ピリジンジカルボン酸、3,5-ピリジンジカルボン酸、ジフェニルスルホンジカルボン酸、ジフェニルメタンジカルボン酸、オキサロ酢酸、メチルフマル酸、2,6-ピリジンジカルボン酸等が挙げられる。これらの中でも、クエン酸、リンゴ酸、マレイン酸又は酒石酸を用いることが好ましい。これらジカルボン酸は、1種を単独でまたは2種以上を組み合わせて用いることができる。
偏光素子の製造方法は特に限定されないが、予めロール状に巻かれたPVA系樹脂フィルムを送り出して延伸、染色、架橋等を行って作製する方法(以下、「製造方法1」とする。)やPVA系樹脂を含む塗布液を基材フィルム上に塗布して塗布層であるPVA系樹脂層を形成し、得られた積層体を延伸する工程を含む方法(以下、「製造方法2」とする。)が典型的である。
架橋工程は1回だけ実施されてもよく、必要に応じて複数回実施されてもよい。
本実施形態において用いられる透明保護フィルム(以下、単に「保護フィルム」とも称す。)は、偏光素子の少なくとも片面に接着剤層を介して貼り合わされる。この透明保護フィルムは偏光素子の片面又は両面に貼り合わされるが、両面に貼り合わされていることが好ましい。
偏光素子に保護フィルムを貼合するための接着剤層は、以下の接着剤から形成される。
接着剤は、第1化合物、第2化合物、及び第3化合物を含有する。接着剤は、水系接着剤、溶剤系接着剤、活性エネルギー線硬化型接着剤等であってよく限定されないが、水系接着剤であることが好ましく、PVA系樹脂を含むことが好ましい。第1化合物、第2化合物、及び第3化合物を含有する接着剤を用いて偏光素子と保護フィルムを貼合するための接着剤層を形成することにより、偏光板の高温環境下での透過率の低下を抑制することができる。また、第2化合物及び第3化合物を有する接着剤を用いることにより、生産上充分なポットライフを有する接着剤とすることができる。本発明に係る接着剤の用途は限定されることはなく、光学素子において好適に用いられ、例えば偏光素子と保護フィルムを貼合する用途に好適に用いられる。
水系接着剤としては、任意の適切な水系接着剤が採用され得るが、好ましくはPVA系樹脂を含む水系接着剤(PVA系接着剤)が用いられる。水系接着剤に含まれるPVA系樹脂の平均重合度は、接着性の点から、好ましくは100以上5500以下、さらに好ましくは1000以上4500以下である。平均鹸化度は、接着性の点から、好ましくは85モル%以上100モル%以下であり、さらに好ましくは90モル%以上100モル%以下である。
活性エネルギー線硬化型接着剤は、紫外線等の活性エネルギー線を照射することによって硬化する接着剤であり、例えば重合性化合物及び光重合性開始剤を含む接着剤、光反応性樹脂を含む接着剤、バインダー樹脂及び光反応性架橋剤を含む接着剤等を挙げることができる。重合性化合物としては、光硬化性エポキシ系モノマー、光硬化性アクリル系モノマー、光硬化性ウレタン系モノマー等の光重合性モノマー、及びこれらモノマーに由来するオリゴマー等を挙げることができる。上記光重合開始剤としては、紫外線等の活性エネルギー線を照射して中性ラジカル、アニオンラジカル、カチオンラジカルといった活性種を発生する物質を含む化合物を挙げることができる。
第1の化合物、第2の化合物及び第3化合物は、上記のように接着剤層に含有される場合に限定されることはなく、偏光板の高温耐久性向上の観点から、接着剤層以外の他の層に含有されていてもよい。片面にのみ透明保護フィルムを有する偏光板において、物理強度の向上の観点から、偏光素子の透明保護フィルムとは反対の面に硬化層を積層してもよく、かかる硬化層が第1化合物、第2化合物及び第3化合物の含有層であってもよい。
