WO2024058058A1 - ポリエステルフィルムとその用途 - Google Patents
ポリエステルフィルムとその用途 Download PDFInfo
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- WO2024058058A1 WO2024058058A1 PCT/JP2023/032746 JP2023032746W WO2024058058A1 WO 2024058058 A1 WO2024058058 A1 WO 2024058058A1 JP 2023032746 W JP2023032746 W JP 2023032746W WO 2024058058 A1 WO2024058058 A1 WO 2024058058A1
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- film
- polyester film
- polyester
- display
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- 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
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- 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
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
- C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
- C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
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- 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 with excellent heat resistance and bending resistance, a polyester film for foldable displays, a hard coat film for foldable displays, a foldable display, and a mobile terminal device.
- the present invention relates to a back protective film for a foldable display, a foldable display, and a mobile terminal device in which image distortion is unlikely to occur.
- mobile terminal devices As mobile terminal devices become thinner and lighter, mobile terminal devices typified by smartphones are becoming more widespread. While mobile terminal devices are required to have various functions, they are also required to be convenient. Therefore, the popular mobile terminal devices must have a small screen size of about 6 inches because they can be easily operated with one hand and are intended to be stored in clothing pockets.
- tablet terminals with a screen size of 7 inches to 10 inches are expected to be used not only for video content and music, but also for business purposes, drawing purposes, reading, etc., and have high functionality.
- it cannot be operated with one hand has poor portability, and has problems in terms of convenience.
- Patent Document 1 a method has been proposed to make the display compact by connecting multiple displays (see Patent Document 1).
- Patent Document 1 since the bezel portion remains, the image is cut off, resulting in a problem of reduced visibility, and it has not become popular.
- the surface of the display could be protected with a non-flexible material such as glass.
- a folding display when a one-page display is created through the folding portion, it is necessary to use a hard coat film or the like that is flexible and capable of protecting the surface.
- Plastic films have excellent flexibility, and polyester films are especially suitable in terms of mechanical properties, optical properties, and price.
- polyester films when the device itself becomes hot during operation, or when the device is placed in a high-temperature environment such as in a car, it can easily become deformed, distorting the image.
- foldable displays since the folded portion is repeatedly folded, the film in that portion deforms over time, causing problems such as distorting the image of the folded portion displayed on the display.
- films are used in various parts of foldable displays, including not only surface protection films, but also polarizing plates, retardation plates, touch panel base materials, display cell base materials such as organic EL, and back protection members. These films were also required to have durability against repeated folding.
- Patent Document 2 a method of partially changing the film thickness has also been proposed.
- Patent Document 2 See Patent Document 2.
- the manufacturing process is complicated because the film thickness is changed, and there is a problem that mass productivity is poor.
- the present invention aims to solve the above-mentioned problems with conventional display members, and is superior in heat resistance and mass production.
- To provide a polyester film for a foldable display in order to make it possible to provide a foldable display that is less likely to cause damage, and a mobile terminal device equipped with such a foldable display.
- the present invention aims to provide a polyester film for foldable displays that does not easily cause creases in the folded portion even when folded in a high temperature range.
- the present invention typically consists of the following configuration.
- a polyester film having a tan ⁇ of 0.040 or less at 100° C. obtained by dynamic viscoelasticity measurement by tension in at least one direction of the longitudinal direction and the width direction. 2.
- the thickness is 10 to 125 ⁇ m, and the high temperature hold angle at 60°C is 100° or more in either the longitudinal direction or the width direction, and the high temperature hold angle at 85°C is 80° or more.
- the high temperature hold angle refers to the folding angle that occurs after the polyester film is fixed for 18 hours under heating at 60°C or 85°C so that a strain of 1.7% is generated on both surfaces of the bent portion. refers to the angle formed by 3.
- the polyester film of the present invention maintains good mass productivity, is resistant to deformation even after being repeatedly folded under high temperature conditions, and is resistant to image distortion at the folded portion of the display even when used in foldable displays. .
- a mobile terminal device equipped with a foldable display using a polyester film as described above provides beautiful images even when folded repeatedly, is highly functional, and has excellent convenience such as portability.
- FIG. 2 is a schematic diagram showing a foldable display and a bending radius when folded. It is a schematic diagram for showing the bending direction of the polyester film in the present invention.
- FIG. 3 is a schematic diagram for explaining a method of measuring a high temperature hold angle in a bending direction. An enlarged schematic diagram of a sample film (number 3) sandwiched between two PTFE plates is shown. A schematic diagram of an outward-bending foldable smartphone and a foldable display is shown.
- display used in the present invention generally refers to display devices, and types of displays include LCDs, organic EL displays, inorganic EL displays, LEDs, and FEDs.
- LCDs organic EL displays
- inorganic EL displays that have a bendable structure.
- Organic EL displays and inorganic EL displays are more preferred because they can reduce the layer structure, and organic EL displays are particularly preferred because they have a wide color gamut.
- a foldable display is a single continuous display that can be folded into two for carrying. By folding it, you can reduce the size by half and improve portability.
- the bending radius of the foldable display is preferably 5 mm or less, more preferably 3 mm or less. If the bending radius is 5 mm or less, it is possible to make the foldable display thinner in the folded state. It can be said that the smaller the bending radius, the better.
- the foldable display of the present invention can suppress the occurrence of crease marks in the polyester film even when used with such a bending radius.
- the bending radius of the foldable display is preferably 0 to 5 mm, more preferably 0 to 3 mm. If the bending radius is 5 mm or less, the folded state can be made thinner. The smaller the bending radius is, the better, but it may be 0.1 to 5 mm, 0.1 to 3 mm, 0.5 to 3 mm, 0.5 to 5 mm, or 1 to 5 mm. Even if the bending radius is 1 to 5 mm, it is possible to achieve a practically sufficient thickness reduction in the folded form compared to a display without a folding structure.
- the bending radius when folded is the value measured at the point 11 of the foldable display 1 in the schematic diagram of FIG. 1, and means the inner radius of the folded portion when folded.
- the surface protection film which will be described later, may be located on the outside of the folded display, or may be located on the inside of the folded display.
- the foldable display may be folded in three or four, or may be a roll-up type called a rollable display, and all of these fall within the scope of the foldable display in the present invention.
- polyester film of the present invention can be used for folding displays not only by folding in the longitudinal direction as shown in FIG. 1 but also by folding in the width direction.
- the foldable display may be bent outward or bent inward.
- Inward-bending type foldable displays have a display located on the inside when folded, and normally the display cannot be viewed in the folded state.
- the display In a foldable display that bends outward, the display is located on the outside when folded, and the display can be viewed even in the folded state ( Figure 5).
- the polyester film of the present invention can be used in any embodiment.
- the polyester film of the present invention may be placed either on the outside or inside of the display, or may be placed on both the outside and inside of the display.
- the polyester film of the present invention does not easily leave fold marks even with a small bending radius, so it can be used in such various embodiments.
- the polyester film for foldable displays of the present invention may be used in any component of foldable displays.
- FIG. 5 shows a diagram schematically showing the structure of a foldable display.
- a typical structure of a foldable display and a portion to which the polyester film of the present invention can be used will be explained using an organic EL display as an example.
- the polyester film for foldable displays of the present invention may be simply referred to as the polyester film of the present invention.
- a foldable organic EL display has an organic EL module as an essential component, but is further provided with a circularly polarizing plate, a touch panel module, a front protection film, a back protection film, etc., as necessary.
- Organic EL module The general structure of an organic EL module consists of an electrode/electron transport layer/light emitting layer/hole transport layer/transparent electrode.
- the polyester film of the present invention can be used as a base material on which an electrode is provided, and further an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode are provided. In particular, it can be preferably used as a base material for transparent electrodes.
- the polyester film of the present invention is preferably provided with a barrier layer such as a metal oxide layer. In order to improve barrier properties, a plurality of barrier layers may be provided, or a plurality of polyester films each provided with a barrier layer may be used.
- the mobile terminal device has a touch panel.
- a touch panel module is disposed above the organic EL display or between the organic EL module and the circularly polarizing plate.
- a touch panel module has a transparent base material such as a film and a transparent electrode disposed on the transparent base material.
- the polyester film of the present invention can be used as this transparent substrate.
- the polyester film is preferably provided with a hard coat layer or a refractive index adjusting layer.
- the circularly polarizing plate prevents external light from being reflected by members inside the display and deteriorating image quality.
- the circularly polarizing plate includes a linearly polarizing plate and a retardation plate.
- the linearly polarizing plate has a protective film on at least the viewing side.
- a protective film may also be provided on the surface of the linearly polarizing plate opposite to the viewing side, or a retardation plate may be directly laminated on the linearly polarizing plate.
- the retardation plate used is a resin film having a retardation such as polycarbonate or cyclic olefin, or a resin film provided with a retardation layer made of a liquid crystal compound.
- the polyester film of the present invention can be used as a polarizer protective film or a resin film for a retardation plate.
- the slow axis direction of the polyester film of the present invention be parallel or perpendicular to the absorption axis direction of the polarizer. Note that a deviation of up to 10 degrees, preferably up to 5 degrees with respect to this parallel or perpendicular direction is allowed.
- the polyester film of the present invention can be used as this surface protection film.
- the polyester film of the present invention can be used as any film.
- the after-film is a film that is attached to the cover window by the manufacturer during the manufacturing process to protect the cover window, or a replaceable film that is attached to the cover window by the user.
- the polyester film of the present invention is used as a surface protection film, it is preferable that a hard coat layer is laminated on at least the surface side of the polyester film.
- the polyester film is provided on the surface of the foldable display with the hard coat layer facing the viewing side. Note that the hard coat layer may be provided on both sides of the polyester film.
- back side protective film It is also preferable that a protective film is provided on the back side of the display. Specifically, an adhesive layer is provided on the non-visible side of the organic EL module, and a protective film is attached.
- the polyester film of the present invention can be used as a protective film on the back side.
