Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
• • 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
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
• • 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
• • 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
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
  • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/87—Passivation; Containers; Encapsulations
  • H10K59/871—Self-supporting sealing arrangements
  • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

• the present invention relates to a polarizing plate and an image display device.
• Liquid crystal displays are widely used not only for liquid crystal televisions, but also for mobile devices 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 bonded to both sides of the liquid crystal cell with an adhesive, and the display is performed by controlling the light from the backlight with the liquid crystal panel.
• organic EL display devices like liquid crystal display devices, have been widely used in mobile applications such as televisions and mobile phones, and in-vehicle applications such as car navigation systems.
• a circular polarizing plate (polarizing element and ⁇ / 4 plate) is formed on the visible side surface of the image display panel. (Laminated body containing) may be arranged.
• polarizing plates are increasingly mounted on vehicles as members of image display devices such as liquid crystal displays and organic EL display devices.
• Polarizers used in in-vehicle image display devices are often exposed to high-temperature environments compared to mobile applications such as televisions and mobile phones, so their characteristic changes at higher temperatures are smaller (high-temperature durability). Gender) is required.
• a front plate such as a transparent resin plate or a glass plate is provided on the visual side of the image display panel.
• a front plate such as a transparent resin plate or a glass plate is provided on the visual side of the image display panel.
• interlayer filler a layer other than the air layer and is usually referred to as a solid layer (hereinafter, referred to as "interlayer filler”.
• interlayer filling structure The movement to adopt the structure of filling with (.) (Hereinafter, may be referred to as "interlayer filling structure") is widespread.
• the interlayer filler is preferably a material having a refractive index close to that of the polarizing plate or the transparent member.
• an adhesive or a UV curable adhesive is used for the purpose of suppressing deterioration of visibility due to reflection at the interface and adhesively fixing between the members (see, for example, Patent Document 1).
• the interlayer filling configuration is widely used in mobile applications such as mobile phones, which are often used outdoors.
• a front transparent plate is arranged 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.
• Patent Document 2 as a solution to the problem, the amount of water per unit area of the polarizing plate is set to a predetermined amount or less, and the saturated water absorption amount of the transparent protective film adjacent to the polarizing element is set to a predetermined amount or less to increase the transmittance. A method of suppressing the decrease has been proposed.
• An object of the present invention is to provide a novel polarizing plate capable of suppressing a decrease in transmittance even when exposed to a high temperature environment, and an image display device using the polarizing plate.
• the present invention provides a polarizing plate and an image display device exemplified below.
• a polarizing element in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin layer, a first transparent protective film laminated on one surface of the polarizing element, and laminated on the other surface of the polarizing element.
• a polarizing plate having a second transparent protective film, The polarizing element and the first transparent protective film are bonded to each other by a first adhesive layer formed from a first adhesive containing the first compound.
• the polarizing element and the second transparent protective film are bonded to each other by a second adhesive layer formed of a second adhesive containing the second 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 polarizing plate, which is a compound having a nitroxy radical or a nitroxide group. [2] The polarizing plate according to [1], wherein the second compound is an N-oxyl compound. [3] The polarizing plate according to [1] or [2], wherein the first compound is at least one urea-based compound selected from the group consisting of a urea derivative and a thiourea derivative.
• the polarizing plate is used in an image display device, and the polarizing plate is used in an image display device.
• An image display device comprising the polarizing plate according to item 1.
• the transparent member is a touch panel.
• a polarizing plate having improved high temperature durability and suppressed decrease in transmittance even when used in an image display device having an interlayer filling configuration and exposed to a high temperature environment. Is possible. Further, 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.
• the polarizing plate according to the present embodiment includes a polarizing element in which a dichroic dye is adsorbed and oriented on a layer containing a polyvinyl alcohol-based resin, a first transparent protective film laminated on one surface of the polarizing element, and a polarizing element. It has a second transparent protective film laminated on the other surface.
• the polarizing element and the first transparent protective film are bonded by a first adhesive layer formed from a first adhesive containing the first compound.
• the polarizing element and the second transparent protective film are bonded by a second adhesive layer formed of a second adhesive containing the second 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 nitroxy radical or a compound having a nitroxide group.
• a polarizing plate having excellent high temperature durability for example, a polarizing plate in which a decrease in transmittance is suppressed even when the polarizing plate alone is left in an environment of a temperature of 95 ° C. for 1000 hours is known.
• a polarizing plate in which a decrease in transmittance is suppressed even when the polarizing plate alone is left in an environment of a temperature of 95 ° C. for 1000 hours is known.
• a significant decrease in transmittance may be observed in the central portion of the polarizing plate surface.
• the water content of the polarizing plate or the polarizing element is out of a specific range, a significant decrease in the transmittance or the degree of polarization may be observed in the central portion of the polarizing plate surface.
• the significant decrease in the transmittance of the polarizing plate in a high temperature environment is due to the interlayer filling configuration 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 a front plate. It is considered that this is a problem that is particularly likely to occur when the image display device that adopts the above 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 configuration, and can suppress a decrease in transmittance even when exposed to a high temperature environment of, for example, a temperature of 105 ° C. It is presumed that such an effect is due to the fact that the polyene formation of the polyvinyl alcohol constituting the polarizing element is suppressed by the synergistic action of the first compound and the second compound present in the adhesive layer. Such an effect is not limited to the case where the water content of the polarizing plate or the polarizing element is in a specific range, and the water content of the polarizing plate or the polarizing element is low or high.
• the polarizing plate according to the present embodiment can have, for example, at least one of the following features (a) and (b).
• (A) The water content of the polarizing element is equal to or higher than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 30%, and equal to or lower than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 80%.
• (B) 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 equal to or lower than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 80%.
