WO2020158113A1 - ポリエステルフィルム、および該ポリエステルフィルムを含む偏光板 - Google Patents
ポリエステルフィルム、および該ポリエステルフィルムを含む偏光板 Download PDFInfo
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- WO2020158113A1 WO2020158113A1 PCT/JP2019/044777 JP2019044777W WO2020158113A1 WO 2020158113 A1 WO2020158113 A1 WO 2020158113A1 JP 2019044777 W JP2019044777 W JP 2019044777W WO 2020158113 A1 WO2020158113 A1 WO 2020158113A1
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- polyester film
- polarizer
- polarizing plate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/025—Electric or magnetic properties
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
-
- 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
-
- 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
- B32B2307/518—Oriented bi-axially
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- the present invention relates to a polyester film and a polarizing plate including the polyester film.
- a polarizing plate In image display devices (for example, liquid crystal display devices and organic EL display devices), a polarizing plate is often arranged on at least one side of the display cell due to the image forming method. In recent years, image display devices have tended to further diversify their functions and applications, and it is required that they can withstand use in more severe environments.
- a polarizing plate generally has a structure in which a polarizer is sandwiched between two protective films, and as the protective film, triacetyl cellulose, acrylic resin, cycloolefin resin, etc. are widely used.
- a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) having excellent mechanical properties, chemical resistance, and moisture barrier properties is used as a polarizer protective film. It has been proposed (for example, Patent Document 1). However, while the polyester film has excellent mechanical properties, it has birefringence, which may cause visibility deterioration such as rainbow unevenness. In particular, with the recent increase in brightness and color purity of image display devices, such a problem of rainbow unevenness becomes remarkable.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- a polarizing plate constituted by using a protective film formed of triacetyl cellulose, an acrylic resin or a cycloolefin resin which has been frequently used, has a crack in the polarizer due to a temperature change.
- thinning of the polarizer has been required along with the thinning of the image display device, and while the number of image display devices expected to be used at high temperature is increasing, the polarizing plate with excellent durability without cracks in the polarizer. Plates are strongly desired.
- the present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to reduce the occurrence of rainbow unevenness when applied to an image display device, and may contribute to improving the durability of a polarizing plate. To provide a polyester film.
- the polyester film of the present invention has a coefficient of linear expansion of 3.5 ⁇ 10 ⁇ 5 /° C. or less in the first direction, and a coefficient of linear expansion of 3. in the second direction orthogonal to the first direction. It is 5 ⁇ 10 ⁇ 5 /° C. or less, and has a slow axis in the direction of ⁇ 5° to 5° with respect to the first direction.
- the polyester film has a crystallinity of 30% or more by DSC measurement.
- a polarizing plate is provided. This polarizing plate includes a polarizer and the polyester film according to claim 1 disposed on one side of the polarizer.
- the thickness of the above-mentioned polarizer is 20 micrometers or less.
- the polarizing plate further includes an easy-adhesion layer arranged on the polarizer side of the polyester film.
- the easily adhesive layer contains fine particles.
- the thickness of the easy-adhesion layer is 0.35 ⁇ m or less.
- the easy-adhesion layer has a refractive index of 1.55 or less.
- the present invention by selectively reducing the linear expansion coefficient in a predetermined direction, the occurrence of rainbow unevenness when combined with a polarizer is small, and a polyester film that can contribute to improving the durability of a polarizing plate. Can be provided.
- FIG. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention.
- FIG. 6 is a schematic cross-sectional view of a polarizing plate according to another embodiment of the present invention.
- polyester film of the present invention has a coefficient of linear expansion of 3.5 ⁇ 10 ⁇ 5 /° C. or less in the first direction, and a coefficient of linear expansion in a second direction orthogonal to the first direction. It is 3.5 ⁇ 10 ⁇ 5 /° C. or less.
- a polyester film having such a linear expansion coefficient it is possible to prevent cracking of the polarizer while effectively protecting the polarizer by laminating it on the polarizer. More specifically, when the polyester film of the present invention is laminated on a polarizer as a polarizer protective film to form a polarizing plate, dimensional change of the polarizer (for example, dimensional change due to heat) can be suppressed by the polyester film.
- the above-mentioned 1st direction is equivalent to a conveyance direction (MD) at the time of manufacturing a polyester film.
- the second direction may correspond to TD orthogonal to MD.
- the linear expansion coefficient can be determined by TMA measurement according to JIS K 7197.
- the expression “substantially parallel” includes the case where the angle formed by the two directions is 0° ⁇ 10°, preferably 0° ⁇ 7°, and more preferably 0° ⁇ 5°.
- the polyester film of the present invention has a slow axis in the -5° to 5° direction with respect to the first direction. Within such a range, it is possible to obtain a polyester film that causes less rainbow unevenness when combined with a polarizer. More specifically, as described above, when the polarizer and the polyester film are laminated so that the absorption axis of the polarizer and the first direction are substantially parallel to each other to form a polarizing plate, rainbow unevenness is effective. Can be prevented.
- the angle formed by the first direction and the slow axis is preferably -3° to 3°, more preferably -1° to 1°, and particularly preferably -0.5° to 0. It is 5°, most preferably 0°. Within such a range, the above effect becomes more remarkable.
- the coefficient of linear expansion of the polyester film in the first direction is preferably 3.0 ⁇ 10 ⁇ 5 /° C. or less, more preferably 2.5 ⁇ 10 ⁇ 5 /° C. or less, and further preferably 1. It is 5 ⁇ 10 ⁇ 5 /° C. or less, particularly preferably 1.3 ⁇ 10 ⁇ 5 /° C. or less. Within such a range, the above effect becomes more remarkable.
- the linear expansion coefficient in the first direction of the polyester film is preferably as small as possible, but the lower limit thereof is, for example, 0.3 ⁇ 10 ⁇ 5 /° C. (preferably 0.1 ⁇ 10 ⁇ 5 /° C., more preferably 0. ⁇ 10 ⁇ 5 /° C.).
- the coefficient of linear expansion in the second direction of the polyester film is preferably 3.4 ⁇ 10 ⁇ 5 /° C. or less, more preferably 2.3 ⁇ 10 ⁇ 5 /° C. or less. Within such a range, the above effect becomes more remarkable.
- the linear expansion coefficient in the first direction of the polyester film is preferably as small as possible, but the lower limit thereof is, for example, 1 ⁇ 10 ⁇ 5 /° C. (preferably 0.5 ⁇ 10 ⁇ 5 /° C., more preferably 0.3). ⁇ 10 ⁇ 5 /° C.).
- the polyester film may be a stretched film obtained through a stretching process.