- the polyester film of the present invention may be used for purposes other than those described above, as long as it is used in a folded part of a foldable display component.
- the polyester film of the present invention is preferably used for a cover window surface protection film, a surface protection film as an aftermarket product, a touch panel module base film, and a back surface protection film. It is preferable to use it as a cover window surface protection film or a surface protection film as an aftermarket product.
- the polyester film of the present invention does not need to be used for all of the above films.
- polyimide films, polyamide films, polyamide-imide films, polyester films other than the polyester film of the present invention polycarbonate films, acrylic films, triacetyl cellulose films, cycloolefin polymer films, polyphenylene Sulfide films, polymethylpentene films, and the like can be appropriately selected and used depending on the purpose of use and the like.
- the polyester film of the present invention may be a single layer film or a multilayer film having two or more layers, and each layer constituting the multilayer film may contain the same polyester resin or may contain different polyester resins. . Furthermore, the multilayer film may have a super multilayer structure in which different layers are alternately and repeatedly laminated. The multilayer film may have a structure of 2 to 30 layers, or a structure of 2 to 20 layers, for example.
- the polyester film may be a single layer film made of one or more types of polyester resin. When two or more types of polyester resins are used, the polyester film may be a multilayer film having a super multilayer structure, or may be another multilayer film.
- polyester resin used in the polyester film examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene-2,6-naphthalate, or copolymers containing the constituent components of these resins as main components. Can be mentioned. Among these, polyethylene naphthalate film, particularly stretched polyethylene naphthalate film, is preferred from the viewpoint of mechanical properties, heat resistance, transparency, and the like.
- the polyester film contains polyethylene naphthalate resin as a main component (for example, more than 50% by mass).
- the polyester film may further contain other polyester resins, and the content thereof is, for example, less than 50% by mass, 40% by mass or less, and 10% by mass or less, based on 100% by mass of the polyester film. Generally, it is preferably 5% by weight or less, and more preferably less than 5% by weight. When the content of other polyester resins is less than 5% by mass, the crystallinity of the polyester film can be maintained highly, and the high temperature hold angle can be maintained well.
- the content thereof is, for example, 0.1% by mass or more and less than 50% by mass, 0.1 to 40% by mass, 0.1% by mass, based on 100% by mass of the polyester film. It can be 10% by mass, 0.1% by mass to 5% by mass, 0.1% by mass or more and less than 5% by mass, etc.
- the content of polyethylene naphthalate resin in the polyester film may be more than 50% by mass, 60% by mass or more, 90% by mass or more, preferably 95% by mass or more, and 95% by mass or more, based on the mass of the polyester film. More preferably more than %.
- the proportion of polyethylene naphthalate in the raw material ratio of the polyester film is 100% by weight.
- a polyester film may contain multiple types of polyethylene naphthalates with different characteristics. By increasing the proportion of polyethylene naphthalate, deformation of the polyester film after folding in a high temperature region is suppressed, and image disturbance at the folded portion of the display can be suppressed.
- a mobile terminal device equipped with a foldable display using the polyester film of the present invention provides beautiful images, is rich in functionality, and has excellent convenience such as portability.
- examples of the dicarboxylic acid component of the polyester include aliphatic dicarboxylic acids such as adipic acid and sebacic acid; terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalene dicarboxylic acid. aromatic dicarboxylic acids such as; and polyfunctional carboxylic acids such as trimellitic acid and pyromellitic acid.
- glycol components of polyester include, for example, fatty acid glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, propylene glycol, and neopentyl glycol; aromatic glycols such as p-xylene glycol; Examples include alicyclic glycols such as methanol; polyethylene glycols having an average molecular weight of 150 to 20,000.
- the preferred mass ratio of the copolymer components in the polyester copolymer is less than 3% by mass. When the amount is less than 3% by mass, film strength, transparency, and heat resistance are maintained, which is preferable.
- the intrinsic viscosity of the resin pellets as a raw material for the polyester film is preferably in the range of 0.40 to 1.0 dl/g.
- the intrinsic viscosity is 0.40 dl/g or more, the impact resistance of the obtained film is improved and the internal circuit of the display is less likely to be disconnected due to external impact, which is preferable. It is preferable that the intrinsic viscosity is 1.00 dl/g or less because it is easy to stably operate film production without increasing the filtration pressure of the molten fluid too much.
- the intrinsic viscosity of all of these multiple types of resin pellets may be in the range of 0.40 to 1.0 dl/g, and at least one type of pellet may have an intrinsic viscosity in the range of 0.40 to 1.0 dl/g.
- the intrinsic viscosity of the main component resin pellets is in the range of 0.40 to 1.0 dl/g.
- the intrinsic viscosity of the polyester film is preferably in the range of 0.40 to 0.95 dl/g. It is preferable that the film has an intrinsic viscosity of 0.40 dl/g or more, since the impact resistance of the obtained film is improved and the internal circuit of the display is less likely to be disconnected due to external impact. It is preferable that the intrinsic viscosity is 0.95 dl/g or less, since the filtration pressure of the molten fluid will not increase too much and it will be easy to stably operate the film production.
- the thickness of the polyester film is, for example, 10 ⁇ m to 125 ⁇ m, preferably 25 ⁇ m to 100 ⁇ m.
- the thickness is 10 ⁇ m or more, the effect of improving pencil hardness and impact resistance is improved, and when the thickness is 125 ⁇ m or less, it is advantageous for weight reduction, and also has excellent flexibility, workability, and handling properties.
- the surface of the polyester film may be smooth or uneven. When used as a display cover window, it is preferable to have a smooth film surface.
- the haze of the polyester film is preferably 3% or less, more preferably 2% or less, particularly preferably 1.3% or less. When the haze is 3% or less, image visibility can be improved.
- the lower limit of haze is better, but from the viewpoint of stable production, it is preferably 0.1% or more, and may be 0.3% or more. Haze is, for example, 0.1-3%, 0.1-2%, 0.1-1.3%, 0.3-3%, 0.3-2%, 0.3-1.3%, etc. It can be done.
- the film may have irregularities.
- irregularities can be formed by adding particles to the polyester film disposed on the surface layer, by coating the polyester film with a coating layer containing particles during film formation, and the like.
- particles can be added at any stage of manufacturing the polyester.
- a slurry of particles dispersed in ethylene glycol or the like is added, and the polycondensation reaction is allowed to proceed. good.
- a method of blending a slurry of particles dispersed in ethylene glycol or water with a polyester raw material using a kneading extruder with a vent, or a method of blending dried particles and a polyester raw material using a kneading extruder Particles can be mixed using methods such as
- the filtered particles are added to the remainder of the polyester raw material before, during, or after the esterification reaction.
- the addition method is preferred as a method for blending particles. According to this method, since the monomer liquid has a low viscosity, homogeneous dispersion of particles and high-precision filtration of slurry can be easily performed. Aggregates are also less likely to occur. From this point of view, it is particularly preferable to homogeneously disperse inorganic particles in the remainder of the raw material in a low temperature state before the esterification reaction, and then add the resultant mixture after filtration.
- the number of protrusions on the film surface can be further reduced by a method (masterbatch method) in which a polyester containing particles is obtained in advance and then the pellets are kneaded and extruded with pellets not containing particles.
- the tan ⁇ obtained by dynamic viscoelasticity measurement by stretching the polyester film in the width direction or longitudinal direction is preferably smaller, and tan ⁇ at 100° C. is preferably 0 to 0.040, more preferably 0 to 0.038.
- Tan ⁇ in dynamic viscoelasticity measurement is determined from the ratio of loss modulus to storage modulus, and the smaller tan ⁇ indicates that the film maintains its elasticity. It has high elasticity compared to viscosity, and if the elasticity is maintained, irreversible deformation is less likely to occur, and bending resistance is also less likely to cause crease marks.
- tan ⁇ can be adjusted by the stretching ratio and temperature conditions, it can be adjusted more effectively by heat treatment (BTA treatment) after film formation.
- BTA treatment heat treatment
- Examples include aging and annealing treatments.
- An example of the annealing treatment includes heating below the Tg of the polyester film, preferably at 90°C to 120°C, more preferably at 95°C to 115°C. By keeping the temperature within the above range, the amorphous region can be effectively changed. It is preferable to heat at the above temperature for 6 hours or more, preferably 12 hours or more, more preferably 24 hours or more, and then return to room temperature over 1 hour or more, preferably 6 hours or more, and even more preferably 12 hours or more.
- the polyester film may contain various additives within the range that maintains the preferable range of total light transmittance.
- additives include antistatic agents, UV absorbers, and stabilizers.
- the total light transmittance of the polyester film is preferably 85% or more, more preferably 87% or more. If the transmittance is 85% or more, visibility can be sufficiently ensured. It can be said that the higher the total light transmittance of the polyester film, the better, but from the standpoint of stable production, it is preferably 99% or less, and may be 97% or less.
- the total light transmittance of the polyester film may be 85-99%, 85-97%, 87-99%, 87-97%.
- the maximum thermal shrinkage rate of the polyester film after heat treatment at 150° C. for 30 minutes may be 2% or less, preferably 1.5% or less, and more preferably 1.2% or less. If the maximum thermal shrinkage rate is 2% or less, dimensional changes due to heat generation of the organic EL display itself can be suppressed. It can be said that the lower the maximum thermal shrinkage rate, the better, but it is preferably ⁇ 1% or more, and preferably 0% or more. The negative value here means that the material expanded after heating, and if it is less than -1%, flatness may be defective.
- the maximum heat shrinkage rate of polyester film after heat treatment at 150°C for 30 minutes is -1 to 2%, -1 to 1.5%, -1 to 1.2%, 0 to 2%, 0 to 1.5%, It may be 0 to 1.2%.
- One or both sides of the polyester film of the present invention can be treated to improve adhesion with the resin forming the hard coat layer or the like.
- the treatment for improving adhesion may be, for example, a method of treating the surface of the polyester film, a method of providing an adhesion-improving layer on the surface of the polyester film, or the like.
