WO2016132960A1 - 偏光子の製造方法 - Google Patents

偏光子の製造方法 Download PDF

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Publication number
WO2016132960A1
WO2016132960A1 PCT/JP2016/053749 JP2016053749W WO2016132960A1 WO 2016132960 A1 WO2016132960 A1 WO 2016132960A1 JP 2016053749 W JP2016053749 W JP 2016053749W WO 2016132960 A1 WO2016132960 A1 WO 2016132960A1
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resin layer
stretching
laminate
pva
polyvinyl alcohol
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PCT/JP2016/053749
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English (en)
French (fr)
Japanese (ja)
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後藤　周作
将寛 八重樫
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日東電工株式会社
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Publication of WO2016132960A1 publication Critical patent/WO2016132960A1/ja

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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

Definitions

  • the present invention relates to a method for manufacturing a polarizer.
  • this invention relates to the manufacturing method of the polarizer which has a non-polarizing part.
  • Some image display devices such as mobile phones and notebook personal computers (PCs) are equipped with internal electronic components such as cameras.
  • Various studies have been made for the purpose of improving the camera performance and the like of such an image display device, but further improvement in camera performance and the like is desired due to the rapid spread of smartphones and touch panel type information processing devices. .
  • a polarizer having a partially non-polarizing portion is required.
  • the non-polarizing part is formed by drilling the polarizer, but there is a problem that a crack occurs in the polarizer during the processing. Therefore, after stretching a laminated film obtained by forming a polyvinyl alcohol-based resin layer on the surface of the resin base film, a stain-proof layer is formed on the surface of the polyvinyl alcohol-based resin layer, and dyed with a dichroic dye.
  • a method of manufacturing a polarizer having a polarizing portion has been proposed (see Patent Document 1).
  • the dye-resisting layer formed on the surface of the polyvinyl alcohol-based resin layer needs to be washed and removed after dyeing depending on the forming material. Even when the stain-proof layer is not removed, since the stain-proof layer is partially present on the surface of the polarizer, for example, there is a problem that bubbles are easily generated when the protective film is bonded. In addition, there is a problem that a non-polarized portion having a predetermined shape cannot be obtained due to a problem such that a part of the dye-proof layer peels off from the surface of the polyvinyl alcohol resin layer at the time of dyeing, and the accuracy is poor. Therefore, a new method for producing a polarizer having a non-polarizing part is desired.
  • the present invention has been made to solve the above-mentioned problems, and a main object of the present invention is to provide a method for manufacturing a polarizer having a non-polarizing part with high productivity.
  • the method for producing a polarizer of the present invention includes a step of forming a polyvinyl alcohol resin layer on a resin substrate to obtain a laminate, a step of dyeing the polyvinyl alcohol resin layer with iodine, and stretching the laminate. And a step of forming a non-polarizing part by bringing a basic solution into contact with the polyvinyl alcohol-based resin layer after the dyeing and stretching.
  • the iodine content in the non-polarizing part is 1.0% by weight or less.
  • the said basic solution is made to contact in the state coat
  • a through hole is formed in the surface protective film.
  • the basic solution is brought into contact with a polyvinyl alcohol resin layer having a thickness of 13 ⁇ m or less.
  • the laminate is obtained by applying a coating solution containing a polyvinyl alcohol-based resin to the resin base material.
  • the laminate is stretched after the dyeing. In one embodiment, the stretching is underwater stretching.
  • the resin base material is peeled off, and the polarization obtained by attaching the surface protective film to the peeled surface so as to be peeled off. The basic solution is brought into contact with the film laminate.
  • the polarizing film laminate is elongated, and through holes are formed in the surface protection film at predetermined intervals in the longitudinal direction and / or the width direction.
  • the acidic solution is brought into contact with the portion of the polyvinyl alcohol-based resin layer in contact with the basic solution.
  • a polarizer having a non-polarizing part can be obtained by a simple operation of bringing a basic solution into contact with a dyed / stretched polyvinyl alcohol resin layer. Further, according to the present invention, the laminate can be stretched even after dyeing, and a polarizer having excellent optical characteristics can be obtained.
  • FIG. 1 is a plan view of a polarizer according to one embodiment of the present invention.
  • FIG. 1 is a plan view of a polarizer according to one embodiment of the invention.
  • the polarizer 1 has a non-polarizing portion 2 formed thereon.
  • the non-polarization part 2 is formed by making content of the dichroic substance contained in a polarizer smaller than the other site
  • FIG. According to such a configuration, cracks and delamination are mechanically compared (for example, by a method of mechanical engraving using a sculpture blade punching, a plotter, a water jet, or the like), compared to a case where a through hole is formed. Quality problems such as (delamination) and paste sticking are avoided. Also, since the content of the dichroic substance itself is reduced, the transparency of the non-polarizing part is maintained better than when the non-polarizing part is formed by decomposing the dichroic substance with laser light or the like. Is done.