- the manufacturing conditions in the stretching step and the linear expansion coefficient (and the in-plane retardation Re(590) described later) in the first direction and the second direction can be well controlled.
- a polyester film having excellent properties as a polarizer protective film can be obtained from the viewpoints of rainbow unevenness and durability as described above.
- stretching conditions stretch temperature, stretching ratio, stretching speed, MD/TD stretching order
- preheating temperature before stretching heat treatment temperature after stretching, heat treatment time after stretching, MD/TD direction after stretching
- the relaxation rate and the like The stretching temperature, the stretching ratio and the stretching speed can be appropriately adjusted for each MD/TD.
- the in-plane retardation Re(590) of the polyester film is, for example, more than 0 nm and 10,000 nm or less.
- the in-plane retardation Re( ⁇ ) is the in-plane retardation of the film measured with light having a wavelength of ⁇ nm at 23°C. Therefore, Re(590) is the in-plane retardation of the film measured with light having a wavelength of 590 nm.
- nx is the refractive index in the direction in which the in-plane refractive index becomes maximum (that is, the slow axis direction), and ny is the refractive index in the in-plane direction orthogonal to the slow axis.
- the above-mentioned polyester film has a crystallinity measured by differential scanning calorimetry (DSC) of preferably 30% or more, more preferably 40% or more, and further preferably 50% or more.
- the upper limit of the crystallinity is, for example, 70%. Within such a range, a polyester film having excellent heat resistance and mechanical properties and suitable as a polarizer protective film can be obtained.
- the thickness of the polyester film is typically 10 ⁇ m to 100 ⁇ m, preferably 20 ⁇ m to 80 ⁇ m, and more preferably 20 ⁇ m to 50 ⁇ m.
- the total light transmittance of the polyester film is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more, and particularly preferably 95% or more.
- the haze of the polyester film is preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less, and particularly preferably 0.3% or less.
- the water vapor permeability of the polyester film is preferably 100 g/m 2 ⁇ 24 hr or less, more preferably 50 g/m 2 ⁇ 24 hr or less, and further preferably 15 g/m 2 ⁇ 24 hr or less. Within such a range, a polarizing plate excellent in durability and moisture resistance can be obtained.
- the polyester film of the present invention is formed from a polyester resin.
- the polyester resin can be obtained by condensation polymerization of a carboxylic acid component and a polyol component.
- Carboxylic acids include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids.
- aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, benzylmalonic acid, 1,4-naphthalic acid, diphenic acid, 4,4'-oxybenzoic acid and 2,5-naphthalenedicarboxylic acid.
- aliphatic dicarboxylic acid examples include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, zebacic acid, fumaric acid, Maleic acid, itaconic acid, thiodipropionic acid, diglycolic acid may be mentioned.
- Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and 2,5-norbornanedicarboxylic acid. Examples thereof include acids and adamantane dicarboxylic acids.
- the carboxylic acid component may be a derivative such as an ester, a chloride or an acid anhydride, and examples thereof include dimethyl 1,4-cyclohexanedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate and dimethyl terephthalate. And diphenyl terephthalate.
- the carboxylic acid components may be used alone or in combination of two or more.
- a typical example of the polyol component is a dihydric alcohol.
- the dihydric alcohol include aliphatic diols, alicyclic diols, and aromatic diols.
- the aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2, 2-Dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3- Examples include butadiol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentaned
- alicyclic diol examples include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, spiroglycol, tricyclodecanedimethanol, adamantanediol, 2,2,4. , 4-tetramethyl-1,3-cyclobutanediol.
- aromatic diols examples include 4,4'-thiodiphenol, 4,4'-methylenediphenol, 4,4'-(2-norbornylidene)diphenol, 4,4'-dihydroxybiphenol, o-, Mention may be made of m- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 4,4'-isopropylidenebis(2,6-cyclolophenol)2,5-naphthalenediol and p-xylenediol.
- the polyol component may be used alone or in combination of two or more kinds.
- polyester resin polyethylene terephthalate and/or modified polyethylene terephthalate is preferably used, and more preferably polyethylene terephthalate is used. By using these resins, it is possible to obtain a polyester film which has excellent mechanical properties and has less rainbow unevenness. Polyethylene terephthalate and modified polyethylene terephthalate may be blended and used.
- modified polyethylene terephthalate examples include modified polyethylene terephthalate containing a constitutional unit derived from diethylene glycol, 1,4-butanediol, 1,3-propanediol or isophthalic acid.
- the proportion of diethylene glycol in the polyol component is preferably more than 0 mol% and 10 mol% or less, more preferably more than 0 mol% and 3 mol% or less.
- the proportion of 1,4-butanediol in the polyol component is preferably more than 0 mol% and 10 mol% or less, more preferably more than 0 mol% and 3 mol% or less.
- the proportion of 1,3-propanediol in the polyol component is preferably more than 0 mol% and 10 mol% or less, more preferably more than 0 mol% and 3 mol% or less.
- the proportion of isophthalic acid in the carboxylic acid component is preferably more than 0 mol% and 10 mol% or less, more preferably more than 0 mol% and 8 mol% or less. Within such a range, a polyester film having good crystallinity can be obtained.
- the mol% described above is the mol% based on the total of all repeating units of the polymer.
- the weight average molecular weight of the polyester resin is preferably 10,000 to 100,000, more preferably 20,000 to 75,000. With such a weight average molecular weight, a film that is easy to handle during molding and has excellent mechanical strength can be obtained.
- the weight average molecular weight can be measured by GPC (solvent: THF).
- a polyester film with an easily adhesive layer is provided.
- the easy-adhesion layer contains, for example, a water-based polyurethane and an oxazoline-based crosslinking agent. Details of the easy-adhesion layer are described in, for example, JP-A-2010-55062. The entire disclosure of this publication is incorporated herein by reference.
- the easy-adhesion layer contains any appropriate fine particles.
- the fine particles may be inorganic fine particles or organic fine particles.
- the inorganic fine particles include silica, titania, alumina, zirconia, and other inorganic oxides, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and the like.
- the organic fine particles include silicone resins, fluorine resins, (meth)acrylic resins, and the like. Of these, silica is preferable.
- the particle size (number average primary particle size) of the fine particles is preferably 10 nm to 200 nm, more preferably 20 nm to 60 nm.
- the thickness of the easily adhesive layer is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, and further preferably 0.35 ⁇ m or less. Within such a range, it is possible to obtain a polyester film with an easy-adhesion layer that is hard to impair the optical characteristics of other members when applied to an image display device.
- the refractive index of the easy-adhesion layer is preferably 1.45 to 1.60. Within such a range, it is possible to obtain a polyester film with an easy-adhesion layer that is hard to impair the optical characteristics of other members when applied to an image display device. In one embodiment, the easy-adhesion layer has a refractive index of 1.54 or more.
