CN111183380A - Polarizing plate, image display device, and method for manufacturing polarizing plate - Google Patents
Polarizing plate, image display device, and method for manufacturing polarizing plate Download PDFInfo
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- CN111183380A CN111183380A CN201880064522.4A CN201880064522A CN111183380A CN 111183380 A CN111183380 A CN 111183380A CN 201880064522 A CN201880064522 A CN 201880064522A CN 111183380 A CN111183380 A CN 111183380A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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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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- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
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Abstract
The invention provides a method for manufacturing a polarizing plate, which has high adhesion with other optical members and can improve the display characteristics of an image display device. The method for producing a polarizing plate of the present invention is a method for producing a polarizing plate having a polyester-based resin substrate and a polarizer laminated on one side of the polyester-based resin substrate and having a thickness of 10 μm or less, the method comprising: dyeing and stretching a laminate having a polyvinyl alcohol resin layer formed on one side of a polyester resin base material to form a polarizer from the polyvinyl alcohol resin layer; and heat treating a laminate of the polyester resin base material and the polarizer, wherein the stretching comprises a stretching treatment in an aqueous solution having a stretching ratio of 2.55 times or more, and the maximum heating temperature in the heat treatment is 100 ℃ or more.
Description
Technical Field
The invention relates to a polarizing plate, an image display device and a method for manufacturing the polarizing plate.
Background
A method of forming a polyvinyl alcohol resin layer on a polyester resin substrate, and stretching and dyeing the laminate to obtain a thin polarizer has been proposed (for example, patent document 1). Such a method of manufacturing a polarizer can contribute to, for example, a reduction in thickness of an image display device, and is attracting attention.
The polarizer can be used as it is in a state of being laminated on the polyester resin base material, and in this case, the polyester resin base material is used as a protective layer of the polarizer (patent document 2). Thus, the laminate of the polyester resin base material and the polarizer can be used as a polarizing plate without attaching a protective film to the polarizer, and this can contribute to cost reduction of the image display device, for example.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2000-338329
Patent document 2: japanese patent No. 4979833
Disclosure of Invention
Problems to be solved by the invention
However, the above-described polarizing plate has insufficient adhesion to other optical members, and has a problem of insufficient display characteristics when used in an image display device.
The present invention has been made to solve the above conventional problems, and a main object thereof is to provide a polarizing plate which has high adhesion to other optical members and can improve display characteristics of an image display device, a method for manufacturing such a polarizing plate, and an image display device including such a polarizing plate.
Means for solving the problems
The method for producing a polarizing plate of the present invention is a method for producing a polarizing plate having a polyester-based resin substrate and a polarizer laminated on one side of the polyester-based resin substrate and having a thickness of 10 μm or less, the method comprising: dyeing and stretching a laminate having a polyvinyl alcohol resin layer formed on one side of the polyester resin base material to form a polarizer from the polyvinyl alcohol resin layer; and heat treating a laminate of the polyester resin base material and the polarizer; wherein the stretching comprises a stretching treatment in an aqueous solution having a stretching ratio of 2.55 times or more, and the maximum heating temperature in the heating treatment is 100 ℃ or more.
In one embodiment, the maximum heating temperature in the heating treatment is 115 ℃ or lower.
According to another aspect of the present invention, there is provided a polarizing plate. The polarizing plate comprises a polyester resin substrate and a polarizer laminated on one side of the polyester resin substrate, wherein the thickness of the polarizer is 10 [ mu ] m or less, the haze value of the polarizing plate is less than 1.6%, the surface of the polarizer is bonded to glass by an adhesive, and the polarizing plate is stored at 60 ℃/90% Rh for 500 hours without peeling off from the glass.
According to another aspect of the present invention, there is provided an image display device. The image display device has the polarizing plate.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a polarizing plate which has high adhesion to other optical members and can improve display characteristics of an image display device, a method for manufacturing such a polarizing plate, and an image display device including such a polarizing plate.
Drawings
Fig. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of a laminate of a polyester-based resin substrate and a PVA-based resin layer used in the method for producing a polarizing plate according to one embodiment of the present invention.
Fig. 3 is a schematic diagram showing a manufacturing step of a polarizing plate of one embodiment.
Description of the symbols
10 polarizer
11 PVA-based resin layer
20 polyester resin base Material
100 polarizing plate
200 laminated body
Detailed Description
The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.
A. Method for manufacturing polarizing plate
Fig. 1 is a schematic cross-sectional view of a polarizing plate obtained by a method for producing a polarizing plate according to an embodiment of the present invention. The polarizing plate 100 includes a polyester resin substrate 20 and a polarizer 10 laminated on one side of the polyester resin substrate 20. The polarizer 10 has a thickness of 10 μm or less.
The method of manufacturing the polarizing plate 100 includes: a polarizing mirror 10 is produced by dyeing and stretching a laminate 200 (fig. 2) in which a polyvinyl alcohol resin layer (PVA type resin layer) 11 is formed on one side of a polyester type resin substrate 20, thereby forming the PVA type resin layer 11; and heat treating the laminate of the polyester resin base material 20 and the polarizer 10. The stretching includes a stretching treatment in an aqueous solution having a stretching ratio of 2.55 times or more, and the maximum heating temperature in the heating treatment is 100 ℃ or more. The maximum heating temperature of the heat treatment is preferably 115 ℃ or lower. According to the above production method, a polarizing plate can be obtained which has both of adhesion to other optical members and display characteristics of an image display device. In some cases, a polarizing plate obtained by stretching and dyeing a laminate of a polyester resin base material and a PVA resin layer, which is a conventional production method, cannot achieve both sufficient adhesion to other optical members and good display characteristics of an image display device. Specifically, when the polarizer obtained by the above-described conventional manufacturing method is placed in a high-temperature and high-humidity environment with the polarizer side surface bonded to another optical member, both ends of the polarizer in the stretching direction may be peeled off from the optical member, or glare may be generated on the display screen when the polarizer is used in an image display device. According to the novel findings of the present invention, it is found that the crystallinity and crystal size of the polyester-based resin substrate of the polarizing plate can be controlled within appropriate ranges by the above-mentioned production method, whereby adhesion to other optical members and display characteristics (antiglare property) of the image display device can be achieved at the same time.