• the polarizing plate according to the present embodiment has high temperature durability with respect to the above-mentioned characteristics (a) or (b) even when it has further limited characteristics such as the following (a1) or (b1). The effect of being able to improve is achieved.
• A1 The water content of the polarizing element is greater than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 45% or 50%, and equal to or less than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 80% or 70%.
• B1 The water content of the polarizing plate is greater than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 45% or 50%, and equal to or less than the equilibrium water content at a temperature of 20 ° C.
• the polarizing plate does not have a step of adjusting the water content, it is likely that the polarizing plate usually has the above-mentioned characteristics (a) and (b).
• the step of adjusting the water content may be included or the step of adjusting the water content may not be provided so as to have at least one of the above-mentioned characteristics (a) and (b). May be good.
• polarizing element As a polarizing element in which a dichroic dye is adsorbed and oriented on a layer containing a polyvinyl alcohol (hereinafter, also referred to as “PVA”) resin (hereinafter, also referred to as a “PVA-based resin layer”), a well-known polarizing element is used. Can be used.
• the 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 applying a coating liquid containing a PVA-based resin on a base film.
• Examples thereof include a stretched layer obtained by dyeing a coating layer with a dichroic dye using the laminated film having the film and uniaxially stretching the laminated film. Stretching may be performed after dyeing with a dichroic dye, stretching while dyeing, or stretching and then dyeing.
• the PVA-based resin is obtained by saponifying a polyvinyl acetate-based resin.
• the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and a copolymer of vinyl acetate and another monomer copolymerizable therewith.
• examples of other copolymerizable monomers include unsaturated carboxylic acids, olefins such as ethylene, vinyl ethers, unsaturated sulfonic acids and the like.
• the degree of saponification of the PVA-based resin is preferably about 85 mol% or more, more preferably about 90 mol% or more, still more preferably about 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, and may be, for example, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, etc. modified with aldehydes.
• 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 further 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 polyene formation of the PVA-based resin on the deterioration of optical characteristics in a high temperature environment.
• the thickness of the polarizing element is 3 ⁇ m or more, it becomes easy to configure the structure to achieve the desired optical characteristics.
• the polarizing element preferably contains a first compound and a second compound.
• the polarizing element and the first transparent protective film are bonded by a first adhesive layer formed of a first adhesive containing the first compound, and the polarizing element and the second transparent protective film are attached to each other. Since it is bonded by the second adhesive layer formed from the second adhesive containing the two compounds, a part of the first compound transferred from the first adhesive layer and a part of the first compound transferred from the second adhesive layer. It is presumed that a part of the second compound is contained in the polarizing element.
• the first compound and the second compound in the polarizing element may include those added in the process of manufacturing 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 first adhesive layer containing the first compound and the second adhesive layer containing the second compound, it is possible to suppress a decrease in the degree of polarization even when the polarizing plate is exposed to a high temperature environment. ..
• cross loss light loss
• the degree of polarization is less likely to decrease, so that it becomes easier to suppress cross omission. It is presumed that the synergistic effect of the first compound and the second compound contained in the polarizing element suppresses the polyene formation of the PVA-based resin.
• a method of immersing the PVA-based resin layer in the treatment solvent containing the first compound and / or the second compound, or a method of immersing the treatment solvent in the PVA-based treatment solvent examples thereof include a method of spraying, flowing down or dropping onto the resin layer.
• a method of immersing the PVA-based resin layer in a treatment solvent containing both the first compound and the second compound is preferably used.
• Specific examples of the first compound and the second compound include those exemplified as those contained in the adhesive described later.
• the step of immersing the PVA-based resin layer in the treatment solvent containing the first compound and the second compound may be performed at the same time as the steps of swelling, stretching, dyeing, crosslinking, washing and the like in the method for manufacturing a polarizing element described later. It may be provided separately from these steps.
• the step of incorporating the first compound and the second compound in the PVA-based resin layer is preferably performed after dyeing the PVA-based resin layer with iodine, and more preferably performed at the same time as the cross-linking step after dyeing. According to such a method, the hue change is small and the influence on the optical characteristics of the polarizing element can be reduced.
• both the addition at the time of manufacturing the polarizing element and the addition to the adhesive may be performed. Further, at the time of manufacturing the polarizing element, one of the first compound and the second compound may be contained and both may be contained in the adhesive.
• the first compound is at least one selected from the group consisting of urea, urea derivatives, thiourea and thiourea derivatives.
• the first compound may be used alone or in combination of two or more.
• the first compound includes a water-soluble compound and a poorly water-soluble compound, and either of the first compounds can be used.
• the poorly water-soluble first compound is used as a water-soluble adhesive, it is preferable to devise a dispersion method so that haze does not increase after the adhesive layer is formed.
• a urea derivative is a compound in which at least one of the four hydrogen atoms of a urea molecule is substituted with a substituent.
• the substituent is not particularly limited, but is preferably a substituent composed of a carbon atom, a hydrogen atom and an oxygen atom.
• urea derivatives include methyl urea, ethyl urea, propyl urea, butyl urea, isobutyl urea, N-octadecyl urea, 2-hydroxyethyl urea, hydroxyurea, acetylurea, allylurea, and 2-propynyl as monosubstituted ureas.
• examples thereof include urea, cyclohexyl urea, phenylurea, 3-hydroxyphenylurea, (4-methoxyphenyl) urea, benzylurea, benzoylurea, o-tolylurea and p-tolylurea.
• urea As 4-substituted urea, tetramethylurea, 1,1,3,3-tetraethylurea, 1,1,3,3-tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, 1,3-dimethyl- Examples thereof include 2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone.
• a thiourea derivative is a compound in which at least one of the four hydrogen atoms of a thiourea molecule is substituted with a substituent.