  • the small circular non-polarizing part 2 is formed at the center of the upper end of the polarizer 1, but the number, arrangement, shape, size, etc. of the non-polarizing part can be appropriately designed. For example, it is designed according to the position, shape, size, etc. of the camera hole part of the mounted image display device. In this case, it is preferable that the non-polarizing part is substantially circular with a diameter of 10 mm or less.
  • the transmittance of the non-polarizing part is preferably 50% or more, more preferably 60% or more, still more preferably 75% or more, and particularly preferably 90% or more. It is. With such transmittance, desired transparency can be ensured. For example, when the non-polarization part is made to correspond to the camera hole part of the image display device, it is possible to prevent an adverse effect on the photographing performance of the camera.
  • the polarizer (excluding the non-polarized part) preferably exhibits absorption dichroism at any wavelength from 380 nm to 780 nm.
  • the single transmittance of the polarizer (excluding the non-polarizing part) is preferably 40.0% or more, more preferably 42.0% or more, still more preferably 42.5% or more, and particularly preferably 43.0% or more. is there.
  • the degree of polarization of the polarizer (excluding the non-polarizing part) is preferably 99.8% or more, more preferably 99.9% or more, and further preferably 99.95% or more.
  • the thickness of the polarizer is preferably 13 ⁇ m or less, more preferably 8 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the non-polarizing part which was excellent in surface smoothness (for example, generation
  • a non-polarizing part can be favorably formed by setting it as the said thickness.
  • a non-polarizing part can be formed in a short time in contact with a basic solution described later.
  • the thickness of the polarizer is preferably 1.0 ⁇ m or more, more preferably 2.0 ⁇ m or more.
  • iodine is preferably used as the dichroic substance.
  • iodine for example, a non-polarizing part can be satisfactorily formed by contact with a basic solution described later.
  • the non-polarizing part is a part having less dichroic substance content than the other parts.
  • the content of the dichroic material in the non-polarizing part is preferably 1.0% by weight or less, more preferably 0.5% by weight or less, and still more preferably 0.2% by weight or less.
  • desired transparency can be imparted to the non-polarizing part.
  • the lower limit value of the content of the dichroic substance in the non-polarizing part is usually not more than the detection limit value.
  • the iodine content of the non-polarizing part is obtained from a calibration curve prepared in advance using a standard sample, for example, from the X-ray intensity measured by fluorescent X-ray analysis.
  • the difference between the content of the dichroic substance in the other part and the content of the dichroic substance in the non-polarizing part is preferably 0.5% by weight or more, more preferably 1% by weight or more.
  • any appropriate resin can be used as a material for forming the polarizer.
  • PVA resin polyvinyl alcohol resin
  • examples of the PVA resin include polyvinyl alcohol and ethylene-vinyl alcohol copolymer.
  • Polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
  • the ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-vinyl acetate copolymer.
  • the degree of saponification of the PVA-based resin is usually 85 to 100 mol%, preferably 95.0 mol% or more, more preferably 99.0 mol% or more, and particularly preferably 99.93 mol% or more. .
  • the degree of saponification can be determined according to JIS K 6726-1994. By using a PVA-based resin having such a saponification degree, a polarizer having excellent durability can be obtained.
  • the average degree of polymerization of the PVA resin can be appropriately selected according to the purpose.
  • the average degree of polymerization is usually 1000 to 10000, preferably 1200 to 6000, more preferably 2000 to 5000.
  • the average degree of polymerization can be determined according to JIS K 6726-1994.
  • the polarizer includes, for example, a step of forming a PVA resin layer on a resin substrate to obtain a laminate, a step of dyeing the PVA resin layer with iodine, and a step of stretching the laminate And a step of forming a non-polarizing part by bringing a basic solution into contact with the PVA resin layer after dyeing and stretching. According to such a method, a polarizer satisfying the thickness and the optical characteristics (single transmittance, polarization degree) can be obtained.
  • Any appropriate resin can be used as a material for forming the resin base material.
  • ester resins such as polyethylene terephthalate resins, olefin resins such as cycloolefin resins and polypropylene, (meth) acrylic resins, polyamide resins, polycarbonate resins, and copolymer resins thereof.
  • a polyethylene terephthalate resin is used.
  • amorphous polyethylene terephthalate resin is preferably used.
  • amorphous polyethylene terephthalate resin examples include a copolymer further containing isophthalic acid as a dicarboxylic acid, and a copolymer further containing cyclohexanedimethanol as a glycol.
