WO2014148639A1 - Film stratifié de polarisation et procédé permettant de fabriquer une plaque de polarisation - Google Patents

Film stratifié de polarisation et procédé permettant de fabriquer une plaque de polarisation Download PDF

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Publication number
WO2014148639A1
WO2014148639A1 PCT/JP2014/057931 JP2014057931W WO2014148639A1 WO 2014148639 A1 WO2014148639 A1 WO 2014148639A1 JP 2014057931 W JP2014057931 W JP 2014057931W WO 2014148639 A1 WO2014148639 A1 WO 2014148639A1
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film
layer
polyvinyl alcohol
parts
crosslinking
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PCT/JP2014/057931
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English (en)
Japanese (ja)
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直子 竹之熊
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住友化学株式会社
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Priority to KR1020157029212A priority Critical patent/KR102157406B1/ko
Publication of WO2014148639A1 publication Critical patent/WO2014148639A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/516—Oriented mono-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays

Definitions

  • the present invention relates to a method for producing a polarizing laminated film and a method for producing a polarizing plate.
  • the polarizing plate is widely used as a polarized light supplying element and a polarized light detecting element in a display device such as a liquid crystal display device.
  • a polarizing film polarizer layer
  • a protective film made of triacetyl cellulose
  • a polarizing film is produced by performing a dyeing treatment or a crosslinking treatment, and a protective film or the like is laminated thereon to form a polarizing plate.
  • a polarizing film is produced by performing a dyeing treatment or a crosslinking treatment, and a protective film or the like is laminated thereon to form a polarizing plate.
  • the polyvinyl alcohol-type resin layer used as a polarizer layer is dry-stretched with the base film, dyeing
  • Patent Document 1 discloses a stretched laminate in which a laminate in which a base material layer and a hydrophilic polymer layer are laminated is stretched, and has a high hydrophilicity.
  • An invention relating to a polarizing plate containing a stretched laminate in which at least a dichroic substance is adsorbed in the molecular layer is disclosed.
  • As a specific cross-linking method after dyeing the hydrophilic polymer layer with a dichroic substance 1 to 10% by weight of a cross-linking agent represented by boric acid and 0.05 to 15% by weight of iodide are used.
  • a method of immersing in an aqueous solution containing 10 to 60 ° C. is described.
  • Patent Document 2 a polarizing film made of a polyvinyl alcohol resin in which a dichroic material is oriented is formed on an amorphous ester thermoplastic resin substrate of a continuous web.
  • An invention relating to a method for producing a laminated optical film is disclosed.
  • an aqueous solution at 65 ° C. containing 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water After being immersed in a water solution, or after being immersed in a 40 ° C.
  • JP 2009-98653 A paragraphs [0059] and [0060]
  • Japanese Patent No. 4691205 paragraphs [0099], [0100], [0106] to [0109]
  • an object of the present invention is to produce a polarizing laminate film and a polarizing plate that are thin and have high polarization performance.
  • a resin layer forming step for forming a laminated film by forming a polyvinyl alcohol-based resin layer on at least one surface of the base film; the obtained laminated film has a polyvinyl alcohol-based resin layer having a thickness of 10 ⁇ m.
  • Stretching step to obtain a stretched film by uniaxial stretching as follows: The obtained stretched film is immersed in a dyeing solution containing a dichroic dye to dye the polyvinyl alcohol-based resin layer, and with a dyed layer Dyeing step for obtaining a laminated film; and crosslinking obtained by immersing the obtained laminated film with a dyed layer in a crosslinking solution containing boric acid to crosslink the dyed polyvinyl alcohol resin layer to form a polarizer layer
  • the crosslinking step includes a first crosslinking step and a second crosslinking step in this order, and a laminated film with a dyed layer obtained in the dyeing step,
  • the boric acid content per 100 parts by weight of water is 1 to 20 parts by weight, and the iodide content is less than 1 part by weight, and is immersed at a temperature of 60 ° C. or higher.
  • the boric acid content per 100 parts by weight of water is 1 to 20
  • the stretching step is preferably performed by uniaxially stretching the laminated film at a stretching ratio exceeding 5 times.
  • a method for producing a polarizing plate comprising a step and a base film peeling step for peeling the base film from the polarizing laminated film after the protective film is bonded.
  • the present invention provides an aqueous solution containing 1 to 20 parts by weight of boric acid per 100 parts by weight of water and having an iodide content of less than 1 part by weight with respect to the laminated film with a dyed layer obtained in the dyeing step.
  • the second immersing is performed at a temperature of 60 ° C. or higher in an aqueous solution containing 1 to 20 parts by weight of boric acid and 2 parts by weight or more of iodide per 100 parts by weight of water.
  • a polarizing property film with high polarization performance and a thin polarizing film and a polarizing plate can be produced efficiently.
  • FIG. 1 is a flowchart showing an embodiment of a method for producing a polarizing laminated film according to the present invention.
  • FIG. 2 is a flowchart showing an embodiment of a method for producing a polarizing plate according to the present invention.
  • FIG. 1 is a flowchart showing an embodiment of a method for producing a polarizing laminated film.
  • a resin layer forming step (S10) for obtaining a laminated film by forming a polyvinyl alcohol-based resin layer on at least one surface of a base film
  • Stretching step (S20) to obtain a stretched film by uniaxial stretching so that the thickness of the alcohol-based resin layer is 10 ⁇ m or less, the obtained stretched film is immersed in a dyeing solution containing a dichroic dye
  • a dyeing step (S30) for dyeing a polyvinyl alcohol-based resin layer to obtain a laminated film with a dyed layer, and the obtained dyed layered laminated film was immersed in a crosslinking solution containing boric acid and dyed as described above
  • a crosslinking step (S40) of crosslinking the polyvinyl alcohol-based resin layer to form a polarizer layer is included
  • a polarizing laminate film having a polarizer layer having a thickness of 10 ⁇ m or less and having sufficient polarization performance on the base film can be obtained.
  • this polarizing laminated film can also be used as an intermediate product for transferring a polarizer layer to a protective film.
  • this polarizing laminated film is used.
  • the film can be used as a polarizing plate as it is.
  • FIG. 2 is a flowchart showing an embodiment of a method for manufacturing a polarizing plate.
  • a resin layer forming step (S10) in which a polyvinyl alcohol-based resin layer is formed on at least one surface of a base film to obtain a laminated film
  • Stretching step (S20) to obtain a stretched film by uniaxial stretching so that the thickness of the alcohol-based resin layer is 10 ⁇ m or less, the obtained stretched film is immersed in a dyeing solution containing a dichroic dye
  • a polarizing plate having a polarizer layer having a thickness of 10 ⁇ m or less and having sufficient polarization performance on the protective film can be obtained.