- the polyester film may include an antiblock layer on at least one side thereof.
- the structure of the anti-block layer the structure of the easy-adhesion layer described above can be adopted.
- the antiblock layer contains the fine particles.
- the polyester film can be obtained through a molding step of molding a film-forming material (resin composition) containing the polyester resin into a film, and a stretching step of stretching the molded film.
- the stretching step includes a preheat treatment of the film performed before the film stretching and a heat treatment performed after the film stretching.
- the polyester film is provided in an elongated shape (or a shape cut out from an elongated body).
- the film-forming material may contain an additive or a solvent in addition to the polyester resin.
- an additive any appropriate additive can be adopted depending on the purpose. Specific examples of additives include reactive diluents, plasticizers, surfactants, fillers, antioxidants, antioxidants, ultraviolet absorbers, leveling agents, thixotropic agents, antistatic agents, conductive materials, flame retardants. Are listed. The number, type, combination, addition amount, etc. of the additives can be appropriately set according to the purpose.
- any appropriate forming method can be adopted. Specific examples include compression molding method, transfer molding method, injection molding method, extrusion molding method, blow molding method, powder molding method, FRP molding method, cast coating method (for example, casting method), calender molding method, heat press. Law etc. are mentioned.
- An extrusion molding method or a cast coating method is preferable. This is because the smoothness of the obtained film can be improved and good optical uniformity can be obtained.
- the method of stretching the film may be uniaxial stretching or biaxial stretching.
- uniaxial stretching is adopted as a stretching method for the film, and the film is stretched in the longitudinal direction (MD).
- the biaxial stretching may be sequential biaxial stretching or simultaneous biaxial stretching. Sequential biaxial stretching or simultaneous biaxial stretching is typically performed using a tenter stretching machine. Therefore, the stretching direction of the film is typically the length direction (MD) and the width direction (TD) of the film.
- sequential biaxial stretching is adopted as the stretching method for the film.
- MD stretching is preferably performed to obtain the polyester film. By doing so, it becomes possible to reduce the influence of bowing that occurs during TD stretching and to make the angle between the slow axis and the first direction (MD) in the polyester film an appropriate value. ..
- the stretching temperature is preferably Tg+5° C. to Tg+50° C. with respect to the glass transition temperature (Tg) of the film, more preferably Tg+5° C. to Tg+30° C., and further preferably Tg+6° C. to Tg+10° C.
- Tg glass transition temperature
- the stretch ratio in MD is preferably 1 to 7 times, more preferably 2.5 to 6.5 times, and further preferably 3 to 6 times. Within such a range, a polyester film having good crystallinity and excellent durability can be obtained while keeping the coefficient of linear expansion within a desired range.
- the stretch ratio in TD is preferably 1 to 7 times, more preferably 1.2 to 4 times, and further preferably 1.5 to 3.5 times. Within such a range, a polyester film having good crystallinity and excellent durability can be obtained while keeping the coefficient of linear expansion within a desired range.
- the ratio of the draw ratio in TD and the draw ratio in MD is preferably 1 to 4, and more preferably 1 to 2. Within such a range, it is possible to obtain a polyester film in which the occurrence of rainbow unevenness is particularly small. Further, by using the obtained polyester film, it is possible to prevent cracking of the polarizer and obtain a polarizing plate having excellent durability.
- the stretching speed in MD is preferably 5%/sec to 100%/sec, more preferably 8%/sec to 80%/sec, and further preferably 8%/sec to 60%/sec. Within such a range, a polyester film having excellent optical properties, good crystallinity, and excellent durability can be obtained.
- the stretching speed in TD is preferably 5%/sec to 100%/sec, more preferably 8%/sec to 80%/sec, and further preferably 8%/sec to 60%/sec. Within such a range, a polyester film having excellent optical properties, good crystallinity, and excellent durability can be obtained.
- the temperature of the preheat treatment is preferably 80°C to 150°C, more preferably 90°C to 130°C.
- the preheat treatment time is preferably 10 seconds to 100 seconds, more preferably 15 seconds to 80 seconds. Within such a range, a polyester film having excellent optical properties, good crystallinity, and excellent durability can be obtained.
- the temperature of the heat treatment is preferably 100°C to 250°C, more preferably 120°C to 200°C, and further preferably 130°C to 180°C. Within such a range, a polyester film having excellent transparency, good crystallinity, and excellent durability can be obtained.
- the heat treatment time is preferably 2 seconds to 50 seconds, more preferably 5 seconds to 40 seconds, and further preferably 8 seconds to 30 seconds. Within such a range, a polyester film having excellent transparency, good crystallinity, and excellent durability can be obtained.
- FIG. 1 is a schematic cross-sectional view of a polarizing plate according to one embodiment of the present invention.
- the polarizing plate 100 includes a polarizer 10 and a polyester film 20 arranged on one side of the polarizer 10.
- the polyester film 20 the polyester film of the present invention described in the section A is used. Any other suitable polarizer protective film may be disposed on the other side of the polarizer, and the polarizer protective film may not be disposed.
- the polarizer 10 and the polyester film 20 are laminated via the adhesive layer 30.
- the polarizing plate may be applied to the image display device such that the side on which the polyester film is arranged is the viewing side.
- the polarizing plate including the polyester film may be arranged on the viewing side or the back side of the liquid crystal cell.
- the resin film forming the polarizer may be a single-layer resin film or a laminate of two or more layers.
- the polarizer composed of a single-layer resin film include hydrophilic polymer films such as polyvinyl alcohol (PVA) film, partially formalized PVA film, and ethylene/vinyl acetate copolymer partially saponified film.
- hydrophilic polymer films such as polyvinyl alcohol (PVA) film, partially formalized PVA film, and ethylene/vinyl acetate copolymer partially saponified film.
- PVA polyvinyl alcohol
- partially formalized PVA film partially formalized PVA film
- ethylene/vinyl acetate copolymer partially saponified film examples thereof include polyene oriented films such as those that have been subjected to dyeing treatment and stretching treatment with a dichroic substance such as iodine or a dichroic dye, and dehydrated products of PVA and dehydrochlorinated products of polyvinyl chloride.
- a polarizer obtained by dyeing a PVA-based film with iodine and uniaxially stretching it is used
- the above dyeing with iodine is performed, for example, by immersing the PVA film in an aqueous iodine solution.
- the stretching ratio of the uniaxial stretching is preferably 3 to 7 times. Stretching may be performed after the dyeing treatment or may be performed while dyeing. Further, it may be stretched and then dyed.