本実施形態の偏光板は、液晶表示装置や有機EL表示装置等の各種画像表示装置に用いられる。画像表示装置について、偏光板の両面が空気層以外の層、具体的には粘着剤層等の固体層が接するように構成されている層間充填構成である場合には、高温環境下で透過率が低下しやすい。本実施形態の偏光板を用いた画像表示装置においては、層間充填構成であっても、高温環境下での偏光板の透過率の低下を抑制することができる。画像表示装置としては、画像表示セルと、画像表示セルの視認側表面に積層された第1粘着剤層と、第1粘着剤層の視認側表面に積層された偏光板とを有する構成が例示される。かかる画像表示装置は、偏光板の視認側表面に積層された第2粘着剤層と、第2粘着剤層の視認側表面に積層された透明部材とをさらに有してもよい。特に、本実施形態の偏光板は、画像表示装置の視認側に透明部材が配置され、偏光板と画像表示セルとが第1粘着剤層により貼り合わされ、偏光板と透明部材とが第2粘着剤層により貼り合わせられた層間充填構成を有する画像表示装置に好適に用いられる。本明細書においては、第1粘着剤層及び第2粘着剤層のいずれか一方又は両者を、単に「粘着剤層」と称する場合がある。なお、偏光板と画像表示セルとの貼り合わせに用いられる部材、及び偏光板と透明部材との貼り合わせに用いられる部材としては、粘着剤層に限定されることはなく接着剤層であってもよい。
画像表示セルとしては、液晶セルや有機ELセルが挙げられる。液晶セルとしては、外光を利用する反射型液晶セル、バックライト等の光源からの光を利用する透過型液晶セル、外部からの光と光源からの光の両者を利用する半透過半反射型液晶セルのいずれを用いてもよい。液晶セルが光源からの光を利用するものである場合、画像表示装置(液晶表示装置)は、画像表示セル(液晶セル)の視認側と反対側にも偏光板が配置され、さらに光源が配置される。光源側の偏光板と液晶セルとは、適宜の粘着剤層を介して貼り合せられていることが好ましい。液晶セルの駆動方式としては、例えばVAモード、IPSモード、TNモード、STNモードやベンド配向(π型)等の任意なタイプのものを用い得る。
有機発光層は、種々の有機薄膜の積層体であり、例えばトリフェニルアミン誘導体等からなる正孔注入層と、アントラセン等の蛍光性の有機固体からなる発光層との積層体や、これらの発光層とペリレン誘導体等からなる電子注入層の積層体、あるいは正孔注入層、発光層及び電子注入層の積層体等、種々の層構成が採用され得る。
画像表示セルと偏光板との貼り合せには、粘着剤層(粘着シート)が好適に用いられる。中でも、偏光板の一方の面に粘着剤層が付設された粘着剤層付き偏光板を画像表示セルと貼り合わせる方法が、作業性等の観点から好ましい。偏光板への粘着剤層の付設は、適宜な方式で行い得る。その例としては、トルエンや酢酸エチル等の適宜な溶剤の単独物又は混合物からなる溶剤にベースポリマー又はその組成物を溶解あるいは分散させた10質量%以上40質量%以下の粘着剤溶液を調製し、それを流延方式や塗工方式等の適宜な展開方式で偏光板上に直接付設する方式、セパレータ上に粘着剤層を形成してそれを偏光板に移着する方式等が挙げられる。
粘着剤層は、1層又は2層以上からなってもよいが、好ましくは1層からなる。粘着剤層は、(メタ)アクリル系樹脂、ゴム系樹脂、ウレタン系樹脂、エステル系樹脂、シリコーン系樹脂、ポリビニルエーテル系樹脂を主成分とする粘着剤組成物から構成することができる。中でも、透明性、耐候性、耐熱性等に優れる(メタ)アクリル系樹脂をベースポリマーとする粘着剤組成物が好適である。粘着剤組成物は、活性エネルギー線硬化型又は熱硬化型であってもよい。
画像表示装置の視認側に配置される透明部材としては、透明板(ウインドウ層)やタッチパネル等が挙げられる。透明板としては、適宜の機械強度及び厚みを有する透明板が用いられる。このような透明板としては、例えばポリイミド系樹脂、アクリル系樹脂やポリカーボネート系樹脂のような透明樹脂板、あるいはガラス板等が挙げられる。透明板の視認側には反射防止層などの機能層が積層されていても構わない。また、透明板が透明樹脂板の場合は、物理強度を上げるためにハードコート層や、透湿度を下げるために低透湿層が積層されていても構わない。タッチパネルとしては、抵抗膜方式、静電容量方式、光学方式、超音波方式等の各種タッチパネルや、タッチセンサー機能を備えるガラス板や透明樹脂板等が用いられる。透明部材として静電容量方式のタッチパネルが用いられる場合、タッチパネルよりもさらに視認側に、ガラス又は透明樹脂板からなる透明板が設けられることが好ましい。