• the substituent is not particularly limited, but is preferably a substituent composed of a carbon atom, a hydrogen atom and an oxygen atom.
• thiourea derivative as one-substituted thiourea, N-methylthiourea, ethylthiourea, propylthiourea, isopropylthiourea, 1-butylthiourea, cyclohexylthiourea, N-acetylthiourea, N-allylthiourea, (2).
• 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, Examples thereof include 1-benzyl-3-phenylthiourea, 1-methyl-3-phenylthiourea, N-allyl-N'-(2-hydroxyethyl) thiourea and ethylenethiourea.
• Examples of the 3-substituted thiourea include trimethylthiourea, and examples of the 4-substituted thiourea include tetramethylthiourea and 1,1,3,3-tetraethylthiourea.
• a urea derivative or a thiourea derivative is preferable, and a urea derivative is more preferable.
• the urea derivatives mono-substituted urea or di-substituted urea is preferable, and mono-substituted urea is more preferable.
• the bi-substituted urea includes 1,1-substituted urea and 1,3-substituted urea, but 1,3-substituted urea is more preferable.
• the second compound is a nitroxy radical or a compound having a nitroxide group.
• the second compound is an N-oxyl compound (a compound having CN (-C) -O .
• a functional group O. is an oxy radical
• Examples of the N-oxyl compound include compounds having an organic group having the following structure.
• the nitroxy radical or the compound having a nitroxide group may be used alone or in combination of two or more.
• R 1 represents an oxy radical
• R 2 to R 5 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
• n represents 0 or 1.
• the left side of the dotted line indicates an arbitrary organic group. Any organic group contains a hydrogen atom.
• Examples of the above-mentioned compound having an organic group include compounds represented by the following general formulas (2) to (5).
• R 1 to R 5 and n are the same as above, and R 6 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an acyl group, or an aryl group. , N represents 0 or 1.
• R 1 to R 5 and n are the same as described above, and R 7 and R 8 are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. Represents an acyl group or an aryl group.
• R 1 to R 5 and n are the same as above, and R 9 to R 11 are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. Represents an acyl group, an amino group, an alkoxy group, a hydroxy group, or an aryl group.
• R 1 to R 5 and n are the same as above, and R 12 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an amino group, an alkoxy group and a hydroxy group. Represents a group or an aryl group.
• R 2 to R 5 are preferably alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, from the viewpoint of easy availability. It is more preferably an alkyl group.
• R6 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom.
• R 7 and R 8 are preferably hydrogen atoms independently or alkyl groups having 1 to 10 carbon atoms, and are hydrogen atoms. Is more preferable.
• R 9 to R 11 are preferably hydrogen atoms or alkyl groups having 1 to 10 carbon atoms.
• R 12 is preferably a hydroxy group, an amino group, or an alkoxy group.
• n is preferably 1 from the viewpoint of availability.
• N-oxyl compound for example, N- described in JP-A-2003-64022, JP-A-11-222462, JP-A-2002-284737, International Publication No. 2016/047655 and the like. Oxyl compounds can be mentioned.
• N-oxyl compound 4-hydroxy-2,2,6,6-tetramethylpiperidin 1-oxyl is preferably used.
• examples of the second compound include the following compounds.
• R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an acyl group, or an aryl group.
• the molecular weight of the second compound is preferably 1000 or less, more preferably 500 or less, still more preferably 300 or less, from the viewpoint of efficiently capturing radicals generated in the polyene conversion reaction. ..
• the lower limit of the molecular weight is not particularly limited, but may be, for example, 80.
• the water content of the polarizing element is equal to or more than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 30%, and is equal to or less than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 80%.
• the water content of the polarizing element may be greater than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 45% or 50%, and may be equal to or less than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 80% or 70%.
• the water content of the polarizing element is lower than the equilibrium water content of a temperature of 20 ° C.
• the handleability of the polarizing element is lowered and the polarizing element is easily cracked.
• the water content of the polarizing element is as high as the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 45% or 50%, it is presumed that polyene formation of the PVA-based resin is likely to proceed. Since the adhesive layer containing the compound and the second compound is provided, the polyene formation of the PVA-based resin can be suppressed.
• the above temperature and the above relative humidity As a method for confirming whether the water content of the polarizing element is within the range of the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 30% or less and the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 80% or less, the above temperature and the above relative humidity.
• a method of calculating the equilibrium water content of the above in advance and comparing the water content of the polarizing element with the pre-calculated equilibrium water content can be mentioned.
• the method for manufacturing a polarizing element having a water content of 20 ° C. and a relative humidity of 30% or more and an equilibrium water content of a temperature of 20 ° C. and a relative humidity of 80% or less is not particularly limited. Examples thereof include a method of storing the polarizing element in an environment adjusted to a relative humidity range of 10 minutes or more and 3 hours or less, or a method of heat-treating at 30 ° C. or higher and 90 ° C. or lower.
• a laminated body in which a protective film is laminated on at least one surface of the polarizing element, or a polarizing plate configured by using the polarizing element is provided with the temperature and the relative humidity.
• Examples thereof include a method of storing in an environment adjusted to the above range for 10 minutes or more and 120 hours or less, or a method of heat-treating at 30 ° C. or more and 90 ° C. or less.
• the image display panel in which the polarizing plate is laminated on the image display cell is stored or stored in an environment adjusted to the above temperature and the above relative humidity range for 10 minutes or more and 3 hours or less.
• the front plate may be bonded after heating at 30 ° C. or higher and 90 ° C. or lower.
• 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 equal to or lower than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 80%.
• the water content of the polarizing plate may be greater than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 45% or 50%, and may be equal to or less than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 80% or 70%.