  • This polarizing plate can be used, for example, by being bonded to another optical film or a liquid crystal cell via a pressure-sensitive adhesive.
  • the resin used for the base film examples include thermoplastic resins excellent in transparency, mechanical strength, thermal stability, stretchability, etc., and an appropriate resin can be selected according to the glass transition temperature Tg or the melting point Tm. That's fine.
  • thermoplastic resins include polyolefin resins such as chain polyolefin resins and cyclic polyolefin resins, polyester resins, (meth) acrylic resins, cellulose ester resins, polycarbonate resins, polyvinyl alcohol resins.
  • the base film can be a single layer or a multilayer composed of the resin described above.
  • chain polyolefin-based resin polyethylene, polypropylene, and the like are preferable because they can be stably stretched at a high magnification.
  • a propylene-ethylene copolymer obtained by copolymerizing propylene with ethylene can also be suitably used. Copolymerization can be performed with other types of monomers, and examples of monomers other than ethylene that can be copolymerized with propylene include ⁇ -olefins.
  • the ⁇ -olefin has 4 or more carbon atoms and is preferably an ⁇ -olefin having 4 to 10 carbon atoms.
  • ⁇ -olefin having 4 to 10 carbon atoms include linear monoolefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene; 3 -Branched monoolefins such as methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene; vinylcyclohexane and the like.
  • the copolymer of propylene and other monomers copolymerizable therewith may be a random copolymer or a block copolymer.
  • the content of the structural unit derived from the other monomer in the copolymer is determined by infrared (IR) spectrum according to the method described on page 616 of “Polymer Analysis Handbook” (1995, published by Kinokuniya). It can be obtained by measuring.
  • IR infrared
  • propylene-based resins constituting propylene-based resin films include propylene homopolymers, propylene-ethylene random copolymers, propylene-1-butene random copolymers, and propylene-ethylene-1-butene. Random copolymers are preferred.
  • the stereoregularity of the propylene resin constituting the propylene resin film is preferably substantially isotactic or syndiotactic.
  • a film made of a propylene-based resin having substantially isotactic or syndiotactic stereoregularity has relatively good handleability and excellent mechanical strength in a high temperature environment.
  • Cyclic polyolefin resin is a general term for resins that are polymerized using cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Resins that are included. Specific examples include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and ⁇ -olefins such as ethylene or propylene (typically random copolymers). There are graft polymers obtained by modifying these with unsaturated carboxylic acids or derivatives thereof, and hydrides thereof. Specific examples of the cyclic olefin include norbornene monomers.
  • cyclic polyolefin resins Various products are commercially available as cyclic polyolefin resins. Specific examples of commercially available products include TOPAS (manufactured by Topas Advanced Polymers, available from Polyplastics Co., Ltd. in Japan), Arton (manufactured by JSR Co., Ltd.), ZEONOR (ZEONOR Co., Ltd., Japan) )], ZEONEX (manufactured by Nippon Zeon Co., Ltd.), and Apel (manufactured by Mitsui Chemicals, Inc.).
  • TOPAS manufactured by Topas Advanced Polymers, available from Polyplastics Co., Ltd. in Japan
  • Arton manufactured by JSR Co., Ltd.
  • ZEONOR ZEONOR Co., Ltd., Japan
  • ZEONEX manufactured by Nippon Zeon Co., Ltd.
  • Apel manufactured by Mitsui Chemicals, Inc.
  • the polyester-based resin is a polymer having an ester bond in the main chain, and is specifically composed of a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol.
  • the polyvalent carboxylic acid used for the production of the polyester-based resin is mainly a divalent dicarboxylic acid or an ester thereof, and examples thereof include terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalenedicarboxylate.
  • Polyhydric alcohols are also mainly divalent diols, and examples thereof include ethylene glycol, propanediol, butanediol, neopentyl glycol, and cyclohexanedimethanol.
  • polyester resin is polyethylene terephthalate, which is a polycondensate of terephthalic acid and ethylene glycol.
  • Polyethylene terephthalate is a crystalline resin, but the state before the crystallization treatment is more easily subjected to treatment such as stretching. If necessary, it can be crystallized by heat treatment during stretching or after stretching.
  • a copolyester having a crystallinity lowered (or made amorphous) by further copolymerizing another monomer with a polyethylene terephthalate skeleton is also preferably used.
  • examples of such resins include those obtained by copolymerizing cyclohexanedimethanol and isophthalic acid. Since these resins are also excellent in stretchability, they can be suitably used.
  • polyester resins other than polyethylene terephthalate and copolymers thereof include polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, polycyclohexanedimethyl. And naphthalate. These blend resins and copolymers can also be used.
  • the (meth) acrylic resin is a polymer having a compound having a (meth) acryloyl group as a main constituent monomer.
  • Specific examples include poly (meth) acrylic acid ester such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate- Acrylate ester- (meth) acrylic acid copolymer, methyl methacrylate-styrene copolymer (such as what is called MS resin), copolymer of methyl methacrylate and a compound having an alicyclic hydrocarbon group (for example, Methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.).
  • such poly (meth) acrylate include polymer mainly comprising C 1-6 alkyl esters of (meth) acrylic acid.
  • More preferred examples of the (meth) acrylic resin include a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).
  • the cellulose ester resin is a fatty acid ester of cellulose.
  • Specific examples of the cellulose ester resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate.
  • these copolymers and those in which a part of the hydroxyl group is modified with another group are also included.
  • cellulose triacetate is particularly preferable.
  • Many products of the cellulose triacetate film are commercially available, which is advantageous in terms of availability and cost.
  • Examples of commercially available cellulose triacetate films include Fujitac TD80, Fujitac TD80UF, Fujitac TD80UZ, Fujitac TD40UZ (manufactured by Fuji Film Co., Ltd.), KC8UX2M, KC4UY (manufactured by Konica Minolta Advanced Layer Co., Ltd.), etc. There is.
  • the polycarbonate resin is a polymer having a carbonate bond (—O—CO—O—) in the main chain. It is a kind of engineering plastic and is a resin having high impact resistance, heat resistance and flame retardancy. Moreover, since it has high transparency, it is used suitably also for an optical use. For optical applications, resins called modified polycarbonates in which the polymer skeleton is modified in order to lower the photoelastic coefficient, copolymerized polycarbonates with improved wavelength dependence, and the like are commercially available and can be suitably used. Such polycarbonate resins are widely commercially available.
  • Panlite manufactured by Teijin Chemicals Ltd.
  • Iupilon manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • SD Polyca manufactured by Sumitomo Dow Co., Ltd.
  • Caliber Caliber [Dow Chemical Company].
  • thermoplastic resin which comprises a base film.
  • additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, and coloring agents.