偏光板と透明部材との貼り合せには、粘着剤又は活性エネルギー線硬化型接着剤が好適に用いられる。粘着剤が用いられる場合、粘着剤の付設は適宜な方式で行い得る。具体的な付設方法としては、例えば、前述の画像表示セルと偏光板の貼り合せで用いた粘着剤層の付設方法が挙げられる。
従って、本発明は以下の実施例に限定され制限されるものではない。
株式会社ニコン製のデジタルマイクロメーター“MH-15M”を用いて測定した。
積分球付き分光光度計〔日本分光株式会社製の「V7100」、2度視野;C光源〕を用いて測定した。
偏光素子0.2gを1.9質量%のマンニトール水溶液200gに溶解させた。次いで、得られた水溶液を1モル/Lの水酸化ナトリウム水溶液で滴定し、中和に要した水酸化ナトリウム水溶液の量と検量線との比較により、偏光素子のホウ素含有率を算出した。
精秤した偏光素子に硝酸を加え、マイルストーンゼネラル製マイクロ波試料前処理装置(ETHOS D)で酸分解して得られた溶液を測定液とした。亜鉛イオン含有率は、アジレントテクノロジー製ICP発光分光分析装置(5110 ICP-OES)で測定液の亜鉛濃度を定量し、偏光素子質量に対する亜鉛質量で算出した。
100mm四方に裁断したPVA系樹脂フィルムを、30℃の純水に60秒間浸漬し、その後、ホウ酸5部を含む60℃の水溶液に120秒浸漬させた。ホウ酸水溶液から取り出したPVA系樹脂フィルムを80℃オーブンで11分間乾燥した。23℃55%%RHの環境で24時間調湿し、ホウ素含有PVAフィルムを得た。こうして得られたホウ素含有PVA系樹脂フィルム0.2gを、1.9質量%のマンニトール水溶液200gに溶解させた。次いで、得られた水溶液を1モル/Lの水酸化ナトリウム水溶液で滴定し、中和に要した水酸化ナトリウム水溶液の量と検量線との比較により、PVA系樹脂フィルムのホウ素含有率を算出した。こうして得られたPVA系樹脂フィルムのホウ素含有率を、PVA系樹脂フィルムのホウ素吸着率として用いた。
ホウ素吸着率が5.71質量%である厚さ30μmのポリビニルアルコール系樹脂フィルムを、21.5℃の純水に79秒浸漬した後(膨潤処理)、ヨウ化カリウム/ホウ酸/水の質量比が2/2/100であり、ヨウ素を1.0mM含む水溶液に23℃で151秒浸漬した(染色工程)。その後、ヨウ化カリウム/ホウ酸/水の質量比が2.5/4/100の水溶液に68.5℃で76秒浸漬した(第1架橋工程)。引き続き、ヨウ化カリウム/ホウ酸/塩化亜鉛/水の質量比が3/5.5/0.6/100の水溶液に45℃で11秒浸漬した(第2架橋工程、金属イオン処理工程)。その後、洗浄浴に浸漬させて洗浄し(洗浄工程)、38℃で乾燥して(乾燥工程)、ポリビニルアルコールにヨウ素が吸着配向された厚み12μmの偏光素子を得た。延伸は、主に、染色工程および第1架橋工程の工程で行い、トータル延伸倍率は5.85倍であった。得られた偏光素子の亜鉛イオン含有率は0.17質量%、ホウ素含有率は4.62質量%であった。
アセトアセチル基を含有する変性PVA系樹脂(三菱ケミカル株式会社製:ゴーセネックスZ-410)50gを950gの純水に溶解し、90℃で2時間加熱後常温に冷却し、接着剤用PVA溶液を得た。
PVA、尿素、グリオキサール、及びマレイン酸の含有量が表1に示す含有量になるように、PVA溶液、尿素、市販のグリオキサール40質量%溶液、マレイン酸、及び純水を配合し、接着剤1~3を調製した。尚、接着剤は、調製してから3日後に使用した。
市販のセルロースアシレートフィルムTJ40UL(富士フイルム株式会社製:膜厚40μm)を、55℃に保った1.5mol/LのNaOH水溶液(鹸化液)に2分間浸漬し、フィルムを水洗した。その後、フィルムを25℃の0.05mol/Lの硫酸水溶液に30秒浸漬し、更に水洗浴を30秒流水下に通して、フィルムを中性の状態にした。そして、エアナイフによる水切りを3回繰り返した。水を落とした後、フィルムを70℃の乾燥ゾーンに15秒間滞留させて乾燥し、鹸化処理したフィルムを作製した。