• the water content of the polarizing plate is lower than the equilibrium water content of a temperature of 20 ° C.
• the handleability of the polarizing plate is lowered and the polarizing plate is easily cracked.
• the water content of the polarizing plate is as high as the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 45% or 50%, it is presumed that polyene formation of the PVA-based resin is likely to proceed. Since the adhesive layer containing the compound and the second compound is provided, the polyene formation of the PVA-based resin can be suppressed.
• the above temperature and the above relative humidity As a method for confirming whether the water content of the polarizing plate is within the range of the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 30% or less and the equilibrium water content of a temperature of 20 ° C. and a relative humidity of 80% or less, the above temperature and the above relative humidity.
• a method of calculating the equilibrium water content of the above in advance and comparing the water content of the polarizing plate with the pre-calculated equilibrium water content can be mentioned.
• the method for producing a polarizing plate having a water content of 20 ° C. and a relative humidity of 30% or more and an equilibrium water content of a temperature of 20 ° C. and a relative humidity of 80% or less is not particularly limited. Examples thereof include a method of storing the polarizing plate in an environment adjusted to a relative humidity range of 10 minutes or more and 3 hours or less, or a method of heat-treating at 30 ° C. or higher and 90 ° C. or lower.
• the image display panel in which the polarizing plate is laminated on the image display cell is stored or stored in an environment adjusted to the above temperature and the above relative humidity range for 10 minutes or more and 3 hours or less.
• the front plate may be bonded after heating at 30 ° C. or higher and 90 ° C. or lower.
• the manufacturing method of the polarizing element is not particularly limited, but a method of feeding out a PVA-based resin film wound in a roll shape in advance and performing stretching, dyeing, cross-linking, etc. (hereinafter referred to as “manufacturing method 1”) or A method including a step of applying a coating liquid containing a PVA-based resin on a base film to form a PVA-based resin layer as a coating layer, and stretching the obtained laminate (hereinafter referred to as "manufacturing method 2"). .) Is typical.
• the production method 1 includes a step of uniaxially stretching a PVA-based resin film, a step of dyeing a PVA-based resin film with a dichroic dye such as iodine to adsorb a dichroic dye, and a PVA-based dye having a dichroic dye adsorbed.
• the resin film 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.
• the swelling step is a treatment step of immersing the PVA-based resin film in the swelling bath.
• the swelling step By the swelling step, stains on the surface of the PVA-based resin film, blocking agents, and the like can be removed, and by swelling the PVA-based resin film, uneven dyeing can be suppressed.
• a medium containing water as a main component such as water, distilled water, and pure water, is usually used.
• a surfactant, alcohol or the like may be appropriately added to the swelling bath according to a conventional method.
• potassium iodide may be used in the swelling bath, and in this case, the concentration of potassium iodide in the swelling bath may be 1.5% by mass or less. It is more preferably 1.0% by mass or less, and even 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 further 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, but is preferably 5 seconds or more and 300 seconds or less, preferably 10 seconds or more and 200 seconds or less. It is more preferable that it is 20 seconds or more and 100 seconds or less.
• the swelling step may be performed only once, or may be performed a plurality of times as needed.
• the dyeing step is a treatment step of immersing the PVA-based resin film in a dyeing bath (iodine solution), and can adsorb and orient a dichroic dye such as iodine on the PVA-based resin film.
• iodine solution is usually preferably an aqueous iodine solution and contains iodine and iodide as a solubilizing agent.
• iodide examples include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, titanium iodide and the like. Can be 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, and 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. It is more preferably mass% or less.
• 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 further 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 is preferably 10 seconds or more and 300 seconds or less, preferably 20 seconds or more and 240 seconds or less. Is more preferable.
• the dyeing step may be carried out only once or may be carried out multiple times as needed.
• 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, and the polyvinyl alcohol-based resin film is cross-linked by the boron compound to form iodine.
• a treatment bath cross-linking bath
• the polyvinyl alcohol-based resin film is cross-linked by the boron compound to form iodine.
• Mole or dye molecule can be adsorbed on the crosslinked structure.
• the boron compound include boric acid, borate, borax and the like.
• the cross-linking bath is generally an aqueous solution, but may be a mixed solution of an organic solvent and water that is miscible with water.
• the cross-linking bath preferably contains potassium iodide from the viewpoint of controlling the content of potassium in the polarizing element.
• the concentration of the boron compound 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.
• the concentration of potassium iodide in the cross-linking bath is preferably 1% by mass or more and 15% by mass or less, and 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, and 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 is preferably 5 seconds or more and 300 seconds or less, preferably 10 seconds or more and 200 seconds or less. Is more preferable.
• the cross-linking step may be carried out only once, or may be carried out a plurality of times as needed.
• the stretching step is a treatment step of stretching the PVA-based resin film to a predetermined magnification in at least one direction.
• the PVA-based resin film is uniaxially stretched in the transport direction (longitudinal direction).
• the stretching method is not particularly limited, and either a wet stretching method or a dry stretching method can be adopted.
• the stretching step may be carried out only once, or may be carried out a plurality of times as needed.
• the stretching step may be performed at any stage in the manufacture of the polarizing element.
• the stretching bath preferably contains potassium iodide from the viewpoint of controlling the content of potassium in the polarizing element.
• concentration of potassium iodide in the stretching bath is preferably 1% by mass or more and 15% by mass or less, and more preferably 2% by mass or more and 10% by mass or less. It is more preferably 3% by mass or more and 6% by mass or less.
• the treatment bath (stretching bath) can contain a boron compound from the viewpoint of suppressing film breakage during stretching.
• the concentration of the boron compound in the stretching 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 preferably 5% by mass or less.
