WO2018159285A1 - Film de polyester en tant que film de protection de surface pour un dispositif d'affichage pliable et son application - Google Patents

Film de polyester en tant que film de protection de surface pour un dispositif d'affichage pliable et son application Download PDF

Info

Publication number
WO2018159285A1
WO2018159285A1 PCT/JP2018/004956 JP2018004956W WO2018159285A1 WO 2018159285 A1 WO2018159285 A1 WO 2018159285A1 JP 2018004956 W JP2018004956 W JP 2018004956W WO 2018159285 A1 WO2018159285 A1 WO 2018159285A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
foldable display
hard coat
polyester
polyester film
Prior art date
Application number
PCT/JP2018/004956
Other languages
English (en)
Japanese (ja)
Inventor
正太郎 西尾
賢二 吉野
有記 本郷
明子 西尾
Original Assignee
東洋紡株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to JP2018517640A priority Critical patent/JP7247584B2/ja
Publication of WO2018159285A1 publication Critical patent/WO2018159285A1/fr

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a polyester film for a surface protective film of a foldable display, a hard coat film for a surface protective film of a foldable display, a foldable display, and a portable terminal device.
  • the present invention relates to a foldable display and a portable terminal device in which image disturbance hardly occurs, and a polyester film and a hard coat film for a surface protective film of the foldable display.
  • tablet terminals having a screen size of 7 inches to 10 inches have high functionality for not only video content and music but also business use, drawing use, and reading. However, it cannot be operated with one hand, has poor portability, and has a problem in convenience.
  • Patent Document 1 a method of making a compact by connecting a plurality of displays has been proposed (Patent Document 1), but since the bezel portion remains, the video is cut off, and the visibility is problematic. It is not popular.
  • the surface of the display could be protected with a non-flexible material such as glass.
  • a non-flexible material such as glass.
  • a portion corresponding to a certain folding portion is repeatedly bent, so that there is a problem that a film in the portion is deformed with time and an image displayed on the display is distorted.
  • Patent Document 2 a method of partially changing the film thickness has been proposed (see Patent Document 2), but there is a problem that the mass productivity is poor.
  • the present invention is intended to solve the problems of the surface protection member of the conventional display as described above, is excellent in mass productivity, and may cause disturbance in the image displayed at the folded portion after repeated folding.
  • it is intended to provide a polyester film for a surface protective film of a foldable display or a hard coat film for a surface protective film. Is.
  • a foldable display comprising a polyester film having a thickness of 10 to 75 ⁇ m and a 0.2% yield strength strain in at least one of a longitudinal direction and a width direction of 2.6 to 5.0% Polyester film for surface protection film.
  • 3. 3 The polyester film for a surface protective film for a foldable display as described in the above 1 or 2, wherein the intrinsic viscosity of the film is 0.60 to 1.0 dl / g. 4).
  • a surface protective film for a foldable display comprising a hard coat layer having a thickness of 1 to 50 ⁇ m on at least one surface of the polyester film for a surface protective film for a foldable display according to any one of the first to third shifts.
  • the hard coat film for a surface protective film of the foldable display according to the fourth or fifth aspect is a foldable display arranged as a surface protective film so that the hard coat layer is positioned on the surface, and when folded, A folding display having a bending radius of 5 mm or less. 7).
  • the foldable display according to the sixth aspect wherein a single continuous hard coat film is disposed through a foldable portion of the foldable display. 8).
  • the foldable display using the polyester film or hard coat film for the surface protective film of the foldable display of the present invention does not cause deformation after the polyester film or hard coat film is repeatedly folded while maintaining mass productivity. Therefore, the image is not disturbed at the folding portion of the display.
  • a portable terminal device equipped with a foldable display as described above provides beautiful images, is rich in functionality, and has excellent convenience such as portability.
  • the display referred to in the present invention generally refers to a display device, and types of display include LCD, organic EL display, inorganic EL display, LED, FED, etc.
  • Organic EL and inorganic EL are preferable.
  • organic EL and inorganic EL that can reduce the layer structure are particularly preferable, and organic EL having a wide color gamut is more preferable.
  • the foldable display preferably has a structure in which one continuous display is folded in half when carried and the size is reduced by half and the portability is improved. At the same time, it is desirable that the thickness and weight be reduced. Therefore, the bending radius of the foldable display is preferably 5 mm or less, and more preferably 3 mm or less. If the bending radius is 5 mm or less, it is possible to reduce the thickness in a folded state. It can be said that the smaller the bending radius, the better. However, it may be 0.1 mm or more, and may be 0.5 mm or more. Even if it is 1 mm or more, the practicality is sufficiently good as compared with a conventional display having no folding structure.
  • the bending radius at the time of folding is to measure a portion indicated by reference numeral 11 in the schematic diagram of FIG. 1 and means a radius inside the folding portion at the time of folding.
  • the surface protection film mentioned later may be located in the folded outer side of a foldable display, and may be located inside.
  • Organic EL A general configuration of the organic EL display includes an organic EL layer composed of an electrode / electron transport layer / light emitting layer / hole transport layer / transparent electrode, a retardation plate for improving image quality, and a polarizing plate.
  • a touch panel module is disposed on the organic EL display or between the organic EL layer / phase difference plate. At this time, if an impact is applied from above, there is a possibility that the circuit of the organic EL or touch panel may be disconnected. Therefore, a surface protection film is necessary, and the film disposed on the front surface of the display as the surface protection film is at least the surface of the display. It is preferable that a hard coat layer is laminated on the side.
  • the surface protective film As the surface protective film, it can be used as long as it is a film having high light transmittance and low haze, such as a polyimide film, a polyester film, a polycarbonate film, an acrylic film, a triacetyl cellulose film, and a cycloolefin polymer film. Polyimide films and polyester films having high impact resistance and sufficient pencil hardness are preferred, and polyester films that can be produced at low cost are particularly preferred.
  • the polyester film may be a single-layer film composed of one or more kinds of polyester resins, and when two or more kinds of polyester are used, it may be a multilayer structure film or a super multi-layer laminate film having a repeating structure. Good.
  • polyester resin examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, or a polyester film made of a copolymer mainly composed of components of these resins.