上記で調製し、3日間保存した接着剤1を介して、偏光素子1の両面に鹸化処理したセルロースアシレートフィルムを、ロール貼合機を用いて貼合した後に、80℃で5分間乾燥し、偏光板1を得た。接着剤層は、乾燥後の厚みが両面共に50nmになるように調整した。
上記で得られた偏光板1~3を温度20℃で、相対湿度30%、35%、40%、45%、50%又は55%の条件で、72時間保管した。保管66時間、69時間及び72時間でカールフィッシャー法を用いて、含水率を測定した。何れの湿度条件でも、保管66時間、69時間、72時間で含水率の値が変わらなかった。したがって、偏光板1~3の含水率は、本実験例で用いられる72時間の保管環境の平衡含水率と同じになっているとみなすことができる。偏光板の含水率が、ある保管環境で平衡に達したときは、偏光板中の偏光素子の含水率も同様に、その保管環境で平衡に達したとみなすことができる。また、偏光板中の偏光素子の含水率が、ある保管環境で平衡に達したときは、偏光板の含水率も同様に、その保管環境で平衡に達したとみなすことができる。
偏光板1~3の含水率が20℃で55%の環境の平衡含水率となるように温度20℃で相対湿度55%の条件で72時間保管して、偏光板1~3の含水率を調整した。
(評価用サンプルの作製)
含水率を調整した偏光板1~3について、その両面にアクリル系粘着剤(リンテック株式会社製、品番:#7)を形成し、さらに吸収軸が長辺と平行になるように、50mm×100mmの大きさに裁断して、それぞれの粘着剤表面に無アルカリガラス(コーニング社製「EAGLE XG」)を貼合することによって評価サンプルを作製した。
偏光板1~3の評価サンプルに、温度50℃、圧力5kgf/cm2(490.3kPa)で1時間オートクレーブ処理を施した後、温度23℃、相対湿度55%の環境下で24時間放置した。その後、偏光板1~3の評価サンプルについて、透過率を測定し(初期値)、温度105℃の加熱環境下に保管し、100~200時間まで50時間おきに透過率を測定した。初期値に対し透過率低下が5%以上に達した時間を基に以下の基準で評価を行った。得られた結果を表2に示す。
200時間経過した時点で透過率の低下が5%以下のもの :A
150~200時間で透過率の低下が5%以上に達したもの:B
100~150時間で透過率の低下が5%以上に達したもの:C
100時間経過した時点で透過率の低下が5%以上のもの :D
本実施例の耐水性試験は特開2009-025728号公報[0060]に記載の耐水性試験に準じて行った。上記で作製した偏光板の片面にアクリル系粘着剤(リンテック株式会社製、品番:#7)を形成し、さらに偏光板の吸収軸(延伸方向)を長辺として50mm×20mmの大きさに短冊状に裁断し、長辺方向の寸法を正確に測定した。ここで、評価サンプルは、偏光素子に吸着されたヨウ素に起因して、全面にわたって均一に特有の色を呈している。
このサンプルの1短辺側を、把持具で把持し、長手方向の8割ほどを60℃の水槽に浸漬し、4時間保持した。その後、サンプルを水槽から取り出し、水分を拭き取った。温水の浸漬により偏光板の偏光素子は収縮する。この偏光素子の収縮の程度をサンプル短辺の中央における、サンプルの端(保護フィルムの端)から収縮した偏光素子の端までの距離を測定することにより、以下の基準で、3段階評価した。結果を表2に示す。
サンプルの端から偏光素子の端までの距離が1mm以下のもの :A
サンプルの端から偏光素子の端までの距離が1mmを超え3mm以下のもの:B
サンプルの端から偏光素子の端までの距離が3mmより大きいもの :C
Claims (13)
- ポリビニルアルコール系樹脂層に二色性色素を吸着配向させた偏光素子と、前記偏光素子の少なくとも一方の面に積層された透明保護フィルムと、を有する偏光板であって、