• the temperature of the stretching bath is preferably 25 ° C. or higher and 80 ° C. or lower, more preferably 40 ° C. or higher and 75 ° C. or lower, and further preferably 50 ° C. or higher and 70 ° C. or lower.
• 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, but is preferably 10 seconds or more and 800 seconds or less, preferably 30 seconds or more and 500 seconds or less. Is more preferable.
• the stretching treatment in the wet stretching method may be performed together with any one or more of the swelling step, the dyeing step, the crosslinking step and the washing step.
• dry stretching method examples include an inter-roll stretching method, a heating roll stretching method, a compression stretching method, and the like.
• the dry stretching method may be applied together with the drying step.
• the total draw ratio (cumulative draw ratio) applied to the polyvinyl alcohol-based resin film can be appropriately set according to the purpose, but is preferably 2 times or more and 7 times or less, and is preferably 3 times or more and 6.8 times or less. It is more preferable, and it is more preferable that it is 3.5 times or more and 6.5 times or less.
• the cleaning step is a treatment step of immersing the polyvinyl alcohol-based resin film in the washing bath, and can remove foreign substances remaining on the surface of the polyvinyl alcohol-based resin film and the like.
• a medium containing water as a main component such as water, distilled water, and pure water, is usually used.
• potassium iodide in the washing bath.
• the concentration of potassium iodide in the washing bath is 1% by mass or more and 10% by mass. It 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 further preferably 15 ° C. or higher and 30 ° C. or lower.
• the immersion time in the washing bath cannot be unconditionally determined because the degree of washing of the PVA-based resin film is affected by the temperature of the washing bath, but it is preferably 1 second or more and 100 seconds or less, preferably 2 seconds or more and 50 seconds or less. It is more preferable that it is 3 seconds or more and 20 seconds or less.
• the cleaning step may be performed only once, or may be performed a plurality of times as needed.
• the drying step is a step of drying the PVA-based resin film washed in the washing step to obtain a polarizing element. Drying is carried out by any suitable method, and examples thereof include natural drying, blast drying, and heat drying.
• the production method 2 includes a step of applying a coating liquid containing a PVA-based resin on a base film, a step of uniaxially stretching the obtained laminated film, and a step of uniaxially stretching the PVA-based resin layer of the uniaxially stretched laminated film with a dichroic dye. It can be produced through a step of adsorbing it to form a polarizing element by dyeing, 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 the treatment with the aqueous boric acid solution.
• the base film used for forming 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 first transparent protective film used in the present embodiment is bonded to one side of the polarizing element via the first adhesive layer, and the second transparent protective film is attached to the other surface of the polarizing element via the second adhesive layer. Will be pasted together.
• first transparent protective film and the second transparent protective film it may be simply referred to as "protective film”.
• the protective film may have other optical functions at the same time, or may be formed in a laminated structure in which a plurality of layers are laminated.
• the film thickness of the protective film is preferably thin from the viewpoint of optical characteristics, but if it is too thin, the strength is lowered and the workability is inferior.
• the appropriate 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 film made of a polycarbonate resin, a film made of a cycloolefin resin such as norbornene, a (meth) acrylic polymer film, or a polyester resin film such as polyethylene terephthalate is used.
• a protective film is attached to both sides of a polarizing element using a water-based adhesive such as PVA adhesive, 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. Of these, a cellulose acylate film is preferable.
• At least one protective film may have a phase difference function for the purpose of compensating the viewing angle or the like.
• the protective film itself may have a retardation function, may have a separate retardation layer, or may be a combination of both.
• the film having the retardation function may be directly attached to the polarizing element via an adhesive, but may be attached via an adhesive or an adhesive via another protective film attached to the polarizing element. It may have a different configuration.
• An adhesive containing the first compound is used as the first adhesive constituting the first adhesive layer for adhering the first transparent protective film to the polarizing element.
• An adhesive containing the second compound is used as the second adhesive constituting the second adhesive layer for adhering the second transparent protective film to the polarizing element.
• a water-based adhesive a solvent-based adhesive, an active energy ray-curable adhesive, or the like can be used, but it is preferably a water-based adhesive and preferably contains a PVA-based resin.
• the first adhesive containing the first compound and the second adhesive containing the second compound it is possible to suppress a decrease in the transmittance of the polarizing plate in a high temperature environment.
• the thickness at the time of application of the adhesive can be set to an arbitrary value, and for example, after curing or heating (drying), an adhesive layer having a desired thickness can be set.
• 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 following description of the adhesive is a description of a preferable range in the case where the polarizing element does not contain the first compound and the second compound at the time of manufacturing the polarizing element.
• the polarizing element contains the first compound or the second compound
• the following values may be appropriately adjusted. Specific examples of the first compound and the second compound are as described above. Even if a part of the first compound and a part of the second compound move from the adhesive layer to the polarizing element or the like in the process of forming the adhesive layer through the drying step at the time of bonding the polarizing element and the protective film. I do not care.
• the content of the first compound is preferably 0.1 part by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the PVA-based resin. It is more preferably 1 part by mass or more and 200 parts by mass or less, and further 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 polyene formation of the polarizing element in a high temperature environment may not be sufficient. On the other hand, if it exceeds 400 parts by mass, urea may precipitate after the polarizing plate is produced and the haze may increase.
• the content of the second compound is preferably 0.1 part by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the PVA-based resin. It is more preferably 1 part by mass or more and 200 parts by mass or less, and further 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 polyene formation 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 disecond compound may precipitate after the polarizing plate is produced.
• Water-based adhesive As the water-based adhesive, any suitable water-based adhesive can be adopted, but a water-based adhesive containing a PVA-based resin (PVA-based adhesive) is preferably 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, and more preferably 1000 or more and 4500 or less from the viewpoint of adhesiveness. From the viewpoint of adhesiveness, the average saponification degree is preferably 85 mol% or more and 100 mol% or less, and more preferably 90 mol% or more and 100 mol% or less.
