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WO2019208181A1 - Polariseur, rouleau de plaque de polariseur et procédé de production de film polarisant - Google Patents

Polariseur, rouleau de plaque de polariseur et procédé de production de film polarisant Download PDF

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Publication number
WO2019208181A1
WO2019208181A1 PCT/JP2019/015244 JP2019015244W WO2019208181A1 WO 2019208181 A1 WO2019208181 A1 WO 2019208181A1 JP 2019015244 W JP2019015244 W JP 2019015244W WO 2019208181 A1 WO2019208181 A1 WO 2019208181A1
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Prior art keywords
polarizing film
stretching
pva
laminate
less
Prior art date
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PCT/JP2019/015244
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English (en)
Japanese (ja)
Inventor
後藤　周作
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日東電工株式会社
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Publication date
Priority claimed from JP2018089243A external-priority patent/JP7219017B2/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN201980027817.9A priority Critical patent/CN112005144A/zh
Priority to KR1020207030350A priority patent/KR102721828B1/ko
Publication of WO2019208181A1 publication Critical patent/WO2019208181A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • 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
    • 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
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source

Definitions

  • the present invention relates to a polarizing plate, a polarizing plate roll, and a method for producing a polarizing film.
  • OLEDs organic EL panels
  • QLEDs organic light emitting materials
  • These panels have a highly reflective metal layer and are liable to cause problems such as external light reflection and background reflection. Therefore, it is known to prevent these problems by providing a circularly polarizing plate having a polarizing film and a ⁇ / 4 plate on the viewing side.
  • a method for producing a polarizing film for example, there is a method in which a laminate having a resin base material and a polyvinyl alcohol (PVA) resin layer is stretched and then subjected to a dyeing treatment to obtain a polarizing film on the resin base material.
  • PVA polyvinyl alcohol
  • Patent Document 1 It has been proposed (for example, Patent Document 1). According to such a method, a polarizing film having a small thickness can be obtained, and thus has been attracting attention as being able to contribute to the recent thinning of image display devices. In addition, as the display panel performance is improved, if the reflectance of the panel is kept low, the required characteristic of the degree of polarization is lowered, and a polarizing plate with higher transmittance is required. However, attempts to increase the transmittance with conventional thin polarizing films have caused problems such as dissolution of PVA-based resins, and it has not been possible to produce films that can withstand optical applications.
  • the present invention has been made to solve the above-described conventional problems, and its main purpose is to have a polarizing plate, a polarizing plate roll, and a polarizing plate having excellent optical properties and suppressing variations in optical properties, and the same.
  • An object of the present invention is to provide a method for producing such a polarizing film.
  • the polarizing plate of the present invention has a polarizing film having a thickness of 8 ⁇ m or less, a single transmittance of 48% or more, and a polarization degree of 85% or more, and a protective layer disposed on at least one side of the polarizing film The difference between the maximum value and the minimum value of the single transmittance within a 50 cm 2 region is 0.5% or less.
  • Another polarizing plate of the present invention is disposed on at least one side of a polarizing film having a thickness of 8 ⁇ m or less, a single transmittance of 48% or more, and a polarization degree of 85% or more.
  • a polarizing plate having a protective layer the width is 1000 mm or more, and the difference between the maximum value and the minimum value of the single transmittance at a position along the width direction is 1% or less.
  • the single transmittance of the polarizing film is 50% or less, and the degree of polarization is 92% or less.
  • a polarizing plate roll is provided. The polarizing plate roll is formed by winding the polarizing plate into a roll. According to another situation of this invention, the manufacturing method of a polarizing film is provided.
  • This manufacturing method is a manufacturing method of a polarizing film having a thickness of 8 ⁇ m or less, a single transmittance of 48% or more, and a degree of polarization of 85% or more, and is provided on one side of a long thermoplastic resin substrate. And forming a laminate by forming a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin, and in the above-described laminate, an air auxiliary stretching treatment in which a stretching ratio is 2.0 times or more, It includes performing in this order a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment that shrinks 2% or more in the width direction by heating while transporting in the longitudinal direction.
  • the content of the halide in the polyvinyl alcohol-based resin layer is 5 to 20 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol-based resin.
  • the drying shrinkage treatment step is a step of heating using a heating roll. In one embodiment, the temperature of the heating roll is 60 ° C. to 120 ° C., and the shrinkage ratio in the width direction of the laminate by the drying shrinkage treatment is 2% or more.
  • the present invention has a polarizing film having a thickness of 8 ⁇ m or less, a single transmittance of 48% or more, and a polarization degree of 85% or more, and has excellent optical characteristics and variations in optical characteristics. Can be provided.
  • FIG. 1 is a schematic cross-sectional view of a polarizing plate according to one embodiment of the present invention.
  • the polarizing plate 100 includes a polarizing film 10, a first protective layer 20 disposed on one side of the polarizing film 10, and a second protective layer 30 disposed on the other side of the polarizing film 10.
  • the polarizing film has a thickness of 8 ⁇ m or less, a single transmittance of 48% or more, and a degree of polarization of 85% or more.
  • One of the first protective layer 20 and the second protective layer 30 may be omitted.
  • One of the first protective layer and the second protective layer may be a resin substrate (described later) used for manufacturing the polarizing film.