  • the glass transition temperature (Tg) of the resin base material is preferably 120 ° C. or lower, more preferably 100 ° C. or lower. This is because, when the laminate is stretched, stretchability (particularly in water stretching) can be sufficiently secured while suppressing crystallization of the PVA-based resin layer. As a result, a polarizer having excellent optical properties (for example, the degree of polarization) can be manufactured.
  • the glass transition temperature of the resin substrate is preferably 60 ° C. or higher.
  • the glass transition temperature (Tg) is a value determined according to JIS K 7121.
  • the water absorption rate of the resin base material is preferably 0.2% or more, and more preferably 0.3% or more.
  • a resin base material absorbs water, and the water can act as a plasticizer to be plasticized. As a result, the stretching stress can be greatly reduced and the stretchability can be excellent.
  • the water absorption rate of the resin base material is preferably 3.0% or less, more preferably 1.0% or less.
  • the thickness of the resin substrate is preferably 20 ⁇ m to 300 ⁇ m, more preferably 50 ⁇ m to 200 ⁇ m.
  • the surface of the resin base material may be subjected to surface modification treatment (for example, corona treatment) or an easy-adhesion layer may be formed. According to such a process, the laminated body excellent in the adhesiveness of a resin base material and a PVA-type resin layer can be obtained.
  • the resin base material can be used as it is as a protective film.
  • the laminate can be produced by any appropriate method. For example, it is produced by applying a coating liquid containing the PVA-based resin to a resin substrate and drying it as necessary. Moreover, it produces by laminating
  • the coating solution a solution obtained by dissolving the PVA resin in a solvent is typically used.
  • the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. These may be used alone or in combination of two or more. Among these, water is preferable.
  • the PVA resin concentration of the solution can be set to any appropriate value. For example, it is set according to the polymerization degree or saponification degree of the PVA resin.
  • the concentration of the PVA resin in the solution is, for example, 3 to 20 parts by weight with respect to 100 parts by weight of the solvent.
  • the additive may contain an additive.
  • the additive include a plasticizer and a surfactant.
  • the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin.
  • the surfactant include nonionic surfactants. These can be used for the purpose of further improving the uniformity, dyeability and stretchability of the resulting PVA-based resin layer.
  • an easily bonding component is mentioned, for example. By using the easy-adhesion component, the adhesion between the resin base material and the PVA-based resin layer can be improved. As a result, for example, problems such as peeling of the PVA resin layer from the resin base material can be suppressed, and dyeing and underwater stretching described later can be performed satisfactorily.
  • modified PVA such as acetoacetyl-modified PVA is used.
  • Arbitrary appropriate methods can be employ
  • examples thereof include a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, a knife coating method (comma coating method and the like).
  • the coating / drying temperature of the coating solution is, for example, 20 ° C. or higher.
  • the thickness of the PVA resin layer (before stretching) is preferably 3 ⁇ m to 40 ⁇ m, more preferably 3 ⁇ m to 20 ⁇ m, and still more preferably 3 ⁇ m to 15 ⁇ m.
  • Dyeing for example, a method of immersing a PVA resin layer (laminated body) in a dyeing solution containing iodine, a method of applying the dyeing solution to a PVA resin layer, and a method of applying the dyeing solution to a PVA resin The method of spraying on a layer is mentioned.
  • a method of immersing the PVA resin layer in the staining solution is used.
  • the staining solution is preferably an iodine aqueous solution.
  • the amount of iodine is preferably 0.1 to 0.5 parts by weight with respect to 100 parts by weight of water.
  • an iodide to the aqueous iodine solution.
  • the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. Etc. Among these, potassium iodide is preferable.
  • the blending amount of iodide is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of water.
  • the liquid temperature of the staining liquid is preferably 20 ° C. to 50 ° C.
  • the immersion time is preferably 5 seconds to 5 minutes.
  • the staining conditions can be set so that the polarization degree or single transmittance of the finally obtained polarizer falls within a predetermined range.
  • Stretching Any appropriate method can be adopted as a stretching method of the laminate. Specifically, it may be fixed end stretching (for example, a method using a tenter stretching machine) or free end stretching (for example, a method of uniaxial stretching through a laminate between rolls having different peripheral speeds). Moreover, simultaneous biaxial stretching (for example, a method using a simultaneous biaxial stretching machine) or sequential biaxial stretching may be used.
  • the stretching of the laminate may be performed in one stage or in multiple stages. When performed in multiple stages, the stretch ratio of the laminate described later is the product of the stretch ratios of the respective stages.
  • Arbitrary appropriate directions can be selected as the extending
  • the laminate is preferably stretched 4.0 times or more from the original length, more preferably 5.0 times or more.
  • the stretching method is not particularly limited, and may be, for example, an in-air stretching method or an underwater stretching method in which the laminate is immersed in a stretching bath.