- surface treatment methods include sandblasting, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone and ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc. can be used without particular limitation.
- an adhesion-improving layer such as an easy-adhesion layer between the polyester film and the hard coat layer
- an adhesion-improving layer such as an easy-adhesion layer between the polyester film and the hard coat layer
- the resin for forming the easily adhesive layer acrylic resin, polyester resin, polyurethane resin, polyether resin, etc. can be used without particular limitation, and the easily adhesive layer can be formed by a general coating method, preferably a so-called in-line coating method.
- the above-mentioned polyester film is produced by, for example, homogeneously dispersing inorganic particles in a monomer liquid that is part of the polyester raw material, filtering it, and adding the inorganic particles in the form of a slurry to the remainder of the polyester raw material to polymerize the polyester. It can be manufactured through a polymerization step and a film forming step in which the polyester is melt-extruded into a sheet through a filter, cooled, and stretched to form a base film.
- PET polyethylene terephthalate
- the number of layers is not limited, such as a single layer structure or a multilayer structure. Note that even in an embodiment in which a polyethylene naphthalate (PEN) film is used instead of a PET film, the polyester film according to the present invention can be manufactured by the same method.
- PEN polyethylene naphthalate
- PET pellets After PET pellets are mixed at a predetermined ratio and dried, they are fed to a known extruder for melt lamination, extruded into a sheet through a slit-shaped die, and cooled and solidified on a casting roll to form an unstretched film. .
- an unstretched film can be formed using one extruder, but when producing a film with a multilayer structure, two or more extruders and a manifold with two or more layers are required.
- a merging block for example, a merging block with a square merging part
- a merging block to laminate multiple film layers constituting each outermost layer, extrude two or more layers of sheets from a die, cool them with a casting roll, and leave them unused.
- a stretched film can be formed.
- the filter medium used for high-precision filtration of molten resin is not particularly limited, but a filter medium of stainless steel sintered body has excellent ability to remove aggregates and high melting point organic substances mainly composed of Si, Ti, Sb, Ge, and Cu. Therefore, it is preferable.
- the filtration particle size (initial filtration efficiency of 95%) of the filter medium is preferably 20 ⁇ m or less, particularly preferably 15 ⁇ m or less.
- the filtration particle size (initial filtration efficiency of 95%) of the filter medium exceeds 20 ⁇ m, foreign matter having a size of 20 ⁇ m or more cannot be sufficiently removed.
- the refractive index of the polyester film in at least one of the longitudinal direction (machine flow direction) and the width direction is preferably 1.610 to 1.750, for example, 1.610 to 1.710, More preferably, it is 1.630 to 1.680. It is preferable that the refractive index in at least one of the longitudinal direction and the width direction is 1.610 to 1.750, since there is little deformation when repeatedly folded and there is no risk of degrading the image quality of the foldable display.
- the degree of crystallinity can be efficiently improved, and the high-temperature hold angle can be improved. If it is 1.750 or less, stress during bending can be lowered, and both the hold angle at room temperature and the hold angle at high temperature can be improved.
- the refractive index in the width direction of the polyester film is within the above range, it is desirable that the refractive index in the longitudinal direction of the polyester film is higher than the refractive index in the width direction of the polyester film.
- the refractive index of the polyester film in the bending direction is preferably 1.610 to 1.750, for example, 1.610 to 1.710, and more preferably 1.630 to 1.680.
- the refractive index in the bending direction is 1.610 or more, the degree of crystallinity can be efficiently improved and the high temperature hold angle can be improved.
- the refractive index in the bending direction is 1.750 or less, stress during bending can be lowered, and both the hold angle at room temperature and the hold angle at high temperatures can be improved.
- the bending direction is the direction indicated by the reference numeral 22 on the polyester film (reference numeral 2) in FIG. There is.
- the refractive index of the polyester film in the bending direction is more preferably 1.630 to 1.680.
- the refractive index of the polyester film can be effectively adjusted by adjusting the stretching ratio and stretching temperature. Further, in order to adjust the refractive index, a relaxation process in the stretching direction or multistage stretching may be used. When performing multi-stage stretching, it is preferable to set the stretching ratio in the second and subsequent stages higher than the stretching ratio in the first stage.
- the folding effect can be improved during folding. Fatigue due to compressive stress applied to the inside can be reduced. Fatigue due to compressive stress is thought to occur mainly in crystal parts, and the fewer crystals in the bending direction, the less fatigue occurs. Therefore, since the refractive index in the bending direction is smaller than the refractive index in the direction perpendicular to the bending direction, the amount of oriented crystals in the bending direction is reduced, and fatigue due to compressive stress is suppressed.
- the creep phenomenon caused by the tensile stress applied to the outside of the fold during folding can be suppressed by reducing the refractive index.
- Fatigue due to tensile stress is thought to occur mainly in the amorphous region, and repeated stress causes molecular chains to be aligned, resulting in deformation. It can be inferred that the fewer molecular chains are aligned in the bending direction, the less deformation will occur due to alignment.
- the crystallinity that is, the density is high.
- the stretching ratio of the unstretched polyester sheet in at least one of the longitudinal direction (machine flow direction) and the width direction is preferably 1.0 to 3.4 times, and 1.4 to 2.3 times. is even more preferable.
- the stretching direction in which the magnification is given is preferably the bending direction when the polyester film is used in a folding display. It is preferable that the stretching ratio is 3.4 times or less because uneven thickness of the film does not occur.
- the stretching temperature is preferably 120°C to 150°C, more preferably 125°C to 145°C.
- conventionally known means such as a hot air heating method, a roll heating method, an infrared heating method, etc. can be employed. By setting the stretching temperature to 125° C. to 145° C., large thickness unevenness due to stretching at the above-mentioned stretching ratio can be prevented.
- the polyester film preferably has a refractive index of 1.750 to 1.870 in a direction in which the refractive index is 1.610 to 1.750 and in a direction perpendicular to that direction.
- the polyester film has a refractive index of 1.610 to 1.750 in the bending direction, and a refractive index of 1.750 to 1.870 in a direction perpendicular to the bending direction (folding direction).
- the refractive index in the direction of the folded portion By setting the refractive index in the direction of the folded portion to 1.870 or less, it is possible to suppress the occurrence of cracks in the direction of the folded portion, and further suppress the occurrence of breakage. Moreover, breakage in the winding process after stretching can be suppressed.
- the refractive index in the direction of the folded portion By setting the refractive index in the direction of the folded portion to 1.750 or more, the density of the polyester film can be increased and the high temperature hold angle can be improved.
- the direction perpendicular to the bending direction corresponds to the width direction of the polyester film.
- the refractive index in the direction perpendicular to the bending direction is more preferably 1.750 to 1.830. Further, when comparing the refractive index in the bending direction and the refractive index in a direction perpendicular to the bending direction (folding section direction), it is desirable that the refractive index in the bending direction is low. Since the refractive index in the bending direction is lower than the refractive index in the folding direction, deformation when folded in the bending direction can be reduced. Moreover, it is possible to suppress the occurrence of cracks in the direction of the folded portion, and it is also possible to suppress the occurrence of breakage. Moreover, breakage in the winding process after stretching can be suppressed.
- the density can be increased and the high temperature hold angle can be improved.
- methods for adjusting the refractive index in the direction orthogonal to the bending direction include methods for adjusting the stretching ratio, stretching preheating temperature, stretching temperature, multistage stretching, film relaxation, etc. in the direction.
- the stretching ratio in the direction perpendicular to the bending direction is preferably 3.3 to 5.0 times, more preferably 3.5 to 4.5 times.
- the stretching preheating temperature in the direction perpendicular to the bending direction is preferably 125 to 145°C.
- the stretching ratio in the second stage and subsequent stages is higher than that in the first stage.
- the film may be relaxed by 0 to 10% in either the machine flow direction (longitudinal direction) or the vertical direction (width direction).
- the refractive index in the thickness direction is preferably 1.520 or less. It is more preferably 1.515 or less, still more preferably 1.510 or less, particularly preferably 1.505 or less, and most preferably 1.500 or less.
- the refractive index in the thickness direction is preferably low, but in terms of stable production, it is preferably 1.300 or more, more preferably 1.400 or more, particularly preferably 1.410 or more.
- the refractive index in the thickness direction is 1.300-1.520, 1.300-1.515, 1.300-1.510, 1.300-1.500, 1.400-1.520, 1.400- 1.515, 1.400-1.510, 1.400-1.500, 1.410-1.520, 1.410-1.515, 1.410-1.510, 1.410-1. It may be 500.
- the density of the polyester film is 1.349 g/cm 3 or more. More preferably, it is 1.350 g/cm 3 or more. By setting it to 1.349 g/cm 3 or more, the high temperature hold angle can be improved. Although the density depends somewhat on the presence or absence of particles in the film, it is preferably 1.400 g/cm 3 or less, and more preferably 1.395 g/cm 3 or less.
- the density of the polyester film is 1.349-1.400g/cm 3 , 1.349-1.395g/cm 3 , 1.350-1.400g/cm 3 , 1.350-1.395g/cm 3 There may be.
- the polyester film of the present invention can be sufficiently crystallized and deformation at 85° C. can be suppressed. Further, it is possible to suppress an increase in the thermal shrinkage rate, and it is possible to suppress dimensional changes due to heat generation of the device. By setting the heat setting temperature at 210 to 270° C. during film formation, crystallization can proceed and the density can be effectively increased within the above range.
- the bending direction of the polyester film corresponds to the longitudinal direction (machine flow direction). By doing so, it is easy to lower the refractive index in the bending direction at the biaxial stretching stitches, and it is easy to improve the flexibility. That is, it is preferable to stretch the unstretched polyester sheet in the longitudinal direction at a stretching ratio of 1.0 to 3.5 times, preferably 1.0 to 3.3 times, more preferably 1.0 to 2.4 times.