  • a stretched polyethylene terephthalate film is particularly preferable from the viewpoint of mechanical properties, heat resistance, transparency, price, and the like.
  • 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-naphthalenedicarboxylic acid.
  • Aromatic dicarboxylic acids such as: polyfunctional carboxylic acids such as trimellitic acid and pyromellitic acid.
  • glycol component examples include fatty acid glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, propylene glycol, and neopentyl glycol, aromatic glycols such as p-xylene glycol, and 1,4-cyclohexanedimethanol. And polyethylene glycol having an average molecular weight of 150 to 20,000.
  • the mass ratio of the copolymer component of the preferred copolymer is less than 20% by mass. When it is less than 20% by mass, film strength, transparency and heat resistance are maintained, which is preferable.
  • the intrinsic viscosity of at least one kind of resin pellets is preferably in the range of 0.60 to 1.0 dl / g.
  • the intrinsic viscosity is 0.60 dl / g or more, the impact resistance of the obtained film is improved, and it is preferable that the internal circuit is not easily broken by an external impact. Moreover, it contributes to the small deformation when bent repeatedly, which is preferable.
  • the intrinsic viscosity is 1.00 dl / g or less, it is preferable that the film production can be stably operated without excessively increasing the filtration pressure of the molten fluid.
  • the intrinsic viscosity of the film is preferably 0.60 dl / g or more. More preferably, it is 0.62 dl / g or more. More preferably, it is 0.68 dl / g or more. If it is 0.60 dl / g or more, fatigue resistance can be imparted and a sufficient bending resistance effect can be obtained. On the other hand, a film having an intrinsic viscosity of 1.00 dl / g or less is preferable because it can be produced with good operability.
  • the thickness of the polyester film is preferably 10 to 75 ⁇ m, more preferably 25 to 75 ⁇ m.
  • the thickness is 10 ⁇ m or more, an effect of improving pencil hardness is observed, and when the thickness is 75 ⁇ m or less, it is advantageous for weight reduction and excellent in flexibility, workability and handling properties.
  • the surface of the polyester film of the present invention may be smooth or uneven, but since it is used for a display surface cover, a decrease in optical properties due to the unevenness is not preferable.
  • the haze is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. If the haze is 3% or less, the visibility of the image can be improved. The lower limit of the haze is better, but it may be 0.1% or more, or 0.3% or more.
  • the surface polyester resin It can be formed by blending a layer with a filler or coating a coating layer containing a filler during film formation.
  • a known method can be adopted.
  • it can be added at any stage for producing polyester, but it is preferably added as a slurry dispersed in ethylene glycol or the like at the stage of esterification or after the end of the transesterification reaction and before the start of the polycondensation reaction. Then, the polycondensation reaction may proceed.
  • a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material or a method of blending dried particles and a polyester raw material using a kneading extruder Etc.
  • the filtered material is used in the remainder of the polyester raw material before, during or after the esterification reaction.
  • the method of adding is preferable. According to this method, since the monomer liquid has a low viscosity, it is easy to perform homogeneous dispersion of particles and high-accuracy filtration of the slurry, and when added to the rest of the raw material, the dispersibility of the particles is good and new Aggregates are also unlikely to occur. From this point of view, it is particularly preferable to add to the remainder of the raw material in a low temperature state before the esterification reaction.
  • the number of protrusions on the film surface can be further reduced by a method (master batch method) in which polyester containing particles is obtained in advance and the pellets and pellets not containing particles are kneaded and extruded.
  • the polyester film may contain various additives within a range that maintains a preferable range of the total light transmittance.
  • the additive include an antistatic agent, a UV absorber, and a stabilizer.
  • the total light transmittance of the polyester film is preferably 85% or more, and more preferably 87% or more. If there is a transmittance of 85% or more, sufficient visibility can be secured. The higher the total light transmittance of the polyester film, the better. However, it may be 99% or less, or 97% or less.
  • the surface of the polyester film of the present invention can be treated to improve the adhesion with a resin that forms a hard coat layer or the like.
  • Surface treatment methods include, for example, sand blast treatment, roughening treatment by solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc.
  • An oxidation process etc. are mentioned, It can use without limitation.
  • adhesion can be improved by an adhesion improving layer such as an easy adhesion layer.
  • the easy-adhesion layer can be used without particular limitation, such as an acrylic resin, a polyester resin, a polyurethane resin, or a polyether resin, and can be formed by a general coating technique, preferably a so-called in-line coating formulation.
  • the polyester film described above includes, for example, a polymerization process in which inorganic particles are homogeneously dispersed in a monomer liquid that is a part of a polyester raw material and filtered, and then added to the remainder of the polyester raw material to polymerize the polyester, and the polyester is added. It can be manufactured through a film-forming step of forming a base film by melting and extruding it into a sheet form through a filter, and cooling and extruding it.
  • PET polyethylene terephthalate
  • the number of layers is not limited, such as a single layer configuration or a multilayer configuration.
  • PET pellets After PET pellets are mixed and dried at a predetermined ratio, they are supplied to a known melt laminating extruder, extruded into a sheet from a slit-shaped die, and cooled and solidified on a casting roll to form an unstretched film.
  • a single extruder may be used, but in the case of producing a multilayer film, two or more extruders, two or more manifolds or a merge block (for example, a merge having a square merge portion) A plurality of film layers constituting each outermost layer are laminated using a block, two or more sheets are extruded from the die, and cooled with a casting roll to form an unstretched film.
  • the filter medium used for high-precision filtration of the molten resin is not particularly limited, but the filter medium of the stainless sintered body is excellent in removing aggregates and high-melting-point organic substances mainly composed of Si, Ti, Sb, Ge, and Cu. Therefore, it is preferable.
  • the filter particle size (initial filtration efficiency 95%) of the filter medium is preferably 20 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
  • the filter particle size of the filter medium (initial filtration efficiency 95%) exceeds 20 ⁇ m, foreign matters having a size of 20 ⁇ m or more cannot be sufficiently removed.
  • the 0.2% proof stress at least in any one of the longitudinal direction (machine flow direction) and the width direction of the polyester film is preferably 2.6 to 5.0%, more preferably 3.0 to 5.%. More preferably, it is 0%.
