WO2012081390A1 - 偏光膜の製造方法 - Google Patents
偏光膜の製造方法 Download PDFInfo
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- WO2012081390A1 WO2012081390A1 PCT/JP2011/077468 JP2011077468W WO2012081390A1 WO 2012081390 A1 WO2012081390 A1 WO 2012081390A1 JP 2011077468 W JP2011077468 W JP 2011077468W WO 2012081390 A1 WO2012081390 A1 WO 2012081390A1
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- polarizing film
- stretching
- laminate
- film
- pva
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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
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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
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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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
- B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
- B29K2029/04—PVOH, i.e. polyvinyl alcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0034—Polarising
Definitions
- the present invention relates to a method for manufacturing a polarizing film.
- a liquid crystal display device which is a typical image display device, has polarizing films disposed on both sides of a liquid crystal cell due to the image forming method.
- a method for producing a polarizing film for example, a method is proposed in which a laminate having a thermoplastic resin substrate and a polyvinyl alcohol (PVA) resin layer is stretched and then immersed in a dyeing solution to obtain a polarizing film.
- PVA polyvinyl alcohol
- the present invention has been made to solve the above-described conventional problems, and a main object thereof is to provide a method for producing a polarizing film having excellent optical characteristics.
- the method for producing a polarizing film of the present invention includes a step of forming a PVA-based resin layer on a thermoplastic resin substrate to produce a laminate, a step of dyeing the PVA-based resin layer of the laminate with iodine, After the step of stretching the laminate, the dyeing step, and the stretching step, the surface of the PVA-based resin layer of the laminate is covered with a coating film having a moisture permeability of 100 g / m 2 ⁇ 24 h or less. Heating. In preferable embodiment, the said heating temperature is 60 degreeC or more. In preferable embodiment, the said PVA-type resin layer surface is coat
- the moisture permeability of the thermoplastic resin substrate after the stretching step is 100 g / m 2 ⁇ 24 h or less.
- the laminate is stretched in water in an aqueous boric acid solution.
- stretching the said laminated body in air at 95 degreeC or more is included.
- the maximum draw ratio of the said laminated body is 5.0 times or more.
- the thermoplastic resin substrate is composed of an amorphous polyethylene terephthalate resin.
- a polarizing film is provided. The polarizing film obtained by the above production method.
- an optical laminate is provided. The optical laminate has the above polarizing film.
- the PVA resin layer formed on the thermoplastic resin substrate is subjected to a dyeing process and a stretching process, and then the moisture permeability of the PVA resin layer surface is 100 g / m 2 ⁇ 24 h or less.
- a polarizing film having extremely excellent optical characteristics can be produced.
- the manufacturing method of the polarizing film of the present invention includes a step of forming a PVA resin layer on a thermoplastic resin substrate to produce a laminate (Step A), and dyeing the PVA resin layer of the laminate with iodine.
- each step will be described.
- FIG. 1 is a schematic cross-sectional view of a laminate according to a preferred embodiment of the present invention.
- the laminate 10 includes a thermoplastic resin substrate 11 and a PVA resin layer 12, and is produced by forming the PVA resin layer 12 on the thermoplastic resin substrate 11. Any appropriate method can be adopted as a method of forming the PVA-based resin layer 12.
- the PVA-based resin layer 12 is formed by applying a coating liquid containing a PVA-based resin on the thermoplastic resin substrate 11 and drying it.
- thermoplastic resin base material any appropriate material can be adopted as the constituent material of the thermoplastic resin base material.
- 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 thermoplastic resin substrate absorbs water, and the water can be plasticized by acting as a plasticizer.
- the stretching stress can be greatly reduced, the film can be stretched at a high magnification, and the stretchability of the thermoplastic resin substrate can be superior to that during air stretching.
- a polarizing film having excellent optical characteristics can be produced.
- the thermoplastic resin substrate preferably has a water absorption rate of 0.2% or more, and more preferably 0.3% or more.
- the water absorption rate of the thermoplastic resin substrate is preferably 3.0% or less, and more preferably 1.0% or less.
- thermoplastic resin substrate By using such a thermoplastic resin substrate, it is possible to prevent problems such as the dimensional stability of the thermoplastic resin substrate being significantly reduced during production and the appearance of the resulting polarizing film being deteriorated. Moreover, it can prevent that a base material fractures
- the water absorption rate of a thermoplastic resin base material can be adjusted by introduce
- the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 170 ° C. or lower.
- Tg thermoplastic resin base material
- the stretchability of the laminate can be sufficiently ensured while suppressing the crystallization of the PVA-based resin layer.
- the temperature is more preferably 120 ° C. or lower.
- the glass transition temperature of the thermoplastic resin substrate is preferably 60 ° C. or higher.
- the PVA-based resin layer can be satisfactorily stretched at a suitable temperature (for example, about 60 ° C.).
- a glass transition temperature lower than 60 ° C. may be used as long as the thermoplastic resin base material is not deformed when a coating solution containing a PVA resin is applied and dried.
- the glass transition temperature of a thermoplastic resin base material can be adjusted by heating using the crystallizing material which introduce
- the glass transition temperature (Tg) is a value determined according to JIS K 7121.
- the thickness of the thermoplastic resin substrate 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 Step C, it takes a long time for the thermoplastic resin substrate to absorb water, and an excessive load may be required for stretching.
- any appropriate resin can be adopted as the PVA resin.
- Examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymer.
- Polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
- the ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-vinyl acetate copolymer.
- the degree of saponification of the PVA-based resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, more preferably 99.0 mol% to 99.93 mol%. .
- the degree of saponification can be determined according to JIS K 6726-1994. By using a PVA-based resin having such a saponification degree, a polarizing film having excellent durability can be obtained. If the degree of saponification is too high, there is a risk of gelation.
- the average degree of polymerization of the PVA resin can be appropriately selected according to the purpose.
- the average degree of polymerization is usually 1000 to 10,000, preferably 1200 to 4500, and more preferably 1500 to 4300.
- the average degree of polymerization can be determined according to JIS K 6726-1994.
- 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 thermoplastic 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.
- 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 thickness of the PVA resin layer before stretching is preferably 3 ⁇ m to 40 ⁇ m, and more preferably 3 ⁇ m to 20 ⁇ m.
- the thermoplastic resin substrate Before forming the PVA resin layer, the thermoplastic resin substrate may be subjected to a surface treatment (for example, corona treatment), or an easy-adhesion layer may be formed on the thermoplastic resin substrate. By performing such a treatment, the adhesion between the thermoplastic resin substrate and the PVA resin layer can be improved.
- a surface treatment for example, corona treatment
- an easy-adhesion layer may be formed on the thermoplastic resin substrate.
- the PVA resin layer is dyed with iodine. Specifically, it is performed by adsorbing iodine to the PVA resin layer.
- adsorption method for example, a method of immersing a PVA resin layer (laminate) in a staining solution containing iodine, a method of applying the staining solution to the PVA resin layer, and applying the staining solution to the PVA resin layer The method of spraying etc. are mentioned.
- it is a method of immersing the laminate in the staining solution. This is because iodine can satisfactorily adsorb.
- the staining solution is preferably an iodine aqueous solution.
- the amount of iodine is preferably 0.1 to 0.5 parts by weight with respect to 100 parts by weight of water.
- an iodide to the aqueous iodine solution.
- the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide.
- potassium iodide is preferable.
- 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) can be set so that the polarization degree or single transmittance of the finally obtained polarizing film is within a predetermined range. In one embodiment, immersion time is set so that the polarization degree of the polarizing film obtained may be 99.98% or more. In another embodiment, the immersion time is set so that the obtained polarizing film has a single transmittance of 40% to 44%.
- Process B may be performed before process C described later, or may be performed after process C. As will be described later, when the underwater stretching method is adopted in the step C, the step B is preferably performed before the step C.
- Process C The step C, and stretching the laminate.
