CN108351453B - Polarizing plate and method for producing same - Google Patents
Polarizing plate and method for producing same Download PDFInfo
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- CN108351453B CN108351453B CN201680062513.2A CN201680062513A CN108351453B CN 108351453 B CN108351453 B CN 108351453B CN 201680062513 A CN201680062513 A CN 201680062513A CN 108351453 B CN108351453 B CN 108351453B
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- 238000007602 hot air drying Methods 0.000 claims description 5
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 27
- 238000010521 absorption reaction Methods 0.000 description 22
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 17
- 230000001681 protective effect Effects 0.000 description 17
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 14
- -1 polyethylene terephthalate Polymers 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 10
- 239000004327 boric acid Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- 150000001639 boron compounds Chemical class 0.000 description 9
- 230000010287 polarization Effects 0.000 description 9
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- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
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- 230000001678 irradiating effect Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229920006254 polymer film Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
- B29D11/00788—Producing optical films
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising 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
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ophthalmology & Optometry (AREA)
- Mechanical Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention provides a polarizing plate with an arithmetic average height (Sa) of 21.0nm or less.
Description
Technical Field
The present invention relates to a polarizing plate and a method for producing the same, and more particularly, to a polarizing plate having a small contraction force in the absorption axis (stretching) direction and having little striped unevenness extending in the stretching direction with irregularities, and a method for producing the same.
Background
Polarizing plates used in various image display devices such as liquid crystal display devices (LCDs), Electroluminescence (EL) display devices, plasma display devices (PDPs), field emission display devices (FEDs), OLEDs, and the like generally include a polarizing plate in which an iodine-based compound or a dichroic polarizing substance is adsorbed and oriented on a polyvinyl alcohol-based (PVA) film, and have a multilayer structure in which a polarizing plate protective film is sequentially stacked on one surface of the polarizing plate, and a polarizing plate protective film, an adhesive layer joined to other members, and a release film are sequentially stacked on the other surface of the polarizing plate.
A polarizer constituting a polarizing plate is suitable for an image display device, and is basically required to have both high transmittance and high degree of polarization in order to provide an image with excellent color reproducibility. In order to achieve this, a polarizing plate is manufactured by modifying a polyvinyl alcohol film itself or using a non-sublimable dichroic dye instead of a sublimable iodine polarizing element.
On the other hand, a stretching step is generally required to impart a polarizing function to the polarizing plate, but there is a problem that the polarizing plate is deformed during use due to a contractile force in the stretching (absorption axis) direction inherent in the polarizing plate after being manufactured. The deformation of the polarizing plate causes a reduction in the optical function of the polarizing plate and a failure of the image display device.
In addition, there is a problem that stripe-like unevenness occurs in the polarizing plate in the stretching step, which is caused by the unevenness extending in the stretching direction.
A method for manufacturing a polarizing plate with small over-shrinkage stress is disclosed in japanese laid-open patent No. 2010-145866, however, a satisfactory degree of alternative to the above-described problem cannot be proposed.
Documents of the prior art
Patent literature
Patent document 1: japanese patent application laid-open No. 2010-145866
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a polarizing plate with small contraction force in an absorption axis direction and a manufacturing method thereof.
Another object of the present invention is to provide a polarizing plate in which stripe-like unevenness caused by projections and depressions extending in a stretching direction is reduced, and a method for manufacturing the same.
Means for solving the problems
1. A polarizing plate having an arithmetic average height (Sa) of 21.0nm or less.
2. The polarizing plate according to the above item 1, wherein the thickness is 5 to 30 μm.
3. The polarizing plate according to 1 or 2, wherein the shrinkage force in the absorption axis direction is 3N/2mm or less.
4. A method for producing a polarizing plate, comprising the steps of swelling, dyeing, stretching, crosslinking, and drying a polarizing plate-forming film,
the drying step includes a step of drying the polarizer-forming film by contacting it with a heat roll,
the time for which the polarizing plate-forming film is brought into contact with a hot roll is 50% or more of the total drying time.
5. The method for manufacturing a polarizing plate according to the above 4, wherein the drying step further comprises a hot air drying step.
6. The method for producing a polarizing plate according to the above 5, wherein the temperature of the heat roller is equal to or higher than the temperature of hot air.
7. The method for producing a polarizing plate according to any one of the above 4 to 6, wherein a dry neck-in value defined by the following equation 1 is 10 to 15%:
[ mathematical formula 1]
Dry neck-in { (W1-W2)/W1 } × 100 (%).
(in the formula, W1 represents the width of the polarizing plate-forming film before the drying step, and W2 represents the width of the polarizing plate-forming film after the drying step).
8. A polarizing plate comprising the polarizer according to any one of 1 to 3 and a polarizer protective film bonded to at least one surface of the polarizer.
9. An image display device comprising the polarizing plate according to 9.
Effects of the invention
The polarizing plate of the present invention has a low arithmetic mean height, thereby exhibiting a low shrinkage force in the absorption axis direction, and can significantly reduce the stripe-like unevenness accompanying the elongation of the irregularities in the stretching direction.