- a polyester film can be obtained. It can be said that a preferred embodiment is stretching in the width direction at a stretching ratio of 3.3 to 5.0 times, more preferably 3.5 to 4.5 times.
- the polyester film of the present invention has a high temperature hold angle of 100° or more at 60°C in either the longitudinal direction or the width direction, and a high temperature hold angle of 80° or more at 85°C.
- the high temperature hold angle means that the polyester film is fixed for 18 hours under heating at a predetermined temperature (for example, 60°C or 85°C) so that a strain of 1.7% is generated on both surfaces of the bent portion. Refers to the angle formed by the crease that occurs afterwards.
- the high temperature hold angle may be 101° or more and 102° or more under 60°C heating conditions, and may be 81° or more and 82°C or more under 85°C heating conditions.
- the high temperature hold angle under the 60° C. heating condition may be 100-180°, 110-180°, 120-180, 100-170°, 110-170°, 120-170°.
- the high temperature hold angle under the 85°C heating condition was 100-180°, 105-180°, 100-170°, 105-170°, 100-160°, 105-160°, 100-150°, 105-150°. It's fine.
- a mobile terminal device equipped with a foldable display using the polyester film of the present invention provides beautiful images, is rich in functionality, and has excellent convenience such as portability. Note that a method for measuring the high temperature hold angle in the bending direction will be exemplified in Examples.
- the easy-adhesion layer is formed by applying a coating solution for forming an easy-adhesion layer to one or both sides of an unstretched or longitudinally uniaxially stretched film, then subjecting it to heat treatment and drying as necessary, and then applying the coating solution to at least one unstretched direction. It can be obtained by stretching. Heat treatment and drying can also be performed after biaxial stretching.
- the final coating amount of the adhesive layer is preferably controlled to 0.005 to 0.20 g/m 2 . It is preferable that the coating amount is 0.005 g/m 2 or more because adhesiveness is improved. On the other hand, it is preferable that the coating amount is 0.20 g/m 2 or less because blocking resistance improves.
- the resin to be contained in the coating liquid used for laminating the easily adhesive layer for example, polyester resins, polyether polyurethane resins, polyester polyurethane resins, polycarbonate polyurethane resins, acrylic resins, etc. can be used without particular limitation.
- the crosslinking agent to be included in the coating solution for forming an easily adhesive layer include melamine compounds, isocyanate compounds, oxazoline compounds, epoxy compounds, and carbodiimide compounds. It is also possible to use a mixture of two or more of each. Due to the nature of the in-line coating, these are preferably applied using a water-based coating liquid.
- the resin and crosslinking agent described above are preferably water-soluble or water-dispersible resins or compounds.
- the average particle size of the particles is preferably 2 ⁇ m or less. If the average particle diameter of the particles is 2 ⁇ m or less, the particles will be difficult to fall off from the adhesive layer.
- particles to be included in the adhesive layer include titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay, calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, Examples include inorganic particles such as calcium fluoride, and organic polymer particles such as styrene, acrylic, melamine, benzoguanamine, and silicone. These may be added to the adhesive layer singly or in combination of two or more.
- a known method can be used as a method for applying the coating liquid for forming an easily adhesive layer.
- reverse roll coating method gravure coating method, kiss coating method, roll brushing method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, etc. Or it can be done in combination.
- the polyester film of the present invention When the polyester film of the present invention is placed on the surface of a folding display and used as a surface protection film for protecting the display, it is preferable that at least one surface thereof has a hard coat layer.
- the hard coat layer is preferably used by being located on the display surface side on the polyester film.
- resins such as acrylic, siloxane, inorganic hybrid, urethane acrylate, polyester acrylate, and epoxy can be used without particular limitation.
- two or more types of materials can be mixed and used, and particles such as inorganic filler or organic filler can also be added.
- the thickness of the hard coat layer is preferably 1 to 50 ⁇ m. It is preferable that the thickness is 1 ⁇ m or more because it will be sufficiently cured and the pencil hardness will be high. Further, by setting the thickness to 50 ⁇ m or less, curling due to curing shrinkage of the hard coat can be suppressed, and the handling properties of the film can be improved.
- a coating method for the hard coat layer As a coating method for the hard coat layer, a Meyer bar, a gravure coater, a die coater, a knife coater, etc. can be used without particular limitation, and can be appropriately selected depending on the viscosity and film thickness.
- energy rays such as ultraviolet rays and electron beams, and heat curing methods can be used.
- curing method curing with energy rays such as ultraviolet rays or electron beams is preferred in order to reduce damage to the film.
- the pencil hardness of the hard coat layer is preferably 3H or higher, more preferably 4H or higher. If it has a pencil hardness of 3H or higher, it will not be easily scratched and will not reduce visibility. Generally, the pencil hardness of the hard coat layer is preferably higher, but it may be 9H or less, 8H or less, and 6H or less can be used practically without any problem. The pencil hardness of the hard coat layer may be 3H to 9H, 3H to 8H, or 3H to 6H.
- the hard coat layer in the present invention can be used for the purpose of protecting the display by increasing the pencil hardness of the surface as described above, and preferably has high transmittance.
- the total light transmittance of a film provided with a hard coat layer (sometimes referred to as a hard coat film) is preferably 87% or more, more preferably 88% or more. If the total light transmittance is 87% or more, sufficient visibility can be obtained. Generally, the higher the total light transmittance of the hard coat film is, the more preferable it is, but from the viewpoint of stable production, it may be 99% or less, or 97% or less.
- the total light transmittance of the hard coat film may be 87 to 99%, 88 to 99%, 87 to 98%, or 88 to 98%.
- the haze of the hard coat film is generally preferably low, and preferably 3% or less.
- the haze of the hard coat film is more preferably 2% or less, most preferably 1% or less. When the haze is 3% or less, image visibility can be improved. From the viewpoint of stable production, the haze is preferably 0.1% or more, and may be 0.3% or more.
- the haze of the hard coat film is 0.1-3%, 0.1-2%, 0.1-1%, 0.3-3%, 0.3-2%, 0.3-1%. You can.
- the hard coat layer may further have other functions added to it.
- hard coat layers with added functionality such as anti-glare layers, anti-glare anti-reflection layers, anti-reflection layers, low reflection layers and antistatic layers having a certain pencil hardness as described above can also be used in the present invention. is preferably applied.
- a hard coat layer may also be provided when used as a base film for a touch panel module.
- a refractive index adjustment layer is preferably provided between the base film and the transparent electrode layer in order to make the electrode pattern less visible.
- the hard coat layer itself may also serve as a refractive index adjusting layer, or a separate refractive index adjusting layer may be laminated.
- the polyester film of the present invention can be used as a back protection film for foldable displays.
- the polyester film of the present invention can be placed as a single continuous backside protective film across the folded portion of a foldable display.
- a mobile terminal device having the polyester foldable display of the present invention is provided.
- Density of polyester film The density of the polyester film was measured according to a method based on JIS K 7112:1999 (density gradient tube method). (Unit: g/cm 3 ).
- Heat shrinkage rate (%) [(A-B) x 100]/A
- the heat shrinkage rate was defined as the maximum heat shrinkage rate (%).
- FIG. 3 is a schematic diagram for explaining a method of measuring the high temperature hold angle in the bending direction.
- a sample film (number 3) was cut to a width of 10 mm and a length of 50 mm in the machine flow direction.
- a space was formed by sandwiching a PTFE plate (32) as a spacer between two PTFE plates (31). In the case of a 50 ⁇ m thick sample film, the spacer thickness was 3 mm.
- the thickness of the PTFE plate used as a spacer was changed depending on the thickness of the film.
- FIG. 4 shows an enlarged schematic diagram of a sample film (number 3) sandwiched between two PTFE plates (number 31 in FIG. 3).
- numeral 41 is the diameter of the semicircle formed by the outermost surface of the sample film
- numeral 42 is the diameter of the semicircle formed by the neutral surface of the sample film
- numeral 43 is the diameter of the semicircle formed by the outermost surface of the sample film. It shows the diameter of the semicircle formed by the innermost surface of .
- the neutral plane on which neither the compressive stress nor the tensile stress is applied is defined as the center in the thickness direction (broken line in the figure), and the difference between the neutral plane and both surfaces is defined as the strain.
- strain (1.7%) (
- the semicircle is the thickness t (mm) of the sample film
- the bending diameter (The diameter of the outermost surface, that is, the thickness of the spacer used) d (mm), each can be determined by the following formula.
- the diameter of the outermost surface (reference numeral 41) is the same as the thickness d of the spacer, which is 3 mm.
- the diameter of the innermost surface (numeral 43) is 2.9 mm, and the diameter of the neutral surface (numeral 42) is 2.95 mm.
- the semicircumference of the outermost surface and the semicircumference of the innermost surface can be selected as appropriate.
- the spacer thickness (d) relative to the typical film thickness (t) is shown below.
- reaction product is transferred to a polymerization reactor, heated to 290°C, and subjected to a polycondensation reaction under a high vacuum of 27 Pa or less, and has an intrinsic viscosity of 0.48 dl/g and substantially does not contain particles.
- Polyethylene-2,6-naphthalene dicarboxylate was obtained.
- PET polyethylene terephthalate
- a continuous esterification reactor consisting of a three-stage complete mixing tank having a stirrer, a partial condenser, a raw material inlet, and a product outlet was used.
- the amount of antimony trioxide was set at 2 mol to mol, and the amount of antimony trioxide was set so that Sb atoms were 160 ppm with respect to the produced PET, and the slurry was continuously supplied to the first esterification reactor of the esterification reactor and heated at normal pressure.
- the reaction was carried out at 255° C. with an average residence time of 4 hours.
- the reaction product in the first esterification reactor is continuously taken out of the system and supplied to the second esterification reactor, and the reaction product is distilled from the first esterification reactor into the second esterification reactor.
- an EG solution containing magnesium acetate in an amount such that Mg atoms are 65 ppm with respect to the generated PET, and 20 ppm of P atoms with respect to the generated PET is supplied.