- the stretching of the laminate may be performed in one stage or in multiple stages. When performed in multiple stages, the draw ratio (maximum draw ratio) of the laminate described later is the product of the draw ratios of the respective stages.
- the stretching method is not particularly limited, and may be an air stretching method or an underwater stretching method.
- the underwater stretching method is preferable.
- the thermoplastic 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 PVA resin layer is crystallized. It is possible to stretch at a high magnification while suppressing. As a result, a polarizing film having excellent optical characteristics can be produced.
- the stretching temperature of the laminate can be set to any appropriate value depending on the forming material of the thermoplastic resin substrate, the stretching method, and the like.
- the stretching temperature is preferably not less than the glass transition temperature (Tg) of the thermoplastic resin substrate, more preferably glass transition temperature (Tg) of the thermoplastic resin substrate + 10 ° C. or more, particularly Preferably it is Tg + 15 degreeC or more.
- the stretching temperature of the laminate is preferably 170 ° C. or lower.
- the liquid temperature of the stretching bath is preferably 40 ° C. to 85 ° C., more preferably 50 ° C. to 85 ° C. If it is such temperature, it can extend
- the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 60 ° C. or higher in relation to the formation of the PVA resin layer. In this case, when the stretching temperature is lower than 40 ° C., there is a possibility that stretching cannot be performed satisfactorily even in consideration of plasticization of the thermoplastic resin substrate with water.
- the higher the temperature of the stretching bath the higher the solubility of the PVA-based resin layer, and there is a possibility that excellent optical properties cannot be obtained.
- the 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 preferably 1 to 10 parts by weight with respect to 100 parts by weight of water. By setting the boric acid concentration to 1 part by weight or more, dissolution of the PVA resin layer can be effectively suppressed, and a polarizing film having higher characteristics can be produced.
- an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal, glutaraldehyde, or the like in a solvent can also be used.
- iodide is blended in the stretching bath (boric acid aqueous solution).
- the stretching bath boric acid aqueous solution
- concentration of iodide is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of water.
- the immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.
- 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. .
- Step D the surface of the PVA-based resin layer of the laminate is covered with a coating film, and the laminate is heated in this state.
- the optical properties of the resulting polarizing film can be improved. It can be considered as one of the factors for improving the optical characteristics that the iodine complex having a low orientation with low contribution to the optical characteristics can be selectively decomposed by the process D.
- the PVA-based resin layer formed on the thermoplastic resin substrate and subjected to the dyeing process and the stretching process has a different configuration on the thermoplastic resin substrate side (lower side) and on the surface side (upper side). .
- the orientation of the PVA resin is different between the lower side and the upper side, and the upper side tends to have a lower orientation than the lower side.
- the iodine complex present in the low-orientation portion also has low orientation, and not only has a low contribution to optical properties (particularly the degree of polarization), but can also cause a reduction in optical properties (particularly transmittance).
- such an iodine complex is easily decomposed due to its low orientation and weak binding force.
- Step D an iodine complex having low orientation can be selectively decomposed, absorption in the visible light region can be reduced, and transmittance can be improved.
- the iodine complex with low orientation originally has a low contribution to the degree of polarization, a decrease in the degree of polarization is minimized even if it is decomposed.
- the moisture permeability is preferably 100 g / m 2 ⁇ 24 h or less, more preferably 90 g / m 2 ⁇ 24 h or less.
- heat treatment can be performed in a state where moisture present in the PVA-based resin layer remains in the layer.
- a water-soluble (low-orientation) iodine complex is easily decomposed and can be decomposed into iodine ions, reducing the absorption in the visible light region of the resulting polarizing film.
- the transmittance can be improved.
- the moisture permeability of the thermoplastic resin substrate after the stretching step (step C) is preferably 100 g / m 2 ⁇ 24 h or less, and more preferably 90 g / m 2 ⁇ 24 h or less.
- the “moisture permeability” is the amount of water vapor (g) passing through a sample of 1 m 2 in 24 hours in an atmosphere of a temperature of 40 ° C. and a humidity of 92% RH in accordance with a moisture permeability test (cup method) of JIS Z0208. ) Is a value obtained by measuring.
- any appropriate material that can satisfy the above moisture permeability can be adopted as the constituent material of the coating film.
- the constituent material of the covering film include cycloolefin resins such as norbornene resins, olefin resins such as polyethylene and polypropylene, polyester resins, and (meth) acrylic resins.
- the “(meth) acrylic resin” refers to an acrylic resin and / or a methacrylic resin.
- the thickness of the coating film can be set to a thickness that satisfies the above moisture permeability. Typically, it is 10 ⁇ m to 100 ⁇ m.
- the surface of the PVA resin layer is coated with a coating film via an adhesive.
- the adhesive it is possible to prevent the gap from being generated between the PVA resin layer and the coating film, thereby improving the adhesion. As a result, an iodine complex with low orientation can be efficiently decomposed.
- the adhesive any appropriate adhesive is used, which may be a water-based adhesive or a solvent-based adhesive.
- a water-based adhesive is used. Moisture contained in the water-based adhesive can migrate to the PVA-based resin layer. As a result, the stability of the iodine complex decreases, and an iodine complex having a particularly low orientation is likely to be decomposed because the original stability is low. As a result, it is possible to selectively promote the decomposition of the iodine complex having low orientation.
- any appropriate aqueous adhesive can be adopted as the aqueous adhesive.
- an aqueous adhesive containing a PVA resin is used.
- the average degree of polymerization of the PVA resin contained in the aqueous adhesive is preferably about 100 to 5000, and more preferably 1000 to 4000 from the viewpoint of adhesiveness.
- the average saponification degree is preferably about 85 mol% to 100 mol%, more preferably 90 mol% to 100 mol%, from the viewpoint of adhesiveness.
- the PVA resin contained in the aqueous adhesive preferably contains an acetoacetyl group. This is because the adhesiveness between the PVA resin layer and the coating film is excellent and the durability can be excellent.
- the acetoacetyl group-containing PVA resin can be obtained, for example, by reacting a PVA resin and diketene by an arbitrary method.
- the degree of acetoacetyl group modification of the acetoacetyl group-containing PVA resin is typically 0.1 mol% or more, preferably about 0.1 mol% to 40 mol%, more preferably 1 mol% to 20 mol. %, Particularly preferably 2 to 7 mol%.
- the degree of acetoacetyl group modification is a value measured by NMR.
- the resin concentration of the water-based adhesive is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight.
- an adhesive is applied to the surface of the PVA resin layer, and a covering film is bonded.
- coating of an adhesive agent can be set to arbitrary appropriate values. For example, it is set so that an adhesive layer having a desired thickness is obtained after heating (drying).
- the thickness of the adhesive layer is preferably 10 nm to 300 nm, more preferably 10 nm to 200 nm, and particularly preferably 20 nm to 150 nm.
- the water content per unit area contained in the adhesive is preferably 0.05 mg / cm 2 or more. By satisfying such a water content, an iodine complex having low orientation can be efficiently decomposed.
- the moisture content is preferably 2.0 mg / cm 2 or less, more preferably 1.0 mg / cm 2 or less. This is because it may take time to dry the adhesive.
- the laminate is dried before Step D, and after drying, an adhesive is applied to the surface of the PVA-based resin layer and a covering film is bonded thereto, and the PVA-based resin layer is heated in a state where the adhesive contains water. Is done.
- the amount of water per unit contained in the adhesive is as described above, and the amount of water is determined by the amount of water contained in the adhesive and the amount of adhesive applied to the surface of the PVA resin layer.
- the heating temperature of the laminate coated with the coating film is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, still more preferably 60 ° C. or higher, and particularly preferably 80 ° C. or higher. By heating at such a temperature, the iodine complex can be efficiently decomposed. On the other hand, the heating temperature is preferably 120 ° C. or lower. The heating time is preferably 3 minutes to 10 minutes.