• the PVA-based resin contained in the water-based adhesive is preferably one containing an acetoacetyl group, because the PVA-based resin layer and the protective film have excellent adhesion and durability.
• the acetoacetyl group-containing PVA-based resin can be obtained, for example, by reacting the PVA-based resin with diketene by an arbitrary method.
• the degree of acetoacetyl group modification of the acetoacetyl group-containing PVA-based 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, and more preferably 0.5% by mass or more and 10% by mass or less.
• the water-based adhesive can also contain a cross-linking agent.
• a cross-linking agent a known cross-linking agent can be used.
• the cross-linking agent include water-soluble epoxy compounds, dialdehydes, isocyanates and the like.
• the cross-linking agent is preferably glyoxal, glyoxal salt, or methylol melamine, and may be glyoxal or glyoxal salt. More preferably, glyoxal is particularly preferable.
• the water-based adhesive can also contain an organic solvent.
• the organic solvent is preferably alcohols in that it is miscible with water, and more preferably methanol or ethanol among the alcohols.
• 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 further 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.
• the content of methanol is 70% by mass or less, deterioration of hue can be suppressed.
• Some urea derivatives have low solubility in water, but some have sufficient solubility in alcohol. In that case, it is also preferable to dissolve the first compound in alcohol to prepare an alcohol solution of the first compound, and then add the alcohol solution of the first compound to the PVA aqueous solution to prepare the first adhesive. It is one.
• the active energy ray-curable adhesive is an adhesive that cures by irradiating with active energy rays such as ultraviolet rays, and is, for example, an adhesive containing a polymerizable compound and a photopolymerizable initiator, and an adhesive containing a photoreactive resin.
• the polymerizable compound include a photopolymerizable monomer such as a photocurable epoxy-based monomer, a photocurable acrylic-based monomer, and a photocurable urethane-based monomer, and an oligomer derived from these monomers.
• the photopolymerization initiator include compounds containing substances that generate active species such as neutral radicals, anionic radicals, and cationic radicals by irradiating them with active energy rays such as ultraviolet rays.
• the first compound and the second compound are not limited to the case where they are contained in the adhesive layer as described above, and from the viewpoint of improving the high temperature durability of the polarizing plate, they can be added to layers other than the adhesive layer. It may be contained. From the viewpoint of improving the physical strength of the polarizing plate, the cured layer may be laminated.
• such a cured layer may contain the first compound and the second compound to form a urea-based compound-containing layer.
• a cured layer is formed from a curable composition containing an organic solvent, but paragraphs [0020] to [0042] of JP-A-2017-075986 indicate that the active energy ray-curable polymer composition is aqueous. A method of forming such a hardened layer from a solution is described. Water-soluble first and second compounds may be included in such compositions.
• the urea-based compound-containing layer preferably has at least one first compound, at least one second compound, and a binder.
• the binder include a polymer binder, a heat-curable resin binder, an active energy ray-curable resin binder, and the like, and any of these binders can be preferably used.
• the thickness of the urea-based compound-containing layer 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 further preferably 1 ⁇ m or more and 10 ⁇ m or less.
• the method for manufacturing a polarizing plate of the present embodiment includes a laminating step.
• the method for producing a polarizing plate of the present embodiment may include a water content adjusting step.
• the water content adjusting step when the polarizing plate having the characteristic (a) is manufactured, the water content of the polarizing element is equal to or higher than the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 30%, and the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 80%. Adjust the water content of the polarizing element so that it is less than or equal to the rate.
• the water content of the polarizing element can be adjusted according to the description of the water content of the polarizing element described above.
• the moisture 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 the equilibrium water content at a temperature of 20 ° C. and a relative humidity of 80%. Adjust the water content of the polarizing plate so that it is less than or equal to the rate.
• the water content of the polarizing plate can be adjusted according to the description of the water content of the polarizing plate described above.
• the laminating step the polarizing element and the transparent protective film are laminated via the adhesive layer.
• the polarizing element and the transparent protective film that have not been treated to contain the first compound and the second compound are bonded together with an adhesive containing the first compound and the second compound.
• the order of the water content adjusting step and the laminating step is not limited, and the water content adjusting step and the laminating step may be performed in parallel.
• the polarizing plate of the present embodiment is used in various image display devices such as a liquid crystal display device and an organic EL display device.
• the image display device has an interlayer filling configuration in which both sides of the polarizing plate are in contact with a layer other than the air layer, specifically, a solid layer such as an adhesive layer, the transmittance in a high temperature environment. Is easy to decrease.
• the image display device using the polarizing plate of the present embodiment it is possible to suppress a decrease in the transmittance of the polarizing plate in a high temperature environment even if the interlayer filling configuration is used.
• An example of the image display device is a configuration having an image display cell, a first pressure-sensitive adhesive layer laminated on the visible side surface of the image display cell, and a polarizing plate laminated on the visible side surface of the first pressure-sensitive adhesive layer. Will be done.
• Such an image display device may further include a second pressure-sensitive adhesive layer laminated on the visible side surface of the polarizing plate, and a transparent member laminated on the surface of the second pressure-sensitive adhesive layer.
• a transparent member is arranged on the visual side of the image display device, the polarizing plate and the image display cell are bonded by the first pressure-sensitive adhesive layer, and the polarizing plate and the transparent member are second-bonded.
• first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be simply referred to as "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, but are an adhesive layer. May be good.
• the image display cell examples include a liquid crystal cell and an organic EL cell.
