WO2018159376A1 - Plaque de polarisation et procédé de fabrication d'une plaque de polarisation - Google Patents

Plaque de polarisation et procédé de fabrication d'une plaque de polarisation Download PDF

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Publication number
WO2018159376A1
WO2018159376A1 PCT/JP2018/005902 JP2018005902W WO2018159376A1 WO 2018159376 A1 WO2018159376 A1 WO 2018159376A1 JP 2018005902 W JP2018005902 W JP 2018005902W WO 2018159376 A1 WO2018159376 A1 WO 2018159376A1
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Prior art keywords
film
polarizing plate
polarizing
laminate
polarizing film
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PCT/JP2018/005902
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English (en)
Japanese (ja)
Inventor
後藤　周作
真由美 森崎
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to JP2019502894A priority Critical patent/JP7137554B2/ja
Priority to KR1020197024363A priority patent/KR102593490B1/ko
Priority to CN201880014306.9A priority patent/CN110337601A/zh
Publication of WO2018159376A1 publication Critical patent/WO2018159376A1/fr

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    • 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

Definitions

  • the present invention relates to a polarizing plate and a manufacturing method of the polarizing plate.
  • polarizing films are arranged on both sides of a liquid crystal cell due to the image forming method.
  • 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. 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.
  • PVA polyvinyl alcohol
  • a polarizing film (as a result, a polarizing plate) has a durability problem that optical characteristics are deteriorated in a humidified environment. More specifically, the polarizing film loses the polarization performance at the end in a humidified environment, and a so-called color loss phenomenon may occur.
  • the present invention has been made to solve the above-mentioned problems, and a main object thereof is to provide a polarizing plate capable of maintaining excellent optical properties even in a humidified environment.
  • the polarizing plate of the present invention comprises a polarizing film composed of a polyvinyl alcohol-based resin film containing iodine, a protective film disposed on at least one side of the polarizing film, and a sealing film covering the polarizing film and the peripheral end face of the protective film. And a stop portion.
  • the polarizing film has a thickness of 8 ⁇ m or less.
  • the moisture permeability of the sealing portion is not more than 300g / m 2 / 24hr.
  • the polarizing plate has a color loss of 100 ⁇ m or less after being held at 85 ° C. and 85% RH for 120 hours.
  • the said sealing part is comprised with the adhesive composition.
  • the said sealing part is comprised with the rubber-type adhesive. In these embodiments, the sealing portion has a thickness of 10 ⁇ m to 100 ⁇ m. In one embodiment, the said sealing part is comprised with the metal containing compound. In this embodiment, the sealing portion has a thickness of 10 nm to 200 nm. According to another situation of this invention, the manufacturing method of a polarizing plate is provided.
  • a polyvinyl alcohol-based resin layer is formed on one side of a resin substrate; a laminate of the resin substrate and the polyvinyl alcohol-based resin layer is stretched and dyed to polarize the polyvinyl alcohol-based resin layer Cutting the laminate of the resin base material and the polarizing film into a predetermined size; and forming a sealing layer so as to cover the outer peripheral end face of the cut laminate.
  • the resin substrate functions as a protective film.
  • the said manufacturing method further includes bonding another protective film on the polarizing film surface of the laminated body of the said resin base material and the said polarizing film.
  • Another method for producing a polarizing plate of the present invention is to form a polyvinyl alcohol-based resin layer on one side of a resin substrate; by stretching and dyeing a laminate of the resin substrate and the polyvinyl alcohol-based resin layer, Using a polyvinyl alcohol-based resin layer as a polarizing film; bonding a protective film to the surface of the polarizing film of the laminate; peeling a resin substrate from the laminate having the protective film bonded; and the protective film Cutting the laminate with the polarizing film into a predetermined size; and forming a sealing layer so as to cover the outer peripheral end face of the cut laminate.
  • the said manufacturing method further includes bonding another protective film on the peeling surface of the said resin base material.
  • a polarizing plate capable of maintaining excellent optical characteristics even in a humidified environment can be realized by forming a sealing portion having a predetermined moisture permeability on the outer peripheral end face of the polarizing plate. Such an effect is particularly remarkable in a polarizing plate having a thin polarizing film.
  • FIG. 1A It is a schematic sectional drawing of the polarizing plate by one Embodiment of this invention. It is a schematic plan view of the polarizing plate of FIG. 1A. It is a schematic sectional drawing of the polarizing plate by another embodiment of this invention. It is a schematic diagram for demonstrating calculation of the amount of color loss.
  • 2 is an image showing the amount of color loss after a humidification test of the polarizing plate of Example 1.
  • FIG. It is an image which shows the color loss amount after the humidification test of the polarizing plate of the comparative example 1.