  • the polarizing plate may be long or single-wafer. When a polarizing plate is elongate, it is preferable that it is wound by roll shape and it is set as a polarizing plate roll.
  • the polarizing plate has excellent optical properties and small variations in optical properties.
  • the polarizing plate has a width of 1000 mm or more, and a difference (D1) between the maximum value and the minimum value of the single transmittance at a position along the width direction is 1% or less.
  • the upper limit of D1 is preferably 0.8%, more preferably 0.6%.
  • D1 is preferably as small as possible, but the lower limit is, for example, 0.01%. If D1 is in the above range, a polarizing plate having excellent optical properties can be produced industrially.
  • the polarizing plate has a difference (D2) between the maximum value and the minimum value of the single transmittance within a region of 50 cm 2 of 0.5% or less.
  • the upper limit of D2 is preferably 0.25%, more preferably 0.15%.
  • D2 is preferably as small as possible, but the lower limit is, for example, 0.01%.
  • the polarizing film has a thickness of 8 ⁇ m or less, a single transmittance of 48% or more, and a polarization degree of 85% or more.
  • the single transmittance and the degree of polarization are in a trade-off relationship with each other. Increasing the single transmittance can decrease the degree of polarization, and increasing the degree of polarization can decrease the single transmittance. For this reason, conventionally, it has been difficult to put into practical use a thin polarizing film that satisfies the optical characteristics of a single transmittance of 48% or more and a polarization degree of 85% or more.
  • a thin polarizing film having excellent optical properties such that the single transmittance is 48% or more and the degree of polarization is 85% or more and the variation in optical properties is suppressed, This is one of the achievements of the present invention.
  • a polarizing film can be used for an image display device, and is particularly preferably used for a circular polarizing plate for an organic EL display device.
  • the thickness of the polarizing film is preferably 1 ⁇ m to 8 ⁇ m, more preferably 1 ⁇ m to 7 ⁇ m, and further preferably 2 ⁇ m to 5 ⁇ m.
  • the polarizing film preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
  • the single transmittance of the polarizing film is preferably 50% or less.
  • the polarization degree of the polarizing film is preferably 86% or more, more preferably 87% or more, and further preferably 88% or more.
  • the upper limit of the degree of polarization is preferably 92%.
  • the single transmittance is typically a Y value measured using an ultraviolet-visible spectrophotometer and corrected for visibility.
  • the degree of polarization is typically obtained by the following equation based on the parallel transmittance Tp and orthogonal transmittance Tc measured by using an ultraviolet-visible spectrophotometer and corrected for visibility.
  • Polarization degree (%) ⁇ (Tp ⁇ Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100
  • the transmittance of a thin polarizing film of 8 ⁇ m or less is typically a laminate of a polarizing film (surface refractive index: 1.53) and a protective film (refractive index: 1.50). It is measured using an ultraviolet-visible spectrophotometer with the body as the measurement object.
  • the reflectance at the interface of each layer may change, and as a result, the measured value of transmittance may change.
  • the measured value of the transmittance may be corrected according to the refractive index of the surface of the protective film in contact with the air interface.
  • the transmittance correction value C is expressed by the following equation using the reflectance R 1 (transmission axis reflectance) of polarized light parallel to the transmission axis at the interface between the protective film and the air layer.
  • R 0 ((1.50-1) 2 /(1.50+1) 2) ⁇ (T 1/100)
  • R 1 ((n 1 -1 ) 2 / (n 1 +1) 2) ⁇ (T 1/100)
  • R 0 is the transmission axis reflectance when a protective film having a refractive index of 1.50 is used
  • n 1 is the refractive index of the protective film used
  • T 1 is the transmittance of the polarizing film. It is.
  • the correction amount C is about 0.2%.
  • the change amount of the correction value C when the transmittance T 1 of the polarizing film is changed by 2% is 0.03% or less, and the transmittance of the polarizing film is the correction value C.
  • the effect on the value of is limited.
  • amendment can be performed according to absorption amount.
  • the polarizing film can be typically produced using a laminate of two or more layers.
  • the polarizing film obtained using the laminate include a polarizing film obtained using a laminate of a resin base material and a PVA-based resin layer applied and formed on the resin base material.
  • a polarizing film obtained by using a laminate of a resin base material and a PVA resin layer applied and formed on the resin base material may be obtained by applying a PVA resin solution to a resin base material and drying it.
  • a PVA-based resin layer is formed thereon to obtain a laminate of a resin base material and a PVA-based resin layer; the laminate is stretched and dyed to form a PVA-based resin layer as a polarizing film; obtain.
  • stretching typically includes immersing the laminate in an aqueous boric acid solution and stretching.
  • the stretching may further include, if necessary, stretching the laminate in the air at a high temperature (for example, 95 ° C. or higher) before stretching in the boric acid aqueous solution.
  • the obtained resin substrate / polarizing film laminate may be used as it is (that is, the resin substrate may be used as a protective layer of the polarizing film), and the resin substrate is peeled from the resin substrate / polarizing film laminate. Any appropriate protective layer according to the purpose may be laminated on the release surface. Details of the method for manufacturing such a polarizing film are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580. This publication is incorporated herein by reference in its entirety.