The method for producing a polarizing plate of the present invention can produce a polarizing plate that exhibits a low shrinkage force in the absorption axis direction and significantly reduces the stripe-like unevenness accompanying the elongation of irregularities in the stretching direction by drying a polarizing plate-forming film in contact with a hot roll for a specific period of time to adjust the drying shrinkage value to a specific range.
Detailed Description
The present invention relates to a polarizing plate having an arithmetic mean height (Sa) of 21.0nm or less, which has a low shrinkage force in the absorption axis direction and is reduced in the occurrence of stripe-like unevenness accompanying the elongation of irregularities in the stretching direction, and a method for producing the same.
The present invention will be described in detail below.
In general, a polarizing plate produced by stretching a film for forming a polarizing plate shrinks during drying in the production process, and excessive drying shrinkage occurs in the shrinkage process, resulting in a problem that stripe-like unevenness occurs along with the extension of unevenness in the stretching direction. When a polarizing plate to be used in an image display device or the like thereafter is heated from the outside, a shrinkage force in the absorption axis direction, which cannot be sufficiently eliminated, appears, and there is a problem that the polarizing plate is deformed.
Therefore, by adjusting the arithmetic average height (Sa) of the polarizing plate of the present invention to 21.0nm or less, the shrinkage force in the absorption axis direction and the stripe-like unevenness extending in the stretching direction with the unevenness can be significantly reduced.
The inventors of the present invention supported the polarizing plate-forming film by the heat roll when the polarizing plate-forming film was dried by being brought into contact with the heat roll, and controlled the shrinkage of the polarizing plate in the width direction (direction perpendicular to the stretching direction) to suppress the irregularities due to the deformation of the polarizing plate in the width direction, and therefore suppressed the streaky unevenness accompanying the extension of the irregularities in the stretching direction. Further, by controlling the shrinkage of the polarizing plate in the width direction, the thickness of the polarizing plate forming film is further reduced to such an extent that the shrinkage force in the stretching (absorption axis) direction of the polarizing plate is reduced. Although the determination is made as described above, it is not to be construed as limited thereto.
The present inventors adjusted the arithmetic mean height (Sa) of the polarizing plate to 21.0nm or less, thereby reducing the shrinkage force in the absorption axis direction and significantly reducing the stripe-like unevenness caused by the ruggedness extending in the stretching direction. The lower limit is not particularly limited as long as the arithmetic average height of the polarizing plate is 21.0nm or less, since the effect as the object of the present invention can be achieved, and may be, for example, 1.0nm or more, 0.1nm or more, or more than 0 nm. The arithmetic mean height of the polarizing plate may be 21.0nm or less, but is preferably 19.0nm or less, and more preferably 17.0nm or less. The arithmetic mean height (Sa) can be determined, for example, on the basis of ISO 25178. In the present invention, in order to adjust the arithmetic mean height (Sa) of the polarizing plate to 21.0nm or less, the adjustment can be made by controlling the ratio of the hot roll drying time in the entire drying time to 50% or more.
The polarizing plate of the present invention whose arithmetic mean height is adjusted may have a relatively low thickness as compared with a general polarizing plate, and from these viewpoints, the lower limit of the thickness of the polarizing plate may be 5 μm or 7 μm. The upper limit of the thickness of the polarizing plate may be 30 μm, 28 μm or 23 μm. In the present invention, in order to adjust the thickness of the polarizing plate to the above range, the ratio of the hot roll drying time in the total drying time may be adjusted to 50% or more.
On the other hand, the polarizing plate of the present invention has a low shrinkage force in the absorption axis direction as described above, and for example, the shrinkage force in the absorption axis direction may be 3N/2mm or less. When the contraction force in the absorption axis direction is 3N/2mm or less, the deformation of the polarizing plate can be effectively prevented. The lower limit is not particularly limited as the contraction force in the absorption axis direction is preferably lower, and may be, for example, 2N/2mm or more, 1N/2mm or more, or 0.1N/2mm or more. In the present invention, in order to adjust the shrinkage force of the polarizing plate to the above range, the ratio of the hot roll drying time in the total drying time may be adjusted to 50% or more.
The present invention also provides a method for producing the polarizing plate.
The method for producing a polarizing plate of the present invention comprises steps of swelling, dyeing, stretching, crosslinking and drying of a polarizing plate-forming film, wherein the drying step comprises a step of drying the polarizing plate-forming film by bringing the polarizing plate-forming film into contact with a hot roll, and the time for bringing the polarizing plate-forming film into contact with the hot roll is 50% or more of the total drying time.
The method for producing a polarizing plate of the present invention will be described in more detail below.