- the PVA-based film is subjected to swelling treatment, crosslinking treatment, washing treatment, drying treatment and the like. For example, by immersing the PVA-based film in water and washing it before dyeing, not only can the stains on the surface of the PVA-based film and the anti-blocking agent be washed, but also the PVA-based film can be swollen to prevent uneven dyeing. Can be prevented.
- the polarizer obtained using the laminated body include a laminated body of a resin base material and a PVA-based resin layer (PVA-based resin film) laminated on the resin base material, or a resin base material and the resin.
- a polarizer obtained by using a laminate with a PVA-based resin layer formed by coating on a base material examples thereof include a polarizer obtained by using a laminate with a PVA-based resin layer formed by coating on a base material.
- a polarizer obtained by using a laminate of a resin base material and a PVA-based resin layer formed by coating on the resin base material is, for example, a resin base material obtained by applying a PVA-based resin solution to the resin base material and drying the solution.
- a PVA-based resin layer is formed thereon to obtain a laminate of a resin base material and a PVA-based resin layer; and the PVA-based resin layer is used as a polarizer by stretching and dyeing the laminate.
- the stretching typically includes dipping the laminate in a boric acid aqueous solution and stretching. Further, the stretching may further include, if necessary, stretching the laminate at high temperature (for example, 95° C. or higher) in air before stretching in the aqueous boric acid solution.
- the resin base material/polarizer laminate thus obtained may be used as it is (that is, the resin base material may be used as a protective layer of the polarizer), or the resin base material is peeled from the resin base material/polarizer laminate.
- any appropriate protective layer depending on the purpose may be laminated on the peeled surface and used. Details of the method for manufacturing such a polarizer are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580. The entire disclosure of this publication is incorporated herein by reference.
- the thickness of the polarizer is, for example, 1 ⁇ m to 80 ⁇ m. In one embodiment, the thickness of the polarizer is preferably 20 ⁇ m or less, more preferably 3 ⁇ m to 15 ⁇ m.
- the polarizer and the polarizer protective film may be laminated via any appropriate adhesive layer.
- the adhesive layer is formed from an adhesive composition containing a polyvinyl alcohol resin.
- the absorption axis direction of the polarizer is preferably substantially parallel to the first direction (typically MD) or the second direction (typically TD) of the polyester film, and the first direction (typically From the viewpoint, it is more preferable to be substantially parallel to MD).
- the polyester film and the polarizer can be tuned to preferably change their shapes. As a result, cracking of the polarizer is prevented.
- the slow axis angle of the polyester film is preferably the same as the angle formed by the absorption axis direction of the polarizer, and the angle formed by the two axes is preferably 0° ⁇ 10°, more preferably 0° ⁇ 7°. Yes, and more preferably 0° ⁇ 5°. Within such a range, it is possible to obtain a polyester film with less rainbow unevenness when applied to an image display device.
- the slow axis angle is an angle when the roll flow direction is 0°.
- the absolute value of the difference between the linear expansion coefficient of the polyester film in the first direction and the linear expansion coefficient of the polarizer in the direction parallel to the first direction is preferably 2.0 ⁇ 10 ⁇ . It is 5 /° C. or less, more preferably 1.5 ⁇ 10 ⁇ 5 /° C. or less, still more preferably 1.0 ⁇ 10 ⁇ 5 /° C. or less. Within such a range, cracking of the polarizer can be prevented even under a severe environment such as high temperature and large temperature change.
- the lower limit of the absolute value of the difference between the linear expansion coefficient of the polyester film in the first direction and the linear expansion coefficient of the polarizer in the direction parallel to the first direction is preferably as small as possible. It can be -5 /°C.
- the absolute value of the difference between the linear expansion coefficient of the polyester film in the second direction (the direction orthogonal to the first direction) and the linear expansion coefficient of the polarizer in the direction parallel to the second direction is preferably 2.0 ⁇ 10 ⁇ 5 /° C. or less, more preferably 1.5 ⁇ 10 ⁇ 5 /° C. or less, still more preferably 1.0 ⁇ 10 ⁇ 5 /° C. or less. Within such a range, cracking of the polarizer can be prevented even under a severe environment such as high temperature and large temperature change.
- the lower limit of the absolute value of the difference between the linear expansion coefficient of the polyester film in the second direction and the linear expansion coefficient of the polarizer in the direction parallel to the second direction is preferably as small as possible. It can be -5 /°C.
- the absolute value of the difference between the linear expansion coefficient of the polyester film in the first direction and the linear expansion coefficient of the polarizer in the direction parallel to the first direction, and the second value of the polyester film is both 2.0 ⁇ 10 ⁇ 5. /° C. or less (preferably 1.0 ⁇ 10 ⁇ 5 /° C. or less). Within such a range, cracking of the polarizer can be prevented even under a severe environment such as high temperature and large temperature change.
- FIG. 2 is a schematic sectional view of a polarizing plate according to another embodiment of the present invention.
- the polarizing plate 200 further includes an easy-adhesion layer 40 arranged on the polarizer 10 side of the polyester film 20.
- the easy-adhesion layer-attached polyester film A is arranged on the polarizer 10 such that the easy-adhesion layer 40 is on the polarizer 10 side.
- the easy-adhesion layer the easy-adhesion layer described in the above section A can be adopted.
- the polarizing plate can be applied to an image display device.
- Typical examples of the image display device include a liquid crystal display device and an organic electroluminescence (EL) display device. Since the image display device has a configuration well known in the industry, detailed description thereof will be omitted.
- the linear expansion coefficient in MD (first direction) and TD (second direction) was measured.
- the polarizer measured the linear expansion coefficient of the polarizing plate in the direction parallel to the MD and the direction parallel to the TD.
- Crystallinity The crystallinity of the polyester films used in Examples and Comparative Examples was measured by differential scanning calorimetry (DSC). The calorific value and the heat of fusion observed during the temperature rising of the sample to 300° C. at 10° C./min were calculated, and the crystallinity was calculated by the following formula. The calorific value and the heat of fusion were measured using TA Instruments Q-2000.
- Crystallinity (%) (calorific value of fusion obtained by measurement ⁇ calorific value obtained by measurement)/crystallinity of 100% Polyethylene terephthalate heat of fusion (119 mJ/mg) ⁇ 100 (4) Nijimura
- the liquid crystal cell was taken out from the liquid crystal TV "45UH7500" manufactured by LGD, and the polarizing plate on the backlight side was peeled off.
- the polarizing plate obtained in each of the examples and comparative examples was attached to the surface of the liquid crystal TV from which the polarizing plate was peeled off with an adhesive agent so that the absorption axis of the polarizer was on the short side of the liquid crystal TV.