  • FIG. 1A is a schematic cross-sectional view of a polarizing plate according to one embodiment of the present invention
  • FIG. 1B is a schematic plan view of the polarizing plate of FIG. 1A
  • the polarizing plate 100 includes a polarizing film 10, a protective film 20 disposed on at least one side of the polarizing film 10, and a sealing portion 30 that covers the polarizing film 10 and the peripheral end surfaces of the protective film 20.
  • the polarizing film is composed of a polyvinyl alcohol-based resin (hereinafter referred to as “PVA-based resin”) film containing iodine.
  • PVA-based resin polyvinyl alcohol-based resin
  • the thickness of the polarizing film is typically 8 ⁇ m or less.
  • the polarizing film contains iodine and the thickness thereof is very thin, the iodine density in the polarizing film increases, and the stability of iodine due to humidification tends to decrease, so a sealing portion is provided. The effect becomes more remarkable.
  • the protective film is disposed on one side of the polarizing film (the side away from the display panel), but the protective film may be disposed on the display panel side of the polarizing film depending on the purpose or the like. May be.
  • the pressure-sensitive adhesive layer 40 is provided as the outermost layer on the display panel side of the polarizing plate, and the polarizing plate is bonded to the display panel (for example, liquid crystal panel) 300 through the pressure-sensitive adhesive layer.
  • the sealing portion 30 only needs to cover the peripheral end surfaces of the polarizing film 10 and the protective film 20, and the peripheral end surface of the pressure-sensitive adhesive layer may be entirely covered or partially covered. It does not have to be.
  • the sealing unit 30 covers the peripheral end surfaces of the polarizing film 10, the protective film 20, and the adhesive layer 40.
  • the sealing part 30 may cover only the peripheral end faces of the polarizing film 10 and the protective film 20 as shown in FIG.
  • the sealing portion 30 covers the surface (upper surface in the drawing) on the side away from the display panel of the polarizing plate (substantially protective film) together with the peripheral end surface.
  • the entire surface may be covered as shown in FIG. 2, or only a predetermined portion may be covered.
  • the moisture permeability of the sealing portion is not more than 300g / m 2 / 24hr.
  • the amount of color loss after holding for 120 hours in an environment of 85 ° C. and 85% RH is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and further preferably 30 ⁇ m or less. Particularly preferably, it is 25 ⁇ m or less.
  • the lower limit of the amount of color loss is preferably zero, and in one embodiment is 5 ⁇ m.
  • the amount of color loss can be calculated as follows: From a polarizing plate (or polarizing film), a test piece of a predetermined size is cut out with a direction perpendicular to the stretching direction and two sides facing each other in the stretching direction. Note that the stretching direction typically corresponds to the absorption axis direction of the polarizing film.
  • stretching direction can respond
  • the test piece is bonded to a glass plate with an adhesive, and this is left to humidify in an oven at 85 ° C. and 85% RH for 120 hours.
  • the humidified test piece is placed in the state of a standard polarizing plate and crossed Nicols, the color loss state at the end of the humidified test piece is examined with a microscope. Specifically, the magnitude of color loss (color loss amount: ⁇ m) from the end of the test piece (polarizing plate or polarizing film) is measured. As shown in FIG.
  • the larger one of the color loss amount a from the end portion in the stretching direction and the color loss amount b from the end portion in the direction orthogonal to the stretching direction is defined as the color loss amount.
  • the color loss region has extremely low polarization characteristics and does not substantially function as a polarizing plate. Therefore, the smaller the color loss amount, the better.
  • the polarizing plate according to the embodiment of the present invention may be disposed on the viewing side of the display panel, or may be disposed on the opposite side of the viewing side, and a pair of polarizing plates according to the embodiment of the present invention are disposed on both sides. Also good.
  • the polarizing film 10 is composed of a PVA resin film containing iodine as described above.
  • any appropriate resin can be adopted as the PVA resin for forming the PVA resin film.
  • 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 10000, preferably 1200 to 5000, and more preferably 1500 to 4500.
  • the average degree of polymerization can be determined according to JIS K 6726-1994.
  • the polarizing film contains iodine.
  • the polarizing film is substantially a PVA resin film in which iodine is adsorbed and oriented.
  • the iodine concentration in the PVA resin film is, for example, 5.0% by weight to 12.0% by weight.
  • the boric acid concentration in the PVA-based resin film is, for example, 12% by weight to 25% by weight.
  • the thickness of the PVA-based resin film is 8 ⁇ m or less as described above, preferably 7 ⁇ m or less, more preferably 6 ⁇ m or less.
  • the thickness of the PVA-based resin film is preferably 1.0 ⁇ m or more, more preferably 2.0 ⁇ m or more.
  • 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 40.0% to 46.0%, more preferably 41.0% to 45.0%.
  • the polarization degree of the polarizing film is preferably 99.9% or more, more preferably 99.95% or more, and further preferably 99.98% or more.
  • the polarization degree of the polarizing film is preferably 90% or more, more preferably 93% or more, and still more preferably 95%. That's it.