The polarizer-forming film used for producing the polarizer is not particularly limited as long as it is a polymer film used for producing a polarizing plate, and films which are known in the art and can be dyed with a dichroic substance (e.g., iodine) may be used, and for example, a polyvinyl alcohol film or a partially saponified polyvinyl alcohol film; hydrophilic polymer films such as polyethylene terephthalate films, ethylene-vinyl acetate copolymer films, ethylene-vinyl alcohol copolymer films, cellulose films, and partially saponified films thereof; or a polyolefin-based oriented film such as a dehydrated polyvinyl alcohol-based film or a desalted polyvinyl chloride-based film; and the like. Among them, the polyvinyl alcohol film is preferable in terms of not only having an excellent effect of enhancing uniformity of polarization degree in a plane but also having excellent dyeing affinity for iodine.
The method for manufacturing a polarizing plate of the present invention may include a swelling step, a dyeing step, a crosslinking step, a color-complementing step, a stretching step, a water-washing step, and a drying step, and may be classified by a stretching method. For example, a dry stretching method, a wet stretching method, or a hybrid stretching method in which the 2 stretching methods are mixed may be mentioned. The method for producing the polarizing plate of the present invention will be described below by taking a wet stretching method as an example, but the method is not limited thereto.
The remaining steps other than the drying step among the above steps may be performed in a state where the polarizing plate forming film is immersed in a constant temperature water bath (bath) filled with 1 or more kinds of solutions selected from various solutions.
< swelling step >
The swelling step is a step of immersing the unstretched polarizing plate-forming film in a swelling tank filled with an aqueous swelling solution before dyeing, and is a step of removing impurities such as dust and an anti-blocking agent accumulated on the surface of the polarizing plate-forming film to swell the polarizing plate-forming film, thereby improving the stretching efficiency, preventing dyeing unevenness, and improving the physical properties of the polarizing plate.
The aqueous solution for swelling may be any one known in the art, and for example, water (pure water or deionized water) may be used alone, and when a small amount of glycerin or potassium iodide is added thereto, the polymer film may be swollen and the processability may be improved. Preferably, the content of glycerin is 5 wt% or less and the content of potassium iodide is 10 wt% or less with respect to 100 wt% of water.
The temperature of the swelling bath is not particularly limited, and may be 20 to 45 ℃, for example, 25 to 40 ℃.
The execution time of the swelling step (swelling bath immersion time) may be any one known in the art, and may be, for example, 180 seconds or less, preferably 150 seconds or less. When the immersion time is in the above range, swelling is suppressed from excessively reaching a saturated state, and breakage due to softening of the polarizing plate forming film can be prevented, so that iodine adsorption in the dyeing step becomes uniform, and the degree of polarization can be improved.
The stretching step may be performed simultaneously with the swelling step, and in this case, the stretching ratio may be about 1.1 to 3.5 times, is not limited, and may preferably be 1.3 to 3.0 times. If the stretching ratio is less than 1.1 times, wrinkles may be generated, and in the case of more than 3.5 times, the initial optical characteristics may become weak.
< dyeing step >
The dyeing step is a step of immersing the polarizing plate-forming film in a dyeing bath filled with an aqueous solution for dyeing containing a dichroic substance such as iodine to adsorb iodine to the polarizing plate-forming film.
The aqueous solution for dyeing may be any aqueous solution for dyeing known in the art without particular limitation, and may contain water, a water-soluble organic solvent or a mixed solvent thereof, and iodine. The content of iodine may be 0.4 to 400mmol/L in the aqueous solution for dyeing, however, is not limited thereto, and is preferably 0.8 to 275mmol/L, and most preferably 1 to 200 mmol/L.
The aqueous solution for dyeing may further contain an iodide as a dissolution assistant in order to improve dyeing efficiency. As the iodide, an iodide known in the art may be used without limitation, and for example, at least 1 selected from potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide may be contained, and among them, potassium iodide is preferable in terms of its high solubility in water. The content of the iodide may be 0.01 to 10% by weight with respect to 100% by weight of water, however, is not limited, and may preferably be 0.1 to 5% by weight.
In addition, in order to increase the content of the iodine complex in the polarizing plate-forming film, boric acid may be added in an amount of 0.3 to 5 wt% with respect to 100 wt% of water in the dyeing bath, but is not limited thereto. In the case where the boric acid content of the dyeing bath is less than 0.3% by weight, it is possible for PVA-I3 －Complex and PVA-I5 －The increase in the complex content is not effective, and in the case where the boric acid in the dyeing bath is at a concentration higher than 5% by weight, the risk of film breakage may increase.
The temperature of the dyeing bath may be 5 to 42 ℃, however, is not limited thereto, and may preferably be 10 to 35 ℃. The time for immersing the polarizing plate-forming film in the dyeing bath is not particularly limited, and may be 1 to 20 minutes, and preferably 2 to 10 minutes.
In the present invention, the stretching step may be carried out simultaneously with the dyeing step, and in this case, the stretching ratio may be 1.01 to 2.0 times, but is not limited thereto, and may preferably be 1.1 to 1.8 times.
In addition, the cumulative stretching ratio up to the dyeing step including the swelling and the dyeing step may be 1.2 to 4.0 times. If the cumulative stretching ratio is less than 1.2 times, wrinkles of the film may occur to cause poor appearance, and if it is more than 4.0 times, the initial optical characteristics may become weak.