  • the 0.2% yield strength point strain is a value used as a substitute for the yield point whether or not the yield point appears in the stress-strain curve, and can be used as an index of the elastic region.
  • FIG. 3 shows a schematic diagram of a stress-strain curve for obtaining 0.2% proof stress.
  • FIG. 3 shows an example where no yield point appears.
  • the 0.2% proof stress is determined by a normal tensile test.
  • the stress-strain curve In the stress-strain curve, a parallel line is drawn from the point Q where the stress is 0 MPa and the strain is 0.2% to OA where the Hooke's law is established, and the point where the stress-strain curve intersects is defined as the proof stress point P.
  • the value of the strain at the intersection H with the strain axis when the angle is lowered is the 0.2% proof stress. As described above, the 0.2% proof stress strain can be obtained from the stress-strain curve.
  • the 0.2% proof stress in the bending direction of the polyester film is preferably 2.6 to 5.0%, and more preferably 3.0 to 5.0%.
  • the bending direction means a direction orthogonal to the folding portion (reference numeral 21) assumed in the use of the surface protection film of the folding display, as indicated by reference numeral 22 on the polyester film (reference numeral 2) in FIG. pointing.
  • the bending direction is not limited to either the longitudinal direction or the width direction of the film.
  • 0.2% proof stress can be adjusted within the above range by adjusting the draw ratio, draw temperature, heat setting temperature, polyester raw material, and the like.
  • the 0.2% proof stress of the polyester film can be adjusted effectively by adjusting the draw ratio.
  • the unstretched polyester sheet preferably has a stretch ratio in at least one of the longitudinal direction (machine flow direction) and the width direction of 1.0 to 3.4 times, more preferably 1.0 to 3.0 times. .
  • the 0.2% yield strength strain can be adjusted to the above-mentioned range, and deformation at the time of repeated folding is small.
  • stretching direction is the said bending direction.
  • the stretching temperature is preferably 80 to 130 ° C, more preferably 90 to 130 ° C.
  • stretching can employ
  • a hot-air heating system such as a hot-air heating system, a roll heating system, and an infrared heating system.
  • the draw ratio in the direction perpendicular to the bending direction when folded is preferably larger than the bending direction.
  • the draw ratio in the direction perpendicular to the bending direction is 2.5-5. .0 can be exemplified. Stable productivity can be obtained by setting the draw ratio to 2.5 times or more, and good impact resistance can be obtained by setting the draw ratio to 5.0 times or less.
  • the crystallinity of the polyester film is preferably 35 to 54%, more preferably 43 to 54%. By increasing the crystallinity, the 0.2% yield strength strain and impact resistance can be improved. In order to effectively increase the crystallinity, it is preferable to perform heat treatment at 180 to 250 ° C. after biaxial stretching. If it is 180 degreeC or more, a crystallinity degree can be raised effectively, and if it is 250 degrees C or less, there is no possibility that the polyester film surface may melt
  • PET pellets are sufficiently vacuum-dried, then supplied to an extruder, melted and extruded into a sheet at about 280 ° C., and cooled and solidified to form an unstretched PET sheet.
  • the obtained unstretched sheet is stretched 1.0 to 3.4 times in the longitudinal direction with a roll heated to 80 to 130 ° C. to obtain a uniaxially oriented PET film.
  • the end of the film is gripped with a clip, guided to a hot air zone heated to 80 to 180 ° C., dried, and stretched 2.5 to 5.0 times in the width direction.
  • a heat treatment zone at 180 to 250 ° C., and heat treatment is performed for 1 to 60 seconds to complete crystal orientation.
  • a relaxation treatment of 1 to 12% may be performed in the width direction or the longitudinal direction as necessary.
  • the polyester film that protects the display by being positioned on the surface of the foldable display preferably has a hard coat layer on the surface.
  • the hard coat layer is preferably used in the display by being positioned on the display surface side on the polyester film.
  • the resin for forming the hard coat layer can be used without particular limitation, such as acrylic, siloxane, inorganic hybrid, urethane acrylate, polyester acrylate, and epoxy.
  • two or more kinds of materials can be mixed and used, and particles such as an inorganic filler and an organic filler can be added.
  • the film thickness of the hard coat layer is preferably 1 to 50 ⁇ m. 1 to 40 ⁇ m is more preferable. If it is thicker than 1 ⁇ m, it is sufficiently cured and a good pencil hardness is obtained. Further, by setting the thickness to 50 ⁇ m or less, curling due to curing shrinkage of the hard coat can be suppressed, and the handleability of the film can be improved. More preferably, it is 2 to 25 ⁇ m, particularly preferably 2 to 20 ⁇ m, and most preferably 3 to 15 ⁇ m.
  • a coating method of a hard-coat layer it can use without limitation, such as a Mayer bar, a gravure coat, a die coater, a knife coater, and can be suitably selected according to a viscosity and a film thickness.
  • the pencil hardness of the hard coat layer is preferably B or higher, more preferably H or higher, and particularly preferably 2H or higher. If the pencil hardness is greater than or equal to B, it will not be easily scratched and visibility will not be reduced. Generally, the pencil hardness of the hard coat layer is preferably higher, but it may be 10H or less, 8H or less, and 6H or less can be used practically without any problem.
  • the hard coat layer in the present invention may be provided with other functions as long as it can be used for the purpose of protecting the display by increasing the pencil hardness of the surface as described above.
  • a hard coat layer to which functionality such as an antiglare layer having a certain pencil hardness as described above, an antiglare antireflection layer, an antireflection layer, a low reflection layer, and an antistatic layer is added in the present invention. Is preferably applied.
  • the density of the film sample was measured at three points. The average value was defined as the crystallinity.
  • the resin component is a mixture of completely amorphous and completely crystal, and the density is as described later.
  • the density of the sample is a value obtained by dividing the total mass of each component constituting the sample by the total volume of each component.
  • the crystallinity (weight ratio) of each resin was estimated based on the assumption that The sample density was measured in accordance with a method (density gradient tube method) based on JISK-7112-1980.
  • the density of each component used the following value (unit: g / cm3)
  • Polyethylene terephthalate resin complete amorphous 1.34, complete crystal 1.46
  • Polyethylene naphthalate resin complete amorphous 1.32, complete crystal 1.41
  • a polyester film was cut into a size of 200 mm (bending direction) ⁇ 50 mm (perpendicular direction) to prepare a measurement sample.
  • Spacers were formed by arranging spacers of various thicknesses at the ends of two glass plates having a thickness of 5 mm, and the film was held for 10 seconds. Immediately after that, the film was made to reflect the light of the fluorescent lamp, the folding part was observed, and the interval at which no folding marks were made was recorded.