  • the proportion of the thermoplastic resin exemplified above in the base film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. %. This is because if the ratio of the thermoplastic resin in the base film is less than 50% by weight, the high transparency inherent in the thermoplastic resin may not be sufficiently exhibited.
  • the thickness of the base film can be determined as appropriate, but generally it is preferably 1 to 500 ⁇ m, more preferably 1 to 300 ⁇ m, especially 5 to 200 ⁇ m from the viewpoint of workability such as strength and handleability. Is more preferable. Further, a base film having a thickness in the range of 5 to 150 ⁇ m is more preferable.
  • the base film may be subjected to corona treatment, plasma treatment, flame treatment or the like on at least the surface on which the resin layer is formed in order to improve the adhesion with the resin layer.
  • a thin layer such as a primer layer or an adhesive layer may be formed on the surface of the base film on the side where the resin layer is formed.
  • a base film means the thing of the state which does not contain them.
  • the polyvinyl alcohol-based resin layer is typically prepared by dissolving polyvinyl alcohol-based resin powder in a solvent having high solubility such as water to prepare a polyvinyl alcohol-based resin solution. It is formed by coating on at least one surface, evaporating the solvent and drying. By forming the resin layer by such a method, it is possible to reduce the thickness.
  • the coating of the polyvinyl alcohol resin solution on the base film includes wire bar coating method, roll coating method such as reverse coating and gravure coating, die coating method, comma coating method, lip coating method, spin coating method, screen coating method, What is necessary is just to select suitably from various well-known methods, such as the fountain coating method, the dipping method, and the spray method.
  • the drying temperature is, for example, 50 to 200 ° C., preferably 60 to 150 ° C.
  • the drying time is, for example, 2 to 20 minutes.
  • the thickness of the resin layer to be formed is preferably more than 3 ⁇ m and not more than 30 ⁇ m, and more preferably in the range of 5 to 20 ⁇ m.
  • the layer thickness may exceed 10 ⁇ m.
  • a primer layer may be provided on the surface of the base film on which the resin layer is formed.
  • the primer layer is preferably formed from a composition containing a crosslinking agent or the like in a polyvinyl alcohol resin from the viewpoint of adhesion.
  • the polyvinyl alcohol resin used as the primer layer can be a saponified polyvinyl acetate resin.
  • the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers with other monomers copolymerizable with vinyl acetate.
  • examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
  • the polyvinyl alcohol resin used for forming the resin layer preferably has a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and particularly 94 mol% or more. If the degree of saponification is too low, the water resistance and heat-and-moisture resistance after making the polarizing plate may not be sufficient. Also, it may be a completely saponified product (having a saponification degree of 100 mol%), but if the saponification degree is too high, the dyeing speed becomes slow, and the production time is required to give sufficient polarization performance. In some cases, the polarizer may become long or a polarizer having sufficient polarization performance may not be obtained. Therefore, the saponification degree is preferably 99.5 mol% or less, more preferably 99 mol% or less, or 99.0 mol% or less.
  • the saponification degree can be determined by a method defined in JIS K6726-1994 “Testing method for polyvinyl alcohol”.
  • the polyvinyl alcohol resin used in the present invention may be a modified polyvinyl alcohol partially modified.
  • polyvinyl alcohol resin modified with olefins such as ethylene or propylene
  • unsaturated carboxylic acids such as acrylic acid, methacrylic acid or crotonic acid
  • alkyl ester of unsaturated carboxylic acid And those modified with acrylamide modified with acrylamide.
  • the proportion of modification is preferably less than 30 mol%, and more preferably less than 10 mol%. When modification of 30 mol% or more is performed, it is difficult to adsorb the dichroic dye, and the problem that the polarization performance is lowered is likely to occur.
  • the average degree of polymerization of the polyvinyl alcohol resin is usually in the range of about 100 to 10,000, preferably 1,500 to 8,000, more preferably 2,000 to 5,000.
  • the average degree of polymerization here can also be determined by a method defined in JIS K6726-1994 “Testing method for polyvinyl alcohol”.
  • polyvinyl alcohol resins having such characteristics include PVA124 (saponification degree: 98.0 to 99.0 mol%) and PVA117 (saponification degree: 98.0 to 99.0 mol%) manufactured by Kuraray Co., Ltd.
  • PVA624 degree of saponification 95.0-96.0 mol%) and PVA617 (degree of saponification 94.5-95.5 mol%); for example, AH-26 (degree of saponification) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
  • the laminated film is uniaxially stretched so that the thickness of the polyvinyl alcohol-based resin layer is 10 ⁇ m or less to produce a stretched film.
  • the draw ratio of uniaxial stretching is preferably more than 5 times and 17 times or less, more preferably more than 5 times and 8 times or less.
  • the draw ratio is 5 times or less, the orientation of the polyvinyl alcohol-based resin layer is not sufficient, and as a result, there may be a problem that the degree of polarization of the polarizer layer is not sufficiently high.
  • the stretching process in the stretching step (S20) is not limited to one-stage stretching, and can be performed in multiple stages.
  • the second and subsequent stretching steps may be performed in the stretching step (S20), but may be performed simultaneously with the dyeing process and the crosslinking process in the dyeing process (S30).
  • stretching in multistage it is preferable to extend
  • the stretching step (S20) in the present embodiment can be performed by a longitudinal stretching process performed in the longitudinal direction of the laminated film, a lateral stretching process performed by stretching in the width direction, or the like.
  • Examples of the longitudinal stretching method include an inter-roll stretching method and a compression stretching method, and examples of the transverse stretching method include a tenter method.
  • the stretching treatment either a wet stretching method or a dry stretching method can be adopted, but it is preferable to use the dry stretching method because the temperature at which the laminated film is stretched can be selected from a wide range.
  • the stretching temperature is set to be higher than the temperature at which the polyvinyl alcohol-based resin layer and the entire base film are fluid enough to be stretched, and preferably from the [base film phase transition temperature-30] ° C.
  • the phase transition temperature of the base film +30] ° C. and more preferably, the range of [base film phase transition temperature ⁇ 25] ° C. to [base film phase transition temperature +30] ° C.
  • the stretching temperature is lower than [phase transition temperature of base film ⁇ 30] ° C., it is difficult to achieve a high magnification stretching of more than 5 times.
  • the stretching temperature exceeds [phase transition temperature of base film + 30] ° C., the fluidity of the base film tends to be too high and stretching tends to be difficult. Since it is easier to achieve a high draw ratio of more than 5 times, the drawing temperature is within the above range, and more preferably 120 ° C. or higher.
  • the temperature adjustment of the stretching process is usually performed by adjusting the temperature of the heating furnace.
  • the stretched film obtained in the above stretching process is immersed in a dyeing solution containing a dichroic dye, and the polyvinyl alcohol-based resin layer in the stretched film is dyed to obtain a laminated film with a dyed layer.