Fig. 3 is a schematic diagram showing a manufacturing step of a polarizing plate of one embodiment. In the process for producing the polarizing plate of the present embodiment, typically, the laminate 200 of the polyester resin substrate 20 and the PVA resin layer 11 is fed out from the feeding unit 101, immersed in the bath 110 of an aqueous boric acid solution by the rollers 111 and 112 (insolubilization treatment), and then immersed in the bath 120 of an aqueous solution of a dichroic material (iodine) and potassium iodide by the rollers 121 and 122 (dyeing treatment). Next, the substrate was immersed in a bath 130 of an aqueous solution of boric acid and potassium iodide by rollers 131 and 132 (crosslinking treatment). Next, the laminate 200 is stretched (stretching treatment in an aqueous solution) by applying tension in the longitudinal direction (longitudinal direction, conveyance direction, MD direction) by rolls 141 and 142 having different speed ratios while being immersed in a stretching bath 140 of an aqueous boric acid solution. Next, the laminate 200 stretched in an aqueous solution is immersed in a bath 150 of an aqueous potassium iodide solution by rollers 151 and 152 (cleaning treatment), and subjected to a drying treatment (not shown). Next, the laminate 200 is put into an oven 160 (heat treatment), thereby obtaining the polarizing plate 100 of the present embodiment. Then, the obtained polarizing plate 100 is wound by a winding unit 170. Although not shown in the drawings, the laminate 200 may be subjected to stretching treatment in a gas atmosphere before being subjected to insolubilization treatment. The manufacturing steps shown in fig. 3 are only examples, and the number, order, and the like of the above-described processes are not particularly limited.
A-1. laminate of polyester resin base Material and PVA resin layer
The laminate of the polyester resin substrate and the PVA resin layer can be produced by any suitable method. Preferably, a coating solution containing a PVA type resin is applied to a polyester type resin substrate and dried, whereby a laminate having a PVA type resin layer formed on one side of the polyester type resin substrate can be obtained. In one embodiment, an easy adhesion layer is formed by applying and drying an easy adhesion layer-forming composition on a polyester resin substrate, and a PVA type resin layer is formed on the easy adhesion layer.
As the material for forming the polyester-based resin substrate, for example, there can be used: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), isophthalic acid, copolymerized PET (PET-G) containing alicyclic dicarboxylic acids or alicyclic diols containing a cyclohexane ring or the like, other polyesters, copolymers thereof, mixtures thereof, and the like. Among them, amorphous (uncrystallized) PET or copolymerized PET is preferably used. These resins are amorphous in an unstretched state and have excellent stretchability suitable for stretching at a high ratio, and are crystallized by stretching and heating to impart heat resistance and dimensional stability. Further, the PVA-based resin can be applied and dried in an unstretched state with sufficient heat resistance.
The glass transition temperature (Tg) of the polyester-based resin substrate is preferably 170 ℃ or lower. By using such a polyester resin base material, sufficient stretchability can be ensured while suppressing crystallization of the PVA resin layer. From the viewpoints of plasticization of the polyester resin substrate with water and satisfactory stretching in an aqueous solution, it is more preferably 120 ℃ or lower. In one embodiment, the glass transition temperature of the polyester-based resin substrate is preferably 60 ℃ or higher. By using such a polyester-based resin substrate, it is possible to prevent a problem such as deformation (for example, generation of unevenness, sagging, wrinkles, and the like) of the polyester-based resin substrate when a coating liquid containing a PVA-based resin, which will be described later, is applied and dried. The laminate may be stretched at an appropriate temperature (for example, about 60 to 70 ℃). In another embodiment, when a coating liquid containing a PVA-based resin is applied and dried, the glass transition temperature may be lower than 60 ℃ as long as the polyester-based resin substrate is not deformed. The glass transition temperature (Tg) is a value determined according to JIS K7121.
In one embodiment, the water absorption rate of the polyester resin base material is preferably 0.2% or more, more preferably 0.3% or more. Such a polyester resin base material absorbs water, and the water can play a role of a plasticizer to plasticize. As a result, the tensile stress can be greatly reduced during stretching in an aqueous solution, and the resulting fiber exhibits excellent stretchability. On the other hand, the water absorption of the polyester resin base material is preferably 3.0% or less, more preferably 1.0% or less. By using such a polyester resin base material, it is possible to prevent problems such as a significant decrease in dimensional stability of the polyester resin base material during production and deterioration in appearance of the resulting laminate. Further, the PVA-based resin layer can be prevented from being broken when stretched in an aqueous solution and being peeled from the polyester-based resin substrate. The water absorption rate is a value obtained according to JISK 7209.
The thickness of the polyester resin base material (thickness before stretching described later) is preferably 20 to 300. mu.m, and more preferably 50 to 200. mu.m. If the thickness is less than 20 μm, the PVA based resin layer may be difficult to form. If it exceeds 300 μm, for example, when stretching in an aqueous solution, it may take a long time for the polyester resin substrate to absorb water and an excessive load may be required for stretching.