  • ⁇ The interval at which no folding marks were made was less than 6.5 mm.
  • ⁇ Even when the sample is not deformed or deformed, when it is placed horizontally, the maximum height is less than 3 mm.
  • ⁇ The sample is deformed, and when placed horizontally, the maximum height is 3 mm or more and less than 5 mm.
  • X The sample has a crease or when the sample is placed horizontally, the maximum height is 5 mm or more.
  • Pencil hardness The hard coat-coated polyester film prepared in accordance with JIS K 5600-5-4: 1999 was measured at a load of 750 g and a speed of 0.5 mm / s.
  • Coating liquid 1 for forming a hard coat layer To 100 parts by weight of hard coat material (manufactured by JSR, Opstar (registered trademark) Z7503, concentration 75%), 0.1 part by weight of a leveling agent (BYK307, concentration 100%) is added, and methyl ethyl ketone is added. Diluted to prepare a hard coat coating solution 1 having a solid concentration of 40% by weight.
  • a leveling agent BYK307, concentration 100%
  • a continuous esterification reaction apparatus comprising a three-stage complete mixing tank having a stirrer, a partial condenser, a raw material charging port, and a product take-out port is used.
  • TPA is set to 2 ton / hr
  • EG is set to TPA1.
  • the amount of antimony trioxide is 2 mol per mol
  • the amount of Sb atoms is 160 ppm with respect to the produced PET, and these slurries are continuously supplied to the first esterification reactor of the esterification reactor, 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 reaction can is continuously taken out of the system, supplied to the second esterification reaction can, and distilled from the first esterification reaction can into the second esterification reaction can.
  • An EG solution containing TMPA in an amount of 1 was added and allowed to react at 260 ° C. with an average residence time of 1.5 hours at normal pressure.
  • the reaction product in the second esterification reaction can is continuously taken out of the system and supplied to the third esterification reaction can, and further contains TMPA in an amount of 20 ppm of P atoms with respect to the produced PET.
  • the EG solution was added and reacted at 260 ° C. at normal pressure with an average residence time of 0.5 hours.
  • the esterification reaction product produced in the third esterification reaction can is continuously supplied to a three-stage continuous polycondensation reaction apparatus to carry out polycondensation, and further, a filter medium of a stainless sintered body (nominal filtration accuracy of 5 ⁇ m). The particles were filtered with a 90% cut particle) to obtain polyethylene terephthalate pellets A having an intrinsic viscosity of 0.62 dl / g.
  • Polyethylene terephthalate pellet A is 0.5 mmH using a rotary vacuum polymerization apparatus. Under reduced pressure of g, solid-state polymerization was carried out at 220 ° C. for varying times to prepare polyethylene terephthalate pellets B having an intrinsic viscosity of 0.72 dL / g.
  • Example 1 The polyethylene terephthalate master pellet B is dried under reduced pressure at 150 ° C. for 8 hours ( 3 Torr), polyethylene terephthalate pellets B were fed to the extruder and melted at 285 ° C. This polymer is filtered with a filter material of stainless sintered body (nominal filtration accuracy 10 ⁇ m particles 95% cut), extruded into a sheet form from the die, and then applied to a casting drum having a surface temperature of 30 ° C. using an electrostatic application casting method. It was brought into contact and cooled and solidified to produce an unstretched film. This unstretched film was uniformly heated to 75 ° C. using a heating roll and heated to 100 ° C.
  • a filter material of stainless sintered body nominal filtration accuracy 10 ⁇ m particles 95% cut
  • Example 2 A polyester film was obtained in the same manner as in Example 1 except that the draw ratio and heat treatment temperature described in Table 1 were changed.
  • Example 7 A polyester film was obtained in the same manner as in Example 1 except that the thickness was changed to the thickness described in Table 1.
  • Example 9 A polyester film was obtained in the same manner as in Example 1 except that polyethylene-2,6-naphthalate pellet C was used and the temperature was adjusted as shown in Table 1.
  • Example 10 A polyester film was obtained in the same manner as in Example 1 except that the polyethylene terephthalate master pellet A was changed.
  • Example 1 A polyester film was obtained in the same manner as in Example 1 except that the longitudinal draw ratio was changed to 3.5.
  • the film thickness after drying the hard coat layer forming coating solution 1 is 5.0 ⁇ m. And dried at 80 ° C. for 1 minute, and then irradiated with ultraviolet rays (high pressure mercury lamp, integrated light quantity 200 mJ / cm 2 ) to obtain a hard coat film.
  • a hard coat film was obtained in the same manner as in Example 1 except that the polyester film obtained in Example 1 was applied so that the film thickness after drying was 10.0 ⁇ m.
  • Example 12 a hard coat film was obtained in the same manner as in Example 1, except that the hard coat layer forming coating solution 2 was applied to the polyester film obtained in Example 1.
  • a smartphone-type foldable display in which these hard coat films are bonded to an organic EL module via an adhesive layer with a thickness of 25 ⁇ m and can be folded in half at the center of the entire 3 mm radius corresponding to the bending radius in FIG. It was created.
  • the hard coat film is disposed on the surface of one continuous display through the folding portion, and the hard coat layer is disposed on the surface of the display.
  • the polyester film or the hard coat film positioned on the surface of the foldable display while maintaining mass productivity. Since the image is not deformed after being repeatedly folded, the image is not disturbed at the folded portion of the display.
  • a portable terminal device equipped with a foldable display using the polyester film or hard coat film of the present invention as a surface protective film provides a beautiful image, is rich in functionality, and has excellent convenience such as portability. .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention porte sur un dispositif d'affichage pliable bien approprié pour une production de masse et provoquant peu de distorsion sur une image affichée sur une partie pliée même après un pliage répété, et sur un dispositif de terminal mobile équipé du dispositif d'affichage pliable. À cette fin, la présente invention porte également sur un film de polyester et sur un film de revêtement dur comme film de protection de surface. Un film de polyester servant de film de protection de surface pour un dispositif d'affichage pliable présente une épaisseur comprise entre 10 et 75 µm et une déformation à 0,2 % de contrainte d'épreuve comprise entre 2,6 et 5,0 % au moins soit dans le sens de la longueur, soit dans le sens de la largeur. Un film de revêtement dur, un dispositif d'affichage pliable et un dispositif de terminal mobile utilisent le film de polyester comme film de protection de surface pour un dispositif d'affichage pliable.
PCT/JP2018/004956 2017-03-02 2018-02-14 Film de polyester en tant que film de protection de surface pour un dispositif d'affichage pliable et son application WO2018159285A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018517640A JP7247584B2 (ja) 2017-03-02 2018-02-14 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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-039325 2017-03-02
JP2017039325 2017-03-02