前記偏光素子と前記透明保護フィルムとは、第1化合物、第2化合物、及び第3化合物を含有する接着剤から形成される接着剤層によって貼合されており、
前記第1化合物は、尿素、尿素誘導体、チオ尿素、及びチオ尿素誘導体からなる群より選択される少なくとも1種であり、
前記第2化合物は、ジアルデヒドであり、
前記第3化合物は、ジカルボン酸である、偏光板。 - 前記接着剤は、ポリビニルアルコール系樹脂を含む、請求項1に記載の偏光板。
- 前記接着剤において、前記第3化合物の含有量が、前記ポリビニルアルコール系樹脂100質量部に対して0.01質量部以上400質量部以下である、請求項2に記載の偏光板。
- 前記接着剤において、前記第1化合物の含有量が、前記ポリビニルアルコール系樹脂100質量部に対して0.1質量部以上400質量部以下である、請求項2または3に記載の偏光板。
- 前記接着剤において、前記第2化合物の含有量が、前記第1化合物1質量部に対して0.03質量部以上20質量部以下である、請求項2~4のいずれか1項に記載の偏光板。
- 前記ジアルデヒドはグリオキサールである、請求項1~5のいずれか1項に記載の偏光板。
- 前記接着剤層は、厚みが0.01μm以上7μm以下である、請求項1~6のいずれか1項に記載の偏光板。
- 前記偏光板は画像表示装置に用いられ、
前記画像表示装置において、前記偏光板の両面には固体層が接して設けられている、請求項1~7のいずれか1項に記載の偏光板。 - 画像表示セルと、前記画像表示セルの視認側表面に積層された第1粘着剤層と、前記第1粘着剤層の視認側表面に積層された請求項1~8のいずれか1項に記載の偏光板と、を有する画像表示装置。
- 前記偏光板の視認側表面に積層された第2粘着剤層と、前記第2粘着剤層の視認側表面に積層された透明部材と、をさらに有する請求項9に記載の画像表示装置。
- 前記透明部材がガラス板又は透明樹脂板である、請求項10に記載の画像表示装置。
- 前記透明部材がタッチパネルである、請求項10に記載の画像表示装置。
- 第1化合物、第2化合物、及び第3化合物を含有し、
前記第1化合物は、尿素、尿素誘導体、チオ尿素、及びチオ尿素誘導体からなる群より選択される少なくとも1種であり、
前記第2化合物は、ジアルデヒドであり、
前記第3化合物は、ジカルボン酸である、接着剤。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010276673A (ja) * | 2009-05-26 | 2010-12-09 | Sanritsutsu:Kk | 偏光板、及び、その製造方法、並びに、偏光板製造用接着剤 |
| JP2020204641A (ja) * | 2019-06-14 | 2020-12-24 | 住友化学株式会社 | 偏光板及び偏光板の製造方法並びにその偏光板を用いた画像表示装置 |
| JP2021081716A (ja) * | 2019-11-15 | 2021-05-27 | 住友化学株式会社 | 偏光板並びにその偏光板を用いた画像表示装置 |
| JP2022060763A (ja) * | 2020-10-05 | 2022-04-15 | 住友化学株式会社 | 偏光板及び画像表示装置 |
| JP2022060766A (ja) * | 2020-10-05 | 2022-04-15 | 住友化学株式会社 | 偏光板及び画像表示装置 |
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| JP7853770B2 (ja) | 2026-04-30 |
| KR20240023418A (ko) | 2024-02-21 |
| TW202309566A (zh) | 2023-03-01 |
| CN117597614A (zh) | 2024-02-23 |
| JP2023012249A (ja) | 2023-01-25 |
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