  • the method for producing a polarizing film of the present invention includes forming a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin on one side of a long thermoplastic resin base material to form a laminate, and
  • the above-mentioned laminate is subjected to aerial auxiliary stretching treatment with a draw ratio of 2.0 times or more, dyeing treatment, underwater stretching treatment, and drying shrinkage that shrinks by 2% or more in the width direction by heating while transporting in the longitudinal direction. Processing in this order.
  • a polarizing film having a thickness of 8 ⁇ m or less, a single transmittance of 48% or more, a degree of polarization of 85% or more, having excellent optical characteristics and suppressing variations in optical characteristics can be provided. . That is, by introducing auxiliary stretching, even when PVA is applied onto a thermoplastic resin, the crystallinity of PVA can be increased and high optical properties can be achieved. At the same time, by increasing the orientation of the PVA in advance, it is possible to prevent problems such as a decrease in the orientation of the PVA and dissolution when immersed in water in the subsequent dyeing process or stretching process, and high optical properties. Can be achieved.
  • the disorder of the orientation of the polyvinyl alcohol molecules and the decrease in the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide.
  • the optical characteristic of the polarizing film obtained through the process process performed by immersing a laminated body in a liquid such as a dyeing
  • optical characteristics can be improved by shrinking the laminate in the width direction by a drying shrinkage treatment.
  • the first and second protective layers are formed of any suitable film that can be used as a protective layer of a polarizing film.
  • the material as the main component of the film include cellulose resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone-based materials.
  • transparent resins such as polystyrene, polynorbornene, polyolefin, (meth) acryl, and acetate.
  • thermosetting resins such as (meth) acrylic, urethane-based, (meth) acrylurethane-based, epoxy-based, and silicone-based or ultraviolet curable resins are also included.
  • a glassy polymer such as a siloxane polymer is also included.
  • a polymer film described in JP-A-2001-343529 (WO01 / 37007) can also be used.
  • a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and nitrile group in the side chain for example, a resin composition having an alternating copolymer of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer can be mentioned.
  • the polymer film can be, for example, an extruded product of the resin composition.
  • the thickness of the protective layer (outer protective layer) disposed on the side opposite to the display panel is typically 300 ⁇ m or less, preferably 100 ⁇ m or less, more preferably The thickness is 5 ⁇ m to 80 ⁇ m, more preferably 10 ⁇ m to 60 ⁇ m.
  • the thickness of the outer protective layer is a thickness including the thickness of the surface treatment layer.
  • the thickness of the protective layer (inner protective layer) disposed on the display panel side is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 100 ⁇ m, and even more preferably 10 ⁇ m to 60 ⁇ m. is there.
  • the inner protective layer is a retardation layer having any suitable retardation value.
  • the in-plane retardation Re (550) of the retardation layer is, for example, 110 nm to 150 nm.
  • nx is the refractive index in the direction in which the in-plane refractive index is maximum (that is, the slow axis direction), and “ny” is the direction orthogonal to the slow axis in the plane (that is, fast phase).
  • nz is the refractive index in the thickness direction
  • d is the thickness (nm) of the layer (film).
  • a method for producing a polarizing film according to one embodiment of the present invention comprises a polyvinyl alcohol containing a halide and a polyvinyl alcohol resin (PVA resin) on one side of a long thermoplastic resin substrate.
  • a polymer-based resin layer PVA-based resin layer
  • an air auxiliary stretching treatment in which the draw ratio is 2.0 times or more
  • a dyeing treatment in which the film shrinks by 2% or more in the width direction by heating while being conveyed in the longitudinal direction.
  • the halide content in the PVA resin layer is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the PVA resin.
  • the drying shrinkage treatment is preferably performed using a heating roll, and the temperature of the heating roll is preferably 60 ° C. to 120 ° C.
  • the shrinkage ratio in the width direction of the laminate by the drying shrinkage treatment is preferably 2% or more.
  • the polarizing film described in the above section A can be obtained.
  • by producing a laminate including a PVA-based resin layer containing a halide stretching the laminate to multistage stretching including air-assisted stretching and underwater stretching, and heating the stretched laminate with a heating roll
  • the laminate can be uniformly shrunk over the entire laminate while being conveyed.
  • a heating roll in the drying shrinkage treatment step the laminate can be uniformly shrunk over the entire laminate while being conveyed.
  • a PVA resin layer is formed on the thermoplastic resin substrate by applying a coating solution containing a halide and a PVA resin on the surface of the thermoplastic resin substrate and drying the coating solution.
  • the halide content in the PVA resin layer is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the PVA resin.
  • any appropriate method can be adopted as a coating method of the coating solution.
  • a coating method of the coating solution 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 preferably 50 ° C. or higher.
  • the thickness of the PVA resin layer is preferably 3 ⁇ m to 40 ⁇ m, more preferably 3 ⁇ m to 20 ⁇ m.
  • the thermoplastic resin substrate Before forming the PVA resin layer, the thermoplastic resin substrate may be subjected to a surface treatment (for example, corona treatment), or an easy-adhesion layer may be formed on the thermoplastic resin substrate. By performing such a treatment, the adhesion between the thermoplastic resin substrate and the PVA resin layer can be improved.
  • a surface treatment for example, corona treatment
  • an easy-adhesion layer may be formed on the thermoplastic resin substrate.