  • underwater stretching is performed at least once, and more preferably, air stretching and underwater stretching are combined.
  • the PVA resin layer can be stretched at a temperature lower than the glass transition temperature (typically about 80 ° C.) of the resin base material and the PVA resin layer while suppressing the crystallization. It can be stretched at a high magnification. As a result, a polarizer having excellent optical characteristics can be manufactured.
  • stretching it is preferable to perform underwater extending
  • the stretching temperature of the laminate can be set to any appropriate value depending on the resin base material, the stretching method, and the like.
  • the stretching temperature is preferably equal to or higher than the glass transition temperature (Tg) of the resin substrate, more preferably the glass transition temperature (Tg) of the resin substrate + 10 ° C., and particularly preferably Tg + 15 ° C. That's it.
  • the stretching temperature of the laminate is preferably 170 ° C. or lower.
  • the liquid temperature of the stretching bath is preferably 40 ° C. to 85 ° C., more preferably 50 ° C. to 85 ° C. If it is such temperature, it can extend
  • the glass transition temperature (Tg) of the resin base material is preferably 60 ° C. or higher in relation to the formation of the PVA-based resin layer. In this case, when the stretching temperature is lower than 40 ° C., there is a possibility that the stretching cannot be satisfactorily performed even in consideration of plasticization of the resin base material with water.
  • the higher the temperature of the stretching bath the higher the solubility of the PVA-based resin layer, and there is a possibility that excellent optical properties cannot be obtained.
  • the immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.
  • the laminate When employing an underwater stretching method, it is preferable to stretch the laminate by immersing it in an aqueous boric acid solution (stretching in boric acid in water).
  • an aqueous boric acid solution as the stretching bath, the PVA resin layer can be provided with rigidity that can withstand the tension applied during stretching and water resistance that does not dissolve in water.
  • the boric acid aqueous solution is preferably obtained by dissolving boric acid and / or borate in water as a solvent.
  • the boric acid concentration is preferably 1 to 10 parts by weight with respect to 100 parts by weight of water. By setting the boric acid concentration to 1 part by weight or more, dissolution of the PVA resin layer can be effectively suppressed.
  • an iodide is added to the boric acid aqueous solution. This is because when the PVA resin layer is dyed in advance, elution of iodine can be suppressed.
  • the concentration of iodide is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of water.
  • the underwater stretching is preferably performed after dyeing. This is because the stretchability can be improved.
  • one of the features of the present invention is that the laminate can be stretched after dyeing. According to the present invention, stretching in water can be performed satisfactorily.
  • the laminate is stretched in the air at, for example, 95 ° C. to 150 ° C., and then subjected to a dyeing process, and then stretched in water.
  • the draw ratio of the laminate by air drawing is, for example, 1.5 to 3.5 times, preferably 2.0 to 3.0 times.
  • the draw ratio of the laminate by drawing in water is preferably 2.0 times or more.
  • the non-polarizing part is preferably formed by bringing a basic solution into contact with the PVA resin layer.
  • the iodine content of a contact part can be easily reduced by making a basic solution contact the desired site
  • the basic solution can penetrate into the PVA-based resin layer by contact.
  • the iodine complex contained in the PVA resin layer is reduced by the base contained in the basic solution to become iodine ions. By reducing the iodine complex to iodine ions, the transmittance of the contact portion can be improved.
  • the iodine which became the iodine ion moves to the solvent of a basic solution from a PVA-type resin layer.
  • the non-polarizing part thus obtained can maintain its transparency well. Specifically, when the transmittance is improved by destroying the iodine complex, iodine remaining in the PVA-based resin layer may form an iodine complex again with the use of the polarizer, and the transmittance may decrease. When the iodine content is reduced, such a problem is prevented.
  • any appropriate method can be adopted as the contact method of the basic solution.
  • the method of dripping, coating, and spraying a basic solution with respect to the PVA-based resin layer, and the method of immersing the PVA-based resin layer in the basic solution can be mentioned.
  • any appropriate means for example, protective film, surface protective film
  • the protective film can be used as it is as a protective film for a polarizer.
  • the surface protective film is temporarily used when manufacturing the polarizer. Since the surface protective film is removed from the polarizer at any appropriate timing, typically, the surface protective film is bonded to the PVA-based resin layer via an adhesive layer.
  • any appropriate basic compound can be used as the basic compound contained in the basic solution.
  • the basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, and inorganic alkali metal salts such as sodium carbonate. , Organic alkali metal salts such as sodium acetate, aqueous ammonia and the like. Among these, an alkali metal hydroxide is preferable, and sodium hydroxide, potassium hydroxide, and lithium hydroxide are more preferable.