- the following samples were prepared. A surface of the polarizing plate on which the protective film (polyester film) was not laminated was bonded to a 0.5 mm-thick non-alkali glass via an acrylic pressure-sensitive adhesive to prepare a sample. The obtained sample was put in the test area of the thermal shock tester, and the temperature in the test area was lowered to -40°C over 30 minutes from room temperature. Then, after raising the temperature in the test area to 85° C. over 30 minutes, the temperature was lowered again to ⁇ 40° C. over 30 minutes. The step of raising the temperature from ⁇ 40° C. to 85° C. and lowering it again to ⁇ 40° C.
- a PVA-based resin layer was formed to produce a laminate.
- the obtained laminate was uniaxially stretched 2.0 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 120° C. (in-air auxiliary stretching).
- the laminated body was immersed in an insolubilizing bath having a liquid temperature of 30° C.
- the laminate is immersed in a cleaning bath (liquid solution obtained by mixing 4 parts by weight of potassium iodide with 100 parts by weight of water) having a liquid temperature of 30° C. (cleaning treatment), and a peelable substrate is provided.
- a cleaning bath liquid solution obtained by mixing 4 parts by weight of potassium iodide with 100 parts by weight of water
- a polarizer A was obtained.
- a single-screw extruder manufactured by Toyo Seiki Co., screw diameter 25 mm, cylinder setting temperature: 280° C.), T die (width 500 mm, setting temperature: 280° C.), chill roll (setting temperature: 50) C.
- a film forming apparatus equipped with a winder were used to produce an amorphous polyester resin film having a thickness of 200 ⁇ m.
- the obtained amorphous polyester-based resin film was simultaneously biaxially stretched with a Bruckner stretching machine KAROIV to obtain a polyester film A (slow axis angle to length direction: -0.5°, in-plane phase Re (590): 80 nm, thickness: 17 ⁇ m) was obtained.
- the stretching ratio was 4 times in the length direction (MD) and 3 times in the width direction (TD).
- the stretching temperature was 90° C., and the stretching speed was 30%/sec for both MD and TD. Further, after the stretching treatment, heat treatment was performed at 180° C. for 10 seconds while maintaining the dimensions.
- a single screw extruder manufactured by Toyo Seiki Co., screw diameter 25 mm, cylinder set temperature: 280° C.
- T die width 500 mm, set temperature: 280° C.
- a chill roll set temperature: 50° C.
- the obtained amorphous polyester-based resin film was simultaneously biaxially stretched by a stretching machine KAROIV manufactured by Bruckner Co., Ltd. to obtain a polyester film I (slow axis angle with respect to length direction: ⁇ 2.5°, in-plane phase Re( 590):271 nm and thickness:22 ⁇ m).
- the stretching ratio was 3 times in the length direction (MD) and 3 times in the width direction (TD).
- the stretching temperature was 90° C., and the stretching speed was 2%/sec for both MD and TD. Further, after the stretching treatment, heat treatment was performed at 140° C. for 10 seconds while maintaining the dimensions.
- a single-screw extruder manufactured by Toyo Seiki Co., screw diameter 25 mm, cylinder setting temperature: 280° C.), T die (width 500 mm, setting temperature: 280° C.), chill roll (setting temperature: 50) C.
- a film forming apparatus equipped with a winder were used to produce an amorphous polyester resin film having a thickness of 100 ⁇ m.
- the obtained amorphous polyester-based resin film was simultaneously biaxially stretched by a Bruckner stretching machine KAROIV to obtain a polyester film IV (slow axis angle to length direction: -0.9°, in-plane phase Re (590): 3191 nm, thickness: 38 ⁇ m) were obtained.
- the stretching ratio was 7 times in the length direction (MD) and 1 time in the width direction (TD) in the fixed end stretching.
- the stretching temperature was 90° C., and the stretching speed was 10%/sec for both MD and TD. Further, after the stretching treatment, heat treatment was performed at 140° C. for 10 seconds while maintaining the dimensions.
- Polyester film V (slow axis angle to length direction: 3) was produced in the same manner as in Production Example 7 except that the film-forming thickness was 50 ⁇ m and that stretching was not performed. 0.0°, in-plane phase Re(590): 17 nm, thickness: 50 ⁇ m) were obtained.
- Example 1 Corona treatment is applied to the polyester film A produced in Production Example 3, and the product name “Superflex 210R” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. is 15.2 wt% and the product name manufactured by Nippon Shokubai Co., Ltd. is “WS-700” 2.7 wt%. % Aqueous solution was applied to the coated film so that the film thickness would be 300 ⁇ m after drying, and dried at 80° C. for 1 minute to obtain a polyester film A with an easily adhesive layer.
- a PVA-based resin aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Gosefimer (registered trademark) Z-200”, resin concentration: 3% by weight) was formed on the polarizer surface of the substrate-attached polarizer obtained in Production Example 1. ) was applied, and the polyester film with the easy-adhesion layer was attached. The obtained laminate was heated in an oven maintained at 60°C for 5 minutes. Then, the substrate was peeled from the PVA-based resin layer to obtain a polarizing plate (polarizer (transmittance 42.3%, thickness 5 ⁇ m)/protective film (polyester film)).
- polarizing plate polarizer (transmittance 42.3%, thickness 5 ⁇ m)/protective film (polyester film)
- the polyester film A and the polarizer were laminated so that the MD direction of the polyester film A and the absorption axis direction of the polarizer were substantially parallel to each other.
- the obtained polarizing plate was subjected to the above evaluations (1) to (6). The results are shown in Table 1.
- Example 2 A polarizing plate was obtained in the same manner as in Example 1 except that the polarizer obtained in Production Example 2 was used instead of the polarizer with a substrate obtained in Production Example 1. The obtained polarizing plate was subjected to the above evaluations (1) to (6). The results are shown in Table 1.