Any suitable PVA type resin may be used for forming the PVA type resin layer. Examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymers. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. The ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-vinyl acetate copolymer. The saponification degree of the PVA-based resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, and more preferably 99.0 mol% to 99.93 mol%. The degree of saponification can be determined in accordance with JIS K6726-1994. By using the PVA-based resin having such a saponification degree, a polarizer having excellent durability can be obtained. When the saponification degree is too high, gelation may occur.
The average polymerization degree of the PVA-based resin may be appropriately selected depending on the purpose. The average degree of polymerization is usually 1000 to 10000, preferably 1200 to 4500, and more preferably 1500 to 4300. The average polymerization degree can be determined in accordance with JIS K6726-1994.
The coating liquid containing the PVA-based resin is typically a solution obtained by dissolving the PVA-based resin in a solvent. Examples of the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols such as glycols and trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. They may be used alone or two or more of them may be used in combination. Of these, water is preferred. The concentration of the PVA-based resin in the solution is preferably 3 to 20 parts by weight based on 100 parts by weight of the solvent. When the resin concentration is such as described above, a uniform coating film can be formed which adheres to the polyester resin substrate. In one embodiment, the coating liquid contains a halide. Any suitable halide may be used as the halide. Examples thereof include iodide and sodium chloride. Examples of the iodide include potassium iodide, sodium iodide and lithium iodide. Of these, potassium iodide is preferred. The amount of the halide in the coating liquid is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin, and more preferably 10 to 15 parts by weight based on 100 parts by weight of the PVA-based resin. If the amount of the halide is more than 20 parts by weight based on 100 parts by weight of the PVA-based resin, the halide may bleed out, and the resulting polarizer may be cloudy. The laminate of the PVA type resin layer containing the halide and the polyester type resin base material is stretched at a high temperature in the air (auxiliary stretching) before stretching in boric acid water, whereby the crystallization of the PVA type resin in the PVA type resin layer after the auxiliary stretching can be promoted. As a result, when the PVA-based resin layer is immersed in a liquid, the alignment disorder and the decrease in alignment of the polyvinyl alcohol molecules can be suppressed more than in the case where the PVA-based resin layer does not contain a halide. This improves the optical characteristics of the polarizer to be finally obtained.
Additives may be added to the coating liquid. Examples of the additives include plasticizers and surfactants. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin. Examples of the surfactant include nonionic surfactants. These can be used for further improving the uniformity, dyeing property and stretchability of the PVA-based resin layer obtained. Further, examples of the additive include an easily bondable component. By using the easily adhesive component, the adhesion between the polyester resin base and the PVA resin layer can be improved. As a result, for example, the PVA based resin layer can be prevented from being peeled off from the polyester based substrate, and dyeing and stretching in an aqueous solution described later can be performed satisfactorily. As the easy-adhesion component, for example, a modified PVA such as acetoacetyl-modified PVA can be used.
Any suitable method can be used for applying the coating liquid. Examples of the coating method include roll coating, spin coating, wire bar coating, dip coating, die coating, shower coating, spray coating, and blade coating (e.g., doctor blade coating). The coating and drying temperature of the coating liquid is preferably 50 ℃ or higher.
The thickness of the PVA based resin layer (thickness before stretching described later) is preferably 3 to 20 μm.
Before the PVA-based resin layer is formed, the polyester-based resin substrate may be subjected to a surface treatment (e.g., corona treatment), or a composition for forming an easily adhesive layer may be applied to the polyester-based resin substrate (coating treatment). By performing such treatment, the adhesion between the polyester resin base and the PVA resin layer can be improved. As a result, for example, the PVA-based resin layer can be prevented from being peeled off from the polyester-based resin substrate, and dyeing and stretching described later can be performed satisfactorily.
The composition for forming an easy adhesion layer preferably contains a polyvinyl alcohol component. Any suitable PVA-based resin can be used as the polyvinyl alcohol-based component. Specific examples thereof include polyvinyl alcohol and modified polyvinyl alcohol. Examples of the modified polyvinyl alcohol include polyvinyl alcohols modified with an acetoacetyl group, a carboxylic acid group, an acryloyl group and/or a carbamate group. Among these, acetoacetyl group-modified PVA is preferably used. The acetoacetyl group-modified PVA is preferably a polymer having at least a repeating unit represented by the following general formula (I).
[ chemical formula 1]
In the formula (I), the ratio of n to l + m + n is preferably 1% to 10%.
The average degree of polymerization of the acetoacetyl-modified PVA is preferably 1000 to 10000, more preferably 1200 to 5000. The saponification degree of the acetoacetyl group-modified PVA is preferably 97 mol% or more. The pH of a 4 wt% aqueous solution of the acetoacetyl-modified PVA is preferably 3.5 to 5.5.
The composition for forming an easy-adhesion layer may further contain a polyolefin component, a polyester component, a polyacrylic component, and the like, depending on the purpose and the like. The easy adhesion layer-forming composition preferably further contains a polyolefin component.
Any suitable polyolefin-based resin can be used for the polyolefin-based component. Examples of the olefin component as the main component of the polyolefin resin include olefin hydrocarbons having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, and 1-hexene. They may be used alone or two or more of them may be used in combination. Of these, olefinic hydrocarbons having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene, and 1-butene are preferably used, and ethylene is more preferably used.
The proportion of the olefin component in the monomer components constituting the polyolefin resin is preferably 50 to 95 wt%.
The polyolefin-based resin preferably contains a carboxyl group and/or an acid anhydride group thereof. Such a polyolefin resin can be dispersed in water, and can form an easy-adhesion layer satisfactorily. Examples of the monomer component having such a functional group include unsaturated carboxylic acids and anhydrides thereof, half esters and half amides of unsaturated dicarboxylic acids. Specific examples thereof include acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, and crotonic acid. The polyolefin resin has a molecular weight of 5000 to 80000, for example.