- An EG solution containing an amount of TMPA was added, and the reaction was carried out at 260° C. at normal pressure with an average residence time of 1.5 hours.
- the reaction product in the second esterification reactor is continuously taken out of the system and supplied to the third esterification reactor, and further contains TMPA in an amount such that P atoms are 20 ppm with respect to the produced PET.
- the EG solution was added and reacted at 260° C. with an average residence time of 0.5 hours at normal pressure.
- the esterification reaction product produced in the third esterification reactor is continuously supplied to a three-stage continuous polycondensation reactor for polycondensation, and a stainless steel sintered filter medium (nominal filtration accuracy of 5 ⁇ m 90% of the particles were cut) to obtain polyethylene terephthalate pellets (a) having an intrinsic viscosity of 0.58 dl/g.
- a coating solution was prepared by mixing the following coating materials.
- Polyurethane resin A
- Water-soluble carbodiimide compound B
- 1.22 parts by mass Particles 0.51 parts by mass
- Surfactant 0.05 parts by mass (silicone type, solid content concentration 100% by mass)
- Example 1 Pellets of polyethylene naphthalate (PEN) were fed into the extruder and melted at 310°C. This polymer is filtered through a stainless steel sintered filter medium (nominal filtration accuracy: 95% of particles cut out at 10 ⁇ m), extruded from a die in the form of a sheet, and then cast onto a casting drum with a surface temperature of 60°C using an electrostatic casting method. They were brought into contact and cooled to solidify, producing an unstretched film. The above-mentioned coating solution for forming an easily adhesive layer was applied to both sides of the unstretched film by a roll coating method, and then dried at 80° C. for 20 seconds.
- PEN polyethylene naphthalate
- the final coating amount after drying was adjusted to 0.06 g/m 2 . After that, it is introduced into a tenter and preheated at 130°C, then laterally stretched to 4.2 times at 135°C, fixed in width, heat set at 240°C for 5 seconds, and further relaxed by 1% in the width direction at 180°C.
- a polyethylene naphthalate film having a thickness of 50 ⁇ m was formed by this method. This film was heated at 110° C. for 24 hours and then returned to room temperature at 2° C./h (BTA treatment) to obtain the films shown in Tables 1 and 2. This film was subjected to various tests. Films obtained in other Examples and Comparative Examples were similarly subjected to various tests.
- Example 2 An unstretched film was obtained in the same manner as in Example 1. Before forming the easy-adhesive layer, the unstretched film was uniformly heated to 120°C using a heating roll, heated to 135°C or 140°C using a non-contact heater, and rolled at the stretching ratio in the longitudinal direction listed in Table 1. (longitudinal stretching). Thereafter, a polyester film was obtained in the same manner as in Example 1, except that the heat setting temperature was set as shown in Table 1.
- Example 5 Film formation was performed in the same manner as in Example 1, and a polyester film was obtained without performing heat treatment (BTA treatment) after film formation.
- Example 6 Film formation was performed in the same manner as in Example 3, and a polyester film was obtained without performing heat treatment (BTA treatment) after film formation.
- Example 7 A polyester film was obtained in the same manner as in Example 4, except that the heating time in the heat treatment (BTA treatment) after film formation was 12 hours.
- Example 8 A polyester film was obtained in the same manner as in Example 4, except that the cooling rate for cooling to room temperature in the post-film-forming heat treatment (BTA treatment) was 20° C./h.
- Comparative example 1 Pellets of polyethylene terephthalate (PET) were fed to the extruder and melted at 285°C. This polymer is filtered through a stainless steel sintered filter medium (nominal filtration accuracy: 95% of particles cut out at 10 ⁇ m), extruded from a die in the form of a sheet, and then cast onto a casting drum with a surface temperature of 30°C using an electrostatic casting method. They were brought into contact and cooled to solidify, producing an unstretched film. This unstretched film was uniformly heated to 75° C. using a heating roll, and then heated to 85° C. using a non-contact heater to perform roll stretching (longitudinal direction stretching) by 3.4 times.
- PET polyethylene terephthalate
- the above-mentioned coating solution for forming an easily adhesive layer was applied to both sides of the obtained uniaxially stretched film by a roll coating method, and then dried at 80° C. for 20 seconds.
- the final (after biaxial stretching) dry coating amount was adjusted to 0.06 g/m 2 . Thereafter, it was introduced into a tenter and preheated at 105°C, then laterally stretched to 4.0 times at 95°C, fixed in width, heat set at 230°C for 5 seconds, and further relaxed by 4% in the width direction at 180°C.
- a polyethylene terephthalate film having a thickness of 50 ⁇ m was formed by this method. This film was heated at 70° C. for 24 hours and then returned to room temperature at 2° C./h (BTA treatment) to obtain the films shown in Tables 1 and 2.
- Comparative example 2 A polyester film was obtained in the same manner as Comparative Example 1 except that the stretching ratio in the longitudinal direction was changed to 1.4 times.
- Example 3 A polyester film was obtained in the same manner as in Example 4, except that the heating temperature in the heat treatment (BTA treatment) after film formation was 140° C., which exceeds the glass transition point.