< step of crosslinking >
The crosslinking step is a step of immersing the dyed polarizing plate-forming film in an aqueous solution for crosslinking so that the dyeability due to physically adsorbed iodine molecules is not lowered by the external environment, and fixing the adsorbed iodine molecules.
When the crosslinking reaction of iodine as a dichroic dye is insufficient, iodine molecules are detached by a moist heat environment, and thus a sufficient crosslinking reaction is required. In addition, in order to orient the iodine molecules between molecules of the polarizing plate forming film and improve the optical properties, stretching may be performed at the maximum stretching ratio in the crosslinking step.
In the present invention, the method for producing the polarizing plate may use any crosslinking step known in the art without particular limitation, and for example, a crosslinking step comprising a first and second crosslinking steps may be carried out, and an aqueous solution containing a boron compound for crosslinking may be used for 1 or more of the first and second crosslinking steps. This can improve the optical characteristics and color durability of the polarizing plate.
The aqueous solution for crosslinking may be any aqueous solution for crosslinking known in the art without particular limitation, and may contain, for example, water as a solvent and a boron compound such as boric acid or sodium borate, or may further contain an organic solvent and an iodide which are mutually soluble together with water.
The boron compound imparts a short crosslinking bond and rigidity to the polarizing plate, and suppresses the occurrence of wrinkles in the film during the process, thereby improving the handling properties of the film and forming an iodine orientation effect of the polarizing plate.
The content of the boron compound may be a content known in the art, and for example, may be 1 to 10% by weight, and may preferably be 2 to 6% by weight, with respect to 100% by weight of water. When the content is less than 1% by weight, the crosslinking effect of the boron compound is reduced and it is difficult to impart rigidity to the polarizing plate, and when the content is more than 10% by weight, the crosslinking reaction of the inorganic crosslinking agent is excessively activated and it is difficult to efficiently perform the crosslinking reaction of the organic crosslinking agent.
In this step, an iodide may be used in order to maintain uniformity of the in-plane polarization degree of the polarizing plate and to prevent desorption of the stained iodine. The iodide may be the same as the iodide used in the dyeing step, and the content thereof may be 0.05 to 15% by weight with respect to 100% by weight of water, and is not limited, and may preferably be 0.5 to 11% by weight. If the content is less than 0.05 wt%, iodine ions in the film may be detached to increase the transmittance of the polarizing plate, and if it exceeds 15 wt%, iodine ions in the aqueous solution may penetrate into the film to decrease the transmittance of the polarizing plate.
In the present invention, the temperature of the crosslinking bath may be 20 to 70 ℃, but is not limited thereto. The immersion time of the polarizing plate forming film in the crosslinking bath may be 1 second to 15 minutes, but is not limited thereto, and may be preferably 5 seconds to 10 minutes.
The stretching step may be performed simultaneously with the crosslinking step, and in this case, the stretching ratio of the first crosslinking step may be 1.4 to 3.0 times, and may preferably be 1.5 to 2.5 times.
In addition, the stretching ratio of the second crosslinking step may be 1.01 to 2.0 times, and may preferably be 1.2 to 1.8 times.
The cumulative stretching ratio in the first and second crosslinking steps may be 1.5 to 5.0 times, but is not limited thereto, and may preferably be 1.7 to 4.5 times. If the cumulative stretching ratio is less than 1.5 times, the iodine orientation effect may be insufficient, and if it is more than 5.0 times, the film may be broken by excessive stretching, and the productivity may be lowered.
< step of complementary color >
The method for manufacturing a polarizing plate of the present invention may further include a complementary color step as necessary. In the polarizing plate-forming film physically adsorbed with the iodine complex, the iodine complex located between molecules in the polarizing plate-forming film can be oriented in a manner close to boric acid crosslinking, and the iodine complex can be stabilized by the color compensation step. In addition, the color can be corrected by the color correction step for the polarizing plate-forming film that is insufficiently dyed with the iodine complex in the crosslinking step.
The aqueous solution for color correction in the color correction step may contain, for example, water as a solvent and a boron compound such as boric acid, and may further contain an organic solvent and an iodide which are mutually soluble together with water.
In the present invention, the boron compound imparts a short crosslinking bond and rigidity to the polarizing plate, and suppresses the formation of wrinkles in the film during the process, thereby improving the handling properties of the film and contributing to the formation of iodine orientation in the polarizing plate.
The content of the boron compound may be 1 to 10% by weight with respect to 100% by weight of water, but is not limited thereto, and may preferably be 2 to 6% by weight. When the content is less than 1% by weight, the crosslinking effect of the boron compound is reduced and it is difficult to impart rigidity to the polarizing plate, and when the content is more than 10% by weight, the crosslinking reaction of the inorganic crosslinking agent is excessively activated and it is difficult to efficiently perform the crosslinking reaction of the organic crosslinking agent.