  • the iodine complex can be efficiently ionized, and the non-polarizing part can be formed more easily.
  • These basic compounds may be used alone or in combination of two or more.
  • Any appropriate solvent can be used as a solvent for the basic solution.
  • Specific examples include water, alcohols such as ethanol and methanol, ethers, benzene, chloroform, and mixed solvents thereof.
  • water and alcohol are preferably used because iodine ions can be favorably transferred to the solvent.
  • the concentration of the basic solution is, for example, 0.01N to 5N, preferably 0.05N to 3N, and more preferably 0.1N to 2.5N.
  • concentration of the basic solution is in such a range, the non-polarizing part can be efficiently formed.
  • the liquid temperature of the basic solution is, for example, 20 ° C. to 50 ° C., preferably 25 ° C. to 50 ° C. By contacting the basic solution at such a temperature, the non-polarizing part can be formed efficiently.
  • the contact time of the basic solution is set according to, for example, the thickness of the PVA resin layer and the type and concentration of the basic compound contained in the basic solution.
  • the contact time is, for example, 5 seconds to 30 minutes, preferably 5 seconds to 5 minutes.
  • the thickness of the polarizer may correspond to the thickness of the PVA-based resin layer in contact with the basic solution.
  • the PVA resin layer surface is coated with a surface protective film so that at least a part of the surface is exposed when the basic solution is contacted.
  • the polarizer in the illustrated example is manufactured by, for example, attaching a surface protection film in which small circular through holes are formed to a PVA resin layer, and bringing a basic solution into contact therewith. At that time, it is preferable that the other side of the PVA-based resin layer (side on which the surface protective film is not disposed) is also protected.
  • the thickness of the surface protective film is typically 20 ⁇ m to 250 ⁇ m, preferably 30 ⁇ m to 150 ⁇ m.
  • the surface protective film is preferably a film having a high hardness (for example, elastic modulus). This is because deformation of the through hole can be prevented.
  • Surface protective film forming materials include ester resins such as polyethylene terephthalate resins, cycloolefin resins such as norbornene resins, olefin resins such as polypropylene, polyamide resins, polycarbonate resins, and copolymer resins thereof. Etc. Preference is given to ester resins (especially polyethylene terephthalate resins). The details of the protective film will be described later.
  • a polarizing film laminate obtained by peeling a resin base material after laminating a protective film on the PVA-based resin layer side of the laminate, and attaching the surface protective film to the peeled surface in a peelable manner. Contact with a basic solution.
  • a protective film different from the resin base material on one side of the PVA-based resin layer in advance, even if the thickness of the PVA-based resin layer is thin as described above, the surface protective film is excellently bonded. be able to.
  • the polarizing film laminated body obtained can be extremely excellent in conveyance property.
  • the through-hole is formed in the longitudinal direction and / or the width direction in the surface protection film at predetermined intervals, for example.
  • the protective film is bonded only to one side of the PVA resin layer.
  • curling is likely to occur (particularly when the thickness of the PVA-based resin layer is 15 ⁇ m or more), and problems such as poor bonding of the surface protective film and reduced transportability are likely to occur. Is thin as described above, the occurrence of curling can be satisfactorily suppressed.
  • the PVA resin layer may be subjected to any appropriate treatment other than the dyeing / stretching.
  • any appropriate treatment other than the dyeing / stretching.
  • insolubilization treatment, cross-linking treatment, washing treatment, and drying treatment can be mentioned.
  • the insolubilization treatment is typically performed by immersing the PVA resin layer in a boric acid aqueous solution.
  • a boric acid aqueous solution When an underwater stretching method is employed, water resistance can be imparted to the PVA-based resin layer by performing insolubilization treatment.
  • the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
  • the liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C. to 40 ° C.
  • the insolubilization process is performed after the laminate is manufactured and before the dyeing process or the underwater stretching process.
  • the crosslinking treatment is typically performed by immersing the PVA resin layer in a boric acid aqueous solution. By performing the crosslinking treatment, water resistance can be imparted to the PVA resin layer.
  • the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
  • blend an iodide by performing a crosslinking process after the said dyeing
  • the blending amount of iodide is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water.
  • the liquid temperature of the crosslinking bath is preferably 20 ° C. to 50 ° C.
  • the crosslinking treatment is performed before the underwater stretching treatment.
  • the dyeing process, the crosslinking process and the underwater stretching process are performed in this order.
  • the cleaning treatment is typically performed by immersing the PVA resin layer in an aqueous potassium iodide solution.
  • the drying temperature for the drying treatment is preferably 30 ° C. to 100 ° C.
  • the basic solution is removed from the PVA resin layer by any appropriate means after contacting the PVA resin layer.
  • permeability of the non-polarizing part accompanying use of a polarizer can be prevented more reliably, for example.