- Presence of iodine ions (I ⁇ ) generated by decomposition of the iodine complex can be confirmed by measuring absorbance at a maximum wavelength ⁇ max of 220 nm.
- the rate of increase in parallel absorbance at a wavelength of 220 nm of the PVA resin layer before and after the treatment in Step D is preferably 3% or more, more preferably 5% or more.
- the parallel absorbance of the PVA-based resin layer, ultraviolet-visible-near-infrared spectrophotometer parallel transmittance of the laminate were measured by, determined by log 10 (1 / parallel transmittance)
- the increase rate is calculated by the following formula.
- (Increase rate) [(Absorbance after treatment) ⁇ (Absorbance before treatment)] / (Absorbance after treatment) ⁇ 100
- the manufacturing method of the polarizing film of the present invention may include other processes in addition to the above-mentioned processes A, B, C, and D.
- Examples of other processes include an insolubilization process, a crosslinking process, a stretching process different from the process C, a washing process, and a drying process. The other steps can be performed at any appropriate timing.
- the insolubilization step is typically performed by immersing the PVA resin layer in an aqueous boric acid solution.
- an underwater stretching method is employed, water resistance can be imparted to the PVA-based resin layer by performing insolubilization treatment.
- the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
- the liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C. to 40 ° C.
- the insolubilization process is performed before the process B or the process C after the laminate is manufactured.
- the cross-linking step is typically performed by immersing the PVA resin layer in an aqueous boric acid solution.
- the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
- blend iodide it is preferable to mix
- iodide By blending iodide, elution of iodine adsorbed on the PVA resin layer can be suppressed.
- the blending amount of iodide is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of the iodide are as described above.
- the liquid temperature of the crosslinking bath (boric acid aqueous solution) is preferably 20 ° C. to 50 ° C.
- the crosslinking step is performed before step C.
- step B, crosslinking step and step C are performed in this order.
- Examples of the stretching step different from the above-mentioned step C include a step of stretching the above laminate in the air at a high temperature (for example, 95 ° C. or higher). Such an air stretching step is preferably performed before boric acid water stretching (step C) and dyeing step. Such an air stretching step 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 thermoplastic resin base material when a polyethylene terephthalate-based resin is used as the thermoplastic resin base material, it is preferable to combine the air auxiliary stretching and the boric acid water stretching rather than the boric acid water stretching alone.
- the film can be stretched while suppressing the orientation.
- the orientation of the thermoplastic resin base material is improved, the stretching tension increases, so that stable stretching becomes difficult or the thermoplastic resin base material is broken. Therefore, the laminate can be stretched at a higher magnification by stretching while suppressing the orientation of the thermoplastic 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 method for the air auxiliary stretching may be fixed end stretching as in the above-mentioned step C, or free end stretching (for example, a method of uniaxial stretching through a laminate between rolls having different peripheral speeds).
- the stretching may be performed in one stage or in multiple stages. When performed in multiple stages, the draw ratio described below is the product of the draw ratios at each stage.
- the stretching direction in this step is preferably substantially the same as the stretching direction in step C above.
- 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 cleaning step is typically performed by immersing the PVA resin layer in an aqueous potassium iodide solution.
- the drying temperature in the drying step is preferably 30 ° C. to 100 ° C.
- FIG. 2 is a schematic view showing an example of a method for producing a polarizing film of the present invention.
- the laminated body 10 is fed out from the feeding unit 100 and immersed in a boric acid aqueous solution bath 110 by rolls 111 and 112 (insolubilization step), and then the dichroic substance (iodine) and potassium iodide are rolled by rolls 121 and 122. It is immersed in the aqueous solution bath 120 (step B). Subsequently, it is immersed in the bath 130 of the aqueous solution of boric acid and potassium iodide with the rolls 131 and 132 (crosslinking process).
- the laminate 10 is stretched by applying tension in the longitudinal direction (longitudinal direction) with the rolls 141 and 142 having different speed ratios while being immersed in the bath 140 of the boric acid aqueous solution (step C).
- the stretched laminate (optical film laminate) 10 is immersed in a potassium iodide aqueous solution bath 150 by rolls 151 and 152 (cleaning step) and subjected to a drying step (not shown).
- the surface of the PVA-based resin layer is coated with the coating film 20 and heated in a constant temperature zone 160 maintained at a predetermined temperature (step D) and wound up by the winding unit 170.
- the polarizing film of the present invention is obtained by the above production method.
- the polarizing film of the present invention is substantially a PVA resin film in which a dichroic substance is adsorbed and oriented.
- the thickness of the polarizing film is typically 25 ⁇ m or less, preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 7 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
- the thickness of the polarizing film is preferably 0.5 ⁇ m or more, more preferably 1.5 ⁇ 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% or more, more preferably 41.0% or more, further preferably 42.0% or more, and particularly preferably 43.0% or more.
- the polarization degree of the polarizing film is preferably 99.8% or more, more preferably 99.9% or more, and further preferably 99.95% or more.
- thermoplastic resin substrate and / or the coating film may be used in an integrated state, or the thermoplastic resin substrate and / or the coating film may be peeled off.
- the covering film can be used as an optical functional film described later.
- the optical laminate of the present invention has the polarizing film.
- 3A and 3B are schematic cross-sectional views of an optical film laminate according to a preferred embodiment of the present invention.
- the optical film laminate 100 includes a thermoplastic resin substrate 11 ′, a polarizing film 12 ′, an adhesive layer 13, and a separator 14 in this order.
- the optical film laminate 200 includes a thermoplastic resin substrate 11 ′, a polarizing film 12 ′, an adhesive layer 15, an optical functional film 16, an adhesive layer 13, and a separator 14 in this order.
- the thermoplastic resin base material is used as it is as an optical member without being peeled from the obtained polarizing film 12 ′.
- the thermoplastic resin base material 11 ′ can function as a protective film for the polarizing film 12 ′, for example.
- optical functional film laminate 300 includes the separator 14, the pressure-sensitive adhesive layer 13, the polarizing film 12 ', the adhesive layer 15, and the optical functional film 16 in this order.
- the second optical functional film 16 ′ is provided between the polarizing film 12 ′ and the separator 14 with the adhesive layer 13 interposed therebetween.
- the optical functional film 16 is laminated on the polarizing film 12 ′ via the pressure-sensitive adhesive layer 13, and the second optical functional film 16 ′ is laminated on the polarizing film 12 ′ via the adhesive layer 15.
- the optical functional film laminate 600 the optical functional film 16 and the second optical functional film 16 'are laminated on the polarizing film 12' via the adhesive layer 15.
- the thermoplastic resin base material is removed.
- each layer constituting the optical laminate of the present invention is not limited to the illustrated example, and any appropriate pressure-sensitive adhesive layer or adhesive layer is used.
- the pressure-sensitive adhesive layer is typically formed of an acrylic pressure-sensitive adhesive.
- the adhesive layer is typically formed of a PVA adhesive.
- the optical functional film can function as, for example, a polarizing film protective film or a retardation film.
- thermoplastic resin substrate an amorphous polyethylene terephthalate (A-PET) film (trade name “Novaclear”, thickness: 100 ⁇ m, manufactured by Mitsubishi Chemical Corporation) having a water absorption of 0.60% and a Tg of 80 ° C. was used.
- An aqueous solution of polyvinyl alcohol (PVA) resin having a polymerization degree of 2600 and a saponification degree of 99.9% (trade name “GOHSENOL (registered trademark) NH-26” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) on one surface of a thermoplastic resin substrate was applied and dried at 60 ° C. to form a PVA resin layer having a thickness of 7 ⁇ m. Thus it was produced a laminate.
- PVA polyvinyl alcohol
- the obtained laminate was immersed in an insolubilizing 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 step). Next, it is immersed for 60 seconds in a dyeing bath having a liquid temperature of 30 ° C. (an iodine aqueous solution obtained by blending 0.2 parts by weight of iodine and 1.0 part by weight of potassium iodide with respect to 100 parts by weight of water). (Step B). Subsequently, it was immersed for 30 seconds in a crosslinking bath having a liquid temperature of 30 ° C.