  • a dichroic dye for example, iodine or a dichroic organic dye can be used.
  • dichroic organic dyes for example, Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Spura Blue G, Spura Blue GL, Spura Orange GL, Direct Sky Blue, Direct First Orange S, First Black, etc. can be used.
  • These dichroic organic dyes are commercially available. Only one type of dichroic dye may be used, or two or more types may be used in combination.
  • the dyeing step is performed, for example, by immersing the entire stretched film in a solution (dye solution) containing the dichroic dye.
  • a solution in which the above dichroic dye is dissolved in a solvent can be used.
  • a solvent for the dyeing solution water is generally used, but an organic solvent compatible with water may be further added.
  • the concentration of the dichroic dye is preferably 0.01 to 10% by weight, more preferably 0.02 to 7% by weight, and particularly preferably 0.025 to 5% by weight.
  • iodine When iodine is used as the dichroic dye, it is preferable to further add an iodide because the dyeing efficiency can be further improved.
  • the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and iodide.
  • examples include titanium.
  • the addition ratio of these iodides is preferably 0.01 to 20% by weight in the dyeing solution.
  • potassium iodide is preferably used.
  • the ratio of iodine to potassium iodide is preferably in the range of 1: 5 to 1: 100, more preferably in the range of 1: 6 to 1:80, especially 1: 7. It is preferably in the range of ⁇ 1: 70.
  • the immersion time of the stretched film in the dyeing solution is usually preferably in the range of 15 seconds to 15 minutes, and more preferably in the range of 30 seconds to 3 minutes.
  • the temperature of the dyeing solution is preferably in the range of 10 to 60 ° C, more preferably in the range of 20 to 40 ° C.
  • the unstretched film is subjected to the stretching process. It is preferable to carry out a dyeing treatment after the application. At this time, it may be simply dyed what has been stretched in advance at the target magnification, or may be stretched again during dyeing and stretched at a low magnification in advance to reach the target magnification in total. . Further, when stretching is performed during the subsequent crosslinking treatment, the stretching can be limited to a low magnification. In this case, what is necessary is just to adjust suitably so that the target magnification may be reached after a crosslinking process.
  • Cross-linking step (S40) Following the dyeing process, a crosslinking process is performed.
  • the cross-linking treatment is performed by immersing the laminated film with the dyed layer obtained in the above dyeing step in a solution containing a cross-linking agent (cross-linking solution).
  • a cross-linking agent boron compounds such as boric acid and borax, glyoxal, glutaraldehyde and the like are generally known, but boric acid is used in the present invention. Of course, the presence of other crosslinkers with boric acid is acceptable.
  • iodide is generally added to the crosslinking solution.
  • the presence of iodide makes it possible to make the polarization characteristics in the plane of the resin layer more uniform.
  • 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 particularly preferably used.
  • the cross-linking step In the crosslinking step, better polarization performance can be obtained by using a plurality of crosslinking solutions having different solute types and concentrations.
  • the cross-linking step is divided into two steps, and in the first step (first cross-linking step), a cross-linking solution having a low iodide concentration or containing substantially no iodide is used.
  • first cross-linking step In the first cross-linking step, a crosslinking solution having a higher iodide concentration than the first crosslinking step is used.
  • the crosslinking step can be performed in three or more stages, but even in that case, the first crosslinking step is performed first, and then the second crosslinking step is performed. That is, the first cross-linking step and the second cross-linking step are performed in this order.
  • the first crosslinking step an aqueous solution having a boric acid content of 1 to 20 parts by weight per 100 parts by weight of water and an iodide content of less than 1 part by weight is used as a crosslinking solution,
  • the laminated film with a dyed layer obtained in the dyeing process is immersed at a temperature of 60 ° C. or higher.
  • the iodide content is less than 1 part by weight per 100 parts by weight of water, so that the crosslinking reaction can proceed efficiently.
  • the iodide content in the crosslinking solution used there is less than 1 part by weight per 100 parts by weight of water, preferably 0.8. 6 parts by weight or less, more preferably 0.05 parts by weight or less.
  • the cross-linking solution used in the first cross-linking step may not contain iodide.
  • the second crosslinking step an aqueous solution containing 1 to 20 parts by weight of boric acid and 2 parts by weight or more of iodide per 100 parts by weight of water was used as the crosslinking solution, and the first crosslinking step was performed there.
  • the subsequent laminated film with a dyed layer is immersed at a temperature of 60 ° C. or higher.
  • the iodide content is 2 parts by weight or more per 100 parts by weight of water, so that the orientation tends to remain in the polyvinyl alcohol-based resin layer (dyed layer) in the previous dyeing step and the first crosslinking step. Bad dichroic dyes are easily removed.
  • the hue of the light-polarizing laminated film can be adjusted by adjusting the iodide content in the second crosslinking step.
  • the content of iodide in the second crosslinking step is allowed to be about 15 parts by weight per 100 parts by weight of water, but is preferably 5 parts by weight or more and preferably 8 parts by weight or less.
  • the crosslinking solution a solution in which a crosslinking agent (boric acid) is dissolved in a solvent can be used.
  • a crosslinking agent boric acid
  • water is used in the present invention, but the crosslinking solution (aqueous solution) may further contain an organic solvent compatible with water.
  • the concentration of boric acid in the crosslinking solution is 1 to 20 parts by weight per 100 parts by weight of water in both the first crosslinking step and the second crosslinking step, preferably 3 parts by weight or more, more preferably 4 parts by weight or more, Preferably it is 6 parts by weight or more, and preferably 15 parts by weight or less.
  • the immersion time of the laminated film with the dyed layer in the crosslinking solution is usually preferably 15 seconds to 20 minutes, more preferably 30 seconds or more, as the sum of the entire crosslinking step including the first crosslinking step and the second crosslinking step. Further, it is more preferable that the time is 15 minutes or less.
  • the temperature of the crosslinking solution is 60 ° C. or higher, but the upper limit is preferably 82 ° C. or lower. If the temperature is less than 60 ° C., it becomes difficult to obtain sufficient polarization performance no matter how long the immersion time is extended. On the other hand, if the temperature exceeds 82 ° C., the polyvinyl alcohol-based resin partially dissolves, Unevenness after dyeing is likely to occur.
  • the crosslinking treatment can be performed simultaneously with the dyeing treatment by blending a crosslinking agent in the dyeing solution.
  • a crosslinking agent can be blended in the dyeing solution and the crosslinking reaction can be partially advanced in the dyeing process. Even in this case, after the dyeing process, the first crosslinking process and the first crosslinking process described above can be performed.
  • a crosslinking step including a two-crosslinking step a polarizing laminated film or a polarizing plate exhibiting excellent polarizing performance is obtained.