- Polarizer 10 Polarizer 20 Polyester Film 30 Adhesive Layer 40 Easy Adhesive Layer 100, 200 Polarizing Plate
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Abstract
Description
1つの実施形態においては、上記ポリエステルフィルムは、DSC測定による結晶化度が、30%以上である。
本発明の別の局面によれば、偏光板が提供される。この偏光板は、偏光子と、偏光子の一方の側に配置された請求項1または2に記載のポリエステルフィルムとを備える。
1つの実施形態においては、上記偏光子の厚みが、20μm以下である。
1つの実施形態においては、上記偏光板は、上記ポリエステルフィルムの上記偏光子側に配置された易接着層をさらに含む。
1つの実施形態においては、上記易接着層が、微粒子を含む。
1つの実施形態においては、上記易接着層の厚みが、0.35μm以下である。
1つの実施形態においては、上記易接着層の屈折率が、1.55以下である。
本発明のポリエステルフィルムは、第1の方向における線膨張係数が、3.5×10-5/℃以下であり、該第1の方向に直交する第2の方向における線膨張係数が、3.5×10-5/℃以下である。このような線膨張係数を備えるポリエステルフィルムを用いれば、偏光子に積層して当該偏光子を有効に保護しつつ、当該偏光子のクラック発生を防止することができる。より詳細には、本発明のポリエステルフィルムを偏光子保護フィルムとして偏光子に積層して偏光板を構成すれば、偏光子の寸法変化(例えば、熱による寸法変化)を上記ポリエステルフィルムにより抑制することができる。その結果、本発明のポリエステルフィルムを用いれば、高温、温度変化の大きい等の過酷な環境下においても、偏光子のクラック発生を防止して、耐久性に優れる偏光板を得ることができる。1つの実施形態においては、上記第1の方向は、ポリエステルフィルムを製造する際の搬送方向(MD)に相当する。また、上記第2の方向はMDに直交するTDに相当し得る。線膨張係数は、JIS K 7197に準じたTMA測定により決定され得る。なお、「略平行」という表現は、2つの方向のなす角度が0°±10°である場合を包含し、好ましくは0°±7°であり、さらに好ましくは0°±5°である。
上記ポリエステルフィルムは、上記ポリエステル系樹脂を含むフィルム形成材料(樹脂組成物)をフィルム状に成形する成形工程、および、該成形されたフィルムを延伸する延伸工程を経て得られ得る。好ましくは、延伸工程は、フィルム延伸の前に行われるフィルムの予熱処理、およびフィルム延伸の後に行われる熱処理を含む。1つの実施形態においては、ポリエステルフィルムは長尺状(または長尺体から切り出した形状)で提供される。
図1は、本発明の1つの実施形態による偏光板の概略断面図である。偏光板100は、偏光子10と、偏光子10の一方の側に配置されたポリエステルフィルム20とを備える。ポリエステルフィルム20としては、上記A項で説明した本発明のポリエステルフィルムが用いられる。偏光子の他方の側には任意の適切な別の偏光子保護フィルムが配置されてもよく、偏光子保護フィルムは配置されなくてもよい。1つの実施形態においては、偏光子10とポリエステルフィルム20(または別の偏光子保護フィルム)は、接着剤層30を介して積層される。
上記偏光板は、画像表示装置に適用され得る。画像表示装置の代表例としては、液晶表示装置、有機エレクトロルミネセンス(EL)表示装置が挙げられる。画像表示装置は業界で周知の構成が採用されるので、詳細な説明は省略する。
実施例および比較例で得られたポリエステルフィルムの中央部を、一辺が当該フィルムの幅方向と平行となるようにして幅50mm、長さ50mmの正方形状に切り出して試料を作成した。この試料を、ミュラーマトリクス・ポラリメーター(Axometrics社製 製品名「Axoscan」)を用いて測定し、波長550nm、23℃における配向角θを測定した。なお、配向角θは測定台に試料を平行に置いた状態で測定した。
(2)線膨張係数
ポリエステルフィルムおよび偏光子の線膨張係数を、JIS K 7197 に基づいて、日立ハイテクサイエンス社製の熱機械分析装置「TMA7000」を用い、30℃から150℃まで10℃/分の速度で昇温して、試験フィルムの各温度における変形量を測定した。そして、30℃~70℃の温度範囲における変形量から、当該フィルムの線膨張係数を求めた。なお、温度上昇に伴ってフィルム寸法が大きくなる(膨張する)場合を正(プラス)とし、温度上昇に伴ってフィルム寸法が小さくなる(収縮する)場合を負(マイナス)とした。
ポリエステルフィルムについてはMD(第1の方向)、TD(第2の方向)の線膨張係数を測定した。偏光子は、偏光板において当該MDに平行な方向および当該TDに平行な方向の線膨張係数を測定した。
(3)結晶化度
示差走査熱量測定(DSC)にて実施例および比較例で用いたポリエステルフィルムの結晶化度を測定した。試料を300℃まで10℃/分で昇温させた昇温中に観測される発熱量および融解熱量を求め、下記式により結晶化度を求めた。なお、発熱量および融解熱量の測定は、TA instruments社製Q-2000を使用して行った。
結晶化度(%)=(測定で得られた融解熱量-測定で得られた発熱量)/結晶化度100%ポリエチレンテレフタレートの融解熱量(119mJ/mg)×100
(4)虹ムラ
LGD社製の液晶TV「45UH7500」から液晶セルを取り出し、バックライト側の偏光板をはがした。当該液晶TVの偏光板をはがした面に、実施例および比較例で得られた偏光板を、粘着剤を介して、偏光子の吸収軸が液晶TVの短辺側になるように貼り合せた。実施例および比較例で得られた偏光板が張り合わされた液晶セルを再度設置し、TVを白表示で点灯させた。
点灯させた液晶TVの、極角60°の角度で、全方位目視確認し、虹ムラの有無を観察した。以下の基準で評価した。
○:虹ムラは認められなかった
△:虹ムラがわずかに認められた
×:虹ムラが顕著に認められた
(5)寸法変化
実施例および比較例で用いたポリエステルフィルムを100mm×100mmに裁断した。その後、100℃の加熱オーブンに24時間入れた後、フィルムを取り出し、再度正確に寸法を測定し、金尺で寸法を確認し、寸法の変化を求めた。また目視でサンプルの状態を確認し、以下の基準で評価した。
○:1mm以上の顕著な収縮がない
×:1mm以上の収縮がある、もしくは変形有り
(6)クラック試験(ヒートショック加速試験)
実施例および比較例で得られた偏光板について、冷熱衝撃試験機(ESPEC製)を用いて、評価を行った。
実施例及び比較例で得られた偏光板を、横50mm×縦150mmに裁断した。その際、偏光子の吸収軸方向が裁断後の偏光板の横方向(短辺)と平行となるサンプルと、偏光子の透過軸方向が裁断後の偏光板の横方向(短辺)と平行となるサンプルとを作製した。偏光板の保護フィルム(ポリエステルフィルム)が積層されていない面と、0.5mm厚の無アルカリガラスとを、アクリル系粘着剤を介して貼り合せ、サンプルを作製した。
得られたサンプルを冷熱衝撃試験機のテストエリアに入れ、室温から30分かけてテストエリア内を-40℃まで降温した。次いで、30分かけてテストエリア内を85℃まで昇温した後、30分かけて-40℃まで再度降温した。この-40℃から85℃に昇温し、再度-40℃まで降温する工程を1サイクルとして、100サイクル、200サイクル繰り返した後、積層体を取り出し、目視にてクラック発生の有無を確認し、以下の基準で評価した。