• the liquid crystal cell includes a reflective liquid crystal cell that uses external light, a transmissive liquid crystal cell that uses light from a light source such as a backlight, and a semi-transmissive semi-reflective type that uses 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 side opposite to the visual recognition side of the image display cell (liquid crystal cell), and further arranges the light source. Will be done.
• the polarizing plate on the light source side and the liquid crystal cell are bonded to each other via an appropriate adhesive layer.
• any type such as VA mode, IPS mode, TN mode, STN mode and bend orientation ( ⁇ type) can be used.
• the organic EL cell a cell in which a transparent electrode, an organic light emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light emitting body (organic electroluminescence light emitting body) or the like is preferably used.
• the organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, or light emission thereof.
• Various layer configurations can be adopted, such as a laminated body of an electron-injected layer composed of a layer and a perylene derivative, or a laminated body of a hole-injected layer, a light-emitting layer, and an electron-injected layer.
• An adhesive layer (adhesive sheet) is preferably used for bonding the image display cell and the polarizing plate.
• a method of bonding a polarizing plate with an adhesive layer having an adhesive layer attached to one surface of the polarizing plate to an image display cell is preferable from the viewpoint of workability and the like.
• the pressure-sensitive adhesive layer may be attached to the polarizing plate by an appropriate method.
• a pressure-sensitive adhesive solution of 10% by mass or more and 40% by mass or less is prepared by dissolving or dispersing the base polymer or its composition in a solvent consisting of an appropriate solvent such as toluene or ethyl acetate alone or in a mixture thereof. Examples thereof include a method of directly attaching the adhesive layer on the polarizing plate by an appropriate developing method such as a casting method and a coating method, and a method of forming an adhesive layer on the separator and transferring it to the polarizing plate.
• the pressure-sensitive adhesive layer may be composed of one layer or two or more layers, but is preferably composed of one layer.
• the pressure-sensitive adhesive layer can be composed of a pressure-sensitive adhesive composition containing a (meth) acrylic resin, a rubber-based resin, a urethane-based resin, an ester-based resin, a silicone-based resin, and a polyvinyl ether-based resin as main components.
• a pressure-sensitive adhesive composition using a (meth) acrylic resin having excellent transparency, weather resistance, heat resistance and the like as a base polymer is preferable.
• the pressure-sensitive adhesive composition may be an active energy ray-curable type or a thermosetting type.
• Examples of the (meth) acrylic resin (base polymer) used in the pressure-sensitive adhesive composition include butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
• a polymer or copolymer containing one or more of the (meth) acrylic acid esters as monomers is preferably used. It is preferable that the base polymer is copolymerized with a polar monomer.
• Examples of the polar monomer include (meth) acrylic acid compound, (meth) acrylic acid 2-hydroxypropyl compound, (meth) acrylic acid hydroxyethyl compound, (meth) acrylamide compound, and N, N-dimethylaminoethyl (meth) acrylate compound.
• a monomer having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group and the like, such as a glycidyl (meth) acrylate compound, can be mentioned.
• the pressure-sensitive adhesive composition may contain only the above-mentioned base polymer, but usually further contains a cross-linking agent.
• the cross-linking agent is a metal ion having a valence of 2 or more, which is a metal ion that forms a carboxylic acid metal salt with a carboxyl group, a polyamine compound that forms an amide bond with the carboxyl group, and a carboxyl group. Examples thereof include polyepoxy compounds or polyols that form an ester bond in the above, and polyisocyanate compounds that form an amide bond with a carboxyl group. Of these, polyisocyanate compounds are preferable.
• the active energy ray-curable pressure-sensitive adhesive composition has a property of being cured by being irradiated with active energy rays such as ultraviolet rays and electron beams, and has adhesiveness even before irradiation with active energy rays, such as a film. It has the property that it can be brought into close contact with the adherend of No. 1 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 an ultraviolet-curable type.
• 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, or the like may be contained.
• the pressure-sensitive adhesive composition includes fine particles for imparting light scattering, beads (resin beads, glass beads, etc.), glass fibers, resins other than the base polymer, a pressure-sensitive imparting agent, and a filler (metal powder and other inorganic powders). Etc.), antioxidants, UV absorbers, dyes, pigments, colorants, defoaming agents, corrosion inhibitors, photopolymerization initiators and other additives can be included.
• the pressure-sensitive adhesive layer can be formed by applying an organic solvent diluted solution of the above-mentioned pressure-sensitive adhesive composition on the surface of a base film, an image display cell or a polarizing plate and drying it.
• the base film is generally a thermoplastic resin film, and a typical example thereof is a separate film that has been subjected to a mold release treatment.
• the separate film may be one in which the surface on which the pressure-sensitive adhesive layer of the film made of a resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarate is formed is subjected to a mold release treatment such as a silicone treatment.
• the 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 the pressure-sensitive adhesive layer with the separate film may be laminated on the surface of the polarizing body.
• the pressure-sensitive adhesive composition may be directly applied to the surface of the polarizing plate to form the pressure-sensitive adhesive layer, and a separate film may be laminated on the outer surface of the pressure-sensitive adhesive layer.
• the pressure-sensitive adhesive layer is provided on the surface of the polarizing plate, it is preferable to perform surface activation treatment such as plasma treatment and corona treatment on the bonded surface of the polarizing plate and / or the bonded surface of the pressure-sensitive adhesive layer. It is more preferable to apply the treatment.
• the pressure-sensitive adhesive composition is applied onto the second separate film to form a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet in which the separate film is laminated on the formed pressure-sensitive adhesive layer is prepared, and the second pressure-sensitive adhesive sheet is used as a second.
• the pressure-sensitive adhesive layer with the separate film after the separate film is peeled off may be laminated on the polarizing plate.