  • Specific examples of the method for removing the basic solution include washing, wiping removal with a waste cloth, suction removal, natural drying, heat drying, air drying, vacuum drying, and the like.
  • the basic solution is washed.
  • the solution used for washing include water (pure water), alcohols such as methanol and ethanol, acidic aqueous solutions, and mixed solvents thereof.
  • water is used.
  • the number of washings is not particularly limited, and may be performed a plurality of times.
  • the drying temperature is, for example, 20 ° C. to 100 ° C.
  • the acidic solution is brought into contact with the portion of the PVA-based resin layer in contact with the basic solution.
  • the basic solution remaining in the non-polarizing part can be removed to a better level.
  • the dimensional stability (durability) of a non-polarizing part can be improved.
  • the contact with the acidic solution may be performed after the basic solution is removed or may be performed without removing the basic solution.
  • any appropriate acidic compound can be used as the acidic compound contained in the acidic solution.
  • the acidic compound include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrogen fluoride, and organic acids such as formic acid, oxalic acid, citric acid, acetic acid, and benzoic acid.
  • the acidic compound contained in the acidic solution is preferably an inorganic acid, and more preferably hydrochloric acid, sulfuric acid, or nitric acid. These acidic compounds may be used alone or in combination of two or more.
  • the solvent for the acidic solution those exemplified as the solvent for the basic solution can be used.
  • the concentration of the acidic solution is, for example, 0.01N to 5N, preferably 0.05N to 3N, and more preferably 0.1N to 2.5N.
  • the liquid temperature of the acidic solution is, for example, 20 ° C. to 50 ° C.
  • the contact time of the acidic solution is, for example, 5 seconds to 5 minutes.
  • the contact method of an acidic solution can employ
  • an acidic solution can be removed from a PVA-type resin layer. As a method for removing the acidic solution, a method similar to the method for removing the basic solution may be employed.
  • the polarizing plate of this invention has the said polarizer.
  • the polarizing plate typically includes a polarizer and a protective film disposed on at least one side of the polarizer.
  • the resin base material may be used as it is, or a film different from the resin base material may be used.
  • the material for forming the protective film include cellulose resins such as diacetyl cellulose and triacetyl cellulose, (meth) acrylic resins, cycloolefin resins, olefin resins such as polypropylene, and ester resins such as polyethylene terephthalate resins. , Polyamide resins, polycarbonate resins, and copolymer resins thereof.
  • the surface of the protective film on which the polarizer is not laminated may be subjected to a treatment for the purpose of a hard coat layer, antireflection treatment, diffusion or antiglare as a surface treatment layer.
  • the surface treatment layer is preferably a layer having a low moisture permeability for the purpose of improving the humidification durability of the polarizer.
  • the hard coat treatment is performed for the purpose of preventing scratches on the polarizing plate surface.
  • the hard coat layer can be formed by, for example, a method of adding a cured film excellent in hardness, slipping properties, etc., to an appropriate ultraviolet curable resin such as acrylic or silicone.
  • the hard coat layer preferably has a pencil hardness of 2H or more.
  • the antireflection treatment is performed for the purpose of preventing the reflection of external light on the surface of the polarizing plate, and is based on the interference action of light as disclosed in, for example, Japanese Patent Application Laid-Open No. 2005-248173.
  • Anti-glare treatment is performed for the purpose of preventing the outside light from being reflected on the polarizing plate surface and obstructing the viewing of the transmitted light through the polarizing plate.
  • the surface is roughened by a sandblasting method or an embossing method.
  • a fine concavo-convex structure to the surface of the protective film by an appropriate method such as a blending method of transparent fine particles.
  • the antiglare layer may also serve as a diffusion layer (viewing angle expanding function or the like) for diffusing the light transmitted through the polarizing plate to expand the viewing angle.
  • the thickness of the protective film is preferably 10 ⁇ m to 100 ⁇ m.
  • the protective film is typically laminated on the polarizer via an adhesive layer (specifically, an adhesive layer or an adhesive layer).
  • the adhesive layer is typically formed of a PVA adhesive or an activated energy ray curable adhesive.
  • the pressure-sensitive adhesive layer is typically formed of an acrylic pressure-sensitive adhesive.
  • the image display apparatus of this invention has the said polarizing plate.
  • the image display device include a liquid crystal display device and an organic EL device.
  • the liquid crystal display device includes a liquid crystal panel having a liquid crystal cell and the polarizing plate disposed on one side or both sides of the liquid crystal cell.
  • the organic EL device includes an organic EL panel in which the polarizing plate is disposed on the viewing side.
  • the polarizer is arranged so as to correspond to the camera hole part of the image display device on which the non-polarizing part is mounted.