◎:300サイクル繰り返した後でも、クラックは認められなかった。
○:200サイクル繰り返した後では、クラックは認められなかったが、300サイクル繰り返した後に、クラックが発生していた。
△:100サイクル繰り返した後では、クラックは認められなかったが、200サイクル繰り返した後に、クラックが発生していた。
×:100サイクル繰り返した後に、クラックが発生していた。
基材として、長尺状で、吸水率0.75%、Tg75℃の非晶質のイソフタル酸共重合ポリエチレンテレフタレート(IPA共重合PET)フィルム(厚み:100μm)を用いた。基材の片面に、コロナ処理を施し、このコロナ処理面に、ポリビニルアルコール(重合度4200、ケン化度99.2モル%)およびアセトアセチル変性PVA(重合度1200、アセトアセチル変性度4.6%、ケン化度99.0モル%以上、日本合成化学工業社製、商品名「ゴーセファイマーZ200」)を9:1の比で含む水溶液を25℃で塗布および乾燥して、厚み11μmのPVA系樹脂層を形成し、積層体を作製した。
得られた積層体を、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2.0倍に自由端一軸延伸した(空中補助延伸)。
次いで、積層体を、液温30℃の不溶化浴(水100重量部に対して、ホウ酸を4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(不溶化処理)。
次いで、液温30℃の染色浴に、偏光板が所定の透過率となるようにヨウ素濃度、浸漬時間を調整しながら浸漬させた。本実施例では、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1.5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(染色処理)。
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(架橋処理)。
その後、積層体を、液温70℃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)に総延伸倍率が5.5倍となるように一軸延伸を行った(水中延伸)。
その後、積層体を液温30℃の洗浄浴(水100重量部に対して、ヨウ化カリウムを4重量部配合して得られた水溶液)に浸漬させ(洗浄処理)、剥離可能な基材付き偏光子Aを得た。
水中延伸における延伸倍率を4.6倍としたこと以外は、製造例1と同様にして、剥離可能な基材付き偏光子Bを得た。
ポリエステル樹脂(ポリエチレンテレフタレート、ベルポリエステルプロダクツ社製、イソフタル酸変性量2.5mol%(ポリマー全繰り返し単位の合計に対するmol数)、ジエチレングリコール変性量:1.0mol%(ポリマー全繰り返し単位の合計に対するmol数)、IV値0.77dl/g(フェノール:1,1,2,2,-テトラクロロエタン=6:4混合溶媒 溶液濃度0.4g/dl)を100℃で10時間真空乾燥をした後、単軸押出機(東洋精機社製、スクリュー径25mm、シリンダー設定温度:280℃)、Tダイ(幅500mm、設定温度:280℃)、チルロール(設定温度:50℃)および巻取機を備えたフィルム製膜装置を用いて、厚み200μmの非晶性ポリエステル系樹脂フィルムを作製した。
得られた非晶性ポリエステル系樹脂フィルムをブルックナー社製延伸機KAROIVにて、同時二軸延伸を行い、ポリエステルフィルムA(長さ方向に対する遅相軸角度:-0.5°、面内位相Re(590):80nm、厚み:17μm)を得た。延伸倍率は、長さ方向(MD)に4倍、幅方向(TD)に3倍とした。延伸温度は90℃、延伸速度はMD、TDともに30%/secとした。また、延伸処理後、寸法を維持したまま、180℃で10秒間熱処理を行った。
ポリエステル樹脂(ポリエチレンテレフタレート、ベルポリエステルプロダクツ社製、IV値0.75dl/g(フェノール:1,1,2,2,-テトラクロロエタン=6:4混合溶媒 溶液濃度0.4g/dl)を100℃で10時間真空乾燥をした後、単軸押出機(東洋精機社製、スクリュー径25mm、シリンダー設定温度:280℃)、Tダイ(幅500mm、設定温度:280℃)、チルロール(設定温度:50℃)および巻取機を備えたフィルム製膜装置を用いて、厚み200μmの非晶性ポリエステル系樹脂フィルムを作製した。
得られた非晶性ポリエステル系樹脂フィルムブルックナー社製延伸機KAROIVにて、同時二軸延伸を行い、ポリエステルフィルムI(長さ方向に対する遅相軸角度:-2.5°、面内位相Re(590):271nm、厚み:22μm)を得た。延伸倍率は、長さ方向(MD)に3倍、幅方向(TD)に3倍とした。延伸温度は90℃、延伸速度はMD、TDともに2%/secとした。また、延伸処理後、寸法を維持したまま、140℃で10秒間熱処理を行った。
延伸倍率を長さ方向(MD)に2倍、幅方向(TD)に2倍としたこと、延伸速度をMD、TDともに2%/secとしたこと、延伸処理後に140℃で10秒間熱処理したこと以外は、製造例4と同様にして、ポリエステルフィルムII(長さ方向に対する遅相軸角度:-11.9°、面内位相Re(590):54nm、厚み:50μm)を得た。
延伸倍率を固定端延伸にて長さ方向(MD)に6倍、幅方向(TD)に1倍としたこと、延伸速度をMD、TDともに2%/secとしたこと、延伸処理後140℃で10秒間熱処理したこと以外は、製造例4と同様にして、ポリエステルフィルムIII(長さ方向に対する遅相軸角度:-0.6°、面内位相Re(590):2823nm、厚み:41μm)を得た。
ポリエステル樹脂(ポリエチレンテレフタレート、ベルポリエステルプロダクツ社製、イソフタル酸変性量2.5mol%(ポリマー全繰り返し単位の合計に対するmol数)、ジエチレングリコール変性量:1.0mol%(ポリマー全繰り返し単位の合計に対するmol数)、IV値0.77dl/g(フェノール:1,1,2,2,-テトラクロロエタン=6:4混合溶媒 溶液濃度0.4g/dl)を100℃で10時間真空乾燥をした後、単軸押出機(東洋精機社製、スクリュー径25mm、シリンダー設定温度:280℃)、Tダイ(幅500mm、設定温度:280℃)、チルロール(設定温度:50℃)および巻取機を備えたフィルム製膜装置を用いて、厚み100μmの非晶性ポリエステル系樹脂フィルムを作製した。
得られた非晶性ポリエステル系樹脂フィルムをブルックナー社製延伸機KAROIVにて、同時二軸延伸を行い、ポリエステルフィルムIV(長さ方向に対する遅相軸角度:-0.9°、面内位相Re(590):3191nm、厚み:38μm)を得た。延伸倍率は、固定端延伸にて長さ方向(MD)に7倍、幅方向(TD)に1倍とした。延伸温度は90℃、延伸速度はMD、TDともに10%/secとした。また、延伸処理後、寸法を維持したまま、140℃で10秒間熱処理を行った。
製膜厚みを50μmにしたこと、延伸を行わなかったこと以外は、製造例7と同様にして、ポリエステルフィルムV(長さ方向に対する遅相軸角度:3.0°、面内位相Re(590):17nm、厚み:50μm)を得た。