In the easy-adhesion layer-forming composition, the blending ratio of the polyvinyl alcohol component to the polyolefin component (the former: the latter (solid component)) is preferably 5: 95-60: 40, more preferably 20: 80-50: 50. when the polyvinyl alcohol component is too large, the adhesion may not be sufficiently obtained. Specifically, the peeling force required for peeling the polarizer from the polyester resin substrate may be reduced, and sufficient adhesion may not be obtained. On the other hand, when the polyvinyl alcohol component is too small, the appearance of the obtained polarizing plate may be impaired. Specifically, when the easy-adhesion layer is formed, a defect such as white turbidity of the coating film may occur, and it may be difficult to obtain a polarizing plate having excellent appearance.
The composition for forming an easy-adhesion layer is preferably aqueous. The composition for forming an easy adhesion layer may contain an organic solvent. Examples of the organic solvent include ethanol and isopropanol. The solid content concentration of the composition for forming an easy-adhesion layer is preferably 1.0 to 10% by weight.
The method for applying the composition for forming an easy-adhesion layer may be any appropriate method. After the composition for forming an easy-adhesion layer is applied, the applied film may be dried. The drying temperature is, for example, 50 ℃ or higher.
A-2 stretching treatment in gas atmosphere
The stretching treatment in a gas atmosphere includes a heat roll stretching step of stretching the laminate by a difference in peripheral velocity between heat rolls while conveying the laminate in the longitudinal direction thereof. The stretching treatment in a gas atmosphere typically includes a zone (zone) stretching step and a heat roll stretching step. The order of the zone stretching step and the heat roll stretching step is not limited, and the zone stretching step may be performed first, or the heat roll stretching step may be performed first. The zone stretching step may also be omitted. In one embodiment, the zone stretching step and the hot roll stretching step are performed sequentially.
The stretching temperature of the laminate may be set to any suitable value depending on the material for forming the polyester resin base material, the stretching method, and the like. The stretching temperature in the stretching treatment in the gas atmosphere is preferably not less than the glass transition temperature (Tg) of the polyester-based resin substrate, more preferably not less than the glass transition temperature (Tg) +10 ℃, and particularly preferably not less than Tg +15 ℃. On the other hand, the upper limit of the stretching temperature of the laminate is preferably 170 ℃. Stretching at such a temperature can suppress rapid progress of crystallization of the PVA-based resin, and can suppress defects caused by the crystallization (for example, the orientation of the PVA-based resin layer is hindered by stretching).
A-3. insolubilization treatment
The insolubilization treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing insolubilization treatment, water resistance can be imparted to the PVA-based resin layer. The concentration of the aqueous boric acid solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the insolubilization bath (aqueous boric acid solution) is preferably 20 to 50 ℃. The insolubilization treatment is preferably performed before the stretching in the aqueous solution or the dyeing treatment.
A-4 dyeing treatment
The PVA-based resin layer is typically dyed by adsorbing iodine to the PVA-based resin layer. Examples of the adsorption method include: a method of immersing the PVA-based resin layer (laminate) in a dyeing solution containing iodine; a method of applying the dyeing liquid to a PVA-based resin layer; a method of spraying the dyeing solution onto the PVA-based resin layer, and the like. A method of immersing the PVA-based resin layer (laminate) in a dyeing solution is preferably employed. This is because iodine can be adsorbed well.
The staining solution is preferably an aqueous iodine solution. The amount of iodine is preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of water. In order to increase the solubility of iodine in water, it is preferable to add an iodide to the aqueous iodine solution. Specific examples of the iodide are as described above. The amount of the iodide is preferably 0.02 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of water. In order to suppress dissolution of the PVA based resin, the dyeing liquid is preferably at a liquid temperature of 20 ℃ to 50 ℃ during dyeing. When the PVA-based resin layer is immersed in the dyeing liquid, the immersion time is preferably 5 seconds to 5 minutes in order to ensure the transmittance of the PVA-based resin layer. The dyeing conditions (concentration, liquid temperature, and immersion time) may be set so that the polarization degree or monomer transmittance of the polarizer finally obtained falls within a predetermined range. In one embodiment, the immersion time is set so that the degree of polarization of the polarizer obtained becomes 99.98% or more. In another embodiment, the immersion time is set so that the monomer transmittance of the polarizer obtained is 40% to 44%.
The dyeing treatment may be performed at any appropriate timing. Preferably before stretching in aqueous solution.
A-5. Cross-linking treatment
The crosslinking treatment is typically performed by immersing the PVA-based resin layer (laminate) in an aqueous boric acid solution. The PVA-based resin layer can be provided with water resistance by performing crosslinking treatment. The concentration of the aqueous boric acid solution is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. In addition, when the crosslinking treatment is performed after the dyeing treatment, it is preferable to further incorporate an iodide. The iodine compound can suppress elution of iodine adsorbed on the PVA-based resin layer. The amount of the iodide is preferably 1 to 5 parts by weight based on 100 parts by weight of water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (aqueous boric acid solution) is preferably 20 to 60 ℃. The crosslinking treatment is preferably carried out before the stretching treatment in an aqueous solution. In a preferred embodiment, the stretching treatment, the dyeing treatment and the crosslinking treatment are sequentially performed in a gas atmosphere.