  • the protective film 20 is comprised by arbitrary appropriate films which can be used as a protective film 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.
  • a resin substrate used in the production of a polarizing plate (described later in Section F) may be used as it is as a protective film.
  • the protective film may be subjected to a hard coat treatment or an antireflection treatment as necessary. Further, surface treatment such as anti-sticking treatment and anti-glare treatment may be applied.
  • the thickness of the protective film any appropriate thickness can be adopted as long as the effect of the present invention is obtained.
  • the thickness of the protective film is, for example, 20 ⁇ m to 40 ⁇ m, preferably 25 ⁇ m to 35 ⁇ m.
  • the thickness of the protective film is a thickness including the thickness of the surface treatment layer.
  • the inner protective film is preferably optically isotropic.
  • “optically isotropic” means that the in-plane retardation Re (550) is 0 nm to 10 nm and the thickness direction retardation Rth (550) is ⁇ 10 nm to +10 nm.
  • Re (550) of the inner protective film is preferably 0 nm to 8 nm, more preferably 0 nm to 6 nm, and further preferably 0 nm to 3 nm.
  • Rth (550) of the inner protective film is preferably ⁇ 8 nm to +8 nm, more preferably ⁇ 6 nm to +6 nm, and further preferably ⁇ 3 nm to +3 nm.
  • the sealing portion 30 covers the peripheral end surfaces of the polarizing film and the protective film, thereby maintaining the optical characteristics of the polarizing plate even in a humidified environment and improving the durability of the polarizing plate. Therefore, the sealing part preferably has a barrier function.
  • “having a barrier function” means that the amount of oxygen and / or water vapor penetrating the polarizing film is controlled to substantially block the polarizing film from these.
  • the sealing portion has a barrier property as described above, and typically has a barrier property against moisture and gas (for example, oxygen).
  • the water vapor transmission rate at 90% RH conditions is preferably not more than 300g / m 2 / 24hr, more preferably not more than 100g / m 2 / 24hr, more preferably is less 50g / m 2 / 24hr, most preferably not more than 25g / m 2 / 24hr.
  • the lower limit of the moisture permeability for example, 0.01g / m 2 / 24hr, and preferably below the detection limit. If the moisture permeability of the sealing part is in such a range, the polarizing film can be well protected from moisture and oxygen in the air.
  • the moisture permeability can be measured according to JIS Z0208.
  • the sealing portion can be made of any appropriate material as long as the above properties can be satisfied.
  • the constituent material include an adhesive composition and a metal-containing compound.
  • the “adhesive composition” is intended to include both an adhesive (adhesive composition) and an adhesive composition.
  • Examples of the pressure-sensitive adhesive composition include a rubber-based pressure-sensitive adhesive composition having a rubber-based polymer as a base polymer.
  • Examples of the rubber polymer include a conjugated diene polymer obtained by polymerizing one kind of conjugated diene compound, a conjugated diene copolymer obtained by polymerizing two or more kinds of conjugated diene compounds, and a conjugated diene.
  • Examples thereof include conjugated diene copolymers obtained by copolymerizing a compound and an aromatic vinyl compound, and hydrogenated products thereof.
  • the conjugated diene compound is not particularly limited as long as it is a monomer having a polymerizable conjugated diene.
  • Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, and 1,3-heptadiene. 1,3-hexadiene.
  • 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability.
  • Conjugated diene compounds may be used alone or in combination.
  • the aromatic vinyl compound is not particularly limited as long as it is a monomer having an aromatic vinyl structure copolymerizable with a conjugated diene compound.
  • Specific examples of the aromatic vinyl compound include styrene, p-methylstyrene, ⁇ -methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene and the like. Among these, styrene is preferable from the viewpoint of industrial availability.
  • Aromatic vinyl compounds may be used alone or in combination.
  • the diene copolymer may be a random copolymer or a block copolymer. Moreover, compounds other than a conjugated diene compound and an aromatic vinyl compound may be copolymerized to obtain a diene copolymer.
  • conjugated diene (co) polymers include butadiene rubber (BR), isoprene rubber (IR), styrene-butadiene copolymer (SBR), butadiene-isoprene-styrene random copolymer, isoprene.
  • BR butadiene rubber
  • IR isoprene rubber
  • SBR styrene-butadiene copolymer
  • SIS styrene-isoprene block copolymer
  • SEBS styrene-ethylene-butadiene block copolymer
  • NBR acrylonitrile-butadiene rubber
  • isoprene-styrene copolymers are preferred.
  • these hydrogenated materials can also be used suitably.
  • rubber polymers include isobutylene (IB), styrene-isobutylene-styrene block copolymer (SIBS), styrene-ethylenepropylene copolymer-styrene block copolymer, etc. Can also be used.
  • the rubber-based polymers may be used alone or in combination.