ポリエステル樹脂(ポリエチレンテレフタレート、ベルポリエステルプロダクツ社製、イソフタル酸変性量2.5mol%(ポリマー全繰り返し単位の合計に対するmol数)、IV値0.77dl/g(フェノール:1,1,2,2,-テトラクロロエタン=6:4混合溶媒 溶液濃度0.4g/dl)を100℃で10時間真空乾燥をした後、単軸押出機(東洋精機社製、スクリュー径25mm、シリンダー設定温度:280℃)、Tダイ(幅500mm、設定温度:280℃)、チルロール(設定温度:50℃)および巻取機を備えたフィルム製膜装置を用いて、厚み170μmの非晶性ポリエステル系樹脂フィルムを作製した。
このフィルムを、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2.0倍に自由端一軸延伸した。
次いで、液温30℃の水に120秒間浸漬させた後、液温73℃の水中に浸漬させながら、周速の異なるロール間で縦方向(長手方向)に総延伸倍率が5.5倍となるように一軸延伸を行った(水中延伸)。
得られた延伸フィルムをブルックナー社製延伸機KAROIVにて、90℃で10秒間熱処理を行い、ポリエステルフィルムVI(長さ方向に対する遅相軸角度:-0.2°、面内位相Re(590):3243nm、厚み:35μm)を得た。
製造例9と同様にして延伸フィルムを得た。
得られた延伸フィルムをブルックナー社製延伸機KAROIVにて、90℃で10秒間、さらに140℃で10秒間熱処理を行い、ポリエステルフィルムVII(長さ方向に対する遅相軸角度:-0.4°、面内位相Re(590):4052nm、厚み:35μm)を得た。
製造例3で製造したポリエステルフィルムAにコロナ処理を行い、第一工業製薬社製の商品名「スーパーフレックス210R」15.2wt%と、日本触媒社製の商品名「WS-700」2.7wt%を溶解させた水溶液を乾燥後膜厚が300μmになるように塗工し、80℃で1分間乾燥させた易接着層付ポリエステルフィルムAを得た。
製造例1で得た基材付き偏光子の偏光子表面に、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%)を塗布して、上記易接着層付ポリエステルフィルムを貼り合わせた。得られた積層体を60℃に維持したオーブンで5分間加熱した。その後、基材をPVA系樹脂層から剥離し、偏光板(偏光子(透過率42.3%、厚み5μm)/保護フィルム(ポリエステルフィルム))を得た。なお、ポリエステルフィルムAと偏光子とは、ポリエステルフィルムAのMD方向と偏光子の吸収軸方向とが略平行となるようにして積層した。
得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例1で得た基材付き偏光子に代えて、製造例2で得た偏光子を用いたこと以外は、実施例1と同様にして偏光板を得た。 得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例3で製造したポリエステルフィルムAに代えて、製造例4で製造したポリエステルフィルムIを用いたこと以外は、実施例1と同様にして偏光板を得た。
得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例3で製造したポリエステルフィルムAに代えて、製造例5で製造したポリエステルフィルムIIを用いたこと以外は、実施例1と同様にして偏光板を得た。
得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例3で製造したポリエステルフィルムAに代えて、製造例6で製造したポリエステルフィルムIIIを用いたこと以外は、実施例1と同様にして偏光板を得た。
得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例3で製造したポリエステルフィルムAに代えて、製造例7で製造したポリエステルフィルムIVを用いたこと以外は、実施例1と同様にして偏光板を得た。
得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例3で製造したポリエステルフィルムAに代えて、ポリエステルフィルムa(東洋紡社製、商品名「コスモシャインA4100」、長さ方向に対する遅相軸角度:90°、面内位相Re(590):7800nm、厚み:75μm)を用いたこと以外は、実施例1と同様にして偏光板を得た。
得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例3で製造したポリエステルフィルムAに代えて、ポリエステルフィルムb(三菱ケミカル社製、商品名「T100-J25」、長さ方向に対する遅相軸角度:27°、面内位相Re(590):525nm、厚み:25μm)を用いたこと以外は、実施例1と同様にして偏光板を得た。
得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例3で製造したポリエステルフィルムAに代えて、製造例8で製造したポリエステルフィルムVを用いたこと以外は、実施例1と同様にして偏光板を得た。
得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例3で製造したポリエステルフィルムAに代えて、製造例9で製造したポリエステルフィルムVIを用いたこと以外は、実施例1と同様にして偏光板を得た。
得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例3で製造したポリエステルフィルムAに代えて、製造例10で製造したポリエステルフィルムVIIを用いたこと以外は、実施例1と同様にして偏光板を得た。
得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例1で得た基材付き偏光子に代えて、製造例2で得た偏光子を用いたこと以外は、比較例1と同様にして偏光板を得た。得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例1で得た基材付き偏光子に代えて、製造例2で得た偏光子を用いたこと以外は、比較例3と同様にして偏光板を得た。得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
製造例1で得た基材付き偏光子に代えて、製造例2で得た偏光子を用いたこと以外は、比較例8と同様にして偏光板を得た。得られた偏光板を上記評価(1)~(6)に供した。結果を表1に示す。
20 ポリエステルフィルム
30 接着剤層
40 易接着層
100、200 偏光板
Claims (8)
- 第1の方向における線膨張係数が、3.5×10-5/℃以下であり、
該第1の方向に直交する第2の方向における線膨張係数が、3.5×10-5/℃以下であり、
該第1の方向に対して、-5°~5°の方向に遅相軸を有する、
ポリエステルフィルム。 - DSC測定による結晶化度が、30%以上である、請求項1に記載のポリエステルフィルム。
- 偏光子と、偏光子の一方の側に配置された請求項1または2に記載のポリエステルフィルムとを備える、偏光板。
- 前記偏光子の厚みが、20μm以下である、請求項3に記載の偏光板。
- 前記ポリエステルフィルムの前記偏光子側に配置された易接着層をさらに含む、請求項3または4のいいずれかに記載の偏光板。
- 前記易接着層が、微粒子を含む、請求項5に記載の偏光板。
- 前記易接着層の厚みが、0.35μm以下である、請求項5または6に記載の偏光板。
- 前記易接着層の屈折率が、1.55以下である、請求項5から7のいずれかに記載の偏光板。
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