• As the second separate film a film having a weaker adhesion to the pressure-sensitive adhesive layer than the separate film and being easily peeled off is used.
• the thickness of the pressure-sensitive adhesive layer is not particularly limited, but 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.
• the transparent member arranged on the visual side of the image display device examples include a transparent plate (window layer), a touch panel, and the like.
• a transparent plate 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, an acrylic resin or a 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 may be laminated to increase the physical strength, or a low moisture permeability layer may be laminated to reduce the moisture permeability.
• touch panel various touch panels such as a resistance film method, a capacitance method, an optical method, an ultrasonic method, and a glass plate or a transparent resin plate having a touch sensor function are used.
• a 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 visual 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 pressure-sensitive adhesive can be attached by an appropriate method. Specific examples of the attachment method include the attachment method of the pressure-sensitive adhesive layer used for bonding the image display cell and the polarizing plate described above.
• a dam material is provided so as to surround the peripheral edge on the image display panel in order to prevent the adhesive solution from spreading before curing, and a transparent member is placed on the dam material.
• a method of placing and injecting an adhesive solution is preferably used. After injecting the adhesive solution, alignment and defoaming are performed as necessary, and then activation energy rays are irradiated to perform curing.
• a 40 ⁇ m-thick PVA film made of PVA having an average degree of polymerization of about 2400 and a degree of polymerization of 99.9 mol% or more was uniaxially stretched about 5 times by a dry method, and was purely 60 ° C. while maintaining a tense state. After soaking in water for 1 minute, it was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.05 / 5/100 at 28 ° C. for 60 seconds.
• aqueous solution having a weight ratio of potassium iodide / boric acid / water of 8.5 / 8.5 / 100 at 72 ° C. for 300 seconds. Subsequently, the mixture was washed with pure water at 26 ° C. for 20 seconds and then dried at 65 ° C. to obtain a polarizing element A having a thickness of 15 ⁇ m in which iodine was adsorbed and oriented on PVA.
• a digital micrometer "MH-15M" manufactured by Nikon Corporation was used for measuring the thickness of the polarizing element.
• ⁇ Preparation of transparent protective film A> A commercially available cellulose acylate film TD40 (manufactured by FUJIFILM Corporation, film thickness 40 ⁇ m) was immersed in a 1.5 mol / L NaOH aqueous solution (saponification solution) maintained at 55 ° C. for 2 minutes, and then the film was washed with water. Then, after immersing the film in a 0.05 mol / L sulfuric acid aqueous solution at 25 ° C. for 30 seconds, the film was further passed through a water washing bath for 30 seconds under running water to neutralize the film. Then, after draining with an air knife three times to drain water, the film was allowed to stay in a drying zone at 70 ° C. for 15 seconds to be dried to prepare a saponified film, which was used as a transparent protective film A.
• the transparent protective film A was bonded to both sides of the polarizing element A via the adhesive 3 using a roll bonding machine. After bonding, the mixture was dried at 80 ° C. for 5 minutes to obtain a polarizing plate 1. The adhesive layer was adjusted so that the thickness after drying was 50 nm on both sides.
• the adhesive layer for adhering the transparent protective film A to one surface of the polarizing element A is the first adhesive layer, and the adhesive layer for adhering the transparent protective film A to the other surface is the second adhesive layer. Use as an agent layer.
• the adhesives 3 used on both sides were changed to the adhesives shown in Table 2 to obtain polarizing plates 2 to 8.
• the polarizing plates 1 to 8 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 storage 66 hours, 69 hours and 72 hours. Under any humidity condition, the water content values 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 8 is the same as the equilibrium water content of the storage environment of 72 hours 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 the storage environment. Further, 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 the storage environment.
• optical laminates 1 to 8 were produced using any of the polarizing plates 1 to 8 shown in Table 2.
• the relative humidity was 30%, 45% or 55% at a temperature of 20 ° C. so that the water content of the polarizing plate (polarizing element) used would be the equilibrium water content of the environment shown in Table 2. It was stored for 72 hours and subjected to the following high temperature durability evaluation under the state of each water content.
• Acrylic adhesives manufactured by Lintec Corporation, product number: # 7 are formed on both sides of the optical laminates 1 to 8 in each water content, and 50 mm so that the absorption axis is parallel to the long side. It was cut into a size of ⁇ 100 mm.
• An evaluation sample was prepared by laminating non-alkali glass (“EAGLE XG” manufactured by Corning Inc.) on the surface of each adhesive. In order to evaluate the cross omission of the evaluation sample, an optical laminate R was produced for the purpose of creating a cross Nicol state by superimposing the evaluation sample on the cloth.
• an acrylic pressure-sensitive adhesive (manufactured by Lintec Corporation, product number: # 7) is formed on only one side of the above polarizing plate 1, and 50 mm ⁇ 100 mm so that the absorption axis is parallel to the short side. Cut to the size of.
• An optical laminate R used for cross evaluation was produced by laminating non-alkali glass (“EAGLE XG” manufactured by Corning Inc.) on the surface of the pressure-sensitive adhesive.
• the evaluation samples of the optical laminates 1 to 8 were autoclaved at a temperature of 50 ° C. and a pressure of 5 kgf / cm 2 (490.3 kPa) for 1 hour, and then left for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 55%. bottom. Then, the evaluation samples of the optical laminates 1 to 8 in each water content were evaluated for high temperature durability as follows.
• the polarizing element and the first transparent protective film are bonded by the first adhesive containing the first compound, and the polarizing element and the second transparent protective film are bonded by the second adhesive containing the second compound.
• the polarizing plate (optical laminates 6 to 8) has a low transmittance even when exposed to a high temperature environment of 105 ° C., and has an excellent evaluation of cross loss. It was found that it has excellent high temperature durability.

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