Publications (1)

Publication Number Publication Date
WO2018159285A1 true WO2018159285A1 (fr) 2018-09-07

Family

ID=63370774

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/004956 WO2018159285A1 (fr) 2017-03-02 2018-02-14 Film de polyester en tant que film de protection de surface pour un dispositif d'affichage pliable et son application

Country Status (3)

Country Link
JP (3) JP7247584B2 (fr)
TW (1) TWI782952B (fr)
WO (1) WO2018159285A1 (fr)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019082834A1 (fr) * 2017-10-24 2019-05-02 東洋紡株式会社 Film de polyester destiné à être utilisé en tant que film de protection de surface d'un affichage souple
WO2019216172A1 (fr) * 2018-05-07 2019-11-14 東洋紡株式会社 Dispositif d'affichage de type pliable et dispositif terminal portable
JP2020111640A (ja) * 2019-01-09 2020-07-27 東洋紡株式会社 ポリエステルフィルムとその用途
WO2020162119A1 (fr) * 2019-02-08 2020-08-13 東洋紡株式会社 Film de polyester et son utilisation
WO2020162120A1 (fr) * 2019-02-08 2020-08-13 東洋紡株式会社 Écran pliable et équipement terminal portable
WO2020179643A1 (fr) * 2019-03-01 2020-09-10 大日本印刷株式会社 Couche de résine, film optique et dispositif d'affichage d'image
CN111909403A (zh) * 2019-05-08 2020-11-10 Skc株式会社 聚酯膜及包含其的柔性显示装置
JP2020183528A (ja) * 2019-05-08 2020-11-12 エスケイシー・カンパニー・リミテッドＳｋｃ Ｃｏ．， Ｌｔｄ． ポリエステルフィルムおよびこれを含むフレキシブルディスプレイ装置
WO2020241278A1 (fr) * 2019-05-28 2020-12-03 東洋紡株式会社 Film multicouche et son utilisation
WO2020241281A1 (fr) * 2019-05-28 2020-12-03 東洋紡株式会社 Film de polyester conducteur transparent et son utilisation
WO2020241279A1 (fr) * 2019-05-28 2020-12-03 東洋紡株式会社 Film en polyester, film stratifié et utilisation associée
WO2020241313A1 (fr) * 2019-05-30 2020-12-03 東洋紡株式会社 Écran pliable
WO2021010159A1 (fr) * 2019-07-12 2021-01-21 東洋紡株式会社 Film de revêtement dur pour affichage pliable, et application dudit film
JPWO2021010158A1 (fr) * 2019-07-12 2021-01-21
JP2021009349A (ja) * 2019-02-08 2021-01-28 東洋紡株式会社 ポリエステルフィルムとその用途
CN112714931A (zh) * 2018-09-21 2021-04-27 三菱化学株式会社 折叠式显示器
CN112724432A (zh) * 2019-10-28 2021-04-30 Skc株式会社 聚酯膜和包括其的柔性显示设备
KR20210058787A (ko) * 2018-11-08 2021-05-24 에스케이씨 주식회사 플렉서블 디스플레이 장치를 위한 폴리에스테르 보호 필름
JP2021521039A (ja) * 2018-10-31 2021-08-26 エルジー・ケム・リミテッド ハードコーティング積層体
WO2021215349A1 (fr) * 2020-04-22 2021-10-28 東洋紡株式会社 Film de polyester et son utilisation
WO2022102736A1 (fr) * 2020-11-16 2022-05-19 株式会社ダイセル Film stratifié et dispositif souple
CN114591605A (zh) * 2020-12-07 2022-06-07 Skc株式会社 聚酯膜及其制备方法
WO2022220177A1 (fr) * 2021-04-15 2022-10-20 住友化学株式会社 Plaque polarisante, stratifié et dispositif d'affichage
US11776710B2 (en) 2018-03-09 2023-10-03 Dai Nippon Printing Co., Ltd. Electroconductive film, sensor, touch panel, and image display device
US11796719B2 (en) * 2018-10-11 2023-10-24 Lg Chem, Ltd. Protection film for foldable display and foldable display device comprising same
KR20230161475A (ko) 2021-03-24 2023-11-27 도요보 가부시키가이샤 폴리에스테르 필름 및 그것을 이용한 화상 표시 장치
US11926720B2 (en) 2019-05-28 2024-03-12 Toyobo Co., Ltd. Polyester film and application therefor
WO2024058059A1 (fr) * 2022-09-16 2024-03-21 東洋紡株式会社 Film de polyester et son utilisation
WO2024058058A1 (fr) * 2022-09-16 2024-03-21 東洋紡株式会社 Film de polyester et son utilisation
JP7552072B2 (ja) 2019-05-28 2024-09-18 東洋紡株式会社 積層フィルムとその用途

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7292051B2 (ja) * 2019-02-22 2023-06-16 住友化学株式会社 フレキシブル積層体、およびそれを備えた画像表示装置
CN115556967B (zh) * 2022-10-27 2024-05-28 浙江大学 一种考虑材料厚度的柔性防护结构折叠方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012156436A (ja) * 2011-01-28 2012-08-16 Toray Ind Inc 透明導電性基板
JP2016002764A (ja) * 2014-06-19 2016-01-12 日本合成化学工業株式会社 積層体及びその用途、並びに積層体の製造方法
JP2016126130A (ja) * 2014-12-26 2016-07-11 日東電工株式会社 有機ｅｌ表示装置用積層体及び有機ｅｌ表示装置
JP2017013492A (ja) * 2015-06-26 2017-01-19 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. 積層フィルム及びそれを含む画像表示装置
US20170032737A1 (en) * 2015-07-31 2017-02-02 Lg Display Co., Ltd. Flexible display device and method for fabricating the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5536697B2 (ja) * 2011-03-15 2014-07-02 三菱樹脂株式会社 積層ポリエステルフィルム
JP5883352B2 (ja) * 2012-06-12 2016-03-15 富士フイルム株式会社 積層フィルムおよびタッチパネル
JP6226762B2 (ja) * 2014-01-31 2017-11-08 富士フイルム株式会社 光学用ポリエステルフィルム、偏光板、画像表示装置、光学用ポリエステルフィルムの製造方法、および易接着層用組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012156436A (ja) * 2011-01-28 2012-08-16 Toray Ind Inc 透明導電性基板
JP2016002764A (ja) * 2014-06-19 2016-01-12 日本合成化学工業株式会社 積層体及びその用途、並びに積層体の製造方法
JP2016126130A (ja) * 2014-12-26 2016-07-11 日東電工株式会社 有機ｅｌ表示装置用積層体及び有機ｅｌ表示装置
JP2017013492A (ja) * 2015-06-26 2017-01-19 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. 積層フィルム及びそれを含む画像表示装置
US20170032737A1 (en) * 2015-07-31 2017-02-02 Lg Display Co., Ltd. Flexible display device and method for fabricating the same