A-6 stretching treatment in aqueous solution
The polarizing plate is produced by the steps described above, including: the laminate was subjected to a stretching treatment in an aqueous solution in a stretching bath. Specifically, the stretching in an aqueous solution is performed in a direction parallel to the stretching direction in the gas atmosphere of the laminate. The stretching in an aqueous solution can be performed at a temperature lower than the glass transition temperature (typically, about 80 ℃) of the polyester resin substrate or the PVA resin layer, and the PVA resin layer can be stretched at a high magnification while suppressing crystallization thereof. As a result, a polarizer having excellent optical characteristics (e.g., degree of polarization) can be manufactured. In the present specification, the term "parallel direction" includes a case of 0 ° ± 5.0 °, preferably 0 ° ± 3.0 °, and more preferably 0 ° ± 1.0 °.
The draw ratio in the aqueous solution in the drawing treatment is 2.55 times or more, preferably 2.65 times or more, and more preferably 2.75 times or more as described above. On the other hand, the upper limit of the draw ratio is preferably 5.0 times, and more preferably 5.5 times. If the draw ratio in the aqueous solution is too high, the polarizer may be broken. By setting the stretching ratio within the above range and setting the maximum heating temperature in the heating treatment described later within a predetermined range, a polarizing plate which can suppress peeling from glass in a high-temperature and high-humidity environment and has a sufficiently low haze value can be obtained. Therefore, a polarizing plate having both of adhesiveness to other optical members and display characteristics (antiglare property) of an image display device can be obtained.
The stretching temperature in the aqueous solution is preferably 40 to 85 ℃ and more preferably 50 to 70 ℃. At such a temperature, the PVA-based resin layer can be stretched at a high ratio while dissolution thereof is suppressed. Specifically, as described above, the glass transition temperature (Tg) of the polyester-based resin substrate is preferably 60 ℃ or higher in view of the relationship with the formation of the PVA-based resin layer. In this case, if the stretching temperature is lower than 40 ℃, there is a possibility that the polyester resin substrate cannot be stretched well in consideration of plasticization of the polyester resin substrate by water. On the other hand, the higher the stretching temperature, the higher the solubility of the PVA-based resin layer, and the less excellent optical properties may be obtained. The immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.
The stretching treatment in the aqueous solution may be any suitable method. Specifically, the stretching may be performed at a fixed end or a free end. The stretching direction of the laminate is substantially the stretching direction (longitudinal direction) of stretching in the above-described gas atmosphere. The stretching of the laminate may be performed in one stage or in multiple stages.
The stretching in an aqueous solution is preferably performed by immersing the laminate in an aqueous boric acid solution (stretching in an aqueous boric acid solution). By using an aqueous boric acid solution as a stretching bath, the PVA-based resin layer can be provided with rigidity capable of withstanding the tension applied during stretching and water resistance not dissolving in water. Specifically, boric acid generates tetrahydroxyborate anions in an aqueous solution, and crosslinks with the PVA-based resin through hydrogen bonds. As a result, rigidity and water resistance can be imparted to the PVA-based resin layer, and the PVA-based resin layer can be stretched well, whereby a polarizer having excellent optical characteristics (for example, degree of polarization) can be produced.
The aqueous boric acid solution is preferably obtained by dissolving boric acid and/or a borate in water as a solvent. The boric acid concentration is preferably 1 to 10 parts by weight relative to 100 parts by weight of water. When the boric acid concentration is 1 part by weight or more, the dissolution of the PVA-based resin layer can be effectively suppressed, and a polarizer having higher characteristics can be produced. In addition to boric acid or a borate, an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal, glutaraldehyde, or the like in a solvent may be used.
When a dichroic material (represented by iodine) is adsorbed on the PVA-based resin layer by dyeing treatment in advance, it is preferable to add an iodide to the stretching bath (aqueous boric acid solution). The iodine compound can suppress elution of iodine adsorbed on the PVA-based resin layer. The iodide may be exemplified by: 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. Of these, potassium iodide is preferred. The concentration of the iodide is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of water.
By combining the polyester resin base material with stretching in an aqueous solution (stretching in an aqueous boric acid solution), it is possible to stretch at a high magnification and produce a polarizer having excellent optical characteristics (for example, degree of polarization). Specifically, the maximum stretching ratio is preferably 5.0 times or more, more preferably 5.5 times or more, and still more preferably 6.0 times or more, with respect to the original length of the laminate (including the stretching ratio in a gas atmosphere). In the present specification, "maximum stretching ratio" means a stretching ratio immediately before the laminate is broken, and the stretching ratio at which the laminate is broken is confirmed, and "maximum stretching ratio" means a value lower by 0.2 than this value. The maximum draw ratio of the laminate using the polyester resin base material is higher when the laminate is stretched in an aqueous solution than when the laminate is stretched only by stretching in a gas atmosphere.
A-7. cleaning treatment
The cleaning treatment is typically performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution. The drying temperature in the drying treatment is preferably 30 to 100 ℃.
A-8. heat treatment
The heat treatment is performed after stretching in an aqueous solution. By the heat treatment, crystallization of the polyester resin base material proceeds.
The heating process is typically performed by heating a transport roller disposed in the heating mechanism 160 (using a so-called hot drum roller (heating roller)) (hot drum roller heating method). In one embodiment, the heating mechanism 160 is an oven, and a heating method (oven heating method) by sending hot air into the oven may be used in combination. By using the heat drum roller heating method and the oven heating method in combination, a rapid temperature change between the heat drum rollers can be suppressed, and the shrinkage of the laminate in the width direction can be easily controlled. The oven temperature of the oven is preferably 30 ℃ to 100 ℃. The heating time in the oven is preferably 1 second to 300 seconds. The wind speed of the hot wind is preferably about 10m/s to 30 m/s. The wind speed is the wind speed in the oven and can be measured by a digital anemometer of the mini-fan blade type.