- a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water (Crosslinking step). Thereafter, the laminate was immersed in a boric acid aqueous solution (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 60 ° C. However, uniaxial stretching was performed in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds (step C). The immersion time in the boric acid aqueous solution was 120 seconds, and the laminate was stretched until just before it broke (maximum stretch ratio was 5.0 times).
- the laminate was immersed in a cleaning bath (an aqueous solution obtained by blending 3 parts by weight of potassium iodide with respect to 100 parts by weight of water) and then dried with hot air at 60 ° C. (cleaning and drying) Process).
- a cleaning bath an aqueous solution obtained by blending 3 parts by weight of potassium iodide with respect to 100 parts by weight of water
- hot air 60 ° C. (cleaning and drying) Process
- step D a norbornene-based resin film (manufactured by Nippon Zeon Co., Ltd., trade name" ZEONOR ZB14 ", thickness 70 ⁇ m, moisture permeability 7 g / m 2 ⁇ 24 h) is bonded to 100 ° C. And heated in an oven maintained for 5 minutes (step D). At the time of bonding, the amount of water contained in the adhesive was 0.3 mg / cm 2 per unit area. In this way, a polarizing film having a thickness of 3 ⁇ m was produced. Moreover, the thickness of the thermoplastic resin base material at this time was 40 micrometers, and the water vapor transmission rate was 25 g / m ⁇ 2 > * 24h.
- the moisture permeability is a value measured by separately preparing an A-PET film having a thickness of 40 ⁇ m.
- Example 1-2 A polarizing film was produced in the same manner as in Example 1-1 except that the heating temperature was changed to 80 ° C. in Step D.
- Example 1-3 A polarizing film in the same manner as in Example 1-1, except that a norbornene-based resin film (manufactured by Nippon Zeon Co., Ltd., trade name “Zeonor ZD12”, thickness 33 ⁇ m, moisture permeability 20 g / m 2 ⁇ 24 h) was used as the coating film.
- a norbornene-based resin film manufactured by Nippon Zeon Co., Ltd., trade name “Zeonor ZD12”, thickness 33 ⁇ m, moisture permeability 20 g / m 2 ⁇ 24 h
- Example 1-4 Except for using a norbornene-based resin film (manufactured by Nippon Zeon Co., Ltd., trade name “ZEONOR G film ZF14”, thickness 23 ⁇ m, moisture permeability 27 g / m 2 ⁇ 24 h) as the coating film, the same as Example 1-1 A polarizing film was produced.
- a norbornene-based resin film manufactured by Nippon Zeon Co., Ltd., trade name “ZEONOR G film ZF14”, thickness 23 ⁇ m, moisture permeability 27 g / m 2 ⁇ 24 h
- Example 1-5 A polarizing film was prepared in the same manner as in Example 1-1, except that a polyester resin film (trade name “T100”, thickness 25 ⁇ m, moisture permeability 29 g / m 2 ⁇ 24 h) manufactured by Mitsubishi Plastics Co., Ltd. was used as the coating film. Produced.
- Example 1-6 A polarizing film was prepared in the same manner as in Example 1-1, except that a norbornene-based resin film (manufactured by JSR, trade name “ARTON”, thickness 35 ⁇ m, water vapor transmission rate 85 g / m 2 ⁇ 24 h) was used as the coating film. did.
- a norbornene-based resin film manufactured by JSR, trade name “ARTON”, thickness 35 ⁇ m, water vapor transmission rate 85 g / m 2 ⁇ 24 h
- Example 1-7 A polarizing film was produced in the same manner as in Example 1-1 except that the heating temperature was changed to 50 ° C. in Step D.
- thermoplastic resin substrate A norbornene resin film (manufactured by JSR, trade name “ARTON”, thickness 150 ⁇ m) having a Tg of 130 ° C. was used as the thermoplastic resin substrate.
- PVA polyvinyl alcohol
- the obtained laminate was stretched to a stretch ratio of 4.5 times in the width direction by free-end uniaxial stretching using a tenter apparatus under heating at 140 ° C.
- the thickness of the PVA resin layer after the stretching treatment was 3 ⁇ m (Step C).
- a dyeing bath at 30 ° C.
- iodine aqueous solution obtained by blending 0.5 parts by weight of iodine and 3.5 parts by weight of potassium iodide with respect to 100 parts by weight of water.
- Step B Subsequently, it was immersed for 60 seconds in a crosslinking bath having a liquid temperature of 60 ° C.
- an aqueous PVA resin solution manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., trade name “GOHSFEMER (registered trademark) Z
- GOHSFEMER registered trademark
- Z aqueous PVA resin solution
- a norbornene resin film manufactured by JSR, trade name“ ARTON ”, thickness 35 ⁇ m, moisture permeability 85 g / m 2 ⁇ 24 h
- the amount of water contained in the adhesive was 0.3 mg / cm 2 per unit area. In this way, a polarizing film having a thickness of 3 ⁇ m was produced. Further, the thickness of the thermoplastic resin substrate at this time was 70 ⁇ m, and the moisture permeability was 50 g / m 2 ⁇ 24 h.
- Example 2-2 A polarizing film was produced in the same manner as in Example 2-1, except that the heating temperature was 80 ° C. in Step D.
- Example 2-3 A polarizing film in the same manner as in Example 2-1, except that a norbornene resin film (manufactured by Nippon Zeon Co., Ltd., trade name “ZEONOR ZB14”, thickness 70 ⁇ m, moisture permeability 7 g / m 2 ⁇ 24 h) was used as the coating film.
- a norbornene resin film manufactured by Nippon Zeon Co., Ltd., trade name “ZEONOR ZB14”, thickness 70 ⁇ m, moisture permeability 7 g / m 2 ⁇ 24 h
- Example 3-1 The laminate produced in the same manner as in Example 1-1 was uniaxially stretched by 1.8 times in the longitudinal direction (longitudinal direction) between rolls with different peripheral speeds in an oven at 120 ° C. (air-assisted auxiliary stretching step) ). Thereafter, an insolubilization step was performed in the same manner as in Example 1-1. Next, it is immersed in a dyeing solution containing potassium iodide at an iodine concentration of 0.12 to 0.25% by weight at a solution temperature of 30 ° C. so that the polarization degree of the finally obtained polarizing film is 99.98% or more. (Step B). Here, the mixing ratio of iodine and potassium iodide was 1: 7.
- Step C stretching was performed so that the total stretching ratio (maximum stretching ratio) including air-assisted stretching was 6.0 times. In this way, a polarizing film having a thickness of 3 ⁇ m was produced. Moreover, the thickness of the thermoplastic resin base material at this time was 40 micrometers, and the water vapor transmission rate was 25 g / m ⁇ 2 > * 24h.
- Example 3-2 A polarizing film was produced in the same manner as in Example 3-1, except that the heating temperature was changed to 80 ° C. in Step D.
- Example 3-3 Except that a norbornene-based resin film (manufactured by ZEON Corporation, trade name “ZEONOR G film ZF14”, thickness 23 ⁇ m, moisture permeability 27 g / m 2 ⁇ 24 h) was used as the coating film, the same as Example 3-2 A polarizing film was produced.
- a norbornene-based resin film manufactured by ZEON Corporation, trade name “ZEONOR G film ZF14”, thickness 23 ⁇ m, moisture permeability 27 g / m 2 ⁇ 24 h
- Example 3-4 A polarizing film was prepared in the same manner as in Example 3-2 except that a norbornene resin film (manufactured by JSR, trade name “ARTON FEKP130”, thickness 40 ⁇ m, moisture permeability 60 g / m 2 ⁇ 24 h) was used as the coating film. Produced.