  • the rubber-based polymer that can be used in the present invention is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 80% by weight or more of the conjugated diene-based (co) polymer in the whole rubber-based polymer. Especially preferably, it contains 90% by weight or more.
  • the upper limit of the content of the conjugated diene (co) polymer is not particularly limited, and may be 100% by weight (that is, a rubber polymer composed only of the conjugated diene (co) polymer).
  • the pressure-sensitive adhesive composition contains a rubber-based polymer as a base polymer.
  • the content of the rubber-based polymer in the pressure-sensitive adhesive composition is preferably 40% by weight or more, more preferably 50% by weight or more, and further preferably 60% by weight or more.
  • the upper limit of content of a rubber-type polymer is not specifically limited, For example, it is 90 weight% or less.
  • the pressure-sensitive adhesive composition may further contain any appropriate additive in addition to the rubber-based polymer.
  • additives include cross-linking agents (for example, polyisocyanates, epoxy compounds, alkyl etherified melamine compounds), tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, vinyltoluenes). Resin), plasticizers, fillers (eg, layered silicates, clay materials, etc.), and anti-aging agents.
  • the kind, combination, addition amount, and the like of the additive added to the pressure-sensitive adhesive composition can be appropriately set according to the purpose.
  • the content (total amount) of the additive in the pressure-sensitive adhesive composition is preferably 60% by weight or less, more preferably 50% by weight or less, and still more preferably 40% by weight or less.
  • the adhesive composition typically include an active energy ray curable adhesive composition and a thermosetting adhesive composition.
  • the active energy ray curable adhesive composition include a light (for example, ultraviolet ray) curable adhesive composition and an electron beam curable adhesive composition.
  • the active energy ray curable adhesive composition can be selected as necessary, such as a radical curable type, a cationic curable type, and an anion curable type.
  • a radical curable type and a cationic curable type hybrid can be appropriately combined. It is also possible to use it.
  • the adhesive composition is an ultraviolet curable adhesive composition.
  • the ultraviolet curable adhesive composition for example, an adhesive composition described in JP2013-227419A can be suitably used. The description in this publication is incorporated herein by reference.
  • the thickness thereof is, for example, about 10 ⁇ m to 100 ⁇ m, preferably 15 ⁇ m to 70 ⁇ m, more preferably 20 ⁇ m to 55 ⁇ m, still more preferably 25 ⁇ m to 50 ⁇ m.
  • the “thickness of the sealing portion” is a thickness in a direction extending outward from the peripheral end faces of the polarizing film and the protective film, and corresponds to a width in a plan view as shown in FIG. 1B.
  • Examples of the metal-containing compound include metal elements, alloys, and oxides thereof.
  • Examples of the metal element include aluminum, gold, silver, copper, iron, tin, indium, zinc, nickel, antimony, molybdenum, chromium, tungsten, and lead.
  • the alloy contains two or more of these metal elements.
  • Examples of the metal oxide include silver oxide, indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. . Indium-tin composite oxide is preferred.
  • the thickness can be, for example, about 10 nm to 200 nm.
  • the pressure-sensitive adhesive layer 40 is composed of any appropriate pressure-sensitive adhesive.
  • a typical example of the pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive.
  • the thickness of the pressure-sensitive adhesive layer is, for example, 20 ⁇ m to 100 ⁇ m.
  • a method for producing a polarizing plate according to one embodiment of the present invention typically comprises forming a PVA resin layer on one side of a resin substrate, and the resin substrate and the PVA resin. Stretching and dyeing the laminate with the layer to make the PVA-based resin layer a polarizing film.
  • a laminate of a resin base material and a PVA resin film may be produced, and the laminate may be dyed to use the PVA resin film as a polarizing film.
  • a single PVA resin film may be stretched and dyed to make the PVA resin film a polarizing film.
  • a PVA-type resin layer is formed by applying a coating solution containing a PVA-based resin on a resin base material and drying it.
  • thermoplastic resin any appropriate thermoplastic resin may be employed as the 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 as a dicarboxylic acid, and a copolymer further containing cyclohexanedimethanol as a glycol.
  • the resin base material absorbs water, and the water can be plasticized by acting as a plasticizer. As a result, the stretching stress can be greatly reduced, the film can be stretched at a high magnification, and the stretchability can be superior to that during air stretching. As a result, a polarizing film having excellent optical characteristics can be produced.
  • the resin base material preferably has a water absorption rate of 0.2% or more, and more preferably 0.3% or more. On the other hand, the water absorption rate of the resin base material is preferably 3.0% or less, more preferably 1.0% or less.
  • the water absorption rate of the resin base material can be adjusted, for example, by introducing a modifying group into the forming material.
  • the water absorption is a value determined according to JIS K 7209.
  • the glass transition temperature (Tg) of the resin base material is preferably 170 ° C. or lower.
  • the stretchability of the laminate can be sufficiently ensured while suppressing crystallization of the PVA-based resin layer.