By heating with a hot drum roller, curling is suppressed and a polarizer having excellent appearance can be produced. Specifically, the crystallization of the polyester-based resin substrate can be efficiently promoted by heating the laminate in a state of being along the hot drum roll, and the crystallinity of the polyester-based resin substrate can be increased, and the crystallinity of the polyester-based resin substrate can be favorably increased even at a relatively low heating temperature. As a result, the polyester resin base material has increased rigidity and is in a state of being able to withstand shrinkage of the PVA resin layer by heating, thereby suppressing curling. Further, by using the hot drum roller, the laminate can be heated while being kept flat, and therefore not only curling but also wrinkles can be suppressed.
In the heating mechanism 160, a plurality of heat drum rollers may be arranged, and the respective heat drum rollers may be set to different temperatures. In the heating mechanism 160, 2 to 20 hot drum rollers may be disposed, and 4 to 10 hot drum rollers are preferably disposed. The contact time (total contact time) of the laminate with the hot drum roller is preferably 1 second to 300 seconds. The heating conditions can be controlled by adjusting the temperature of the hot drum rollers, the number of hot drum rollers, the contact time with the hot drum rollers, and the like.
When the temperature of the heat drum roller set to the highest temperature among the plurality of heat drum rollers is set as the "highest heating temperature", the highest heating temperature is 100 ℃ or higher, and more preferably 105 ℃ or higher. The upper limit of the maximum heating temperature is preferably 115 ℃. By setting the maximum heating temperature in the heating treatment within the above range and setting the draw ratio in the drawing treatment in the aqueous solution within a predetermined range, a polarizing plate can be obtained which is suppressed in peeling from glass in a high-temperature high-humidity environment and has a sufficiently low haze value. Therefore, a polarizing plate having both of adhesiveness to other optical members and display characteristics (antiglare property) of an image display device can be obtained. The temperature of the hot drum roller may be measured by a contact thermometer. The contact time of the laminate with the hot drum roller kept at the maximum heating temperature (total contact time when there are a plurality of hot drum rollers at the maximum heating temperature) is preferably 0.2 to 2 seconds, more preferably 0.5 to 2 seconds. The "contact time" refers to a time from any point on the laminate to separation after contacting the outer peripheral surface of the hot drum roller held at the maximum heating temperature.
B. Constitution of polarizing plate
The polarizing plate comprises a polyester resin base material and a polarizer having a thickness of 10 μm or less laminated on one side of the polyester resin base material, as described above. The polarizing plate of the present invention had a haze value of less than 1.6%. The polarizing plate was bonded to glass with an acrylic adhesive on the polarizer side and stored at 60 ℃/90% Rh for 500 hours, and then, the polarizing plate was not peeled from the glass. The thickness of the polyester resin base material is preferably 10 to 200. mu.m, more preferably 20 to 150. mu.m. The polarizer is preferably laminated on one surface of the polyester resin base material (in other words, without interposing an adhesive layer therebetween). The polarizing plate preferably has an easy-adhesion layer between the polyester resin substrate and the polarizer. The polarizing plate may have a protective film on the side of the polarizer opposite to the polyester resin substrate. The polyester resin base material typically functions as a protective layer of a polarizer. The polarizing plate of the present embodiment has high adhesion to other optical members when the polarizer-side surface is bonded to the optical members, can suppress peeling in a high-temperature and high-humidity environment, and can suppress glare on a display screen of an image display device. Therefore, the polarizing plate of the present invention can achieve both of the adhesiveness to other optical members and the display characteristics (antiglare property) of the image display device.
The polarizer is substantially a PVA type resin layer in which iodine is adsorbed and oriented. The thickness of the polarizer is 10 μm or less, preferably 7.5 μm or less, and more preferably 5 μm or less, as described above. On the other hand, the thickness of the polarizer is preferably 0.5 μm or more, and more preferably 1.5 μm or more. If the thickness is too thin, the optical characteristics of the polarizer to be obtained may be deteriorated. The polarizer preferably exhibits dichroism of absorption at any wavelength of 380nm to 780 nm. The monomer transmittance of the polarizer is preferably 40.0% or more, more preferably 41.0% or more, and still more preferably 42.0% or more. The degree of polarization of the polarizer is preferably 99.8% or more, more preferably 99.9% or more, and still more preferably 99.95% or more.
Examples of the material for forming the protective film include (meth) acrylic resins, cellulose resins such as cellulose diacetate and cellulose triacetate, cycloolefin resins, olefin resins such as polypropylene, ester resins such as polyethylene terephthalate resins, polyamide resins, polycarbonate resins, and copolymer resins thereof. The thickness of the protective film is preferably 10 μm to 100 μm.
The easy adhesion layer may be a layer substantially formed only of the composition for forming an easy adhesion layer, or may be a layer or a region in which the composition for forming an easy adhesion layer is mixed (including compatible) with the material for forming the polarizer. By forming the easy adhesion layer, excellent adhesion can be obtained. The thickness of the easy adhesion layer is preferably about 0.05 μm to 1 μm. The easy adhesion layer can be confirmed by observing the cross section of the polarizing plate with a Scanning Electron Microscope (SEM), for example.
C. Image display device
The polarizing plate according to item B obtained by the production method according to item a can be applied to an image display device such as a liquid crystal display device. Accordingly, the present invention includes an image display device using the above polarizing plate. An image display device according to an embodiment of the present invention includes the polarizing plate described in the above item B.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The measurement method and evaluation method of each characteristic are as follows.
(1) Thickness of
Measured using a digital micrometer (product name "KC-351C" manufactured by Anritsu Co., Ltd.).