  • thermoplastic resin substrate The thickness of the thermoplastic resin substrate is preferably 20 ⁇ m to 300 ⁇ m, more preferably 50 ⁇ m to 200 ⁇ m. If it is less than 20 ⁇ m, it may be difficult to form a PVA-based resin layer. If it exceeds 300 ⁇ m, for example, in the below-described underwater stretching treatment, it may take a long time for the thermoplastic resin substrate to absorb water, and an excessive load may be required for stretching.
  • the thermoplastic resin base material preferably has a water absorption rate of 0.2% or more, more preferably 0.3% or more.
  • the thermoplastic resin substrate can absorb water and plasticize by acting as a plasticizer. As a result, the stretching stress can be greatly reduced, and the film can be stretched at a high magnification.
  • the water absorption rate of the thermoplastic resin substrate is preferably 3.0% or less, and more preferably 1.0% or less.
  • thermoplastic resin base material can be adjusted by introduce
  • the water absorption is a value determined according to JIS K 7209.
  • the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 120 ° C. or lower.
  • Tg thermoplastic resin base material
  • the stretchability of the laminate can be sufficiently ensured while suppressing the crystallization of the PVA-based resin layer.
  • the glass transition temperature of the thermoplastic resin substrate is preferably 60 ° C. or higher.
  • the PVA-based resin layer can be satisfactorily stretched at a suitable temperature (for example, about 60 ° C.).
  • the glass transition temperature of a thermoplastic resin base material can be adjusted by heating using the crystallizing material which introduce
  • the glass transition temperature (Tg) is a value determined according to JIS K 7121.
  • thermoplastic resin can be adopted as a constituent material of the thermoplastic resin base material.
  • the thermoplastic resin 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. Is mentioned. Among these, preferred are norbornene resins and amorphous polyethylene terephthalate resins.
  • an amorphous (non-crystallized) polyethylene terephthalate resin is preferably used.
  • amorphous (hard to crystallize) polyethylene terephthalate resin is particularly preferably used.
  • Specific examples of the amorphous polyethylene terephthalate resin include a copolymer further containing isophthalic acid and / or cyclohexanedicarboxylic acid as the dicarboxylic acid, and a copolymer further containing cyclohexanedimethanol and diethylene glycol as the glycol.
  • the thermoplastic resin substrate is composed of a polyethylene terephthalate resin having an isophthalic acid unit.
  • a thermoplastic resin substrate is extremely excellent in stretchability, and crystallization during stretching can be suppressed. This is thought to be due to the introduction of an isophthalic acid unit to give a large bend to the main chain.
  • the polyethylene terephthalate resin has a terephthalic acid unit and an ethylene glycol unit.
  • the content ratio of the isophthalic acid unit is preferably 0.1 mol% or more, more preferably 1.0 mol% or more, based on the total of all repeating units. This is because a thermoplastic resin substrate having extremely excellent stretchability can be obtained.
  • the content ratio of the isophthalic acid unit is preferably 20 mol% or less, more preferably 10 mol% or less, based on the total of all repeating units.
  • the crystallinity can be favorably increased in the drying shrinkage treatment described later.
  • the thermoplastic resin base material may be stretched in advance (before forming the PVA resin layer). In one embodiment, it is extended in the transverse direction of an elongated thermoplastic resin substrate.
  • the lateral direction is preferably a direction orthogonal to the extending direction of the laminate described later.
  • orthogonal includes the case of being substantially orthogonal.
  • substantially orthogonal includes the case of 90 ° ⁇ 5.0 °, preferably 90 ° ⁇ 3.0 °, more preferably 90 ° ⁇ 1.0 °.
  • the stretching temperature of the thermoplastic resin substrate is preferably Tg-10 ° C. to Tg + 50 ° C. with respect to the glass transition temperature (Tg).
  • the draw ratio of the thermoplastic resin substrate is preferably 1.5 to 3.0 times.
  • thermoplastic resin substrate Any appropriate method can be adopted as a method of stretching the thermoplastic resin substrate. Specifically, it may be fixed end stretching or free end stretching. The stretching method may be dry or wet. The stretching of the thermoplastic resin substrate may be performed in one step or in multiple steps. When performing in multiple stages, the above-mentioned draw ratio is the product of the draw ratios of the respective stages.
  • the coating liquid contains a halide and a PVA resin as described above.
  • the coating solution is typically a solution in which the halide and the PVA resin are dissolved in a solvent.
  • 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 concentration of the PVA resin in the solution is preferably 3 to 20 parts by weight with respect to 100 parts by weight of the solvent. With such a resin concentration, a uniform coating film in close contact with the thermoplastic resin substrate can be formed.
  • the content of the halide in the coating solution is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the PVA resin.
  • Additives may be added to the coating solution.
  • 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.
  • any appropriate resin can be adopted as the PVA resin.
  • Examples thereof 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 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, more preferably 99.0 mol% to 99.93 mol%. .
  • 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 polarizing film having excellent durability can be obtained. If the degree of saponification is too high, there is a risk of gelation.
  • 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 10,000, preferably 1200 to 4500, and more preferably 1500 to 4300.
  • the average degree of polymerization can be determined according to JIS K 6726-1994.
  • halide any appropriate halide can be adopted as the halide.
  • examples include iodide and sodium chloride.
  • examples of iodide include potassium iodide, sodium iodide, and lithium iodide. Among these, potassium iodide is preferable.