  • Example 1 (Production of laminate) As the resin substrate, an amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 ⁇ m) having a long water absorption rate of 0.75% and Tg of 75 ° C. was used.
  • IPA copolymerized PET amorphous isophthalic acid copolymerized polyethylene terephthalate
  • One side of the resin substrate was subjected to corona treatment, and polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6) were applied to this corona-treated surface.
  • a saponification degree of 99.0 mol% or more, an aqueous solution containing 9: 1 ratio of Nippon Gosei Kagaku Kogyo Co., Ltd., trade name “Gosefimer Z200”) was applied and dried at 25 ° C. to a thickness of 11 ⁇ m.
  • a PVA resin layer was formed to prepare a laminate.
  • the obtained laminate was immersed in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (insolubilization treatment). Subsequently, it was immersed in a dyeing bath having a liquid temperature of 30 ° C. while adjusting the iodine concentration and the immersion time so that the obtained polarizing plate had a predetermined transmittance.
  • 0.2 parts by weight of iodine was blended with 100 parts by weight of water and immersed in an aqueous iodine solution obtained by blending 1.5 parts by weight of potassium iodide (dyeing treatment). .
  • a PVA resin aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GOHSEIMER (registered trademark) Z-200”, resin concentration: 3% by weight) is applied to the surface of the PVA resin layer of the laminate
  • a triacetyl cellulose film (manufactured by Konica Minolta, trade name “KC4UY”, thickness 40 ⁇ m) were bonded together and heated in an oven maintained at 60 ° C. for 5 minutes to prepare a polarizing plate having a polarizer having a thickness of 5 ⁇ m. .
  • the resin base material was peeled from the obtained polarizing plate, and a surface protective film having a circular through hole with a diameter of 4 mm formed on the peeled surface (polarizer surface) was bonded, and this was bonded to 1 mol / L (1N). It was immersed in an aqueous sodium hydroxide solution for 10 seconds (alkali treatment), and then immersed in 0.1N hydrochloric acid for 30 seconds (acid treatment). Then, it dried at 60 degreeC, the surface protection film was peeled, and the polarizing plate which has a non-polarizing part was obtained. A PET film (thickness 38 ⁇ m, manufactured by Mitsubishi Plastics, trade name: Diafoil) on which a 5 ⁇ m thick adhesive layer was formed was used as the surface protective film.
  • Example 2 The obtained laminate was subjected to the insolubilization treatment after free end uniaxial stretching in the longitudinal direction (longitudinal direction) 2.0 times between rolls having different peripheral speeds in an oven at 120 ° C. (air-assisted stretching).
  • a polarizing plate having a non-polarizing part was obtained in the same manner as in Example 1 except that the stretching in water was performed so that the total stretching ratio was 5.5.
  • Example 3 Polarized light having a non-polarizing part in the same manner as in Example 1 except that a polarizer having a thickness of 12 ⁇ m was formed on the resin substrate and that the immersion time in the aqueous sodium hydroxide solution was 30 seconds in the alkali treatment. I got a plate.
  • Example 4 (Production of laminate) A polyvinyl alcohol film having a thickness of 20 ⁇ m (polymerization degree 4300, saponification degree 99.3 mol%) and a resin base material as an adhesive PVA-based resin aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Gosefimer ( (Registered trademark) Z-200 ", resin concentration: 3% by weight) to obtain a laminate.
  • PVA-based resin aqueous solution manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Gosefimer ( (Registered trademark) Z-200 ", resin concentration: 3% by weight
  • a 100- ⁇ m-thick amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (Tg 75 ° C., water absorption 0.75%) having a corona treatment was used.
  • the obtained laminate was uniaxially stretched in the longitudinal direction (longitudinal direction) 2.0 times between rolls having different peripheral speeds in an oven at 120 ° C. (in-air stretching).
  • the obtained laminate was immersed in a swelling bath (pure water) having a liquid temperature of 30 ° C. (swelling treatment).
  • the laminate was immersed in a dyeing bath having a liquid temperature of 30 ° C. while adjusting the iodine concentration and the immersion time so that the obtained polarizing plate had a predetermined transmittance.
  • 0.15 parts by weight of iodine and 100 parts by weight of potassium iodide were mixed for 60 seconds with 100 parts by weight of water (dyeing treatment). .
  • a PVA-based resin aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GOHSEFIMAR (registered trademark) Z-200”, resin concentration: 3% by weight) was applied to the polyvinyl alcohol film surface of the laminate, A triacetyl cellulose film (manufactured by Konica Minolta, trade name “KC4UY”, thickness 40 ⁇ m) was bonded, and this was heated in an oven maintained at 60 ° C. for 5 minutes to prepare a polarizing plate having a polarizer having a thickness of 8 ⁇ m. Then, the non-polarizing part was formed like Example 1, and the polarizing plate which has a non-polarizing part was obtained.