In this step, an iodide may be used in order to maintain uniformity of the degree of polarization in the plane of the polarizing plate and to prevent desorption of stained iodine. The iodide may be the same as the iodide used in the dyeing step, and the content thereof may be 0.05 to 15% by weight with respect to 100% by weight of water, but is not limited thereto, and may preferably be 0.5 to 11% by weight. If the content is less than 0.05 wt%, iodine ions in the film may be detached to increase the transmittance of the polarizing plate, and if it exceeds 15 wt%, iodine ions in the aqueous solution may penetrate into the film to decrease the transmittance of the polarizing plate.
In the present invention, the temperature of the color compensating tank may be 20 to 70 ℃. The immersion time of the polarizing plate forming film in the color correction bath may be 1 second to 15 minutes, but is not limited thereto, and may be preferably 5 seconds to 10 minutes.
The stretching step may be performed simultaneously with the complementary color step, and in this case, the stretching ratio of the complementary color step may be 1.01 to 1.1 times, but is not limited thereto, and may be preferably 1.02 to 1.08 times.
If the stretching ratio is less than 1.01 times, the effect of stabilizing the iodine complex may become insufficient, and if it is more than 1.1 times, the film may be broken by excessive stretching, and the productivity may be lowered.
< stretching step >
In the present invention, the stretching step may be performed simultaneously with the other steps as described above, or may be performed separately.
The stretching step may be performed at least 1 time, or may be performed a plurality of times. When the polarizing plate is produced a plurality of times, the polarizing plate may be produced separately in an arbitrary step in the production process of the polarizing plate.
In the production method of the present invention, the total cumulative stretching ratio of the polarizing plate is preferably 4.0 to 7.0 times, more preferably 5.3 to 6 times.
In the present specification, the "cumulative stretch ratio" refers to a value obtained by multiplying the stretch ratios of the respective steps.
< Water washing step >
The method for producing a polarizing plate of the present invention may further include a washing step of immersing the crosslinked and stretched polarizing plate-forming film in a washing tank filled with an aqueous washing solution, if necessary, and removing unnecessary residues such as boric acid adhering to the polarizing plate-forming film in the step before the washing step.
In the present invention, the aqueous washing solution may be any aqueous washing solution known in the art, and may be, for example, water, or an iodide may be added thereto, but is not limited thereto.
In the present invention, the temperature of the rinsing bath may be 10 to 60 ℃, but is not limited thereto, and may be preferably 15 to 40 ℃.
The water washing step may be omitted or may be carried out at the end of each step before the water washing step such as the dyeing step or the crosslinking step. The repetition may be carried out 1 or more times, and the number of repetitions is not particularly limited.
< drying step >
In the manufacturing method of the present invention, the drying step is a step of drying the polarizing plate-forming film that has been washed with water, and is a step of obtaining a polarizing plate having excellent optical characteristics by further improving the orientation of the dyed iodine molecules by utilizing the neck-in (neck-in) due to the drying. The neck-in refers to a narrowing of the width of the film.
The drying step of the present invention includes a step of drying the polarizer-forming film by bringing the polarizer-forming film into contact with a heat roll, and a time for bringing the polarizer-forming film into contact with the heat roll is 50% or more of a total drying time.
As shown in the above-described study, the present invention can achieve the effect of the present invention as an object by drying the polarizing plate forming film by contacting it with a heat roll, in which the time for contacting the film with the heat roll is adjusted to 50% or more of the total drying time. Specifically, the time for bringing the polarizing plate forming film into contact with the hot roll may be 30 to 600 seconds, preferably 40 to 120 seconds, more preferably 40 to 60 seconds, and particularly preferably 42 to 58 seconds.
In the present invention, the heat roll is a roll heated at a temperature higher than the ambient temperature. For example, the heat roll may also have a temperature of about 5 to 20 ℃ higher than the ambient temperature. The number of the heat rolls may be 1 or more.
In the present invention, the total drying time is the time during which the drying step is performed, and is the time during which a certain drying method is performed on the polarizing plate forming film. For example, if the drying is carried out by contacting the heat roller, a time for contacting the film with the heat roller is included in the entire drying time, a time for conveying the film between the heat roller and the heat roller is included in the case of using a plurality of heat rollers, a time for blowing hot air to the film is included in the entire drying time if the hot air drying is performed, a time for blowing air to the film is included in the entire drying time if the air drying is performed, a time for heating the film is included in the entire drying time if the heat drying is performed, a time for irradiating far infrared rays to the film is included in the entire drying time if the far infrared drying is performed, and a time for irradiating microwaves to the film is included in the entire drying time if the microwave drying is performed. Therefore, the total drying time includes a time for carrying out a drying method other than the method of drying the polarizing plate forming film by contacting it with a heat roll.
In the present invention, when the time for which the polarizer-forming film is in contact with the hot roll is 50% or more of the total drying time, the polarizer having an arithmetic mean height (Sa) of 21.0nm or less can be easily produced, and the shrinkage force in the absorption axis direction of the produced polarizer and the streaky unevenness accompanying the elongation of the unevenness in the stretching direction can be reduced.