  • stretched by the target magnification may be only bridge
  • Step optionally performed after the crosslinking step After passing through the cross-linking step, it is preferable to perform a washing treatment and a drying treatment.
  • the washing treatment is usually performed by washing the film that has undergone the crosslinking step with water.
  • pure water such as ion exchange water or distilled water is usually used.
  • a washing process can be performed by immersing the film after passing through the crosslinking step.
  • the temperature of the water used for washing is usually 3 to 50 ° C., preferably 4 to 20 ° C.
  • the immersion time is usually 2 to 300 seconds, preferably 3 to 240 seconds.
  • the cleaning treatment may be a combination of cleaning with an aqueous iodide solution and cleaning with water.
  • an aqueous solution containing a liquid alcohol such as methanol, ethanol, isopropanol, propanol, and butanol may be used as appropriate.
  • the resin layer has a function as a polarizer.
  • the resin layer which has a function as a polarizer is called a polarizer layer
  • the laminated body provided with the polarizer layer on the base film is called a polarizing laminated film.
  • a protective film is bonded to the polarizer layer surface of the polarizing laminated film obtained through each process demonstrated above on the opposite side to the base film side.
  • the bonding between the polarizer layer and the protective film can be performed, for example, by a method in which both are bonded via an adhesive layer or an adhesive layer.
  • the protective film may be a simple protective film having no optical function, or may be a film having an optical function such as a retardation film or a brightness enhancement film.
  • cyclic polyolefin resin film cellulose ester resin film made of resin such as triacetyl cellulose or diacetyl cellulose
  • polyester resin film made of resin such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polycarbonate resin
  • acrylic resin film examples thereof include a film, an acrylic resin film, and a polypropylene resin film.
  • the cyclic polyolefin-based resin has a cyclic olefin such as norbornene as a main constituent monomer, and is a suitable commercially available product, for example, TOPAS (manufactured by Topas Advanced Polymers, available from Polyplastics Co., Ltd. in Japan), Arton [JSR Co., Ltd.], ZEONOR (Nippon ZEON Co., Ltd.), ZEONEX (Nippon ZEON Co., Ltd.), Apel (Mitsui Chemicals Co., Ltd.), etc. are preferably used. it can.
  • TOPAS manufactured by Topas Advanced Polymers, available from Polyplastics Co., Ltd. in Japan
  • Arton [JSR Co., Ltd.] ZEONOR (Nippon ZEON Co., Ltd.), ZEONEX (Nippon ZEON Co., Ltd.), Apel (Mitsui Chemicals Co., Ltd.), etc.
  • TOPAS manufactured by Topas Advanced Polymers, available from Polyplastics
  • the cyclic polyolefin resin film may be uniaxially stretched or biaxially stretched.
  • An arbitrary retardation value can be imparted to the cyclic polyolefin-based resin film by stretching. Stretching is usually performed continuously while unwinding the film roll, and in the heating furnace, the roll traveling direction, the direction orthogonal to the traveling direction in the plane, both, or the oblique direction that is neither parallel nor orthogonal to the traveling direction Stretched.
  • the temperature of the heating furnace is usually in the range from the vicinity of the glass transition temperature of the cyclic polyolefin resin to the glass transition temperature + 100 ° C.
  • the draw ratio is usually 1.1 to 6 times, preferably 1.1 to 3.5 times in one direction.
  • cyclic polyolefin-based resin films that have been formed in advance and, in some cases, further provided with a phase difference, such as Essina retardation film (manufactured by Sekisui Chemical Co., Ltd.) and ZEONOR film (manufactured by ZEON Corporation) You may use goods.
  • Essina retardation film manufactured by Sekisui Chemical Co., Ltd.
  • ZEONOR film manufactured by ZEON Corporation
  • the surface to be bonded to the polarizer layer is subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) treatment, and saponification treatment. Is preferred. Among these, plasma treatment and corona treatment that can be performed relatively easily are preferable.
  • the cellulose ester resin is a fatty acid ester of cellulose, and a typical one is cellulose triacetate.
  • a cellulose ester resin film an appropriate commercial product, for example, Fujitac TD80, Fujitac TD80UF, Fujitac TD80UZ, Fujitac TD40UZ (manufactured by Fuji Film Co., Ltd.), KC8UX2M, KC4UY (manufactured by Konica Minolta Advanced Layer Co., Ltd.) ] Etc. can be used suitably.
  • a liquid crystal layer or the like may be formed on the surface of the cellulose ester resin film in order to improve viewing angle characteristics. Moreover, what was extended
  • the cellulose ester resin film is usually subjected to a saponification treatment in order to improve the adhesiveness with the polarizing film.
  • the saponification treatment can be performed by a method of immersing in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.
  • An optical layer such as a hard coat layer, an antiglare layer, and an antireflection layer can also be formed on the surface of the protective film.
  • the method for forming these optical layers on the surface of the protective film is not particularly limited, and a known method can be used.
  • the thickness of the protective film is preferably as thin as possible from the demand for thinning, preferably 90 ⁇ m or less, and more preferably 50 ⁇ m or less. However, if it is too thin, the strength is lowered and the workability becomes difficult, so that the thickness is usually preferably 5 ⁇ m or more.
  • the polarizing plate can also be used as a composite polarizing plate in which other optical layers are laminated.
  • Said protective film may have the function of such another optical layer.
  • optical layers examples include a reflective polarizing film that transmits certain types of polarized light and reflects polarized light that exhibits the opposite properties, a film with an antiglare function having an uneven shape on the surface, and a surface antireflection function.
  • examples thereof include an attached film, a reflective film having a reflective function on the surface, a transflective film having both a reflective function and a transmissive function, and a viewing angle compensation film.
  • DBEF manufactured by 3M, available from Sumitomo 3M Co., Ltd. in Japan
  • APF manufactured by 3M, available from Sumitomo 3M Co., Ltd. in Japan
  • the viewing angle compensation film include an optical compensation film in which a liquid crystal compound is applied to the substrate surface and oriented, a retardation film made of a polycarbonate resin, a retardation film made of a cyclic polyolefin resin, and the like.
  • Examples of commercially available products corresponding to an optical compensation film in which a liquid crystal compound is coated and oriented on the substrate surface are WV films (manufactured by FUJIFILM Corporation), NH films (manufactured by JX Nippon Mining & Energy Corporation) And NV film [manufactured by JX Nippon Oil & Energy Corporation].
  • Examples of commercially available products corresponding to retardation films made of cyclic polyolefin resins include Arton Film [manufactured by JSR Corporation], Essina retardation film [manufactured by Sekisui Chemical Co., Ltd.], Zeonoa Film [Nippon Zeon ( Etc.].
