WO2013111641A1 - Film de polyester et procédé de fabrication associé - Google Patents

Film de polyester et procédé de fabrication associé Download PDF

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Publication number
WO2013111641A1
WO2013111641A1 PCT/JP2013/050620 JP2013050620W WO2013111641A1 WO 2013111641 A1 WO2013111641 A1 WO 2013111641A1 JP 2013050620 W JP2013050620 W JP 2013050620W WO 2013111641 A1 WO2013111641 A1 WO 2013111641A1
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WO
WIPO (PCT)
Prior art keywords
film
polyester
polyester film
acid
temperature
Prior art date
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Ceased
Application number
PCT/JP2013/050620
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English (en)
Japanese (ja)
Inventor
高橋健太
堀江将人
東大路卓司
町田哲也
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Toray Industries Inc
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Toray Industries Inc
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.)
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Publication date
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Priority to CN201380005768.1A priority Critical patent/CN104053535B/zh
Priority to KR1020147019196A priority patent/KR102002798B1/ko
Priority to JP2013502720A priority patent/JP5962648B2/ja
Publication of WO2013111641A1 publication Critical patent/WO2013111641A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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 biaxially oriented polyester film excellent in thermal dimensional stability particularly in a high temperature range.
  • the biaxially oriented polyester film of the present invention can be suitably used for a substrate film for flexible devices.
  • the biaxially oriented polyester film of the present invention is a substrate for organic electroluminescence (hereinafter sometimes abbreviated as EL) displays, electronic paper, organic EL lighting, organic solar cells, and dye-sensitized solar cells.
  • EL organic electroluminescence
  • Biaxially oriented polyester film utilizes its excellent thermal properties, dimensional stability, mechanical properties, electrical properties, heat resistance, and surface properties to provide magnetic recording materials, packaging materials, electrical insulating materials, various photographic materials, graphic arts It is widely used as a base material for many applications such as materials or optical display materials. However, further improvements in physical properties are necessary for the base film for flexible devices.
  • a method of blending other thermoplastic resins with polyester Patent Document 1
  • a method of adding particles at a high concentration to lower the thermal expansion coefficient Patent Document 2
  • heat In order to reduce the shrinkage rate, a method of relaxing and annealing (Patent Document 3) is disclosed.
  • the method of blending the thermoplastic resin described in Patent Document 1 cannot sufficiently reduce the thermal expansion coefficient because polyester is difficult to be oriented. Moreover, in the method disclosed in Patent Document 2, if the particles are added at a high concentration, the stretchability is deteriorated, so that the thermal expansion coefficient cannot be sufficiently reduced. Furthermore, the technique described in Patent Document 3 is intended to reduce the thermal contraction rate, and cannot reduce the thermal expansion coefficient. Thus, it is difficult to achieve both low thermal expansion and low thermal shrinkage.
  • the object of the present invention is to solve the above-mentioned problems and to obtain a biaxially oriented polyester film excellent in thermal dimensional stability particularly in a high temperature range, and in particular, various processes when used as a base film for flexible devices. It is an object of the present invention to provide a biaxially oriented polyester film that can reduce the dimensional change in the film, has a small curl, and has excellent processability.
  • the present invention is intended to achieve the above object and has the following characteristics.
  • a value (fn / ⁇ c) obtained by dividing the plane orientation coefficient (fn) by the crystallinity ( ⁇ c) is 0.50 or more.
  • the polyester film according to (1) or (2) which has a film haze value of 0 to 3%.
  • the polyester contains a crystal nucleating agent, and the content of the crystal nucleating agent is 0.01 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the polyester.
  • the polyester film in any one.
  • the polyester resin is cooled and solidified while being melt-extruded to obtain an unstretched film.
  • the unstretched film is biaxially stretched, and then the heat setting temperature Ths (° C.) is 180 to 220 ° C.
  • Ths ° C.
  • a polyester film having excellent thermal dimensional stability in a high temperature range can be obtained.
  • a base film for a flexible device it is possible to reduce dimensional changes in various processes, and in particular, it is possible to obtain a polyester film having excellent flatness with small curl in the annealing process.