Cited By (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019082834A1 (fr) * 2017-10-24 2019-05-02 東洋紡株式会社 Film de polyester destiné à être utilisé en tant que film de protection de surface d'un affichage souple
US11776710B2 (en) 2018-03-09 2023-10-03 Dai Nippon Printing Co., Ltd. Electroconductive film, sensor, touch panel, and image display device
WO2019216172A1 (fr) * 2018-05-07 2019-11-14 東洋紡株式会社 Dispositif d'affichage de type pliable et dispositif terminal portable
US12066864B2 (en) 2018-05-07 2024-08-20 Toyobo Co., Ltd. Folding-type display and portable terminal device
CN112714931A (zh) * 2018-09-21 2021-04-27 三菱化学株式会社 折叠式显示器
US11796719B2 (en) * 2018-10-11 2023-10-24 Lg Chem, Ltd. Protection film for foldable display and foldable display device comprising same
JP7060202B2 (ja) 2018-10-31 2022-04-26 エルジー・ケム・リミテッド ハードコーティング積層体
JP2021521039A (ja) * 2018-10-31 2021-08-26 エルジー・ケム・リミテッド ハードコーティング積層体
KR102363956B1 (ko) * 2018-11-08 2022-02-17 에스케이씨 주식회사 플렉서블 디스플레이 장치를 위한 폴리에스테르 보호 필름
KR20210058787A (ko) * 2018-11-08 2021-05-24 에스케이씨 주식회사 플렉서블 디스플레이 장치를 위한 폴리에스테르 보호 필름
JP2020111640A (ja) * 2019-01-09 2020-07-27 東洋紡株式会社 ポリエステルフィルムとその用途
US11997916B2 (en) 2019-02-08 2024-05-28 Toyobo Co., Ltd. Polyester film and use thereof
US11934226B2 (en) 2019-02-08 2024-03-19 Toyobo Co., Ltd. Foldable display and portable terminal device
CN113396179A (zh) * 2019-02-08 2021-09-14 东洋纺株式会社 聚酯薄膜及其用途
WO2020162120A1 (fr) * 2019-02-08 2020-08-13 東洋紡株式会社 Écran pliable et équipement terminal portable
WO2020162119A1 (fr) * 2019-02-08 2020-08-13 東洋紡株式会社 Film de polyester et son utilisation
JP2023061931A (ja) * 2019-02-08 2023-05-02 東洋紡株式会社 ポリエステルフィルムとその用途
JP2021009349A (ja) * 2019-02-08 2021-01-28 東洋紡株式会社 ポリエステルフィルムとその用途
JP7484882B2 (ja) 2019-03-01 2024-05-16 大日本印刷株式会社 樹脂層、光学フィルムおよび画像表示装置
WO2020179643A1 (fr) * 2019-03-01 2020-09-10 大日本印刷株式会社 Couche de résine, film optique et dispositif d'affichage d'image
CN111909403A (zh) * 2019-05-08 2020-11-10 Skc株式会社 聚酯膜及包含其的柔性显示装置
US11745470B2 (en) 2019-05-08 2023-09-05 Sk Microworks Co., Ltd. Polyester film and flexible display device comprising the same
CN111909403B (zh) * 2019-05-08 2024-04-09 爱思开迈克沃有限公司 聚酯膜及包含其的柔性显示装置
KR20200129372A (ko) * 2019-05-08 2020-11-18 에스케이씨 주식회사 폴리에스테르 필름 및 이를 포함하는 플렉서블 디스플레이 장치
JP2020183528A (ja) * 2019-05-08 2020-11-12 エスケイシー・カンパニー・リミテッドＳｋｃ Ｃｏ．， Ｌｔｄ． ポリエステルフィルムおよびこれを含むフレキシブルディスプレイ装置
KR102308471B1 (ko) * 2019-05-08 2021-10-05 에스케이씨 주식회사 폴리에스테르 필름 및 이를 포함하는 플렉서블 디스플레이 장치
CN113874212B (zh) * 2019-05-28 2023-10-24 东洋纺株式会社 层叠薄膜及其用途
JP7552072B2 (ja) 2019-05-28 2024-09-18 東洋紡株式会社 積層フィルムとその用途
JP7435449B2 (ja) 2019-05-28 2024-02-21 東洋紡株式会社 透明導電性ポリエステルフィルムとその用途
US11899167B2 (en) 2019-05-28 2024-02-13 Toyobo Co., Ltd. Polyester film, laminated film, and use thereof
CN113874211A (zh) * 2019-05-28 2021-12-31 东洋纺株式会社 透明导电性聚酯薄膜及其用途
CN113874212A (zh) * 2019-05-28 2021-12-31 东洋纺株式会社 层叠薄膜及其用途
CN113924331A (zh) * 2019-05-28 2022-01-11 东洋纺株式会社 聚酯薄膜、层叠薄膜及其用途