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is usually based on an acrylic resin, a styrene resin, a silicone resin, It consists of the composition which added crosslinking agents, such as an isocyanate compound, an epoxy compound, and an aziridine compound there. Furthermore, a pressure-sensitive adhesive layer exhibiting light scattering properties can be formed by mixing fine particles in the pressure-sensitive adhesive.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 to 40 ⁇ m, but it is preferable to make it thin as long as the characteristics including workability and durability are not impaired, and more preferably 3 to 25 ⁇ m.
  • a thickness of 3 to 25 ⁇ m has good processability and is suitable for suppressing the dimensional change of the polarizer layer.
  • the thickness of the pressure-sensitive adhesive layer is less than 1 ⁇ m, the tackiness is lowered.
  • the thickness exceeds 40 ⁇ m problems such as the pressure-sensitive adhesive protruding easily occur.
  • the formation of the pressure-sensitive adhesive layer on the protective film or the polarizer layer may be performed by applying a pressure-sensitive adhesive solution containing each component including the above-described base polymer to the protective film or the polarizer layer and drying it. Then, the pressure-sensitive adhesive layer formed on the separator may be transferred to the protective film surface or the polarizer layer surface.
  • the pressure-sensitive adhesive layer is formed directly on the former protective film or polarizer layer, it is customary to temporarily protect the surface of the pressure-sensitive adhesive layer until a separator is bonded to the other film and bonded to the other film. However, the bonding of the separator may be omitted, and the other film may be bonded directly to the pressure-sensitive adhesive layer.
  • the separator when transferring the pressure-sensitive adhesive layer formed on the latter separator, the separator is peeled off when being bonded to the other film.
  • the pressure-sensitive adhesive solution is directly applied to the protective film or polarizer layer to form the pressure-sensitive adhesive layer
  • the pressure-sensitive adhesive layer formed on the pressure-sensitive adhesive layer-forming surface of the protective film or polarizer layer or on the separator is applied.
  • the adhesive film forming surface of the protective film or the polarizer layer and / or the bonding surface of the adhesive layer may be subjected to an adhesion treatment, for example, corona treatment. You may give it.
  • the adhesive surface of the other film and / or the pressure-sensitive adhesive layer is adhered as necessary. Can be applied.
  • the adhesive constituting the adhesive layer is, for example, a polyvinyl alcohol resin aqueous solution, an aqueous two-component urethane emulsion adhesive, or the like. Can be. Especially, polyvinyl alcohol-type resin aqueous solution is used suitably.
  • Polyvinyl alcohol resins used as adhesives include vinyl alcohol homopolymers obtained by saponifying polyvinyl acetate, which is a homopolymer of vinyl acetate, as well as other single quantities copolymerizable with vinyl acetate.
  • vinyl alcohol copolymers obtained by saponifying the copolymer with the polymer and modified polyvinyl alcohol polymers obtained by partially modifying the hydroxyl groups.
  • a polyhydric aldehyde, a water-soluble epoxy compound, a melamine compound, a zirconia compound, a zinc compound, or the like may be added as an additive to the water-based adhesive.
  • the adhesive layer obtained therefrom is usually much thinner than 1 ⁇ m, and even when the cross section is observed with a normal optical microscope, the adhesive layer is practically not observed.
  • Bonding of a film using a water-based adhesive can be performed by a method of bonding both films through the adhesive, pressing with a roll or the like, and drying. For example, a method in which an adhesive is uniformly applied to the surface of one film and then the other film is stacked thereon, or a method in which an adhesive is poured between the two films is employed.
  • the adhesive is usually applied at a temperature of 15 to 40 ° C. after the preparation, and the bonding temperature is usually in the range of 15 to 30 ° C.
  • the temperature of the drying furnace is preferably 30 to 90 ° C.
  • the drying temperature is below 30 ° C.
  • the adhesive surface tends to be peeled off.
  • the temperature exceeds 90 ° C., the optical performance of the polarizer layer and the like may be deteriorated by heat.
  • the drying time can be 10 to 1,000 seconds.
  • the temperature at the time of curing is generally set lower than the temperature adopted at the time of drying.
  • a photo-curable adhesive can be used as the non-aqueous adhesive.
  • the photocurable adhesive include a mixture of a photocurable epoxy compound and a photocationic polymerization initiator.
  • a photocurable adhesive is an adhesive that cures when irradiated with active energy rays such as ultraviolet rays.
  • a photocurable adhesive includes a polymerizable compound and a photopolymerization initiator, includes a photoreactive resin, and a binder resin. And those containing a photoreactive crosslinking agent.
  • the polymerizable compound include photopolymerizable monomers such as a photocurable epoxy monomer, a photocurable acrylic monomer, and a photocurable urethane monomer, and oligomers derived from these monomers.
  • the photopolymerization initiator examples include those containing substances that generate active species such as neutral radicals, anion radicals, and cation radicals upon irradiation with active energy rays such as ultraviolet rays.
  • active species such as neutral radicals, anion radicals, and cation radicals upon irradiation with active energy rays such as ultraviolet rays.
  • a photocurable adhesive containing a polymerizable compound and a photopolymerization initiator those containing a photocurable epoxy monomer and a photocationic polymerization initiator are preferable.
  • Film lamination using a photo-curable adhesive can be performed by, for example, casting, Meyer bar coating, gravure coating, comma coater, doctor plate, die coating, dip coating, spraying, etc. It is possible to carry out the method by applying an adhesive to the adhesive surface and superimposing two films.
  • the casting method is a method in which two films as an object to be coated are moved in a substantially vertical direction, generally in a horizontal direction, or in an oblique direction between the two, and an adhesive is allowed to flow down and spread on the surface. is there.
  • the adhesive After the adhesive is applied to the surface of the film, it is bonded by sandwiching the film with a nip roll or the like.
  • the method of pressing this laminated body with a roll etc. and spreading it uniformly can also be used suitably.
  • the material of the roll can be metal or rubber.
  • a method in which this laminate is passed between rolls and pressed to spread is preferably employed. In this case, the two rolls may be made of the same material or different materials.
  • the thickness before drying or curing of the adhesive layer after being bonded using a nip roll or the like is preferably 5 ⁇ m or less and 0.01 ⁇ m or more.
  • the surface of the film may be appropriately subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) treatment, saponification treatment.
  • surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) treatment, saponification treatment.
  • the saponification treatment can be performed by a method of immersing in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.
  • the photocurable adhesive is cured by irradiating active energy rays after the films are laminated.
  • the light source of the active energy ray is not particularly limited, but ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable, and specifically, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave An excited mercury lamp, a metal halide lamp, etc. are preferably used.