- a norbornene resin film manufactured by JSR, trade name “ARTON FEKP130”, thickness 40 ⁇ m, moisture permeability 60 g / m 2 ⁇ 24 h
- Example 1-1 Example 1-1, except that a cellulose resin film (trade name “TD80UL”, thickness 80 ⁇ m, water vapor transmission rate 400 g / m 2 ⁇ 24 h) manufactured by Fuji Film Co., Ltd. was used as the coating film, and the heating temperature was 50 ° C. to prepare a polarizing film in the same manner as.
- a cellulose resin film trade name “TD80UL”, thickness 80 ⁇ m, water vapor transmission rate 400 g / m 2 ⁇ 24 h
- Example 1-1 Example 1-1, except that a cellulose resin film (trade name “TD80UL”, thickness 80 ⁇ m, water vapor transmission rate 400 g / m 2 ⁇ 24 h) was used as the coating film, and the heating temperature was 80 ° C. to prepare a polarizing film in the same manner as.
- a cellulose resin film trade name “TD80UL”, thickness 80 ⁇ m, water vapor transmission rate 400 g / m 2 ⁇ 24 h
- Example 2-1 Example 2-1 except that a cellulose resin film (manufactured by FUJIFILM, trade name “TD80UL”, thickness 80 ⁇ m, moisture permeability 400 g / m 2 ⁇ 24 h) was used as the coating film, and the heating temperature was 50 ° C. to prepare a polarizing film in the same manner as.
- a cellulose resin film manufactured by FUJIFILM, trade name “TD80UL”, thickness 80 ⁇ m, moisture permeability 400 g / m 2 ⁇ 24 h
- Example 2-1 except that a cellulose-based resin film (manufactured by Fuji Film, trade name “TD80UL”, thickness 80 ⁇ m, moisture permeability 400 g / m 2 ⁇ 24 h) was used as the coating film, and the heating temperature was 90 ° C. to prepare a polarizing film in the same manner as.
- a cellulose-based resin film manufactured by Fuji Film, trade name “TD80UL”, thickness 80 ⁇ m, moisture permeability 400 g / m 2 ⁇ 24 h
- Example 3-1 Example 3-1 except that a cellulose-based resin film (manufactured by FUJIFILM, trade name “TD80UL”, thickness 80 ⁇ m, moisture permeability 400 g / m 2 ⁇ 24 h) was used as the coating film, and the heating temperature was 50 ° C. to prepare a polarizing film in the same manner as.
- a cellulose-based resin film manufactured by FUJIFILM, trade name “TD80UL”, thickness 80 ⁇ m, moisture permeability 400 g / m 2 ⁇ 24 h
- Example 3-1 Example 3-1 except that a cellulose-based resin film (manufactured by FUJIFILM, trade name “TD80UL”, thickness 80 ⁇ m, moisture permeability 400 g / m 2 ⁇ 24 h) was used as the coating film, and the heating temperature was 80 ° C.
- a polarizing film was produced in the same manner as described above.
- a polyvinyl alcohol (PVA) film having a polymerization degree of 2300 and a saponification degree of 99.9% (trade name “VF-PS7500”, thickness 75 ⁇ m, manufactured by Kuraray Co., Ltd.) is placed in a swelling bath (pure water) at a liquid temperature of 30 ° C. for 30 seconds. It was immersed (swelling process).
- the polarization degree of the finally obtained polarizing film is 99.98% or more in the dyeing solution containing potassium iodide at an iodine concentration of 0.03 to 0.05% by weight at a liquid temperature of 30 ° C. It was immersed (dyeing process).
- the mixing ratio of iodine and potassium iodide was 1: 7. Subsequently, it was immersed for 30 seconds in a crosslinking bath having a liquid temperature of 30 ° C. (a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water). (Crosslinking step). Thereafter, the PVA film is immersed in a boric acid aqueous solution having a liquid temperature of 60 ° C. (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water).
- a PVA-based resin aqueous solution manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GOHSEFIMAR (registered trademark) Z-200”, so that the thickness of the adhesive layer after heating is 90 nm
- An oven in which a norbornene-based resin film manufactured by Nippon Zeon Co., Ltd., trade name “ZEONOR ZB14”, thickness 70 ⁇ m, moisture permeability 7 g / m 2 ⁇ 24 h) is bonded and maintained at 80 ° C.
- the amount of water contained in the adhesive was 0.3 mg / cm 2 per unit area. In this way, a polarizing film having a thickness of 24 ⁇ m was produced.
- Comparative Example 4-2 Comparative Example 4-1 except that a cellulose-based resin film (trade name “TD80UL”, thickness 80 ⁇ m, moisture permeability 400 g / m 2 ⁇ 24 h) was used as the coating film, and the heating temperature was 50 ° C. to prepare a polarizing film in the same manner as.
- a cellulose-based resin film trade name “TD80UL”, thickness 80 ⁇ m, moisture permeability 400 g / m 2 ⁇ 24 h
- the polarization degree of the polarizing film obtained in each example and comparative example was measured by peeling the thermoplastic resin substrate without peeling the coating film.
- an adhesive was applied to the surface of the obtained polarizing film, and a triacetyl cellulose film (TAC film) having a thickness of 80 ⁇ m was bonded thereto, and then the thermoplastic resin substrate was peeled off. Then, it was used for the measurement of the degree of polarization.
- TAC film triacetyl cellulose film having a thickness of 80 ⁇ m
- Polarization degree (P) (%) ⁇ (Tp ⁇ Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100 Note that Ts, Tp, and Tc are Y values measured with a two-degree field of view (C light source) of JIS Z 8701 and corrected for visibility.
- the surface of the PVA resin layer was covered with a coating film having a predetermined moisture permeability and subjected to heat treatment, whereby a polarizing film having a very high single transmittance and degree of polarization could be produced.
- Comparative Example 4-1 in which a polarizing film was produced without using a thermoplastic resin substrate, no improvement in single transmittance was confirmed even when heat treatment was performed using a coating film having low moisture permeability.
- the orientation of the upper side and the lower side (thermoplastic resin substrate side) of the polarizing film obtained in Reference Example 1 was evaluated by an orientation function.
- Method of measuring the orientation function is as follows.
- FT-IR Fourier transform infrared spectrophotometer
- SPECTRUM2000 total reflection attenuation
- the orientation function (f) was calculated according to the following procedure. Measurement was carried out with the measured polarized light at 0 ° and 90 ° with respect to the stretching direction.
- the measurement results are shown in FIG. 5 together with the results of a commercially available polarizing film (a polarizing film produced without using a base material).
- the commercially available polarizing film had no difference in orientation between the upper side and the lower side, but the polarizing film of Reference Example 1 prepared using a substrate showed a difference in orientation between the upper side and the lower side.
- the polarizing film of the present invention is a liquid crystal television, a liquid crystal display, a mobile phone, a digital camera, a video camera, a portable game machine, a car navigation system, a copier, a liquid crystal panel such as a printer, a fax machine, a clock, a microwave oven, and a reflection of an organic EL device. It is suitably used as a prevention film.