In the drying step of the present invention, the neck-in value of the polarizer may be adjusted, and for example, the drying neck-in value defined by the following numerical formula 1 may be 10 to 15%:
[ mathematical formula 1]
Dry neck { (W1-W2)/W1 }. times.100 (%)
(in the formula, W1 represents the width of the polarizing plate-forming film before the drying step, and W2 represents the width of the polarizing plate-forming film after the drying step).
In the present invention, in order to adjust the drying neck-in value of the polarizing plate to the above range, the drying time ratio of the hot roll can be adjusted to 50% or more in the entire drying time.
When the drying shrinkage value is within the above range, the effect of reducing the shrinkage force in the axial direction and the unevenness in the stretching direction can be more remarkably absorbed.
In the present invention, the drying step may be carried out in parallel with hot air drying while the polarizing plate-forming film is in contact with the hot roll. In this case, the temperature of the hot air may be, for example, 20 to 100 ℃, and the temperature of the heat roll may be set to be equal to or higher than the temperature of the hot air, for example, 5 to 20 ℃ higher. The temperature of the heat roller is preferably 100 ℃ or lower from the viewpoint of preventing deterioration of the polarizing plate.
The total drying time is not particularly limited, and may be, for example, 1 to 10 minutes. The drying time by hot air among all drying times is not particularly limited, and may be, for example, 0 to 2 minutes.
In the present invention, drying methods known in the art may be used in combination without limitation other than hot air drying, and for example, air drying, heat drying, far infrared drying, microwave drying, and the like may be used.
The polarizer of the present invention may be provided as a polarizing plate by bonding a polarizer protective film to at least one surface thereof.
The material of the polarizer protective film is not particularly limited, and for example, various transparent resin films including at least 1 selected from an acrylic resin film, a cellulose resin film, a polyolefin resin film, and a polyester resin film can be used.
Specific examples of the protective film include acrylic resin films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; polyester resin films such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate and polybutylene terephthalate; cellulose resin films such as diacetylcellulose, triacetylcellulose, and cellulose acetate propionate; polyolefin resin films such as polyethylene, polypropylene, polyolefin resins having a cyclic or norbornene structure, and ethylene-propylene copolymers; etc., however, are not limited thereto.
The thickness of the protective film is not particularly limited, and may be 10 to 200 μm, preferably 10 to 150 μm. In the case where polarizer protective films are laminated on both sides of the polarizer, the respective protective films may have the same or different thicknesses from each other.
The polarizer and the polarizer protective film may be bonded to each other using an adhesive composition. The bonding of the polarizing plate and the protective film using the adhesive composition can be carried out by a suitable method, and examples thereof include a method in which the adhesive composition is applied to the adhesive surface of the polarizing film and/or the protective film by a casting method, a meyer bar coating method, a gravure coating method, a die coating method, a dip coating method, a spray method, or the like, and the both are superposed. The casting method is a method of applying an adhesive composition to a surface of a polarizing plate or a protective film as an object to be coated while moving the polarizing plate or the protective film in a substantially vertical direction, a substantially horizontal direction, or an oblique direction therebetween.
After the adhesive composition is applied, the polarizing plate and the protective film are sandwiched and bonded by a nip roll.
In order to improve the adhesiveness, the surface of the polarizing plate and/or the protective film may be appropriately subjected to a surface treatment such as a plasma treatment, a corona treatment, an ultraviolet irradiation treatment, a flame treatment, or a saponification treatment. Examples of the saponification treatment include a method of immersing the resin in an aqueous solution of an alkali such as sodium hydroxide or potassium hydroxide.
The polarizing plate and the polarizing plate protective film are laminated and then subjected to a drying treatment. The drying treatment may be performed by, for example, spraying hot air, and the temperature in this case may be appropriately selected from the range of 50 to 100 degrees. The drying time is generally 30 to 1000 seconds.
The polarizing plate of the present invention can be applied not only to a general liquid crystal display device but also to various image display devices such as an organic electroluminescent display device (OLED), a plasma display device, and a field emission display device.
Although the preferred embodiments are described below to facilitate understanding of the present invention, these embodiments are merely examples illustrating the present invention and are not examples limiting the scope of the appended claims, and it will be apparent to those skilled in the art that various changes and modifications may be made to the embodiments within the scope of the present invention and the technical spirit, and these changes and modifications naturally fall within the scope of the claims of the present invention.