  • the temperature is more preferably 120 ° C. or lower.
  • the glass transition temperature of the 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.).
  • a glass transition temperature lower than 60 ° C. may be used as long as the resin base material does not deform when applying and drying a coating solution containing a PVA-based resin.
  • the glass transition temperature of the resin substrate can be adjusted by, for example, heating using a crystallization material that introduces a modifying group into the forming material.
  • the glass transition temperature (Tg) is a value determined according to JIS K 7121.
  • the thickness of the resin base material before stretching 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 stretching in water, it takes a long time for the resin base material to absorb water, and an excessive load may be required for stretching.
  • the coating solution is typically a solution obtained by dissolving the PVA resin 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 resin substrate can be formed.
  • 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.
  • 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-based resin layer from the substrate can be suppressed, and dyeing and underwater stretching described later can be performed satisfactorily.
  • modified PVA such as acetoacetyl-modified PVA is used.
  • any appropriate method can be adopted as 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 resin substrate Before forming the PVA-based resin layer, the resin substrate may be subjected to surface treatment (for example, corona treatment), or an easy-adhesion layer may be formed on the resin substrate. By performing such a treatment, the adhesion between the resin substrate and the PVA resin layer can be improved.
  • surface treatment for example, corona treatment
  • an easy-adhesion layer may be formed on the resin substrate.
  • the thickness of the PVA resin layer (before stretching) is preferably 3 ⁇ m to 20 ⁇ m.
  • Stretching Any appropriate method can be adopted as a stretching method of the laminate. Specifically, it may be fixed end stretching or free end stretching (for example, a method of uniaxial stretching through a laminate between rolls having different peripheral speeds). Preferably, it is free end stretching.
  • the stretching direction of the laminate can be appropriately set. In one embodiment, it extends
  • the stretching method is not particularly limited, and may be an air stretching method or an underwater stretching method.
  • the underwater stretching method is preferable. According to the underwater stretching method, the resin base material and the PVA resin layer can be stretched at a temperature lower than the glass transition temperature (typically about 80 ° C.), and the crystallization of the PVA resin layer is suppressed. However, it can be stretched at a high magnification. As a result, a polarizing film having excellent optical characteristics can be produced.
  • the stretching of the laminate may be performed in one stage or in multiple stages.
  • the free end stretching and the fixed end stretching may be combined, or the underwater stretching method and the air stretching method may be combined.
  • the draw ratio (maximum draw ratio) of the laminated body mentioned later is a product of the draw ratio of each step.
  • 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 temperature of the stretching bath is 60 ° C. or higher, preferably 65 ° C. to 85 ° C., more preferably 65 ° C. to 75 ° 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.
  • the stretching temperature is lower than 60 ° 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.
  • 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 satisfactorily, 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 4.5 wt% or less, preferably 2.0 wt% to 4.5 wt%, more preferably 2.5 wt% to 4.0 wt%.
  • an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal, glutaraldehyde, or the like in a solvent can also be used.
  • a dichroic substance typically iodine
  • an iodide is blended in the stretching bath (boric acid aqueous 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.
  • 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 draw ratio (maximum draw ratio) of the laminate is preferably 5.0 times or more with respect to the original length of the laminate. Such a high draw ratio can be achieved, for example, by employing an underwater drawing method (boric acid underwater drawing).
  • 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 a value that is 0.2 lower than that value. .
  • the laminate is stretched in air at a high temperature (for example, 95 ° C. or higher), and then stretched in boric acid in water and dyeing described later.
  • air stretching can be positioned as preliminary or auxiliary stretching for boric acid water stretching, and is hereinafter referred to as “air-assisted stretching”.
  • the laminate can be stretched at a higher magnification by combining air-assisted stretching.
  • a polarizing film having more excellent optical characteristics for example, the degree of polarization
  • the orientation of the resin base material is suppressed by combining the air auxiliary stretching and the boric acid water stretching rather than stretching by boric acid water stretching alone. While stretching.
  • the orientation of the resin base material is improved, the stretching tension increases, and stable stretching becomes difficult or breaks. Therefore, the laminate can be stretched at a higher magnification by stretching while suppressing the orientation of the resin substrate.
  • the orientation of the PVA-based resin can be improved, whereby the orientation of the PVA-based resin can be improved even after stretching in boric acid water.
  • the PVA resin is easily cross-linked with boric acid during boric acid water stretching, and boric acid is a nodal point. It is presumed that the orientation of the PVA-based resin is increased even after stretching in boric acid solution by being stretched in such a state. As a result, a polarizing film having excellent optical characteristics (for example, the degree of polarization) can be produced.
  • the stretching ratio in the air auxiliary stretching is preferably 3.5 times or less.
  • the stretching temperature of the air auxiliary stretching is preferably equal to or higher than the glass transition temperature of the PVA resin.
  • the stretching temperature is preferably 95 ° C to 150 ° C.