- Example 4 A polyester film was prepared in the same manner as in Example 4, except that the heating time in the heat treatment (BTA treatment) after film formation was 1 hour, and the temperature control cooling time after heating was not taken, and the polyester film was immediately taken out of the heating oven at room temperature. Obtained.
- Example 5 Film formation was performed in the same manner as in Example 4, and a polyester film was obtained without performing heat treatment (BTA treatment) after film formation.
- polyester films obtained in Examples and Comparative Examples were laminated to the non-visible side of an organic EL module via a 25 ⁇ m thick adhesive layer to create a smartphone-type foldable display that could be folded in half at the center of the whole. did.
- the bending radius of this foldable display, which corresponds to numeral 11 in FIG. 1, was 3 mm.
- the polyester film is placed on the non-visible side of one continuous display via the folded portion as a back protection film, and is laminated to a polyimide film having a barrier layer, which is an organic EL substrate.
- the foldable display using the polyester film of each example had satisfactory operation and visibility as a smartphone that can be folded in two at the center and carried. Furthermore, there were no problems with operation or visibility even under high temperatures.
- the foldable display using the polyester film for foldable displays of the present invention maintains mass productivity and, for example, does not cause deformation after the polyester film located on the back side of the foldable display is repeatedly folded. , there will be no image disturbance at the folded portion of the display.
- a mobile terminal device or image display device equipped with a foldable display using the polyester film of the present invention as a back protection film provides beautiful images, is rich in functionality, has excellent portability and other convenience, and is reliable. is high.
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Abstract
Description
更に、本発明は、高温度域で折りたたまれても、折りたたみ部に折り跡が発生し難い、折りたたみ型ディスプレイ用ポリエステルフィルムを提供しようとするものである。
1.長手方向及び幅方向の少なくとも一方向の、引張による動的粘弾性測定によって得られる100℃におけるtanδが0.040以下であるポリエステルフィルム。
2.厚みが10~125μmであり、長手方向及び幅方向のいずれか一方向の、60℃における高温ホールド角が100°以上であり、85℃における高温ホールド角が80°以上である第1に記載のポリエステルフィルム。
ここで、前記高温ホールド角とは、前記ポリエステルフィルムを、その屈曲部分の両表面にそれぞれ1.7%のひずみが生ずるよう60℃又は85℃での加熱下で18時間固定した後に生ずる折れあとのなす角度を指す。
3.折りたたみ型ディスプレイ用である第1又は2に記載のポリエステルフィルム。
4.密度が1.349g/cm3以上である第1~3のいずれかに記載のポリエステルフィルム。
5.前記ポリエステルがポリエチレンナフタレートである第1~4のいずれかに記載のポリエステルフィルム。
6.前記ポリエステルフィルムの少なくとも片面に易接着層を有する第1~5のいずれかに記載の折りたたみ型ディスプレイ用ポリエステルフィルム。
7.折りたたみ型ディスプレイであって、第1~6のいずれかに記載のポリエステルフィルムを含み、前記ポリエステルフィルムが、折りたたみ型ディスプレイの折りたたみ部分を介して連続した単一の裏面保護フィルムとして配置されている、折りたたみ型ディスプレイ。
8.第7に記載の折りたたみ型ディスプレイを有する携帯端末機器。
本発明で言うディスプレイとは、表示装置を全般に指すものであり、ディスプレイの種類としては、LCD、有機ELディスプレイ、無機ELディスプレイ、LED、FEDなどがある。例えば、折曲げ可能な構造を有する、LCD、有機ELディスプレイ、無機ELディスプレイが好ましい。層構成を少なくすることができる点で、有機ELディスプレイ、無機ELディスプレイがさらに好ましく、色域の広い点で、有機ELディスプレイが特に好ましい。
折りたたみ型ディスプレイは、連続した1枚のディスプレイが、携帯時は2つ折りなどに折りたたむことができるものである。折りたたむことでサイズを半減させ、携帯性を向上させることができる。折りたたみ型ディスプレイの屈曲半径は5mm以下が好ましく、3mm以下がさらに好ましい。屈曲半径が5mm以下であれば、折りたたんだ状態での折りたたみ型ディスプレイの薄型化が可能となる。屈曲半径は小さいほど良いと言える。本発明の折りたたみ型ディスプレイであれば、このような屈曲半径で使用されても、ポリエステルフィルムの折れ跡の発生を抑制できる。
折りたたみ型有機ELディスプレイは、有機ELモジュールを必須部材とするが、さらに必要に応じて、円偏光板、タッチパネルモジュール、表面保護フィルム、裏面保護フィルムなどが設けられる。
有機ELモジュールの一般的な構成は、電極/電子輸送層/発光層/ホール輸送層/透明電極からなる。電極を設け、さらに電子輸送層、発光層、ホール輸送層、透明電極を設ける基材として、本発明のポリエステルフィルムを用いることができる。特に、透明電極の基材として好ましく用いることができる。この場合、基材フィルムは高い水蒸気や酸素のバリア性が求められるため、本発明のポリエステルフィルムには、金属酸化物層などのバリア層が設けられることが好ましい。バリア性を上げるため、バリア層は複数設けられていてもよく、バリア層が設けられたポリエステルフィルムを複数枚用いても良い。
携帯端末機器にはタッチパネルを有することが好ましい。有機ELディスプレイを用いた場合、有機ELディスプレイの上部、もしくは有機ELモジュール/円偏光板間にタッチパネルモジュールが配置されていることが好ましい。タッチパネルモジュールはフィルムなどの透明基材とその上に配置された透明電極を有する。本発明のポリエステルフィルムはこの透明基材として用いることができる。タッチパネルの透明基材として用いる場合、ポリエステルフィルムにはハードコート層や屈折率調整層を設けることが好ましい。
円偏光板は、ディスプレイ内部の部材によって外光が反射され、画質が低下することを抑制する。円偏光板は直線偏光板と位相差板を有する。直線偏光板は少なくとも視認側の面に保護フィルムを有する。視認側とは反対の直線偏光板の面にも保護フィルムを有していてもよいし、直線偏光板に位相差板が直接積層されていてもよい。位相差板はポリカーボネートや環状オレフィンなどの位相差を有する樹脂フィルムや、樹脂フィルムに液晶化合物からなる位相差層が設けられたものが用いられる。本発明のポリエステルフィルムは、偏光子保護フィルムや位相差板の樹脂フィルムとして用いることができる。これらの場合、本発明のポリエステルフィルムはポリエステルフィルムの遅相軸方向が偏光子の吸収軸方向と平行または直交となることが好ましい。なお、この平行または直交に対して10度、好ましくは5度までのずれは許容される。
ディスプレイに上部から衝撃が加わると、有機ELモジュールやタッチパネルモジュールの回路が断線するおそれがあり、これを防止するため、多くの場合、表面保護フィルムが設けられている。本発明のポリエステルフィルムはこの表面保護フィルムとして用いることができる。表面保護フィルムはディスプレイの最表面に組み込まれたカバーウインドウと呼ばれるものや、アフターフィルムと呼ばれるものがある。本発明のポリエステルフィルムはいずれのフィルムとしても使用できる。アフターフィルムは、カバーウインドウを保護するために製造工程中に製造者によってカバーウインドウに貼られるフィルムや、使用者によってカバーウインドウに貼られる、交換可能なフィルムである。本発明のポリエステルフィルムを表面保護フィルムとして用いる場合、ポリエステルフィルムの少なくとも表面側にはハードコート層が積層されたものであることが好ましい。ポリエステルフィルムは、ハードコート層を視認側にして折りたたみ型ディスプレイの表面に設けられる。なお、ハードコート層はポリエステルフィルムの両面に設けられていてもよい。
ディスプレイの裏面側にも保護フィルムが設けられることも好ましい。具体的には有機ELモジュールの非視認側に接着層を設け、保護フィルムを貼り合せた構成となる。本発明のポリエステルフィルムはこの裏面側の保護フィルムとして用いることができる。
これらの中でも、本発明のポリエステルフィルムは、カバーウインドウ表面保護フィルム、アフターマーケット製品としての表面保護フィルム、タッチパネルモジュールの基材フィルム、裏面保護フィルムに用いられることが好ましい。カバーウインドウ表面保護フィルム、アフターマーケット製品としての表面保護フィルムに用いられることが好ましい。
本発明のポリエステルフィルムは、単層フィルムであっても2層以上を有する多層フィルムであってもよく、多層フィルムを構成する各層は同一のポリエステル樹脂を含んでもよく、異なるポリエステル樹脂を含んでもよい。また、多層フィルムは、異なる層を交互に繰り返し積層した超多層構造を有してもよい。多層フィルムは、例えば、2~30層の構造を有してもよいし、2~20層の構造を有してもよい。ポリエステルフィルムは、1種類以上のポリエステル樹脂からなる単層フィルムでもよい。ポリエステルフィルムは、2種類以上のポリエステル樹脂を使用する場合、超多層構造を有する多層フィルムでもよいし、他の多層フィルムでもよい。
なお、本発明において、ポリエステルフィルムは、特性の異なるポリエチレンナフタレートを複数種含んでもよい。
ポリエチレンナフタレートの割合を高くすることで、高温度領域で折りたたんだ後のポリエステルフィルムの変形が抑制され、ディスプレイの折りたたみ部分での画像の乱れを抑制できる。更に、本発明のポリエステルフィルムを用いた折りたたみ型ディスプレイを搭載した携帯端末機器は、美しい画像を提供し、機能性に富み、携帯性等の利便性に優れたものとなる。