  • a PVA-based resin aqueous solution manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GOHSEFIMAR (registered trademark) Z-200”, resin concentration: 3% by weight
  • a triacetyl cellulose film manufactured
  • Example 5 The use of a 30 ⁇ m thick PVA film (Kuraray Co., Ltd., PE3000), the iodine concentration of the dyeing bath was set to 0.1% by weight, and the immersion time in the aqueous sodium hydroxide solution was set to 30 seconds in the alkali treatment. Except for this, a polarizing plate having a non-polarizing part was obtained in the same manner as Example 4.
  • Example 6 (Production of laminate) A polyvinyl alcohol film having a thickness of 20 ⁇ m (polymerization degree 4300, saponification degree 99.3 mol%) and a resin base material as an adhesive PVA-based resin aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Gosefimer ( (Registered trademark) Z-200 ", resin concentration: 3% by weight) to obtain a laminate.
  • PVA-based resin aqueous solution manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Gosefimer ( (Registered trademark) Z-200 ", resin concentration: 3% by weight
  • a 100- ⁇ m-thick amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (Tg 75 ° C., water absorption 0.75%) having a corona treatment was used.
  • Example 7 (Production of laminate) A cycloolefin resin film (manufactured by JSR, ARTON) having a Tg of about 120 ° C. was used as the resin base material. An aqueous solution of polyvinyl alcohol resin having a polymerization degree of 4300 and a saponification degree of 99.2% was applied on one side of the resin base material at 80 ° C. and dried to form a PVA resin layer having a thickness of 12 ⁇ m, thereby producing a laminate. .
  • a PVA resin aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GOHSEIMER (registered trademark) Z-200”, resin concentration: 3% by weight) is applied to the surface of the PVA resin layer of the laminate.
  • a triacetyl cellulose film (trade name “KC4UY”, manufactured by Konica Minolta, Inc., thickness 40 ⁇ m) were bonded together and heated in an oven maintained at 60 ° C. for 5 minutes to produce a polarizing plate having a polarizer having a thickness of 5 ⁇ m. .
  • the non-polarizing part was formed like Example 1, and the polarizing plate which has a non-polarizing part was obtained.
  • the polarization degree of the polarizer is a value at a single transmittance of 42.0%. 1.
  • Optical characteristics In each Example, the sample which changed the diameter of the small hole of the surface protection film into 20 mm was produced separately, and these were used for the measurement.
  • a UV-visible spectrophotometer manufactured by JASCO Corporation, product name “V7100”
  • Ts single transmittance
  • Tp parallel transmittance
  • Tc orthogonal transmittance
  • Ts, Tp, and Tc are Y values measured with a two-degree field of view (C light source) of JIS Z 8701 and corrected for visibility.
  • Polarization degree (P) (%) ⁇ (Tp ⁇ Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100 2.
  • Appearance of non-polarizing part The appearance of the non-polarizing part (part corresponding to the small hole of the surface protective film) was observed with an optical microscope (OLYMPUS, MX61, magnification: 5 times).
  • Example 7 a non-polarizing part was formed satisfactorily.
  • the degree of polarization was lower than the others.
  • the wrinkle of the grade which cannot be visually confirmed in the non-polarization part was confirmed. Since wrinkles are generated after the alkali treatment (before the acid treatment), it is predicted that the wrinkles are generated by partially absorbing water in the contact portion of the basic solution and expanding by subsequent treatment.
  • the polarizer of the present invention is suitably used for a mobile phone such as a smartphone, an image display device with a camera (liquid crystal display device, organic EL device) such as a notebook PC or tablet PC.
  • a mobile phone such as a smartphone
  • an image display device with a camera liquid crystal display device, organic EL device
  • a notebook PC or tablet PC such as a notebook PC or tablet PC.

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  • Physics & Mathematics (AREA)
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  • Optics & Photonics (AREA)
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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ophthalmology & Optometry (AREA)
  • Mechanical Engineering (AREA)
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JP2019211528A (ja) * 2018-05-31 2019-12-12 日東電工株式会社 偏光板および画像表示装置
JP2020020973A (ja) * 2018-08-01 2020-02-06 日東電工株式会社 偏光子、偏光板、および、画像表示装置
WO2020121907A1 (ja) * 2018-12-11 2020-06-18 住友化学株式会社 偏光フィルム及びその製造方法
JP7046901B2 (ja) * 2018-12-25 2022-04-04 日東電工株式会社 偏光子、および、その製造方法
CN109890053B (zh) * 2019-01-31 2021-06-11 展讯通信（上海）有限公司 数据发送方法、数据发送设备、多链路系统和存储介质
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