  • the amount of halide in the coating solution is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the PVA resin, and more preferably 10 to 15 parts by weight with respect to 100 parts by weight of the PVA resin. Part. If the amount of halide exceeds 100 parts by weight of PVA-based resin, the halide may bleed out and the finally obtained polarizing film may become cloudy.
  • the orientation of the polyvinyl alcohol molecules in the PVA-based resin is increased by stretching the PVA-based resin layer, but when the stretched PVA-based resin layer is immersed in a liquid containing water, The orientation may be disturbed and the orientation may be lowered.
  • the laminate of the thermoplastic resin and the PVA-based resin layer is stretched in boric acid water
  • the laminate is stretched in boric acid water at a relatively high temperature in order to stabilize the stretching of the thermoplastic resin
  • the tendency of the degree of orientation reduction is remarkable.
  • stretching of a PVA film alone in boric acid water is generally performed at 60 ° C.
  • stretching of a laminate of A-PET (thermoplastic resin substrate) and a PVA resin layer is performed.
  • the orientation of the PVA at the initial stage of stretching can be lowered at a stage before it is increased by stretching in water.
  • a laminate of a PVA-based resin layer containing a halide and a thermoplastic resin substrate by producing a laminate of a PVA-based resin layer containing a halide and a thermoplastic resin substrate, and stretching the laminate at high temperature (auxiliary stretching) in the air before stretching in boric acid water.
  • the crystallization of the PVA resin in the PVA resin layer of the laminate after the auxiliary stretching can be promoted.
  • the disorder of the orientation of the polyvinyl alcohol molecules and the decrease in the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide.
  • the optical characteristic of the polarizing film obtained through the process process performed by immersing a laminated body in a liquid such as a dyeing
  • auxiliary stretching treatment in order to obtain high optical properties, a two-stage stretching method combining dry stretching (auxiliary stretching) and boric acid water stretching is selected.
  • auxiliary stretching such as two-stage stretching
  • the problem that the stretchability is lowered can be solved, and the laminate can be stretched at a higher magnification.
  • a PVA resin on a thermoplastic resin substrate in order to suppress the influence of the glass transition temperature of the thermoplastic resin substrate, compared to the case of applying a PVA resin on a normal metal drum. Therefore, it is necessary to lower the coating temperature.
  • the crystallization of the PVA resin becomes relatively low, and a problem that sufficient optical characteristics cannot be obtained may occur.
  • by introducing auxiliary stretching it is possible to increase the crystallinity of the PVA resin even when applying the PVA resin on the thermoplastic resin, and to achieve high optical characteristics. Become.
  • by increasing the orientation of the PVA resin in advance it is possible to prevent problems such as a decrease in the orientation and dissolution of the PVA resin when immersed in water in the subsequent dyeing process or stretching process. It becomes possible to achieve high optical properties.
  • the air auxiliary stretching method may be fixed-end stretching (for example, stretching using a tenter stretching machine) or free-end stretching (for example, uniaxial stretching through a laminate between rolls having different peripheral speeds). Although good, free end stretching can be actively employed to obtain high optical properties.
  • the air stretching process includes a heating roll stretching process in which the laminate is stretched by a peripheral speed difference between heating rolls while being conveyed in the longitudinal direction.
  • the aerial stretching process typically includes a zone stretching process and a heated roll stretching process.
  • stretching process and a heating roll extending process is not limited, A zone extending process may be performed previously and a heated roll extending process may be performed previously. The zone stretching step may be omitted.
  • a zone extending process and a heating roll extending process are performed in this order.
  • stretching is performed by gripping the film edge and expanding the distance between the tenters in the flow direction (the spread of the distance between the tenters becomes the stretching ratio).
  • the distance of the tenter in the width direction (perpendicular to the flow direction) is set to be arbitrarily close. Preferably, it can be set to be closer to the free end stretching with respect to the stretching ratio in the flow direction.
  • the shrinkage ratio in the width direction (1 / stretch ratio) is calculated by 1/2 .
  • Air-assisted stretching may be performed in one stage or in multiple stages.
  • the draw ratio is the product of the draw ratios at each stage.
  • the stretching direction in the air-assisted stretching is preferably substantially the same as the stretching direction in the underwater stretching.
  • the stretching ratio in the air auxiliary stretching is preferably 2.0 times to 3.5 times.
  • the maximum draw ratio when combining air-assisted stretching and underwater stretching is preferably 5.0 times or more, more preferably 5.5 times or more, and even more preferably 6.0 times the original length of the laminate. That's it.
  • the “maximum stretch ratio” refers to a stretch ratio immediately before the laminate is ruptured. Separately, a stretch ratio at which the laminate is ruptured is confirmed, and is a value 0.2 lower than the value.
  • the stretching temperature for the air-assisted stretching can be set to any appropriate value depending on the material for forming the thermoplastic resin substrate, the stretching method, and the like.
  • the stretching temperature is preferably not less than the glass transition temperature (Tg) of the thermoplastic resin substrate, more preferably not less than 10 ° C., particularly preferably not less than Tg + 15 ° C., more preferably glass transition temperature (Tg) of the thermoplastic resin substrate.
  • the upper limit of the stretching temperature is preferably 170 ° C.
  • the crystallization index of the PVA-based resin after the air auxiliary stretching is preferably 1.3 to 1.8, more preferably 1.4 to 1.7.