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Abstract
Description
好ましい実施形態においては、上記加熱温度が60℃以上である。
好ましい実施形態においては、上記PVA系樹脂層表面を、接着剤を介して上記被覆フィルムで被覆する。
好ましい実施形態においては、上記接着剤が水系接着剤である。
好ましい実施形態においては、上記延伸工程後の熱可塑性樹脂基材の透湿度が100g/m2・24h以下である。
好ましい実施形態においては、上記積層体をホウ酸水溶液中で水中延伸する。
好ましい実施形態においては、上記染色工程および上記ホウ酸水中延伸の前に、上記積層体を95℃以上で空中延伸する工程を含む。
好ましい実施形態においては、上記積層体の最大延伸倍率が5.0倍以上である。
好ましい実施形態においては、上記熱可塑性樹脂基材が、非晶質のポリエチレンテレフタレート系樹脂から構成されている。
本発明の別の局面によれば、偏光膜が提供される。この偏光膜は、上記製造方法により得られる。
本発明のさらに別の局面によれば、光学積層体が提供される。この光学積層体は、上記偏光膜を有する。
A.製造方法
本発明の偏光膜の製造方法は、熱可塑性樹脂基材上にPVA系樹脂層を形成して積層体を作製する工程(工程A)と、積層体のPVA系樹脂層をヨウ素で染色する工程(工程B)と、積層体を延伸する工程(工程C)と、積層体のPVA系樹脂層表面を被覆フィルムで被覆し、この状態で積層体を加熱する工程(工程D)とを含む。以下、各工程について説明する。
図1は、本発明の好ましい実施形態による積層体の概略断面図である。積層体10は、熱可塑性樹脂基材11とPVA系樹脂層12とを有し、熱可塑性樹脂基材11上にPVA系樹脂層12を形成することにより作製される。PVA系樹脂層12の形成方法は、任意の適切な方法を採用し得る。好ましくは、熱可塑性樹脂基材11上に、PVA系樹脂を含む塗布液を塗布し、乾燥することにより、PVA系樹脂層12を形成する。
上記工程Bでは、PVA系樹脂層をヨウ素で染色する。具体的には、PVA系樹脂層にヨウ素を吸着させることにより行う。当該吸着方法としては、例えば、ヨウ素を含む染色液にPVA系樹脂層(積層体)を浸漬させる方法、PVA系樹脂層に当該染色液を塗工する方法、当該染色液をPVA系樹脂層に噴霧する方法等が挙げられる。好ましくは、染色液に積層体を浸漬させる方法である。ヨウ素が良好に吸着し得るからである。
上記工程Cでは、上記積層体を延伸する。積層体の延伸方法は、任意の適切な方法を採用することができる。具体的には、固定端延伸でもよいし、自由端延伸(例えば、周速の異なるロール間に積層体を通して一軸延伸する方法)でもよい。積層体の延伸は、一段階で行ってもよいし、多段階で行ってもよい。多段階で行う場合、後述の積層体の延伸倍率(最大延伸倍率)は、各段階の延伸倍率の積である。
工程Bおよび工程Cの後、上記工程Dでは、積層体のPVA系樹脂層表面を被覆フィルムで被覆し、この状態で積層体を加熱する。積層体のPVA系樹脂層に対して、このような処理を施すことにより、得られる偏光膜の光学特性を向上させることができる。工程Dにより、光学特性への寄与が低い配向性の低いヨウ素錯体が選択的に分解され得ることが、光学特性向上の要因の一つとして考えられる。具体的には、熱可塑性樹脂基材上に形成され、染色工程および延伸工程を経たPVA系樹脂層は、その熱可塑性樹脂基材側(下側)と表面側(上側)とで構成が異なる。具体的には、下側と上側とではPVA系樹脂の配向性が異なり、上側が下側に比べて配向性が低い傾向にある。配向性の低い部分に存在するヨウ素錯体もその配向性は低く、光学特性(特に、偏光度)への寄与が低いだけでなく、光学特性(特に、透過率)の低下の原因となり得る。一方で、このようなヨウ素錯体は、その配向性の低さから結合力も弱く分解されやすい。その結果、工程Dにより、配向性の低いヨウ素錯体を選択的に分解させて、可視光領域の吸収を低減させ、透過率を向上させることができる。なお、配向性の低いヨウ素錯体は、もともと偏光度への寄与が低いため、分解されても偏光度の低下は最小限に抑えられる。
(増加率)=[(処理後の吸光度)-(処理前の吸光度)]/(処理後の吸光度)×100
本発明の偏光膜の製造方法は、上記工程A、工程B、工程Cおよび工程D以外に、その他の工程を含み得る。その他の工程としては、例えば、不溶化工程、架橋工程、上記工程Cとは別の延伸工程、洗浄工程、乾燥工程等が挙げられる。その他の工程は、任意の適切なタイミングで行い得る。
本発明の偏光膜は、上記製造方法により得られる。本発明の偏光膜は、実質的には、二色性物質が吸着配向されたPVA系樹脂膜である。偏光膜の厚みは、代表的には25μm以下であり、好ましくは15μm以下、より好ましくは10μm以下、さらに好ましくは7μm以下、特に好ましくは5μm以下である。一方、偏光膜の厚みは、好ましくは0.5μm以上、より好ましくは1.5μm以上である。偏光膜は、好ましくは、波長380nm~780nmのいずれかの波長で吸収二色性を示す。偏光膜の単体透過率は、好ましくは40.0%以上、より好ましくは41.0%以上、さらに好ましくは42.0%以上、特に好ましくは43.0%以上である。偏光膜の偏光度は、好ましくは99.8%以上、より好ましくは99.9%以上、さらに好ましくは99.95%以上である。
本発明の光学積層体は、上記偏光膜を有する。図3(a)および(b)は、本発明の好ましい実施形態による光学フィルム積層体の概略断面図である。光学フィルム積層体100は、熱可塑性樹脂基材11’と偏光膜12’と粘着剤層13とセパレータ14とをこの順で有する。光学フィルム積層体200は、熱可塑性樹脂基材11’と偏光膜12’と接着剤層15と光学機能フィルム16と粘着剤層13とセパレータ14とをこの順で有する。本実施形態では、上記熱可塑性樹脂基材を、得られた偏光膜12’から剥離せずに、そのまま光学部材として用いている。熱可塑性樹脂基材11’は、例えば、偏光膜12’の保護フィルムとして機能し得る。
1.厚み
デジタルマイクロメーター(アンリツ社製、製品名「KC-351C」)を用いて測定した。
2.ガラス転移温度(Tg)
JIS K 7121に準じて測定した。
3.透湿度
JIS Z0208の透湿度試験(カップ法)に準拠して、温度40℃、湿度92%RHの雰囲気中、面積1m2の試料を24時間に通過する水蒸気量(g)を測定した。
(工程A)
熱可塑性樹脂基材として、吸水率0.60%、Tg80℃の非晶質ポリエチレンテレフタレート(A-PET)フィルム(三菱化学社製、商品名「ノバクリア」、厚み:100μm)を用いた。
熱可塑性樹脂基材の片面に、重合度2600、ケン化度99.9%のポリビニルアルコール(PVA)樹脂(日本合成化学工業社製、商品名「ゴーセノール(登録商標)NH-26」)の水溶液を60℃で塗布および乾燥して、厚み7μmのPVA系樹脂層を形成した。このようにして積層体を作製した。
次いで、液温30℃の染色浴(水100重量部に対して、ヨウ素を0.2重量部配合し、ヨウ化カリウムを1.0重量部配合して得られたヨウ素水溶液)に60秒間浸漬させた(工程B)。
次いで、液温30℃の架橋浴(水100重量部に対して、ヨウ化カリウムを3重量部配合し、ホウ酸を3重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(架橋工程)。
その後、積層体を、液温60℃のホウ酸水溶液(水100重量部に対して、ホウ酸を4重量部配合し、ヨウ化カリウムを5重量部配合して得られた水溶液)に浸漬させながら、周速の異なるロール間で縦方向(長手方向)に一軸延伸を行った(工程C)。ホウ酸水溶液への浸漬時間は120秒であり、積層体が破断する直前まで延伸した(最大延伸倍率は5.0倍)。
その後、積層体を洗浄浴(水100重量部に対して、ヨウ化カリウムを3重量部配合して得られた水溶液)に浸漬させた後、60℃の温風で乾燥させた(洗浄・乾燥工程)。
続いて、積層体のPVA系樹脂層表面に、加熱後の接着剤層の厚みが90nmとなるようにPVA系樹脂水溶液(日本合成化学工業社製、商品名「ゴーセファイマー(登録商標)Z-200」、樹脂濃度:3重量%)を塗布し、ノルボルネン系樹脂フィルム(日本ゼオン社製、商品名「ZEONOR ZB14」、厚み70μm、透湿度7g/m2・24h)を貼り合わせ、100℃に維持したオーブンで5分間加熱した(工程D)。貼り合わせの際、接着剤に含まれる水分量は、単位面積当たり0.3mg/cm2であった。