  • the maximum draw ratio in the case of combining the air auxiliary stretching and the boric acid solution stretching is preferably 5.0 times or more, more preferably 5.5 times or more, and further preferably, the original length of the laminate. Is 6.0 times or more.
  • the dyeing of the PVA resin layer is typically 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 PVA resin layer (laminate) is immersed in the dyeing solution. This is because iodine can be adsorbed well.
  • 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 is added to the aqueous iodine solution. Specific examples of the iodide are as described above.
  • the blending amount of iodide is preferably 0.02 to 20 parts by weight, more preferably 0.1 to 10 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 in order to ensure the transmittance of the PVA resin layer.
  • the staining conditions concentration, liquid temperature, immersion time
  • immersion time is set so that the polarization degree of the polarizing film obtained may be 99.98% or more.
  • the immersion time is set so that the single transmittance of the obtained polarizing film is 40.0% to 42.5%.
  • the staining process can be performed at any appropriate timing.
  • it performs before an underwater extending
  • the PVA-based resin layer (laminate) can be appropriately subjected to treatments for forming a polarizing film.
  • the treatment for forming the polarizing film include insolubilization treatment, crosslinking treatment, washing treatment, and drying treatment.
  • count, order, etc. of these processes are not specifically limited.
  • the insolubilization treatment is typically performed by immersing a PVA resin layer (laminated body) in an aqueous boric acid solution.
  • a PVA resin layer laminated body
  • boric acid aqueous solution 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 insolubilization treatment is performed before the above-described underwater stretching or the above-described dyeing treatment.
  • the cross-linking treatment is typically performed by immersing a PVA resin layer (laminated body) in an aqueous boric acid 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.
  • blend an iodide it is preferable to mix
  • 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 60 ° C.
  • the crosslinking treatment is performed before the underwater stretching. In a preferred embodiment, air stretching, dyeing treatment and crosslinking treatment are performed in this order.
  • the above-described cleaning treatment is typically performed by immersing the PVA resin layer (laminated body) in a potassium iodide aqueous solution.
  • the drying temperature in the drying treatment is preferably 30 ° C. to 100 ° C.
  • the polarizing film is formed on the resin base material.
  • the laminate of the resin base material and the polarizing film obtained in the above section F-1 is used for forming a sealing portion described later.
  • the resin base material on one side of the polarizing film can function as a protective film.
  • a protective film is bonded to the polarizing film surface of a laminate of a resin base material (protective film) and a polarizing film (for convenience, this protective film is referred to as another protective film).
  • the obtained resin base material (protective film) / polarizing film / another protective film laminate is provided for the formation of a sealing portion described later.
  • protective films are disposed on both sides of the polarizing film.
  • a protective film is bonded to the surface of the polarizing film of the laminate of the resin base material and the polarizing film, and then the resin base material is peeled and removed.
  • the obtained polarizing film / protective film laminate is provided for the formation of a sealing portion described later.
  • another protective film is bonded to the polarizing film surface (resin substrate peeling surface) of the polarizing film / protective film laminate, and the protective film / polarizing film / other protective film
  • a laminated body is provided for formation of the below-mentioned sealing part.
  • a sealing portion is formed on the laminate obtained in the above section F-2.
  • the sealing portion is formed after the laminate is cut into a predetermined size. More specifically, an adhesive layer is formed as the outermost layer on the display panel side of the laminate. If necessary, a separator is temporarily attached to the surface of the pressure-sensitive adhesive layer, and can be protected until the pressure-sensitive adhesive layer is actually used. Next, the laminate is cut into a predetermined size. Cutting is done by any suitable means or method.
  • a sealing part is formed in the laminate of the predetermined size obtained above.
  • a sealing part is formed so that the outer peripheral end surface of a laminated body (polarizing film and protective film) may be covered.
  • the sealing part may be formed in a state where the laminated body is placed on the substrate, or may be formed in a state where the laminated body is bonded to the display panel.
  • a sealing part is formed with an adhesive composition, and the case where a sealing part is formed with a metal containing compound are each demonstrated.
  • a sealing part is typically formed by arrange
  • the sealing portion may be formed by applying and curing a liquid (before curing) adhesive composition at a predetermined position, and placing the sheet-like pressure-sensitive adhesive composition at a predetermined position (typically, It may be formed by bonding).
  • the sealing portion may be formed in a state where the laminated body is placed on the base material, or may be formed in a state where the laminated body is bonded to the display panel.
  • arbitrary appropriate base materials may be employ
  • the base material typically has a size larger than that of the laminate, and an extended portion extending from the outer periphery of the laminate is defined.
  • the extension part becomes the arrangement part of the adhesive composition. You may use said separator as a base material. In this case, when the laminate with a separator is cut, only the separator is left in the peripheral portion (as a result, an extension portion is formed).
  • the polarizing plate according to the embodiment of the present invention is formed on the substrate.