  • an insolubilization treatment is performed after the air auxiliary stretching treatment and before the underwater stretching treatment and dyeing treatment.
  • the insolubilization treatment is typically performed by immersing the PVA resin layer in an aqueous boric acid solution.
  • 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 50 ° C.
  • the dyeing process is typically performed by dyeing a PVA resin layer with iodine. Specifically, it is performed by adsorbing iodine to the PVA resin layer.
  • adsorption method for example, a method of immersing a PVA resin layer (laminate) in a staining solution containing iodine, a method of applying the staining solution to the PVA resin layer, and applying the staining solution to the PVA resin layer The method of spraying etc. are mentioned.
  • the laminate is immersed in a dyeing solution (dyeing bath). This is because iodine can be adsorbed well.
  • the staining solution is preferably an iodine aqueous solution.
  • the amount of iodine is preferably 0.05 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.
  • potassium iodide is preferable.
  • the blending amount of iodide is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of water.
  • the liquid temperature during dyeing of the dyeing liquid is preferably 20 ° C. to 50 ° C. in order to suppress dissolution of the PVA resin.
  • the immersion time is preferably 5 seconds to 5 minutes, more preferably 30 seconds to 90 seconds, in order to ensure the transmittance of the PVA resin layer.
  • the staining conditions can be set so that the single transmittance of the finally obtained polarizing film is 48% or more and the degree of polarization is 85% or more.
  • an iodine aqueous solution is preferably used as the dyeing solution, and the ratio of iodine and potassium iodide content in the iodine aqueous solution is 1: 5 to 1:20.
  • the ratio of the content of iodine and potassium iodide in the aqueous iodine solution is preferably 1: 5 to 1:10.
  • the dyeing treatment When the dyeing treatment is performed continuously after the treatment (typically insolubilization treatment) in which the laminate is immersed in a treatment bath containing boric acid, boric acid contained in the treatment bath is mixed into the dyeing bath.
  • the boric acid concentration of the dyeing bath changes with time, and as a result, the dyeability may become unstable.
  • the upper limit of the boric acid concentration in the dyeing bath is preferably 4 parts by weight, more preferably 2 parts by weight with respect to 100 parts by weight of water. Adjusted.
  • the lower limit of the boric acid concentration in the dyeing bath is preferably 0.1 parts by weight, more preferably 0.2 parts by weight, and even more preferably 0.5 parts by weight with respect to 100 parts by weight of water. It is.
  • the dyeing process is performed using a dyeing bath in which boric acid is previously blended. Thereby, the rate of change of boric acid concentration when boric acid in the treatment bath is mixed in the dyeing bath can be reduced.
  • the amount of boric acid blended in advance in the dye bath is preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of water. More preferably, it is 0.5 to 1.5 parts by weight.
  • crosslinking treatment If necessary, a crosslinking treatment is performed after the dyeing treatment and before the underwater stretching treatment.
  • the crosslinking treatment is typically performed by immersing the PVA resin layer in a boric acid aqueous solution.
  • the concentration of the boric acid aqueous solution is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water.
  • the blending amount of iodide is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of the iodide are as described above.
  • the liquid temperature of the crosslinking bath is preferably 20 ° C. to 50 ° C.
  • the underwater stretching treatment is performed by immersing the laminate in a stretching bath. According to the underwater stretching treatment, the thermoplastic resin substrate or the PVA resin layer can be stretched at a temperature lower than the glass transition temperature (typically about 80 ° C.), and the PVA resin layer is crystallized. It is possible to stretch at a high magnification while suppressing. As a result, a polarizing film having excellent optical characteristics can be manufactured.
  • Arbitrary appropriate methods can be employ
  • the stretching of the laminate may be performed in one stage or in multiple stages. When performed in multiple stages, the draw ratio (maximum draw ratio) of the laminate described later is the product of the draw ratios of the respective stages.
  • the stretching in water is preferably performed by immersing the laminate 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.
  • boric acid can form a tetrahydroxyborate anion in an aqueous solution and crosslink with a PVA resin by hydrogen bonding.
  • rigidity and water resistance can be imparted to the PVA-based resin layer, the film can be stretched well, and a polarizing film having excellent optical properties can be produced.
  • 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, more preferably 3.5 to 7 parts by weight, and particularly preferably 4 to 6 parts by weight with respect to 100 parts by weight of water. It is. By setting the boric acid concentration to 1 part by weight or more, dissolution of the PVA resin layer can be effectively suppressed, and a polarizing film having higher characteristics can be produced.
  • an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal, glutaraldehyde, or the like in a solvent can also be used.
  • iodide is blended in the stretching bath (boric acid aqueous solution).
  • the stretching bath boric acid aqueous solution
  • 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 stretching temperature (liquid temperature of the stretching bath) is preferably 40 ° C to 85 ° C, more preferably 60 ° C to 75 ° C. If it is such temperature, it can extend
  • the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 60 ° C. or higher in relation to the formation of the PVA resin layer. In this case, when the stretching temperature is lower than 40 ° C., there is a possibility that stretching cannot be performed satisfactorily even in consideration of plasticization of the thermoplastic resin substrate 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 draw ratio by the underwater drawing is preferably 1.5 times or more, more preferably 3.0 times or more.