EP3978244A4 (fr) * 2019-05-28 2023-06-07 Toyobo Co., Ltd. Film multicouche et son utilisation
JP7435448B2 (ja) 2019-05-28 2024-02-21 東洋紡株式会社 積層フィルムとその用途
JPWO2020241281A1 (fr) * 2019-05-28 2020-12-03
WO2020241278A1 (fr) * 2019-05-28 2020-12-03 東洋紡株式会社 Film multicouche et son utilisation
US11939499B2 (en) 2019-05-28 2024-03-26 Toyobo Co., Ltd. Multilayer film and use of same
WO2020241281A1 (fr) * 2019-05-28 2020-12-03 東洋紡株式会社 Film de polyester conducteur transparent et son utilisation
WO2020241279A1 (fr) * 2019-05-28 2020-12-03 東洋紡株式会社 Film en polyester, film stratifié et utilisation associée
CN113874211B (zh) * 2019-05-28 2024-05-10 东洋纺株式会社 透明导电性聚酯薄膜及其用途
JPWO2020241278A1 (fr) * 2019-05-28 2020-12-03
US11926720B2 (en) 2019-05-28 2024-03-12 Toyobo Co., Ltd. Polyester film and application therefor
JPWO2020241313A1 (ja) * 2019-05-30 2021-09-13 東洋紡株式会社 折りたたみ型ディスプレイ
WO2020241313A1 (fr) * 2019-05-30 2020-12-03 東洋紡株式会社 Écran pliable
WO2021010158A1 (fr) * 2019-07-12 2021-01-21 東洋紡株式会社 Film de revêtement dur destiné à un dispositif d'affichage pliable et son utilisation
JPWO2021010159A1 (fr) * 2019-07-12 2021-01-21
JPWO2021010158A1 (fr) * 2019-07-12 2021-01-21
WO2021010159A1 (fr) * 2019-07-12 2021-01-21 東洋紡株式会社 Film de revêtement dur pour affichage pliable, et application dudit film
US11551584B2 (en) 2019-10-28 2023-01-10 Skc Co., Ltd. Polyester film and flexible display apparatus comprising same
CN112724432A (zh) * 2019-10-28 2021-04-30 Skc株式会社 聚酯膜和包括其的柔性显示设备
JP2021066881A (ja) * 2019-10-28 2021-04-30 エスケイシー・カンパニー・リミテッドＳｋｃ Ｃｏ．， Ｌｔｄ． ポリエステルフィルムおよびこれを含むフレキシブルディスプレイ装置
JP7369112B2 (ja) 2019-10-28 2023-10-25 エスケーマイクロワークス 株式会社 ポリエステルフィルムおよびこれを含むフレキシブルディスプレイ装置
JP7447994B2 (ja) 2020-04-22 2024-03-12 東洋紡株式会社 ポリエステルフィルムとその用途
JPWO2021215349A1 (fr) * 2020-04-22 2021-10-28
WO2021215349A1 (fr) * 2020-04-22 2021-10-28 東洋紡株式会社 Film de polyester et son utilisation
JP2022081716A (ja) * 2020-11-16 2022-06-01 株式会社ダイセル 積層フィルム、及びフォルダブルデバイス
JP7074825B1 (ja) 2020-11-16 2022-05-24 株式会社ダイセル 積層フィルム、及びフォルダブルデバイス
WO2022102736A1 (fr) * 2020-11-16 2022-05-19 株式会社ダイセル Film stratifié et dispositif souple
CN114591605B (zh) * 2020-12-07 2023-08-08 爱思开迈克沃有限公司 聚酯膜及其制备方法
US11642825B2 (en) 2020-12-07 2023-05-09 Skc Co., Ltd. Polyester film and preperation method thereof
JP7212750B2 (ja) 2020-12-07 2023-01-25 エスケイシー・カンパニー・リミテッド ポリエステル系フィルムおよびその製造方法
JP2022090636A (ja) * 2020-12-07 2022-06-17 エスケイシー・カンパニー・リミテッド ポリエステル系フィルムおよびその製造方法
US20220176605A1 (en) * 2020-12-07 2022-06-09 Skc Co., Ltd. Polyester film and preperation method thereof
CN114591605A (zh) * 2020-12-07 2022-06-07 Skc株式会社 聚酯膜及其制备方法
KR20230161475A (ko) 2021-03-24 2023-11-27 도요보 가부시키가이샤 폴리에스테르 필름 및 그것을 이용한 화상 표시 장치
WO2022220177A1 (fr) * 2021-04-15 2022-10-20 住友化学株式会社 Plaque polarisante, stratifié et dispositif d'affichage
WO2024058059A1 (fr) * 2022-09-16 2024-03-21 東洋紡株式会社 Film de polyester et son utilisation
WO2024058058A1 (fr) * 2022-09-16 2024-03-21 東洋紡株式会社 Film de polyester et son utilisation