例えば、ポリエステルフィルムが複数種の樹脂ペレットを含む場合、これら複数種の樹脂ペレットの全てにおいて、極限粘度は、0.40~1.0dl/gの範囲であってもよく、少なくとも1種類のペレットが0.40~1.0dl/gの範囲の極限粘度を有してもよい。一態様において、ポリエステルフィルムが複数種の樹脂ペレットを含む場合、主成分となる樹脂ペレットの極限粘度が0.40~1.0dl/gの範囲である。
なお、PETフィルムの代わりにポリエチレンナフタレート(PEN)フィルムを用いる態様においても、同様の方法で、本発明に係るポリエステルフィルムを製造できる。
本発明において、ポリエステルフィルムの長手方向(機械流れ方向)及び幅方向の少なくとも一方向の屈折率は1.610~1.750であることが好ましく、例えば、1.610~1.710であり、更に好ましくは、1.630~1.680である。長手方向及び幅方向の少なくとも一方向の屈折率が1.610~1.750であると、繰り返し折りたたんだ際の変形が少なく、折りたたみ型ディスプレイの画質を低下させるおそれがなく好ましい。
ポリエステルフィルムの屈折率が1.610~1.750である方向とその方向に直交する方向の屈折率は、1.750~1.870であることが好ましい。例えば、ポリエステルフィルムの屈曲方向の屈折率が1.610~1.750であり、屈曲方向と直交する方向(折りたたみ部方向)の屈折率が1.750~1.870であることが好ましい。折りたたみ部方向の屈折率を1.750~1.870にすることで屈曲方向に折りたたんだ際の変形を少なくすることができる。折りたたみ部方向の屈折率を1.870以下にすることで折りたたみ部方向にクラックが入ることを抑制でき、更に破断することを抑制できる。また、延伸後の巻取り工程における破断を抑制することができる。折りたたみ部方向の屈折率を1.750以上にすることでポリエステルフィルムの密度を上げることができ、高温ホールド角を向上させることができる。
また、屈曲方向の屈折率と、屈曲方向と直交する方向(折りたたみ部方向)の屈折率とを比較した場合に、屈曲方向の屈折率が低いことが望ましい。屈曲方向の屈折率が折りたたみ部方向の屈折率より低いことにより、屈曲方向に折りたたんだ際の変形を少なくすることができる。また、折りたたみ部方向にクラックが入ることを抑制でき、更に破断することを抑制できる。その上、延伸後の巻取り工程における破断を抑制することができる。加えて、密度を上げることができ、高温ホールド角を向上させることができる。
屈曲方向と直交する方向の屈折率を調整する方法として、当該方向における延伸倍率、延伸予熱温度、延伸温度、多段延伸、フィルム弛緩等を調整する方法が挙げられる。屈曲方向と直交する方向への延伸倍率は3.3~5.0倍であることが好ましく、より好ましくは3.5~4.5倍である。また、屈曲方向と直交する方向の延伸予熱温度は125~145℃であることが好ましい。屈曲方向と直交する方向に多段延伸する場合、1段目より2段目以降の延伸倍率を高くすることが好ましい。フィルム弛緩は機械流れ方向(長手方向)、垂直方向(幅方向)の何れにおいても0~10%で行っても良い。
厚み方向の屈折率は1.520以下であることが好ましい。より好ましくは1.515以下、更に好ましくは1.510以下、特に好ましくは1.505以下、最も好ましくは1.500以下である。厚み方向の屈折率は低いことが好ましいが、安定した生産の面で1.300以上が好ましく、1.400以上がより好ましく、特に好ましくは1.410以上である。厚み方向の屈折率は1.300~1.520、1.300~1.515、1.300~1.510、1.300~1.500、1.400~1.520、1.400~1.515、1.400~1.510、1.400~1.500、1.410~1.520、1.410~1.515、1.410~1.510、1.410~1.500であってもよい。
ポリエステルフィルムの密度は1.349g/cm3以上であることが好ましい。1.350g/cm3以上であることがより好ましい。1.349g/cm3以上にすることで高温ホールド角を向上させることができる。密度は、フィルム中の粒子の有無等によっても多少左右されるが、1.400g/cm3以下であることが好ましく、さらには1.395g/cm3以下がより好ましい。ポリエステルフィルムの密度は、1.349~1.400g/cm3、1.349~1.395g/cm3、1.350~1.400g/cm3、1.350~1.395g/cm3であってもよい。
ポリエステルフィルムの密度が1.349g/cm3以上であることで、本発明のポリエステルフィルムの結晶化を十分にでき、85℃での変形を抑制できる。また、熱収縮率が高くなることを抑制でき、デバイスの発熱による寸法変化を抑制できる。
製膜時の熱固定温度を210~270℃に設定することで結晶化を進行させ、上記範囲内で密度を効果的に増大させることができる。
高温ホールド角は、60℃加熱条件において101°以上、102°以上であってよく、また85℃加熱条件において81°以上、82℃以上であってよい。ホールド角は大きい方が好ましく、180°が最も好ましいが、例えば170°以下でも十分な機能を有する。60℃加熱条件における高温ホールド角は100~180°、110~180°、120~180、100~170°、110~170°、120~170°であってよい。85℃加熱条件における高温ホールド角は100~180°、105~180°、100~170°、105~170°、100~160°、105~160°、100~150°、105~150°であってよい。
なお、屈曲方向の高温ホールド角の測定方法は、実施例において例示する。
ポリエステルフィルムとハードコート層などとの接着性を向上させるため、本発明のポリエステルフィルムの少なくとも片面に、易接着層を積層することも好ましい。易接着層は、易接着層形成のための塗布液を未延伸又は縦方向の1軸延伸フィルムの片面または両面に塗布した後、必要に応じて熱処理乾燥し、さらに延伸されていない少なくとも一方向に延伸して得ることができる。二軸延伸後にも熱処理乾燥することができる。最終的な易接着層の塗布量は、0.005~0.20g/m2に管理することが好ましい。塗布量が0.005g/m2以上であると、接着性が向上するため好ましい。一方、塗布量が0.20g/m2以下であると、耐ブロッキング性が向上するため好ましい。
本発明のポリエステルフィルムを折りたたみ型ディスプレイの表面に位置させてディスプレイを保護する表面保護フィルムとして用いる場合は、その少なくとも一方の表面にハードコート層を有していることが好ましい。ディスプレイにおいて、ハードコート層は、ポリエステルフィルム上のディスプレイ表面側に位置させて用いられることが好ましい。ハードコート層を形成する樹脂としては、アクリル系、シロキサン系、無機ハイブリッド系、ウレタンアクリレート系、ポリエステルアクリレート系、エポキシ系などの樹脂を特に限定なく使用できる。また、2種類以上の材料を混合して用いることもできるし、無機フィラーや有機フィラーなどの粒子を添加することもできる。
ハードコート層の膜厚としては、1~50μmが好ましい。1μm以上であると十分に硬化し、鉛筆硬度が高くなり好ましい。また厚みを50μm以下にすることで、ハードコートの硬化収縮によるカールを抑制し、フィルムのハンドリング性を向上させることができる。
ハードコート層の塗布方法としては、マイヤーバー、グラビアコーター、ダイコーター、ナイフコーターなど特に限定なく使用でき、粘度、膜厚に応じて適宜選択できる。
ハードコート層の硬化方法としては、紫外線、電子線などのエネルギー線や、熱による硬化方法など使用できる。硬化方法としては、フィルムへのダメージを軽減させるために、紫外線や電子線などのエネルギー線による硬化が好ましい。
ハードコート層の鉛筆硬度としては、3H以上が好ましく、4H以上が更に好ましい。3H以上の鉛筆硬度があれば、傷がつき難く、視認性を低下させない。一般にハードコート層の鉛筆硬度は高い方が好ましいが9H以下で構わず、8H以下でも構わず、6H以下でも実用上は問題なく使用できる。ハードコート層の鉛筆硬度は、3H~9H、3H~8H、3H~6Hであってもよい。
本発明におけるハードコート層は、上述のような表面の鉛筆硬度を高めてディスプレイの保護をする目的に使用できるものであり、透過率が高いことが好ましい。ハードコート層を備えたフィルム(ハードコートフィルムと称することがある。)の全光線透過率としては、87%以上が好ましく、88%以上がさらに好ましい。全光線透過率が87%以上あれば、十分な視認性が得られる。ハードコートフィルムの全光線透過率は、一般的に高いほど好ましいが、安定した生産の面から99%以下、97%以下であってもよい。ハードコートフィルムの全光線透過率は、87~99%、88~99%、87~98%、88~98%であってもよい。また、ハードコートフィルムのヘイズは、一般的に低いことが好ましく、3%以下が好ましい。ハードコートフィルムのヘイズは2%以下がより好ましく、1%以下が最も好ましい。ヘイズが3%以下であれば、画像の視認性を向上させることができる。ヘイズは、安定した生産の面から0.1%以上が好ましく、0.3%以上であってもよい。ハードコートフィルムのヘイズは、0.1~3%、0.1~2%、0.1~1%、0.3~3%、0.3~2%、0.3~1%であってもよい。
フィルムまたはポリエステル樹脂を粉砕して乾燥した後、フェノール/テトラクロロエタン=60/40(質量比)の混合溶媒に溶解した。この溶液に遠心分離処理を施して無機粒子を取り除いた後に、ウベローデ粘度計を用いて、30℃で0.4(g/dl)の濃度の溶液の流下時間及び溶媒のみの流下時間を測定し、それらの時間比率から、Hugginsの式を用い、Hugginsの定数が0.38であると仮定して極限粘度を算出した。ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)のいずれにも同じ計算式を用いて評価した。
動的粘弾性測定装置「DMA7100」(日立ハイテクサイエンス社製)にて、引張モード、サンプルサイズ幅8mm×チャック間距離20mmで測定を実施した。周波数は1Hz、測定温度は25℃から150℃で10℃/minで昇温した。tanδ=損失弾性率/貯蔵弾性率から算出し、tanδの値をグラフ化し、このグラフから100℃におけるtanδを読み取った。
メトリコン社製レーザー屈折計(モデル2010プリズムカプラー)を用いて、1枚のサンプルフィルムを内蔵圧力計40目盛の圧力で挟み、波長633nmのレーザー光にて測定を行い、スペクトラムチャートを得た。得られたスペクトラムチャート上で、検知器出力が急激に低下する点を読み取り、この値を屈折率とした。測定モードTEにて長手方向と幅方向の屈折率、TMにて厚み方向の屈折率を測定した。
ヘイズメーター(日本電色工業社製、NDH5000)を用いて、ハードコートフィルムの全光線透過率とヘイズを測定した。
JIS K 7112:1999準拠の方法(密度勾配管法)に従ってポリエステルフィルムの密度を測定した。(単位:g/cm3)。
試料フィルムをタテ10mm×ヨコ250mmにカットし、長辺を測定したい方向に合わせて、200mm間隔で印をつけ、5gの一定張力下で印の間の距離A(mm)を測った。続いて、試料フィルムを無荷重で150℃の雰囲気のオーブン中で30分間放置した後、オーブンから取り出し室温まで冷却した。その後、5gの一定張力下で印の間の距離B(mm)を求め、下記式により熱収縮率(%)を求めた。なお、上記距離A及び距離Bは試料フィルムの幅方向に3等分した位置で測定し、3点の距離A及び距離Bの平均値を熱収縮率(%)とした。
熱収縮率(%)=[(A-B)×100]/A
同一のフィルムについて、屈曲方向を長辺とした試料フィルムの熱収縮率と、折りたたみ部方向(屈曲方向と直交する方向)を長辺とした試料フィルムの熱収縮率とを測定し、大きい方の熱収縮率を最大熱収縮率(%)とした。
ポリエステルフィルムの屈曲部分の両表面にそれぞれ1.7%のひずみがかかるよう固定したときにつく折れあとのなす角度を測定した。
ひずみ(1.7%)
=(|最外面または最内面の半円周-中立面の半円周|/中立面の半円周)×100 ここで半円周は、試料フィルムの厚みt(mm)、屈曲直径(最外面の直径、即ち、用いるスペーサーの厚み)d(mm)とから、以下の式でそれぞれ求めることができる。 最外面の半円周=d×π/2
中立面の半円周=(d-t)×π/2
最内面の半円周=(d-2t)×π/2
以上より、ひずみを1.7%に定めるとき、スペーサーの厚み(mm)は、試料フィルムの厚みt(mm)と、屈曲直径(スペーサーの厚み)d(mm)とから、以下の式より決定する。代表的なフィルム厚みに対するスペーサー厚みは、例えば、以下のように示される。
スペーサー厚みd(mm)=フィルム厚み(mm)×60
代表的なフィルム厚み(t)に対するスペーサー厚み(d)を以下に示す。