  • the total draw ratio of the laminate is preferably 5.0 times or more, more preferably 5.5 times or more with respect to the original length of the laminate.
  • the drying shrinkage treatment may be performed by zone heating performed by heating the entire zone, or by heating the transport roll (using a so-called heating roll) (heating roll drying method). Preferably both are used.
  • heating roll heating roll drying method
  • the crystallization of the thermoplastic resin substrate can be efficiently promoted to increase the crystallinity, which is relatively low. Even at the drying temperature, the crystallinity of the thermoplastic resin substrate can be increased satisfactorily.
  • the thermoplastic resin base material increases in rigidity and can withstand the shrinkage of the PVA resin layer due to drying, and curling is suppressed.
  • the laminate can be dried while maintaining a flat state, so that not only curling but also generation of wrinkles can be suppressed.
  • the laminate can be improved in optical characteristics by being contracted in the width direction by a drying contraction process. This is because the orientation of PVA and PVA / iodine complex can be effectively increased.
  • the shrinkage ratio in the width direction of the laminate by the drying shrinkage treatment is preferably 1% to 10%, more preferably 2% to 8%, and particularly preferably 4% to 6%.
  • FIG. 2 is a schematic view showing an example of the drying shrinkage process.
  • the laminate 200 is dried while being conveyed by the conveying rolls R1 to R6 heated to a predetermined temperature and the guide rolls G1 to G4.
  • the transport rolls R1 to R6 are arranged so as to alternately and continuously heat the surface of the PVA resin layer and the surface of the thermoplastic resin base material.
  • one surface of the laminate 200 for example, thermoplastic
  • the conveying rolls R1 to R6 may be arranged so as to continuously heat only the resin base material surface).
  • the drying conditions can be controlled by adjusting the heating temperature of the transport roll (temperature of the heating roll), the number of heating rolls, the contact time with the heating roll, and the like.
  • the temperature of the heating roll is preferably 60 ° C. to 120 ° C., more preferably 65 ° C. to 100 ° C., and particularly preferably 70 ° C. to 80 ° C.
  • the crystallinity of the thermoplastic resin can be increased satisfactorily, curling can be suppressed well, and an optical laminate having extremely excellent durability can be produced.
  • the temperature of a heating roll can be measured with a contact-type thermometer.
  • six transport rolls are provided, but there is no particular limitation as long as there are a plurality of transport rolls. Usually, 2 to 40 conveying rolls, preferably 4 to 30 conveying rolls are provided.
  • the contact time (total contact time) between the laminate and the heating roll is preferably 1 second to 300 seconds, more preferably 1 to 20 seconds, and further preferably 1 to 10 seconds.
  • the heating roll may be provided in a heating furnace (for example, an oven) or may be provided in a normal production line (in a room temperature environment). Preferably, it is provided in a heating furnace provided with a ventilation means.
  • a heating furnace for example, an oven
  • the temperature of hot air drying is preferably 30 ° C. to 100 ° C.
  • the hot air drying time is preferably 1 second to 300 seconds.
  • the wind speed of the hot air is preferably about 10 m / s to 30 m / s. In addition, the said wind speed is a wind speed in a heating furnace, and can be measured with a minivan type digital anemometer.
  • a washing treatment is performed after the underwater stretching treatment and before the drying shrinkage treatment.
  • the cleaning treatment is typically performed by immersing the PVA resin layer in an aqueous potassium iodide solution.
  • Polarization degree P (%) ⁇ (Tp ⁇ Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100
  • the spectrophotometer can perform the same measurement with LPF-200 manufactured by Otsuka Electronics.
  • Table 1 shows measured values of single transmittance Ts and polarization degree P obtained by measurement using V-7100 and LPF-200 for Samples 1 to 3 of polarizing plates having the same configuration as the following examples. Show. As shown in Table 1, the difference between the measured value of the single transmittance of V-7100 and the measured value of the single transmittance of LPF-200 is 0.1% or less, and any spectrophotometer was used.
  • Example 1 Production of Polarizing Film An amorphous isophthalic copolymer polyethylene terephthalate film (thickness: 100 ⁇ m) having a long shape, a water absorption of 0.75%, and a Tg of about 75 ° C. was used as the thermoplastic resin substrate. One side of the resin substrate was subjected to corona treatment.
  • PVA resin 100 weight of PVA resin in which polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Gosefimer Z410”) was mixed at 9: 1 13 parts by weight of potassium iodide was added to the part to prepare an aqueous PVA solution (coating solution). The PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60 ° C., thereby forming a PVA resin layer having a thickness of 13 ⁇ m, thereby producing a laminate.
  • the obtained laminate was stretched uniaxially by 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ° C. (air-assisted stretching process).
  • the laminate was immersed for 30 seconds in an insolubilizing bath having a liquid temperature of 40 ° C. (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) (insolubilization treatment).
  • the polarizing film finally obtained in a dyeing bath (iodine aqueous solution obtained by blending iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C.
  • Uniaxial stretching was performed so as to be doubled (underwater stretching treatment).
  • the laminate was immersed in a cleaning bath having a liquid temperature of 20 ° C. (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) (cleaning treatment).
  • cleaning treatment an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water
  • drying treatment while drying in an oven kept at 90 ° C., it was brought into contact with a SUS heating roll whose surface temperature was kept at 75 ° C. for about 2 seconds (dry shrinkage treatment).