(2) Evaluation of antiglare Property
the haze values of the polarizing plates of examples and comparative examples were measured by a haze meter (product name "HN-150" manufactured by Col. Cumura, Ltd.) according to the method defined in JIS 7136. in the evaluation of the antiglare property of the polarizing plate, a good (. smallcircle.) was obtained when the haze value was less than 1.6%, and a poor (. times.) was obtained when the haze value was 1.6% or more.
(3) Evaluation of adhesion
the polarizing plates obtained in examples and comparative examples were cut into a size of 100mm (MD direction) × 100mm (TD direction) to obtain evaluation samples, the polarizer sides of the evaluation samples were bonded to glass with an acrylic adhesive (thickness 20 μm, manufactured by ritonao electrical corporation, under the name "polarizing plate general-purpose adhesive") and stored at 60 ℃/90% Rh for 500 hours, and then whether or not the ends of the evaluation samples were peeled off from the glass was confirmed.
< example 1>
As the polyester resin base material, a long amorphous ethylene isophthalate copolymer terephthalate (IPA copolymer PET) film (thickness: 100 μm, IPA modification degree: 5 mol%) was used. (degree of modification ═ ethylene isophthalate unit ]/[ ethylene terephthalate unit + ethylene isophthalate unit ])
One surface of a polyester resin substrate was subjected to corona treatment (treatment condition: 50 W.min/m)2) Then, an aqueous dispersion of a modified polyolefin resin (product name "GOHSEFIMER Z200" manufactured by japan synthetic chemical industry co., ltd.) of acetoacetyl-modified polyvinyl alcohol (PVA) (product name "ARROW BASE SE 1030N" manufactured by Unitika) was mixed with pure water, and the resulting mixture (solid content concentration 4.0%) was applied to the corona-treated surface so that the thickness after drying was 2000nm, and dried at 65 ℃ for 2 minutes to form an undercoat layer. Wherein the solid component mixing ratio of the acetoacetyl modified PVA to the modified polyolefin in the mixed solution is 30: 70. subsequently, an aqueous solution in which 90 parts by weight of PVA (polymerization degree 4200, saponification degree 99.2 mol%) and 10 parts by weight of acetoacetyl-modified PVA (product of Nippon synthetic chemical industries, Ltd., trade name "GOHSEFIMERZ 410") were blended, and 13 parts by weight of potassium iodide per 100 parts by weight of the PVA resin were mixed was applied to the surface of the undercoat layer at 25 ℃ and dried at 60 ℃ for 3 minutes to form a PVA resin layer having a thickness of 13 μm. A laminate was produced as described above.
The obtained laminate was stretched in one direction to 2 times the free end in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 140 ℃ (auxiliary stretching in a gas atmosphere).
Next, the laminate was immersed in an insolubilization bath (an aqueous boric acid solution prepared by adding 4 parts by weight of boric acid to 100 parts by weight of water) at a liquid temperature of 40 ℃ for 30 seconds (insolubilization treatment).
Then, the resultant was immersed in a dyeing bath (aqueous iodine solution prepared by adding 0.2 part by weight of iodine and 1.5 parts by weight of potassium iodide to 100 parts by weight of water) at a liquid temperature of 30 ℃ for 60 seconds (dyeing treatment).
Subsequently, the resultant was immersed in a crosslinking bath (an aqueous boric acid solution prepared by adding 3 parts by weight of potassium iodide and 5 parts by weight of boric acid to 100 parts by weight of water) at a liquid temperature of 40 ℃ for 30 seconds (crosslinking treatment).
Thereafter, the laminate was uniaxially stretched to 2.75 times (total stretching ratio: 5.5 times) in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds while being immersed in a stretching bath (stretching bath temperature: 67 ℃) of an aqueous boric acid solution (an aqueous solution prepared by adding 3 parts by weight of boric acid and 5 parts by weight of potassium iodide to 100 parts by weight of water) (stretching treatment in an aqueous solution).
Thereafter, the laminate was immersed in a cleaning bath (aqueous solution containing 3.5 parts by weight of potassium iodide per 100 parts by weight of water) at a liquid temperature of 30 ℃ (cleaning treatment).
Next, in an oven having a plurality of heating rollers maintained at 80 to 100 ℃ and maintained at 80 ℃, a heating treatment is performed while conveying the laminate using the heating rollers so that the contact time between the laminate and the heating rollers maintained at 100 ℃ is 1 second in total.