このようにして、厚み3μmの偏光膜を作製した。また、このときの熱可塑性樹脂基材の厚みは40μmであり、透湿度は25g/m2・24hであった。なお、当該透湿度は、別途、厚み40μmのA-PETフィルムを用意して測定した値である。
工程Dにおいて、加熱温度を80℃としたこと以外は、実施例1-1と同様にして偏光膜を作製した。
被覆フィルムとしてノルボルネン系樹脂フィルム(日本ゼオン社製、商品名「Zeonor ZD12」、厚み33μm、透湿度20g/m2・24h)を用いたこと以外は、実施例1-1と同様にして偏光膜を作製した。
被覆フィルムとしてノルボルネン系樹脂フィルム(日本ゼオン社製、商品名「ZEONOR GフィルムZF14」、厚み23μm、透湿度27g/m2・24h)を用いたこと以外は、実施例1-1と同様にして偏光膜を作製した。
被覆フィルムとしてポリエステル系樹脂フィルム(三菱樹脂社製、商品名「T100」、厚み25μm、透湿度29g/m2・24h)を用いたこと以外は、実施例1-1と同様にして偏光膜を作製した。
被覆フィルムとしてノルボルネン系樹脂フィルム(JSR社製、商品名「ARTON」、厚み35μm、透湿度85g/m2・24h)を用いたこと以外は、実施例1-1と同様にして偏光膜を作製した。
工程Dにおいて、加熱温度を50℃としたこと以外は、実施例1-1と同様にして偏光膜を作製した。
(工程A)
熱可塑性樹脂基材として、Tg130℃のノルボルネン系樹脂フィルム(JSR社製、商品名「ARTON」、厚み150μm)を用いた。
熱可塑性樹脂基材の片面に、重合度2600、ケン化度99.9%のポリビニルアルコール(PVA)樹脂(日本合成化学工業社製、商品名「ゴーセノール(登録商標)NH-26」)の水溶液を80℃で塗布および乾燥して、厚み7μmのPVA系樹脂層を形成した。このようにして積層体を作製した。
次いで、液温30℃の染色浴(水100重量部に対して、ヨウ素を0.5重量部配合し、ヨウ化カリウムを3.5重量部配合して得られたヨウ素水溶液)に60秒間浸漬させた(工程B)。
次いで、液温60℃の架橋浴(水100重量部に対して、ヨウ化カリウムを5重量部配合し、ホウ酸を5重量部配合して得られたホウ酸水溶液)に60秒間浸漬させた(架橋工程)。
その後、積層体を洗浄浴(水100重量部に対して、ヨウ化カリウムを3重量部配合して得られた水溶液)に浸漬させた後、60℃の温風で乾燥させた(洗浄・乾燥工程)。
続いて、積層体のPVA系樹脂層表面に、加熱後の接着剤層の厚みが90nmとなるようにPVA系樹脂水溶液(日本合成化学工業社製、商品名「ゴーセファイマー(登録商標)Z-200」、樹脂濃度:3重量%)を塗布し、ノルボルネン系樹脂フィルム(JSR社製、商品名「ARTON」、厚み35μm、透湿度85g/m2・24h)を貼り合わせ、60℃に維持したオーブンで5分間加熱した(工程D)。貼り合わせの際、接着剤に含まれる水分量は、単位面積当たり0.3mg/cm2であった。
このようにして、厚み3μmの偏光膜を作製した。また、このときの熱可塑性樹脂基材の厚みは70μmであり、透湿度は50g/m2・24hであった。
工程Dにおいて、加熱温度を80℃としたこと以外は、実施例2-1と同様にして偏光膜を作製した。
被覆フィルムとしてノルボルネン系樹脂フィルム(日本ゼオン社製、商品名「ZEONOR ZB14」、厚み70μm、透湿度7g/m2・24h)を用いたこと以外は、実施例2-1と同様にして偏光膜を作製した。
実施例1-1と同様にして作製した積層体を、120℃のオーブン内で周速の異なるロール間で縦方向(長手方向)に1.8倍に自由端一軸延伸した(空中補助延伸工程)。その後、実施例1-1と同様にして、不溶化工程を行った。
次いで、液温30℃で、ヨウ素濃度0.12~0.25重量%でヨウ化カリウムを含む染色液に、最終的に得られる偏光膜の偏光度が99.98%以上になるように浸漬させた(工程B)。ここでは、ヨウ素とヨウ化カリウムの配合比は1:7とした。
次いで、実施例1-1と同様にして架橋工程、工程C、洗浄・乾燥工程および工程Dを行い、偏光膜を作製した。なお、工程Cにおいて、空中補助延伸を含む総延伸倍率(最大延伸倍率)が6.0倍となるように延伸した。
このようにして、厚み3μmの偏光膜を作製した。また、このときの熱可塑性樹脂基材の厚みは40μmであり、透湿度は25g/m2・24hであった。
工程Dにおいて、加熱温度を80℃としたこと以外は、実施例3-1と同様にして偏光膜を作製した。
被覆フィルムとしてノルボルネン系樹脂フィルム(日本ゼオン社製、商品名「ZEONOR GフィルムZF14」、厚み23μm、透湿度27g/m2・24h)を用いたこと以外は、実施例3-2と同様にして偏光膜を作製した。
被覆フィルムとしてノルボルネン系樹脂フィルム(JSR社製、商品名「ARTON FEKP130」、厚み40μm、透湿度60g/m2・24h)を用いたこと以外は、実施例3-2と同様にして偏光膜を作製した。
被覆フィルムとしてセルロース系樹脂フィルム(富士フイルム社製、商品名「TD80UL」、厚み80μm、透湿度400g/m2・24h)を用い、加熱温度を50℃としたこと以外は、実施例1-1と同様にして偏光膜を作製した。
被覆フィルムとしてセルロース系樹脂フィルム(富士フイルム社製、商品名「TD80UL」、厚み80μm、透湿度400g/m2・24h)を用い、加熱温度を80℃としたこと以外は、実施例1-1と同様にして偏光膜を作製した。
被覆フィルムとしてセルロース系樹脂フィルム(富士フイルム社製、商品名「TD80UL」、厚み80μm、透湿度400g/m2・24h)を用い、加熱温度を50℃としたこと以外は、実施例2-1と同様にして偏光膜を作製した。
被覆フィルムとしてセルロース系樹脂フィルム(富士フイルム社製、商品名「TD80UL」、厚み80μm、透湿度400g/m2・24h)を用い、加熱温度を90℃としたこと以外は、実施例2-1と同様にして偏光膜を作製した。
被覆フィルムとしてセルロース系樹脂フィルム(富士フイルム社製、商品名「TD80UL」、厚み80μm、透湿度400g/m2・24h)を用い、加熱温度を50℃としたこと以外は、実施例3-1と同様にして偏光膜を作製した。
被覆フィルムとしてセルロース系樹脂フィルム(富士フイルム社製、商品名「TD80UL」、厚み80μm、透湿度400g/m2・24h)を用い、加熱温度を80℃としたこと以外は、実施例3-1と同様にして偏光膜を作製した。
重合度2300、ケン化度99.9%のポリビニルアルコール(PVA)フィルム(クラレ社製、商品名「VF-PS7500」、厚み75μm)を、液温30℃の膨潤浴(純水)に30秒間浸漬させた(膨潤工程)。
次いで、液温30℃で、ヨウ素濃度が0.03~0.05重量%でヨウ化カリウムを含む染色液に、最終的に得られる偏光膜の偏光度が99.98%以上になるように浸漬させた(染色工程)。ここでは、ヨウ素とヨウ化カリウムの配合比は1:7とした。
次いで、液温30℃の架橋浴(水100重量部に対して、ヨウ化カリウムを3重量部配合し、ホウ酸を3重量部配合して得られたホウ酸水溶液)に30秒間浸漬させた(架橋工程)。
その後、PVAフィルムを、液温60℃のホウ酸水溶液(水100重量部に対して、ホウ酸を4重量部配合し、ヨウ化カリウムを5重量部配合して得られた水溶液)に浸漬させながら、周速の異なるロール間で縦方向(長手方向)に一軸延伸を行った(延伸工程)。ホウ酸水溶液への浸漬時間は120秒であり、延伸倍率を6.0倍とした。
その後、PVAフィルムを洗浄浴(水100重量部に対して、ヨウ化カリウムを3重量部配合して得られた水溶液)に浸漬させた後、60℃の温風で乾燥させた(洗浄・乾燥工程)。
続いて、PVAフィルムの両面に、加熱後の接着剤層の厚みが90nmとなるようにPVA系樹脂水溶液(日本合成化学工業社製、商品名「ゴーセファイマー(登録商標)Z-200」、樹脂濃度:3重量%)を塗布し、ノルボルネン系樹脂フィルム(日本ゼオン社製、商品名「ZEONOR ZB14」、厚み70μm、透湿度7g/m2・24h)を貼り合わせ、80℃に維持したオーブンで5分間加熱した(加熱工程)。貼り合わせの際、接着剤に含まれる水分量は、単位面積当たり0.3mg/cm2であった。