  • the light irradiation intensity to the photocurable adhesive is appropriately determined depending on the composition of the photocurable adhesive, and is not particularly limited, but the irradiation intensity in the wavelength region effective for activating the polymerization initiator is 0.1 to 6, It is preferable to be 000 mW / cm 2 . If the irradiation intensity falls within this range, the reaction time does not become too long, and the curable compound is yellowed and the polarizer layer is deteriorated due to heat radiated from the light source and heat generated when the photocurable adhesive is cured. Less likely to occur.
  • the light irradiation time to the photocurable adhesive is applied according to the adhesive to be cured and is not particularly limited, but the integrated light amount expressed as the product of the irradiation intensity and the irradiation time is It is preferably set to be 10 to 10,000 mJ / cm 2 . If the amount of light integrated into the photocurable adhesive falls within this range, a sufficient amount of active species derived from the polymerization initiator can be generated to allow the curing reaction to proceed more reliably, and the irradiation time does not become too long. Can maintain good productivity.
  • the thickness of the adhesive layer after irradiation with active energy rays is usually about 0.001 to 5 ⁇ m, preferably 0.01 ⁇ m or more and 2 ⁇ m or less, more preferably 0.01 ⁇ m or more and 1 ⁇ m or less.
  • Base film peeling step (S60) In the manufacturing method of the polarizing plate of this embodiment, as shown in FIG. 2, a base film peeling process (S60) is performed after the protective film bonding process (S50) which bonds a protective film to a polarizer layer.
  • the base film used in the resin layer forming step is peeled off from the polarizing laminated film here.
  • the peeling method of a base film is not specifically limited, The method similar to the peeling process of the separator performed in a normal polarizing plate with an adhesive can be employ
  • the base film After the protective film laminating step (S50), the base film may be peeled off as it is, or after winding up once in a roll shape, a base step film may be peeled off by providing another peeling step.
  • the polarizer layer or the primer layer thinly provided on the surface thereof is exposed, but it can be used as it is as a polarizing plate.
  • a pressure-sensitive adhesive layer for bonding to a display element such as a liquid crystal cell or another optical film is usually provided on the surface of the polarizer layer or primer layer.
  • Example 1 (Base film) As the substrate film, an unstretched polypropylene film (melting point: 163 ° C.) having a thickness of 110 ⁇ m was used.
  • Polyvinyl alcohol-based resin layer forming step Polyvinyl alcohol powder (“PVA124” manufactured by Kuraray Co., Ltd.) having an average degree of polymerization of 2,400 and a degree of saponification of 98.0 to 99.0 mol% was dissolved in hot water at 95 ° C. to a concentration of 8%. An aqueous solution was prepared. The obtained aqueous solution was coated on the primer layer using a lip coater and dried at 80 ° C. for 20 minutes to produce a laminated film composed of a base film, a primer layer, and a polyvinyl alcohol resin layer. did. The thickness of the polyvinyl alcohol-based resin layer was 10 ⁇ m.
  • the laminated film obtained above was subjected to 5.8 times free end uniaxial stretching at 160 ° C. to obtain a stretched film.
  • the thickness of the stretched polyvinyl alcohol resin layer was 5.0 ⁇ m.
  • the stretched film obtained above is dyed by immersing it in a dyeing solution maintained at 26-30 ° C. with the following composition for a predetermined time set for 60-180 seconds, and then with pure water at 10 ° C. Excess iodine solution was washed away. The immersion time and the iodine concentration in the dyeing solution were finely adjusted so that the visibility corrected single transmittance (Ty) obtained by the method to be described later of the finally obtained polarizing plate was about 42.0%.
  • a polyvinyl alcohol powder having an average degree of polymerization of 1,800 [“KL-318” manufactured by Kuraray Co., Ltd.] was dissolved in hot water at 95 ° C. to prepare an aqueous polyvinyl alcohol solution having a concentration of 3%.
  • the same cross-linking agent “Smileze Resin 650” used in the previous primer layer forming step was mixed at a ratio of 1 part to 2 parts of the solid content of polyvinyl alcohol, and the adhesive solution and did.
  • a protective film made of triacetyl cellulose (“KC4UY” manufactured by Konica Minolta Advanced Layer Co., Ltd.) is bonded to the protective film.
  • a multilayer film composed of / adhesive layer / polarizer layer / primer layer / base film was obtained.
  • the base film was peeled from the multilayer film obtained above to produce a polarizing plate comprising a protective film / adhesive layer / polarizer layer / primer layer.
  • the base film could be easily peeled from the upper multilayer film.
  • Example 2 A polarizing plate was produced in the same manner as in Example 1 except that the composition of the first crosslinking solution in the crosslinking step was 9.5 parts boric acid and 0.5 parts potassium iodide with respect to 100 parts water.
  • Example 3 A polarizing plate was produced in the same manner as in Example 1 except that the composition of the first crosslinking solution in the crosslinking step was 9.5 parts boric acid and 0.9 parts potassium iodide with respect to 100 parts water.
  • Example 4 A polarizing plate was produced in the same manner as in Example 1 except that the amount of potassium iodide in the second crosslinking solution in the crosslinking step was changed to 7 parts with respect to 100 parts of water.
  • Py 99.995%
  • simple substance a ⁇ 0.92
  • simple substance b 3.78
  • parallel a ⁇ 1. 52
  • parallel b 6.65
  • orthogonal a 0.00
  • orthogonal b 0.09.
  • Example 5 A polarizing plate was produced in the same manner as in Example 1 except that the amount of potassium iodide in the second crosslinking solution in the crosslinking step was changed to 5 parts with respect to 100 parts of water.
  • Py 99.995%
  • simple substance a ⁇ 1.09
  • simple substance b 3.74
  • parallel a ⁇ 1.
  • parallel b 6.56
  • orthogonal a 0.24
  • orthogonal b ⁇ 0.38.
  • Example 6 A polarizing plate was produced in the same manner as in Example 1 except that the temperature of the first crosslinking solution in the crosslinking step was 78 ° C., the immersion time was 120 seconds, and the temperature of the second crosslinking solution was 78 ° C.
  • Example 7 The temperature of the first crosslinking solution in the crosslinking step was 78 ° C., the immersion time was 120 seconds, and the composition of the second crosslinking solution was 9.5 parts of boric acid and 6.8 parts of potassium iodide with respect to 100 parts of water.
  • a polarizing plate was produced in the same manner as in Example 1 except that the temperature was 70 ° C.
  • Py 99.995%
  • simple substance a ⁇ 0.82
  • simple substance b 3.25
  • parallel a ⁇ 1.
  • Example 8 In the crosslinking step, the temperature of the first crosslinking solution was 78 ° C., the immersion time was 120 seconds, and the composition of the second crosslinking solution was 9.5 parts of boric acid and 4.9 parts of potassium iodide with respect to 100 parts of water.
  • a polarizing plate was produced in the same manner as in Example 1 except that the temperature was 70 ° C.