Also Published As

Publication number Publication date
JP7247584B2 (ja) 2023-03-29
TW201842006A (zh) 2018-12-01
JP7568005B2 (ja) 2024-10-16
JP2023153164A (ja) 2023-10-17
JPWO2018159285A1 (ja) 2019-12-19
TWI782952B (zh) 2022-11-11
JP7327629B2 (ja) 2023-08-16
JP2023033345A (ja) 2023-03-10

Similar Documents

Publication Publication Date Title
JP7568005B2 (ja) 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
JP2018072663A (ja) 折りたたみ型ディスプレイ及び携帯端末機器
JP7180375B2 (ja) ポリエステルフィルムとその用途
JPWO2020162120A1 (ja) 折りたたみ型ディスプレイ及び携帯端末機器
WO2020241278A1 (fr) Film multicouche et son utilisation
WO2019202992A1 (fr) Film de polyester pour film de protection de surface ou dispositid d'affichage pliable et son utilisation
JP7447994B2 (ja) ポリエステルフィルムとその用途
WO2021182191A1 (fr) Film de polyester et son utilisation
JP2024059634A (ja) 折りたたみ型ディスプレイ及び携帯端末機器
JP2020196255A (ja) ポリエステルフィルムとその用途
JP2024083397A (ja) ポリエステルフィルムとその用途
JP2024045213A (ja) 折りたたみ型ディスプレイ用表面保護フィルム
WO2024058059A1 (fr) Film de polyester et son utilisation
WO2024058058A1 (fr) Film de polyester et son utilisation
JP2020111640A (ja) ポリエステルフィルムとその用途
JP2020185789A (ja) ハードコートフィルムとその用途
JP2023061931A (ja) ポリエステルフィルムとその用途

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018517640

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18760326

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18760326

Country of ref document: EP

Kind code of ref document: A1