このようにして、厚み24μmの偏光膜を作製した。
被覆フィルムとしてセルロース系樹脂フィルム(富士フイルム社製、商品名「TD80UL」、厚み80μm、透湿度400g/m2・24h)を用い、加熱温度を50℃としたこと以外は、比較例4-1と同様にして偏光膜を作製した。
工程Dを行わなかったこと以外は、実施例1-1と同様にして偏光膜を得た。
工程Dを行わなかったこと以外は、実施例2-1と同様にして偏光膜を得た。
工程Dを行わなかったこと以外は、実施例3-1と同様にして偏光膜を得た。
加熱工程を行わなかったこと以外は、比較例4-1と同様にして偏光膜を得た。
(偏光度の測定方法)
紫外可視分光光度計(日本分光社製、製品名「V7100」)を用いて、偏光膜の単体透過率(Ts)、平行透過率(Tp)および直交透過率(Tc)を測定し、偏光度(P)を次式により求めた。
偏光度(P)(%)={(Tp-Tc)/(Tp+Tc)}1/2×100
なお、上記Ts、TpおよびTcは、JIS Z 8701の2度視野(C光源)により測定し、視感度補正を行ったY値である。
測定装置は、フーリエ変換赤外分光光度計(FT-IR)(Perkin Elmer社製、商品名:「SPECTRUM2000」)を用いた。偏光を測定光として、全反射減衰分光(ATR:attenuated total reflection)測定により、PVA系樹脂層表面の評価を行った。配向関数(f)の算出は、以下の手順で行った。
測定偏光を延伸方向に対して0°と90°にした状態で測定を実施した。
得られたスペクトルの2941cm-1の吸収強度を用いて、下記式に従って算出した(出典:H.W.Siesler,Adv.Polym.Sci.,65,1(1984))。ここで、下記強度Iは、3330cm-1を参照ピークとして、2941cm-1/3330cm-1の値を用いた。なお、f=1のとき完全配向、f=0のときランダムとなる。また、2941cm-1のピークは、PVAの主鎖(-CH2-)の振動起因の吸収といわれている。
f=(3<cos2θ>-1)/2
=[(R-1)(R0+2)]/[(R+2)(R0-1)]
=(1-D)/[c(2D+1)]
=-2×(1-D)/(2D+1)
ただし、
c=(3cos2β-1)/2
β=90deg
θ:延伸方向に対する分子鎖の角度
β:分子鎖軸に対する遷移双極子モーメントの角度
R0=2cot2β
1/R=D=(I⊥)/(I//)
(PETが配向するほどDの値が大きくなる。)
I⊥:測定偏光の振動方向を延伸方向と垂直方向(90°)に入射して測定したときの吸収強度
I//:測定偏光の振動方向を延伸方向と平行方向(0°)に入射して測定したときの吸収強度
11 熱可塑性樹脂基材
12 ポリビニルアルコール系樹脂層
Claims (11)
- 熱可塑性樹脂基材上にポリビニルアルコール系樹脂層を形成して積層体を作製する工程と、
該積層体のポリビニルアルコール系樹脂層をヨウ素で染色する工程と、
該積層体を延伸する工程と、
該染色工程および延伸工程の後に、該積層体のポリビニルアルコール系樹脂層表面を透湿度が100g/m2・24h以下の被覆フィルムで被覆し、この状態で該積層体を加熱する工程と
を含む、偏光膜の製造方法。 - 前記加熱温度が60℃以上である、請求項1に記載の偏光膜の製造方法。
- 前記ポリビニルアルコール系樹脂層表面を、接着剤を介して前記被覆フィルムで被覆する、請求項1または2に記載の偏光膜の製造方法。
- 前記接着剤が水系接着剤である、請求項3に記載の偏光膜の製造方法。
- 前記延伸工程後の熱可塑性樹脂基材の透湿度が100g/m2・24h以下である、請求項1から4のいずれかに記載の偏光膜の製造方法。
- 前記積層体をホウ酸水溶液中で水中延伸する、請求項1から5のいずれかに記載の偏光膜の製造方法。
- 前記染色工程および前記ホウ酸水中延伸の前に、前記積層体を95℃以上で空中延伸する工程を含む、請求項6に記載の偏光膜の製造方法。
- 前記積層体の最大延伸倍率が5.0倍以上である、請求項1から7のいずれかに記載の偏光膜の製造方法。
- 前記熱可塑性樹脂基材が、非晶質のポリエチレンテレフタレート系樹脂から構成されている、請求項1から8のいずれかに記載の偏光膜の製造方法。
- 請求項1から9のいずれかに記載の偏光膜の製造方法により得られた、偏光膜。
- 請求項10に記載の偏光膜を有する、光学積層体。
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CN201180020047.9A CN102859402B (zh) | 2010-12-16 | 2011-11-29 | 偏光膜的制造方法 |
KR1020127017635A KR101330981B1 (ko) | 2010-12-16 | 2011-11-29 | 편광막의 제조 방법 |
EP20110847890 EP2653898B1 (en) | 2010-12-16 | 2011-11-29 | Method for producing polarizing film |
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JP (1) | JP4975186B1 (ja) |
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CN (2) | CN104155713B (ja) |
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- 2011-11-29 WO PCT/JP2011/077468 patent/WO2012081390A1/ja active Application Filing
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- 2011-11-29 CN CN201410382826.9A patent/CN104155713B/zh active Active
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WO2014057950A1 (ja) * | 2012-10-12 | 2014-04-17 | 富士フイルム株式会社 | 光学フィルム、光学フィルムの製造方法、偏光板、及び画像表示装置 |
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JP2016167075A (ja) * | 2012-11-16 | 2016-09-15 | 日東電工株式会社 | 偏光板の製造方法 |
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JP4975186B1 (ja) | 2012-07-11 |
CN102859402A (zh) | 2013-01-02 |
EP2653898B1 (en) | 2015-04-22 |
KR101330981B1 (ko) | 2013-11-18 |
CN104155713A (zh) | 2014-11-19 |
TWI422626B (zh) | 2014-01-11 |
TW201231520A (en) | 2012-08-01 |
KR20120104289A (ko) | 2012-09-20 |
EP2653898A1 (en) | 2013-10-23 |
CN104155713B (zh) | 2017-04-12 |
EP2653898A4 (en) | 2013-11-20 |
US8699135B2 (en) | 2014-04-15 |
US20120281279A1 (en) | 2012-11-08 |
JP2012256018A (ja) | 2012-12-27 |
CN102859402B (zh) | 2015-06-24 |
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