  • the shrinkage ratio in the width direction of the laminate by the drying shrinkage treatment was 5.2%. In this way, a polarizing film having a thickness of 5 ⁇ m was formed on the resin substrate.
  • Example 1 Example 1 except that potassium iodide was not added to the PVA aqueous solution (coating solution), the stretch ratio in the air auxiliary stretching process was 1.8 times, and the heating roll was not used in the drying shrinkage process. In the same manner as described above, an attempt was made to produce a polarizing film. However, the PVA resin layer was dissolved in the dyeing process and the underwater stretching process, and a polarizing film having a single transmittance of 48% or more could not be produced.
  • Comparative Example 2 An attempt was made to prepare a polarizing film and a polarizing plate of 17 in the same manner as in Example 1 except that the draw ratio in the air auxiliary stretching process was 1.8 times and no heating roll was used in the drying shrinkage process. However, as in Comparative Example 1, a polarizing film having a single transmittance of 48% or more could not be produced.
  • the polarizing film obtained by the manufacturing method of the comparative example did not satisfy the single transmittance of 48% or more and the polarization degree of 85% or more at the same time.
  • the degree of polarization is less than 85% when the dyeing treatment is performed so that the single transmittance is 48% or more. Is predicted.
  • the polarizing film obtained by the production method of the example had excellent optical characteristics with a single transmittance of 48% or more and a polarization degree of 85% or more.
  • the long polarizing plate obtained by the manufacturing method of the example has a single transmittance variation of 1% or less, and the single-wafer polarizing plate obtained by the manufacturing method of the example has a single transmittance variation. Is 0.5% or less, and variation in optical characteristics is suppressed to such a degree that there is no problem.
  • the polarizing plate of the reference example obtained through the process of humidifying the polarizing film had a large variation in optical characteristics in both the long shape and the single wafer shape.
  • the polarizing plate having the polarizing film of the present invention is suitably used for a circular polarizing plate for organic EL display devices and inorganic EL display devices.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)

Abstract

La présente invention concerne un polariseur ayant une excellente caractéristique optique et qui réduit au minimum la variation des caractéristiques optiques. Le polariseur selon la présente invention comprend un film polarisant ayant une épaisseur inférieure ou égale à 8 µm, une transmittance unitaire supérieure ou égale à 48 %, et un degré de polarisation supérieur ou égal à 85 %, et une couche protectrice disposée sur au moins un côté du film polarisant, ledit polariseur présentant une différence inférieure ou égale à 0,5 % entre la transmittance unitaire maximale et minimale dans une région de 50 cm2. Un autre polariseur selon la présente invention comprend un film polarisant ayant une épaisseur inférieure ou égale à 8 µm, une transmittance unitaire supérieure ou égale à 48%, un degré de polarisation supérieur ou égal à 85%, et une couche protectrice disposée sur au moins un côté du film polarisant, le polariseur présentant une largeur supérieure ou égale à 1 000 mm, et une différence entre la transmittance unitaire maximale et minimale à une position le long de la direction de la largeur du polariseur étant inférieure ou égale à 1 %.
PCT/JP2019/015244 2018-04-25 2019-04-08 Polariseur, rouleau de plaque de polariseur et procédé de production de film polarisant WO2019208181A1 (fr)

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CN201980027817.9A CN112005144A (zh) 2018-04-25 2019-04-08 偏振片、偏振片卷、及偏振膜的制造方法
KR1020207030350A KR102721828B1 (ko) 2018-04-25 2019-04-08 편광판, 편광판 롤 및 편광막의 제조 방법

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004233871A (ja) * 2003-01-31 2004-08-19 Fuji Photo Film Co Ltd 偏光板、偏光板の製造方法および液晶表示装置
JP2009048179A (ja) * 2007-07-25 2009-03-05 Nitto Denko Corp 偏光子の製造方法、偏光子、偏光板、光学フィルムおよび画像表示装置
JP2011047983A (ja) * 2009-08-25 2011-03-10 Fujifilm Corp 光学フィルムの製造方法および該製造方法により製造された光学フィルム
WO2012033153A1 (fr) * 2010-09-09 2012-03-15 日東電工株式会社 Procédé de fabrication de film polarisant mince
WO2019054273A1 (fr) * 2017-09-13 2019-03-21 日東電工株式会社 Plaque polarisante, rouleau de plaque polarisante, et procédé de production de film polarisant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004233871A (ja) * 2003-01-31 2004-08-19 Fuji Photo Film Co Ltd 偏光板、偏光板の製造方法および液晶表示装置
JP2009048179A (ja) * 2007-07-25 2009-03-05 Nitto Denko Corp 偏光子の製造方法、偏光子、偏光板、光学フィルムおよび画像表示装置
JP2011047983A (ja) * 2009-08-25 2011-03-10 Fujifilm Corp 光学フィルムの製造方法および該製造方法により製造された光学フィルム
WO2012033153A1 (fr) * 2010-09-09 2012-03-15 日東電工株式会社 Procédé de fabrication de film polarisant mince
WO2019054273A1 (fr) * 2017-09-13 2019-03-21 日東電工株式会社 Plaque polarisante, rouleau de plaque polarisante, et procédé de production de film polarisant

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