  • the obtained polarizing plate is bonded to a display panel through an adhesive layer. As a result, the configuration shown in FIGS. 1A and 2 is obtained.
  • the substrate can be peeled off as needed.
  • the adhesive composition may be disposed so as to cover only the outer peripheral end surface of the laminate (finally, the configuration is as shown in FIG. 1A), and the surface on the side away from the display panel together with the outer peripheral end surface. You may arrange
  • the adhesive composition When the adhesive composition is disposed so as to cover the surface of the laminate, it may be disposed so as to cover the entire surface (finally, the configuration is as shown in FIG. 2). You may arrange
  • the sealing portion When the sealing portion is formed of a metal-containing compound, the sealing portion can typically be formed by a vapor deposition method or a coating method. Vapor deposition is preferred in that a uniform thin film with high adhesion can be obtained. Typical examples of the vapor deposition method include PVD (physical vapor deposition method) such as vacuum vapor deposition, ion plating, and sputtering, and CVD (chemical vapor deposition method). Sputtering is preferred. Even when the sealing part is formed of a metal-containing compound, the sealing part may be formed in a state where the laminate is placed on the base material, similarly to the case where the sealing part is formed of the adhesive composition. The laminate may be formed in a state of being bonded to the display panel.
  • PVD physical vapor deposition method
  • CVD chemical vapor deposition method
  • the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
  • the measuring method of each characteristic is as follows.
  • One release liner of the pressure-sensitive adhesive sheet is peeled off to expose the pressure-sensitive adhesive surface, and the pressure-sensitive adhesive sheet is bonded to a triacetyl cellulose film (TAC film, thickness: 25 ⁇ m, manufactured by Konica Minolta Co., Ltd.) via the pressure-sensitive adhesive surface. Cut out into a circle. Finally, the other release liner was peeled off to obtain a measurement sample. About the obtained sample for a measurement, the water vapor transmission rate (water vapor transmission rate) was measured by the water vapor transmission test method (a cup method, according to JIS Z 0208). The measurement conditions were as follows. In addition, a constant temperature and humidity chamber was used for the measurement.
  • the magnitude of color loss from the edge of the polarizing film (color loss amount: ⁇ m) was measured.
  • color loss amount ⁇ m
  • Olympus MX61L as a microscope, the amount of color loss was measured from an image taken at a magnification of 10 times.
  • the larger one of the color loss amount a from the end portion in the stretching direction and the color loss amount b from the end portion in the direction orthogonal to the stretching direction is defined as the color loss amount.
  • Example 1 As the resin substrate, an amorphous polyethylene terephthalate film (thickness: 100 ⁇ m) having a long shape, a water absorption of 0.60%, Tg of 80 ° C., and an elastic modulus of 2.5 GPa was used. One side of the resin base material is subjected to corona treatment (treatment condition: 55 W ⁇ min / m 2 ).
  • Polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) 90 parts by weight, aceto 10 parts by weight of acetyl-modified PVA (polymerization degree of 1200, acetoacetyl modification degree of about 5%, saponification degree of 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Gosefimer Z200”), and potassium iodide
  • An aqueous solution containing 13 parts by weight was applied at room temperature and dried in an environment of 60 ° C. to form a PVA resin layer having a thickness of 13 ⁇ m, thereby producing a laminate.
  • the obtained laminate was uniaxially stretched by 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 140 ° C. (air-assisted stretching).
  • the 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).
  • 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
  • insolubilization treatment immersed for 60 seconds in a dyeing bath (iodine aqueous solution obtained by blending 0.4 parts by weight of iodine and 3.0 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C. (Staining treatment).
  • the laminate was immersed in a cleaning bath (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C. (cleaning treatment). In this way, a polarizing film having a thickness of 5 ⁇ m was formed on the resin substrate.
  • a cleaning bath an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water
  • cleaning treatment an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water
  • an acrylic pressure-sensitive adhesive layer (thickness: 25 ⁇ m) on the polarizing film surface of the laminate of the resin base material and the polarizing film, It cut out to 50 mm x 50 mm, and bonded together to the glass plate of 70 mm x 70 mm through the adhesive layer. So as to cover the outer peripheral end face of the laminate on a glass plate adhesive in the form of sheet having a moisture permeability of 24g / m 2 / 24hr (thickness 25 [mu] m) were placed, and the sealing portion.
  • the pressure-sensitive adhesive is polybutene (JX Nippon Oil & Energy) with respect to 100 parts by weight of a styrene / ethylene propylene copolymer / styrene block copolymer (Kuraray, trade name “Septon 2063”, styrene content: 13% by weight).
  • Example 2 Except that water vapor permeability was formed a seal with 12g / m 2 / 24hr at which the pressure-sensitive adhesive (thickness 50 [mu] m) in the same manner as in Example 1, producing a polarizing plate having a sealing portion on a glass plate did.