< example 1 >
A transparent unstretched polyvinyl alcohol film (PE60, KURARAY) having a degree of saponification of 99.9% or more was immersed in water (deionized water) at 25 ℃ for 2 minutes to swell the film (swelling step), and then immersed in a 30 ℃ aqueous solution for dyeing containing 2.0mM/L of iodine and 100 wt% of water, 1.1 wt% of potassium iodide and 0.3 wt% of boric acid, for 2 minutes and 14 seconds to dye the film (dyeing step). At this time, in the swelling and dyeing steps, stretching was performed at stretching ratios of 1.482 times and 1.607 times, respectively. Then, the sheet was immersed in a crosslinking aqueous solution containing 11.0 wt% of potassium iodide and 4 wt% of boric acid based on 100 wt% of water at 53 ℃ for 39 seconds (crosslinking step) to crosslink the sheet, and simultaneously stretched at a stretching ratio of 2.266 times. Then, the resultant was immersed in an aqueous solution of color-compensating water at 40 ℃ containing 11 wt% of potassium iodide and 4 wt% of boric acid with respect to 100 wt% of water for 9 seconds (color-compensating step), and stretched at 1.05 times.
After the polyvinyl alcohol film having been crosslinked was washed with deionized water (washing step), it was dried with hot rolls and hot air (drying step), and a polarizing plate having a transmittance of 42.5% was produced. Specific conditions of the heat roll and the hot air are shown in table 1 below.
A triacetyl cellulose (TAC) film was laminated on both sides of the manufactured polarizer to manufacture a polarizing plate.
< examples 2 to 9 and comparative examples 1 to 5 >
Polarizing plates were produced in the same manner as in example 1, except that the temperatures of the hot roll and hot air and the drying time were adjusted as shown in table 1 below.
[ Table 1]
[ Table 1]
< test example >
The physical properties of the polarizing plates and polarizers manufactured in the above examples and comparative examples were measured by the following methods, and the results thereof are shown in table 2 below.
< 1. measurement of drying shrinkage breadth >
The drying neck-in, which means a reduction ratio of the polarizing plate before and after drying, was measured by the above equation 1.
< 2. measurement of unevenness
After the production of the polarizing plate, whether or not stripe-like unevenness extending in the stretching direction with the irregularities was observed was visually checked by a fluorescent lamp reflection method according to the following criteria. The fluorescent lamp reflection method is an evaluation method in which light incident on a fluorescent lamp from an oblique direction of about 45 ° is reflected and unevenness of a polarizing plate is visually checked by the reflected light.
Lv 1.: the obtained polarizing plate was not observed in the uneven level
Lv 2.: the obtained polarizing plate was observed to have unevenness by a fluorescent lamp reflection method, but the level of unevenness was not observed by visual observation
Lv 3.: the obtained polarizing plate was observed to have unevenness by a fluorescent lamp reflection method and to have a level of unevenness visually observed
Determination of the arithmetic mean height (Sa) of the PVA surface >
After the manufactured polarizing plate was cut into a size of 1cm × 1cm, the arithmetic average height in the polarizing plate plane was measured based on ISO 25178-2 using a surface interferometer (ZYGO, MetroPro corporation).
< 4. measurement of contractile force >
Here, the shrinkage force in the absorption axis direction per 2mm width in the transmission axis direction of the polarizing plate was measured. The polarizing plates manufactured in examples and comparative examples were cut into a size of 3.0cm (absorption axis direction) × 2mm (transmission axis direction), and then, a shrinkage force in the absorption axis direction was measured after being left stand at 80 ℃ for 4 hours by using DMA Q800(Dynamic mechanical analyzer, TA corporation). In this case, measurement was performed after applying a minimum load in the thickness direction of the polarizing plate to maintain the polarizing plate in a flat state before measurement.
< 5. optical Property (degree of polarization) >
The polarizing plate thus produced was cut into a size of 4cm × 4cm, and then the transmittance was measured by using an ultraviolet-visible light spectrometer (V-7100, JASCO Co., Ltd.). In this case, the degree of polarization is defined by the following equation 2.
[ mathematical formula 2]
Degree of polarization (P) [ (T)1－T2)/(T1+T2)]1/2
(in the formula, T1The parallel transmittance, T, obtained when a pair of polarizing plates are arranged in a state where the absorption axes are parallel to each other2Is a perpendicular transmittance obtained when a pair of polarizing plates are arranged in a state where the absorption axes are perpendicular to each other).
[ Table 2]
[ Table 2]
As can be seen from table 2, the polarizing plate subjected to the drying step of the present invention was substantially not inferior in terms of polarization degree to comparative examples 3 and 5 which were dried only with hot air, but the striped unevenness caused by the unevenness extending in the stretching direction and the shrinkage force in the absorption axis direction were significantly reduced as compared with all of the comparative examples.
Claims (2)
1. A method for manufacturing a polarizing plate is provided,
the manufacturing method comprises the steps of swelling, dyeing, stretching, crosslinking and drying of the film for forming the polarizing plate,
the drying step includes a step of drying the polarizer-forming film by contacting it with a heat roll,
the time for which the polarizing plate-forming film is brought into contact with a hot roll is 50% or more of the total drying time,
the drying step further comprises a hot air drying step,
The temperature of the hot roll is set to be 5 to 20 ℃ higher than the temperature of the hot air.