The long polarizing plate 1 in which polarizers having a thickness of 5 μm were laminated on the polyester resin base material was obtained as described above. The polarizing plate 1 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< example 2>
A polarizing plate 2 was obtained in the same manner as in example 1, except that the maximum heating temperature was set to 105 ℃. The polarizing plate 2 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< example 3>
A polarizing plate 3 was obtained in the same manner as in example 1, except that the maximum heating temperature was 110 ℃. The polarizing plate 3 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< example 4>
A polarizing plate 4 was obtained in the same manner as in example 2, except that the laminate was stretched in the longitudinal direction by 2.55 times (total stretching ratio: 5.1 times) while being immersed in a stretching bath (stretching treatment in an aqueous solution). The polarizing plate 4 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< comparative example 1>
A polarizing plate 5 was obtained in the same manner as in example 1, except that the maximum heating temperature was 80 ℃. The polarizing plate 5 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< comparative example 2>
A polarizing plate 6 was obtained in the same manner as in example 1, except that the maximum heating temperature was 95 ℃. The polarizing plate 6 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< comparative example 3>
A polarizing plate 7 was obtained in the same manner as in example 1, except that the laminate was stretched 2.4 times in the longitudinal direction in an oven (auxiliary stretching in a gas atmosphere), stretched 2.30 times in the longitudinal direction (total stretching ratio: 5.5 times) while being immersed in a stretching bath (stretching treatment in an aqueous solution), and the maximum heating temperature was 65 ℃. The polarizing plate 7 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< comparative example 4>
A polarizing plate 8 was obtained in the same manner as in comparative example 3, except that the maximum heating temperature was 75 ℃. The polarizing plate 8 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< comparative example 5>
A polarizing plate 9 was obtained in the same manner as in comparative example 3, except that the maximum heating temperature was set to 100 ℃. The polarizing plate 9 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< comparative example 6>
A polarizing plate 10 was obtained in the same manner as in comparative example 3, except that the maximum heating temperature was set to 105 ℃. The polarizing plate 10 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< comparative example 7>
A polarizing plate 11 was obtained in the same manner as in comparative example 3, except that the maximum heating temperature was 110 ℃. The polarizing plate 11 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< comparative example 8>
A polarizing plate 12 was obtained in the same manner as in example 1, except that the laminate was stretched 2.6 times in the longitudinal direction in an oven (auxiliary stretching in a gas atmosphere) and 2.10 times in the longitudinal direction (total stretching ratio: 5.5 times) while being immersed in a stretching bath (stretching treatment in an aqueous solution). The polarizing plate 12 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
< comparative example 9>
A polarizing plate 13 was obtained in the same manner as in example 1, except that the laminate was stretched 2.4 times in the longitudinal direction in an oven (auxiliary stretching in a gas atmosphere) and 2.50 times in the longitudinal direction (total stretching ratio: 6.0 times) while being immersed in a stretching bath (stretching treatment in an aqueous solution). The polarizing plate 13 was subjected to evaluation of haze value and adhesion. The results are shown in Table 1.
[ Table 1]
As is clear from table 1, the polarizing plate obtained by setting the draw ratio in the aqueous solution to 2.55 times or more and the maximum heating temperature in the heating treatment to 100 ℃.
Industrial applicability
The polarizing plate produced by the production method of the present invention can be suitably used for image display devices such as liquid crystal display devices and organic EL display devices.
Claims (4)
1. A method for producing a polarizing plate having a polyester resin base material and a polarizer laminated on one side of the polyester resin base material and having a thickness of 10 [ mu ] m or less,
the method comprises the following steps:
dyeing and stretching a laminate having a polyvinyl alcohol resin layer formed on one side of the polyester resin base material to form a polarizer from the polyvinyl alcohol resin layer; and
heat-treating a laminate of the polyester resin base material and the polarizer,
wherein,
the stretching includes a stretching treatment in an aqueous solution having a stretching ratio of 2.55 times or more, and the maximum heating temperature in the heating treatment is 100 ℃ or more.
2. The polarizing plate production method according to claim 1, wherein,
the maximum heating temperature in the heating treatment is 115 ℃ or lower.
3. A polarizing plate comprising a polyester resin base material and a polarizer laminated on one side of the polyester resin base material,
the thickness of the polarizer is less than 10 μm,
the haze value of the polarizing plate is less than 1.6%,
the polarizer-side surface was bonded to glass with an adhesive and stored at 60 ℃/90% Rh for 500 hours without peeling from the glass.
4. An image display device comprising the polarizing plate according to claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2017-193276 | 2017-10-03 | ||
| JP2017193276A JP7240092B2 (en) | 2017-10-03 | 2017-10-03 | Polarizing plate, image display device, and method for manufacturing polarizing plate |
| PCT/JP2018/035615 WO2019069757A1 (en) | 2017-10-03 | 2018-09-26 | Polarizing plate, image display device, and method for producing polarizing plate |
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| CN111183380A true CN111183380A (en) | 2020-05-19 |
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| CN201880064522.4A Pending CN111183380A (en) | 2017-10-03 | 2018-09-26 | Polarizing plate, image display device, and method for manufacturing polarizing plate |
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| JP (1) | JP7240092B2 (en) |
| KR (1) | KR20200066300A (en) |
| CN (1) | CN111183380A (en) |
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| KR102183981B1 (en) * | 2019-06-28 | 2020-11-27 | 에스케이씨 주식회사 | Polyester film and organic light emitting display using same |
| NL2029163B1 (en) * | 2021-09-09 | 2023-03-23 | Lankhorst Touwfab Bv | Polarizing light filter |
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| JP4279944B2 (en) | 1999-06-01 | 2009-06-17 | 株式会社サンリッツ | Manufacturing method of polarizing plate |
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| JPWO2015001980A1 (en) | 2013-07-01 | 2017-02-23 | コニカミノルタ株式会社 | Polarizing plate and liquid crystal display device using the same |
| KR101821801B1 (en) * | 2015-06-18 | 2018-01-25 | 삼성에스디아이 주식회사 | Polarizing plate, method for preparing the same and optical display apparatus comprising the same |
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2017
- 2017-10-03 JP JP2017193276A patent/JP7240092B2/en active Active
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2018
- 2018-09-26 KR KR1020207009197A patent/KR20200066300A/en not_active Ceased
- 2018-09-26 CN CN201880064522.4A patent/CN111183380A/en active Pending
- 2018-09-26 WO PCT/JP2018/035615 patent/WO2019069757A1/en active Application Filing
- 2018-10-02 TW TW107134791A patent/TWI775958B/en active
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| JP2006018089A (en) * | 2004-07-02 | 2006-01-19 | Nippon Zeon Co Ltd | Polarizing plate and liquid crystal display device |
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| JP2019066717A (en) | 2019-04-25 |
| TW201935049A (en) | 2019-09-01 |
| KR20200066300A (en) | 2020-06-09 |
| WO2019069757A1 (en) | 2019-04-11 |
| TWI775958B (en) | 2022-09-01 |
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