  • the obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 3 A polarizing plate having a sealing portion is formed on a glass plate in the same manner as in Example 1 except that a sheet-like pressure-sensitive adhesive (thickness 25 ⁇ m) is laminated so as to cover the entire upper surface and the outer peripheral end surface of the laminate on the glass plate. Made above. Furthermore, a cover glass having a thickness of 1 mm was laminated on the adhesive to obtain a polarizing plate with a cover glass. The obtained polarizing plate was used for the evaluation of the color loss. The results are shown in Table 1.
  • Example 4 While immersing a PVA resin film (manufactured by Kuraray Co., Ltd., trade name “PE-6000”, thickness: 60 ⁇ m, average polymerization degree: 2,400, saponification degree: 99.9 mol%) in a 30 ° C. water bath for 1 minute. Film stretched 1.2 times in the conveying direction, then dipped in a 30 ° C. aqueous solution with an iodine concentration of 0.04% by weight and a potassium concentration of 0.3% by weight, but not stretched at all (original length) The film was stretched 2 times based on the above. Next, this stretched film was further stretched up to 3 times based on the original length while being immersed in an aqueous solution at 30 ° C.
  • a PVA resin film manufactured by Kuraray Co., Ltd., trade name “PE-6000”, thickness: 60 ⁇ m, average polymerization degree: 2,400, saponification degree: 99.9 mol%
  • 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) is applied to both surfaces of the polarizing film, and a cycloolefin film (Zeonor, Zeonor ZF14, thickness: 13 ⁇ m) and a triacetylcellulose film (Konica Minolta, KC4UY) were bonded together and heated in an oven maintained at 60 ° C. for 5 minutes to obtain a polarizing plate. . Subsequent procedures were performed in the same manner as in Example 2 to obtain a polarizing plate having a sealing portion. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 1 A polarizing plate was produced on a glass plate in the same manner as in Example 1 except that the sealing part was not formed. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1. Further, FIG. 5 shows the state of color loss.
  • Example 3 Example 3 except that only the upper surface of the laminate on the glass plate was covered (specifically, an adhesive sheet having the same size as the laminate was matched with the outer peripheral edge of the laminate). In the same manner, a polarizing plate with a cover glass was obtained. The obtained polarizing plate was used for the evaluation of the color loss. The results are shown in Table 1.
  • Example 4 A polarizing plate was produced on a glass plate in the same manner as in Example 3 except that the sealing part was not formed. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • a polarizing plate capable of maintaining excellent optical characteristics even in a humidified environment can be obtained by forming a sealing portion having a predetermined moisture permeability on the outer peripheral end surface of the polarizing plate. .
  • the polarizing plate of the present invention is suitably used for liquid crystal panels such as liquid crystal televisions, liquid crystal displays, mobile phones, digital cameras, video cameras, portable game machines, car navigation systems, copy machines, printers, fax machines, watches, and microwave ovens.
  • liquid crystal panels such as liquid crystal televisions, liquid crystal displays, mobile phones, digital cameras, video cameras, portable game machines, car navigation systems, copy machines, printers, fax machines, watches, and microwave ovens.

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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

L'invention concerne une plaque de polarisation capable de maintenir d'excellentes caractéristiques optiques même dans un environnement humidifié. Cette plaque de polarisation comprend : un film polarisant constitué d'un film de résine à base d'alcool polyvinylique; un film protecteur disposé sur au moins un côté du film polarisant; et une partie d'étanchéité recouvrant les faces d'extrémité périphériques du film polarisant et du film protecteur. Dans un mode de réalisation, l'épaisseur du film polarisant est inférieure ou égale à 8 µm. Dans un mode de réalisation, la perméabilité à l'humidité de la partie d'étanchéité est inférieure ou égale à 300 g/m2/24 h. Dans un mode de réalisation, la plaque de polarisation a une quantité de perte de couleur de 100 µm ou moins après avoir été maintenue dans un environnement RH de 85 °C et 85 % pendant 120 heures.
PCT/JP2018/005902 2017-02-28 2018-02-20 Plaque de polarisation et procédé de fabrication d'une plaque de polarisation WO2018159376A1 (fr)

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WO2021049217A1 (fr) * 2019-09-12 2021-03-18 住友化学株式会社 Polariseur
JP2021043370A (ja) * 2019-09-12 2021-03-18 住友化学株式会社 偏光子
WO2021065731A1 (fr) * 2019-09-30 2021-04-08 日東電工株式会社 Élément de commande de lumière scellé avec film de protection de surface
US20230017351A1 (en) * 2021-07-19 2023-01-19 Sharp Kabushiki Kaisha Method for fabricating polarizing layer including a protective layer

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TW201840433A (zh) 2018-11-16
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CN110337601A (zh) 2019-10-15
KR20190133150A (ko) 2019-12-02
JPWO2018159376A1 (ja) 2019-11-07

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