  • Py 99.995%
  • simple substance a ⁇ 0.89
  • simple substance b 2.99
  • parallel a ⁇ 1.
  • 55, parallel b 5.33
  • orthogonal a 0.66
  • orthogonal b ⁇ 0.91.
  • the second cross-linking step is not performed, and the cross-linking solution is composed of 9.5 parts boric acid and 5 parts potassium iodide with respect to 100 parts water, the temperature is 78 ° C., and the immersion time is 300 seconds.
  • the second cross-linking step is not performed, and the cross-linking solution is composed of 9.5 parts boric acid and 5 parts potassium iodide with respect to 100 parts water, the temperature is 78 ° C., and the immersion time is 300 seconds.
  • Example 6 A polarizing plate was produced in the same manner as in Example 1 except that the temperature of the second crosslinking solution in the crosslinking step was 50 ° C.
  • Example 7 A polarizing plate was produced in the same manner as in Example 1 except that the temperature of the first crosslinking solution in the crosslinking step was 50 ° C. and the temperature of the second crosslinking solution was 50 ° C.
  • the visibility correction is performed by correcting the visibility with a two-degree visual field (C light source) of JIS Z 8701: 1 999 “color display method—XYZ color system and X 10 Y 10 Z 10 color system”.
  • the single transmittance (Ty) and the visibility correction polarization degree (Py) were determined.
  • the immersion time in the dyeing solution in the dyeing process is adjusted so that the visibility corrected single transmittance (Ty) thus obtained is about 42.0%.
  • the obtained visibility-corrected polarization degree (Py) is shown in Table 1 together with main conditions in the crosslinking step.
  • the “MD transmittance” is a transmittance when the direction of polarized light emitted from the Glan-Thompson prism is parallel to the transmission axis of the polarizing plate sample
  • “TD transmittance” Is the transmittance when the direction of polarized light emitted from the Glan-Thompson prism and the transmission axis of the polarizing plate sample are orthogonal to each other.
  • MD and “TD” respectively. I write.
  • the single hues (single a, simple b), parallel hues (parallel a, parallel b), and orthogonal hues (orthogonal a, orthogonal b) of the polarizing plate are also used as spectrophotometers with an integrating sphere [manufactured by JASCO Corporation. V7100 "].
  • the orthogonal hue is the hue of transmitted light when light is incident on two polarizing plates whose transmission axes are orthogonal
  • the parallel hue is the light incident on two polarizing plates whose transmission axes are parallel. It means the hue of transmittance when
  • the single hue means the hue of transmitted light when light is incident on one polarizing plate.
  • the a value and the b value are color values expressed in the Hunter Lab color system, and are calculated according to JIS-Z8729J.
  • a high hue a value represents red, and a low hue a green.
  • a high hue b value represents yellow and a low hue b value represents blue. Also, the closer to 0, the closer to both achromatic colors.
  • the visibility correction polarization degree Py of the obtained polarizing plate can be further increased by performing the crosslinking step in two steps according to the present invention and setting the respective iodide concentrations and temperatures to predetermined conditions.
  • the polarizing plate for the LCD application has a neutral gray as the orthogonal hue so that the original color can be clearly displayed because the black display depends on the orthogonal hue of the polarizing plate. May be desired (orthogonal a and orthogonal b are near zero).
  • a polarizing plate for OLED antireflection use may be preferred, particularly having a high single transmittance in the blue light wavelength region with a short lifetime ( The simple substance b is small).

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

La présente invention comprend : une étape de formation d'une couche de résine consistant à former une couche de résine d'alcool polyvinylique sur un film de substrat et à obtenir une couche stratifiée ; une étape d'étirement consistant à étirer sur un axe le film stratifié de telle sorte que l'épaisseur de la couche de résine d'alcool polyvinylique soit inférieure ou égale à 10 µm, et à obtenir un film étiré ; une étape de coloration consistant à immerger le film étiré dans une solution de colorant qui contient un pigment de dichroïsme, à colorer la couche de résine d'alcool polyvinylique et à obtenir un film stratifié ayant une couche de colorant ; et une étape de réticulation consistant à immerger le film stratifié ayant une couche de colorant dans une solution de réticulation qui contient de l'acide borique et à réticuler la couche de résine d'alcool polyvinylique afin de former une couche de polariseur, l'étape de réticulation étant effectuée en étant divisée en une première étape de réticulation qui utilise une solution aqueuse dans laquelle la teneur en iodure est inférieure à 1 partie en poids, et en une seconde étape de réticulation qui utilise une solution aqueuse dans laquelle la teneur en iodure fait au moins deux parties en poids ; au cours des deux étapes, la teneur en acide borique faisant entre 1 et 20 parties en poids par rapport à 100 parties en poids d'eau.
PCT/JP2014/057931 2013-03-18 2014-03-14 Film stratifié de polarisation et procédé permettant de fabriquer une plaque de polarisation WO2014148639A1 (fr)

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WO2015079967A1 (fr) * 2013-11-29 2015-06-04 住友化学株式会社 Polariseur et plaque polarisante l'utilisant
JP2016153886A (ja) * 2015-02-12 2016-08-25 住友化学株式会社 偏光フィルム及びそれを含む偏光板
JPWO2016052331A1 (ja) * 2014-10-01 2017-06-15 住友化学株式会社 偏光性積層フィルムまたは偏光板の製造方法
CN107144911A (zh) * 2017-06-30 2017-09-08 深圳市华星光电技术有限公司 染料偏光片的制备方法及显示面板
JPWO2018164196A1 (ja) * 2017-03-08 2020-01-09 株式会社クラレ 偏光フィルム、偏光板、及びそれらの製造方法
JPWO2018164176A1 (ja) * 2017-03-08 2020-01-09 株式会社クラレ 偏光フィルム、偏光板、及びそれらの製造方法

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JP6231511B2 (ja) * 2015-02-17 2017-11-15 住友化学株式会社 偏光フィルムの製造方法
JP2018091980A (ja) * 2016-12-02 2018-06-14 住友化学株式会社 偏光フィルム及び偏光性積層フィルムの製造方法

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WO2015079967A1 (fr) * 2013-11-29 2015-06-04 住友化学株式会社 Polariseur et plaque polarisante l'utilisant
US9709719B2 (en) 2013-11-29 2017-07-18 Sumitomo Chemical Company, Limited Polarizer and polarizing plate including same
JPWO2016052331A1 (ja) * 2014-10-01 2017-06-15 住友化学株式会社 偏光性積層フィルムまたは偏光板の製造方法
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CN107144911A (zh) * 2017-06-30 2017-09-08 深圳市华星光电技术有限公司 染料偏光片的制备方法及显示面板
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JP2014206719A (ja) 2014-10-30

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