フィルム厚み(t) スペーサー厚み(d)
38μm 2.3mm
50μm 3.0mm
75μm 4.5mm
100μm 6.0mm
ナフタレン-2,6-ジカルボン酸ジメチル100部およびエチレングリコール60部を、エステル交換触媒として酢酸マンガン四水塩0.03部を使用し、150℃から238℃に徐々に昇温させながら120分間エステル交換反応を行った。途中、反応温度が170℃に達した時点でリン酸トリメチル(エチレングリコール中で135℃、5時間、0.11~0.16MPaの加圧下で加熱処理した溶液として添加:リン酸トリメチル換算量で0.023部)を添加し、エステル交換反応終了後、三酸化アンチモン0.024部を添加した。その後反応生成物を重合反応器に移し、290℃まで昇温し、27Pa以下の高真空下にて重縮合反応を行い、極限粘度が0.48dl/gの、実質的に粒子を含有しない、ポリエチレン-2,6-ナフタレンジカルボキシレートを得た。
エステル化反応装置として、攪拌装置、分縮器、原料仕込口および生成物取り出し口を有する3段の完全混合槽よりなる連続エステル化反応装置を用い、TPAを2トン/hrとし、EGをTPA1モルに対して2モルとし、三酸化アンチモンを生成PETに対してSb原子が160ppmとなる量とし、これらのスラリーをエステル化反応装置の第1エステル化反応缶に連続供給し、常圧にて平均滞留時間4時間で、255℃で反応させた。次いで、上記第1エステル化反応缶内の反応生成物を連続的に系外に取り出して第2エステル化反応缶に供給し、第2エステル化反応缶内に第1エステル化反応缶から留去されるEGを生成ポリマー(生成PET)に対し8質量%供給し、さらに、生成PETに対してMg原子が65ppmとなる量の酢酸マグネシウムを含むEG溶液と、生成PETに対してP原子が20ppmのとなる量のTMPAを含むEG溶液を添加し、常圧にて平均滞留時間1.5時間で、260℃で反応させた。次いで、上記第2エステル化反応缶内の反応生成物を連続的に系外に取り出して第3エステル化反応缶に供給し、さらに生成PETに対してP原子が20ppmとなる量のTMPAを含むEG溶液を添加し、常圧にて平均滞留時間0.5時間で、260℃で反応させた。上記第3エステル化反応缶内で生成したエステル化反応生成物を3段の連続重縮合反応装置に連続的に供給して重縮合を行い、さらに、ステンレス焼結体の濾材(公称濾過精度5μm粒子90%カット)で濾過し、極限粘度0.58dl/gのポリエチレンテレフタレートペレット(a)を得た。
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、1,3-ビス(イソシアネートメチル)シクロヘキサン72.96質量部、ジメチロールプロピオン酸12.60質量部、ネオペンチルグリコール11.74質量部、数平均分子量2000のポリカーボネートジオール112.70質量部、及び溶剤としてアセトニトリル85.00質量部、N-メチルピロリドン5.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン9.03質量部を添加し、ポリウレタンプレポリマーD溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min-1で攪拌混合しながら、イソシアネート基末端プレポリマーを添加して水分散した。その後、減圧下で、アセトニトリルおよび水の一部を除去することにより、固形分35質量%の水溶性ポリウレタン樹脂(A)を調製した。
温度計、窒素ガス導入管、還流冷却器、滴下ロート、および攪拌機を備えたフラスコにイソホロンジイソシアネート200質量部、カルボジイミド化触媒の3-メチル-1-フェニル-2-ホスホレン-1-オキシド4質量部を投入し、窒素雰囲気下、180℃において10時間撹拌し、イソシアネート末端イソホロンカルボジイミド(重合度=5)を得た。次いで、得られたカルボジイミド111.2g、ポリエチレングリコールモノメチルエーテル(分子量400)80gを100℃で24時間反応させた。これに水を50℃で徐々に加え、固形分40質量%の黄色透明な水溶性カルボジイミド化合物(B)を得た。
下記の塗剤を混合し、塗布液を作成した。
水 16.97質量部
イソプロパノール 21.96質量部
ポリウレタン樹脂(A) 3.27質量部
水溶性カルボジイミド化合物(B) 1.22質量部
粒子 0.51質量部
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.05質量部
(シリコーン系、固形分濃度100質量%)
ポリエチレンナフタレート(PEN)のペレットを押出機に供給し、310℃で融解した。このポリマーを、ステンレス焼結体の濾材(公称濾過精度10μm粒子95%カット)で濾過し、口金よりシート状にして押し出した後、静電印加キャスト法を用いて表面温度60℃のキャスティングドラムに接触させ冷却固化し、未延伸フィルムを作った。未延伸フィルムに上記の易接着層形成用塗布液をロールコート法で両面に塗布した後、80℃で20秒間乾燥した。なお、最終の乾燥後の塗布量が0.06g/m2になるように調整した。その後、テンターに導き130℃で予熱後、135℃で4.2倍に横延伸し、幅固定して240℃で5秒間の熱固定を施し、さらに180℃で幅方向に1%緩和させることにより、厚み50μmポリエチレンナフタレートフィルムを製膜した。このフィルムに110℃で24時間加熱後、2℃/hで室温まで戻す処理(BTA処理)を加えて表1及び2に記載のフィルムを得た。このフィルムを各種試験に供した。他の実施例及び比較例で得られたフィルムも同様に各種試験に供した。
実施例1と同様に未延伸フィルムを得た。易接着層形成前に未延伸フィルムを、加熱ロールを用いて120℃に均一加熱し、非接触ヒーターで135℃又は140℃に加熱して表1に記載の長手方向の延伸倍率でのロール延伸(長手方向延伸)を行った。以降は、表1に記載の熱固定温度とした以外は実施例1と同様にしてポリエステルフィルムを得た。
実施例1と同様に製膜を行い、製膜後の熱処理(BTA処理)は実施せずにポリエステルフィルムを得た。
実施例3と同様に製膜を行い、製膜後の熱処理(BTA処理)は実施せずにポリエステルフィルムを得た。
製膜後の熱処理(BTA処理)における加熱時間を12時間とした以外は実施例4と同様にポリエステルフィルムを得た。
製膜後の熱処理(BTA処理)における室温へ冷却する冷却速度を20℃/hとした以外は実施例4と同様にポリエステルフィルムを得た。
ポリエチレンテレフタレート(PET)のペレットを押出機に供給し、285℃で融解した。このポリマーを、ステンレス焼結体の濾材(公称濾過精度10μm粒子95%カット)で濾過し、口金よりシート状にして押し出した後、静電印加キャスト法を用いて表面温度30℃のキャスティングドラムに接触させ冷却固化し、未延伸フィルムを作った。この未延伸フィルムを、加熱ロールを用いて75℃に均一加熱し、非接触ヒーターで85℃に加熱して3.4倍のロール延伸(長手方向延伸)を行った。
得られた一軸延伸フィルムに上記の易接着層形成用塗布液をロールコート法で両面に塗布した後、80℃で20秒間乾燥した。なお、最終(二軸延伸後)の乾燥後の塗布量が0.06g/m2になるように調整した。その後、テンターに導き105℃で予熱後、95℃で4.0倍に横延伸し、幅固定して230℃で5秒間の熱固定を施し、さらに180℃で幅方向に4%緩和させることにより、厚み50μmポリエチレンテレフタレートフィルムを製膜した。このフィルムに70℃で24時間加熱後、2℃/hで室温まで戻す処理(BTA処理)を加えて表1及び2に記載のフィルムを得た。
長手方向の延伸倍率を1.4倍に変更した他は比較例1と同様にしてポリエステルフィルムを得た。
製膜後の熱処理(BTA処理)における加熱温度を、ガラス転位点を超える140℃とした以外は実施例4と同様にしてポリエステルフィルムを得た。
製膜後の熱処理(BTA処理)における加熱時間を1時間とし、加熱後の温調冷却時間を取らず、直ちに加熱オーブンから室温環境下に取り出した以外は実施例4と同様にしてポリエステルフィルムを得た。
実施例4と同様に製膜を行い、製膜後の熱処理(BTA処理)は実施せずにポリエステルフィルムを得た。
一方、各比較例のポリエステルフィルムが、同様にして使用された折りたたみ型ディスプレイでは、高温下での使用頻度が増えるに従って、ディスプレイの折りたたみ部で画像の歪を生じてきたように感じ、あまり好ましいものではなかった。また、折りたたみ部の表面に凹み、キズが確認されるものもあった。
11: 屈曲半径
2 : 折りたたみ型ディスプレイ用ポリエステルフィルム
21: 折りたたみ部
22: 屈曲方向(折りたたみ部と直交する方向)
3 : 試料フィルム
31: PTFE板
32: スペーサー
33: ホールド角
41: 最外面の直径
42: 中立面の直径
43: 最内面の直径
5 : 折りたたみ型ディスプレイ
51: アフターフィルム
52: カバーウインドウ(表面保護フィルム)
53: 偏光板・反射防止部材
54: タッチパネルモジュール
55: 有機ELモジュール
56: 裏面保護フィルム
6 : 外曲げ折りたたみ型スマートフォン
Claims (8)
- 長手方向及び幅方向の少なくとも一方向の、引張による動的粘弾性測定によって得られる100℃におけるtanδが0.040以下であるポリエステルフィルム。
- 厚みが10~125μmであり、長手方向及び幅方向のいずれか一方向の、60℃における高温ホールド角が100°以上であり、85℃における高温ホールド角が80°以上である請求項1に記載のポリエステルフィルム。
ここで、前記高温ホールド角とは、前記ポリエステルフィルムを、その屈曲部分の両表面にそれぞれ1.7%のひずみが生ずるよう60℃又は85℃での加熱下で18時間固定した後に生ずる折れあとのなす角度を指す。 - 折りたたみ型ディスプレイ用である請求項1に記載のポリエステルフィルム。
- 密度が1.349g/cm3以上である請求項1に記載のポリエステルフィルム。
- 前記ポリエステルがポリエチレンナフタレートである請求項1に記載のポリエステルフィルム。
- 前記ポリエステルフィルムの少なくとも片面に易接着層を有する請求項1に記載の折りたたみ型ディスプレイ用ポリエステルフィルム。
- 折りたたみ型ディスプレイであって、請求項1~6のいずれかに記載のポリエステルフィルムを含み、前記ポリエステルフィルムが、折りたたみ型ディスプレイの折りたたみ部分を介して連続した単一の裏面保護フィルムとして配置されている、折りたたみ型ディスプレイ。
- 請求項7に記載の折りたたみ型ディスプレイを有する携帯端末機器。
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| JP2016124218A (ja) * | 2015-01-05 | 2016-07-11 | 帝人デュポンフィルム株式会社 | 積層ポリエステルフィルム |
| WO2018159285A1 (ja) * | 2017-03-02 | 2018-09-07 | 東洋紡株式会社 | 折りたたみ型ディスプレイの表面保護フィルム用ポリエステルフィルムとその用途 |
| WO2021199896A1 (ja) * | 2020-03-30 | 2021-10-07 | 三菱ケミカル株式会社 | 二軸延伸フィルム |
| WO2021215349A1 (ja) * | 2020-04-22 | 2021-10-28 | 東洋紡株式会社 | ポリエステルフィルムとその用途 |
| JP2022122202A (ja) * | 2021-02-09 | 2022-08-22 | 三菱ケミカル株式会社 | 二軸延伸フィルム及び積層フィルム |
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| JP2016124218A (ja) * | 2015-01-05 | 2016-07-11 | 帝人デュポンフィルム株式会社 | 積層ポリエステルフィルム |
| WO2018159285A1 (ja) * | 2017-03-02 | 2018-09-07 | 東洋紡株式会社 | 折りたたみ型ディスプレイの表面保護フィルム用ポリエステルフィルムとその用途 |
| WO2021199896A1 (ja) * | 2020-03-30 | 2021-10-07 | 三菱ケミカル株式会社 | 二軸延伸フィルム |
| WO2021215349A1 (ja) * | 2020-04-22 | 2021-10-28 | 東洋紡株式会社 | ポリエステルフィルムとその用途 |
| JP2022122202A (ja) * | 2021-02-09 | 2022-08-22 | 三菱ケミカル株式会社 | 二軸延伸フィルム及び積層フィルム |
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