2. The polarizing plate production method according to claim 1, wherein,
the drying shrinkage value defined by the following mathematical formula 1 is 10% to 15%:
dry neck-in { (W1-W2)/W1 } × 100 (%) equation 1
In the formula, W1 represents the width of the polarizing plate-forming film before the drying step, and W2 represents the width of the polarizing plate-forming film after the drying step.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150155196A KR20170052991A (en) | 2015-11-05 | 2015-11-05 | Polarizer and method of preparing the same |
| KR10-2015-0155196 | 2015-11-05 | ||
| PCT/JP2016/082655 WO2017078092A1 (en) | 2015-11-05 | 2016-11-02 | Polarizer and method for producing same |
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| Publication Number | Publication Date |
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| CN108351453A CN108351453A (en) | 2018-07-31 |
| CN108351453B true CN108351453B (en) | 2022-07-15 |
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| CN201680062513.2A Active CN108351453B (en) | 2015-11-05 | 2016-11-02 | Polarizing plate and method for producing same |
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| JP (1) | JP6942055B2 (en) |
| KR (2) | KR20170052991A (en) |
| CN (1) | CN108351453B (en) |
| TW (1) | TWI762455B (en) |
| WO (1) | WO2017078092A1 (en) |
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| TWI801395B (en) * | 2017-09-13 | 2023-05-11 | 日商日東電工股份有限公司 | Polarizing film, polarizing plate, polarizing plate roll, and method for manufacturing polarizing film |
| JP7096700B2 (en) * | 2017-09-13 | 2022-07-06 | 日東電工株式会社 | A method for manufacturing a polarizing film, a polarizing plate, a polarizing plate roll, and a polarizing film. |
| TWI823856B (en) * | 2017-09-13 | 2023-12-01 | 日商日東電工股份有限公司 | Polarizing film, polarizing plate, polarizing plate roll material and polarizing film manufacturing method |
| TWI762667B (en) * | 2017-09-13 | 2022-05-01 | 日商日東電工股份有限公司 | Polarizing film, polarizing plate, polarizing plate roll, and manufacturing method of polarizing film |
| TWI775885B (en) * | 2017-09-13 | 2022-09-01 | 日商日東電工股份有限公司 | Polarizing plate and polarizing plate coil |
| JP7355587B2 (en) * | 2018-10-15 | 2023-10-03 | 日東電工株式会社 | Polarizing plate with retardation layer and image display device using the same |
| JP7377024B2 (en) * | 2019-08-26 | 2023-11-09 | 日東電工株式会社 | Polarizing film drying device, drying method and manufacturing method thereof |
| JP2023038489A (en) * | 2021-09-07 | 2023-03-17 | 住友化学株式会社 | Polarizing film and manufacturing method for polarizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020015807A1 (en) * | 2000-06-19 | 2002-02-07 | Youichirou Sugino | Polarizer, polarizing plate, and liquid crystal display using the same |
| JP4421886B2 (en) * | 2003-12-15 | 2010-02-24 | 住友化学株式会社 | Method for producing iodine polarizing film and method for producing polarizing plate |
| US8049850B2 (en) * | 2004-12-28 | 2011-11-01 | Fujifilm Corporation | Liquid crystal display device, optical compensatory sheet, and polarizer and liquid crystal display device employing the same |
| JP4764659B2 (en) * | 2005-04-28 | 2011-09-07 | 日本合成化学工業株式会社 | Method for producing polyvinyl alcohol film |
| JP5335401B2 (en) | 2008-12-19 | 2013-11-06 | 富士フイルム株式会社 | Polarizing film, polarizing film manufacturing method, polarizing plate, polarizing plate manufacturing method, and anti-reflection film for vehicle |
| JP2012014001A (en) * | 2010-07-01 | 2012-01-19 | Nitto Denko Corp | Method for manufacturing polarizer, polarizer, polarizing plate, optical film and image display device |
| JP5616318B2 (en) * | 2011-12-12 | 2014-10-29 | 日東電工株式会社 | Manufacturing method of polarizing film |
| JP6066707B2 (en) * | 2012-12-13 | 2017-01-25 | 日東電工株式会社 | Manufacturing method of polarizing film |
-
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- 2015-11-05 KR KR1020150155196A patent/KR20170052991A/en unknown
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2016
- 2016-11-02 KR KR1020187010613A patent/KR20180066100A/en not_active Application Discontinuation
- 2016-11-02 WO PCT/JP2016/082655 patent/WO2017078092A1/en active Application Filing
- 2016-11-02 JP JP2017548824A patent/JP6942055B2/en active Active
- 2016-11-02 CN CN201680062513.2A patent/CN108351453B/en active Active
- 2016-11-04 TW TW105135899A patent/TWI762455B/en active
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| TW201723541A (en) | 2017-07-01 |
| WO2017078092A1 (en) | 2017-05-11 |
| KR20170052991A (en) | 2017-05-15 |
| JPWO2017078092A1 (en) | 2018-08-23 |
| KR20180066100A (en) | 2018-06-18 |
| CN108351453A (en) | 2018-07-31 |
| TWI762455B (en) | 2022-05-01 |
| JP6942055B2 (en) | 2021-09-29 |
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