  • the crystallization index (hereinafter sometimes referred to as ⁇ Tcg) is 10 ° C. or more and 60 ° C. or less in order to satisfy the thermal dimensional stability in a high temperature range.
  • ⁇ Tcg is in the above range, the formation of microcrystals is promoted in the polyester film, thereby improving the thermal dimensional stability at high temperatures.
  • high-temperature thermal shrinkage before the relaxation annealing process (which is an annealing process while relaxing) described later is reduced, and as a result, the flatness of the film is improved in the relaxation annealing process.
  • ⁇ Tcg When ⁇ Tcg is less than 10 ° C., the crystallinity is excessively increased, which may lead to deterioration of stretchability and make film formation difficult. On the other hand, when ⁇ Tcg exceeds 60 ° C., high temperature thermal shrinkage increases, and thermal dimensional stability at high temperatures may be insufficient. ⁇ Tcg is more preferably 30 to 50 ° C. As a method for setting ⁇ Tcg within the above range, it is preferable to use polyester prepared by adding at least one kind of crystal nucleating agent to polyester and adjusting the crystallization rate to be high by the crystal nucleating agent effect.
  • the crystal nucleating agent may be a compound used as a transesterification catalyst or a polymerization catalyst.
  • a method in which lithium acetate, magnesium acetate, potassium acetate, phosphorous acid, phosphonic acid, phosphinic acid or their derivatives, antimony oxide, and germanium oxide are present during transesterification and polymerization is effective.
  • a particularly preferred desirable combination is magnesium acetate and phosphonic acid (or a derivative thereof) and antimony oxide, and examples of phosphonic acid (or a derivative thereof) include phenylphosphonic acid and dimethylphenylphosphonate.
  • Crystal nucleating agents include talc, aliphatic carboxylic acid amides, aliphatic carboxylates, aliphatic alcohols, aliphatic carboxylic acid esters, aliphatic / aromatic carboxylic acid hydrazides, sorbitol compounds, and organic phosphoric acid compounds. It can be selected preferably. Among these, it is particularly desirable that the polyester of the present invention contains at least one crystal nucleating agent selected from aliphatic carboxylic acid amides, aliphatic carboxylates and sorbitol compounds.
  • the polyester is 100 parts by mass
  • the crystal nucleating agent is 0.01 parts by mass or more and 2 parts by mass or less, and more preferably the crystal nucleating agent is 0.1 parts by mass or more and 2 parts by mass. It is below mass parts.
  • the content of the crystal nucleating agent is less than 0.01 parts by mass, the effect may not be sufficiently exhibited.
  • the content of the crystal nucleating agent exceeds 2 parts by mass, the transparency may be impaired.
  • aliphatic carboxylic acid amides include aliphatic monocarboxylic acids such as lauric acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, and hydroxy stearic acid amide.
  • Acid amides N-oleyl palmitic acid amide, N-oleyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl oleic acid amide, N-stearyl stearic acid amide, N-stearyl erucic acid amide, methylol stearic acid amide N-substituted aliphatic monocarboxylic amides such as methylol behenic acid amide, methylene bis stearic acid amide, ethylene bis lauric acid amide, ethylene bis capric acid amide, ethylene bis oleic acid amide, ethylene bis Arynic acid amide, ethylene biserucic acid amide, ethylene bis behenic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, butylene bisstearic acid amide, hexamethylene bisoleic acid amide, hexamethylene bisstearic acid Alipha
  • aliphatic monocarboxylic acid amides may be one kind or a mixture of two or more kinds.
  • aliphatic monocarboxylic acid amides, N-substituted aliphatic monocarboxylic acid amides, and aliphatic biscarboxylic acid amides are preferably used, particularly palmitic acid amide, stearic acid amide, erucic acid amide, and behenic acid.
  • Amide, ricinoleic acid amide, hydroxystearic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide, ethylene biscapric acid amide, ethylene bisoleic acid amide, ethylene bislauric acid amide, ethylene biserucic acid amide, m -Xylylene bis-stearic acid amide and m-xylylene bis-12-hydroxystearic acid amide are preferably used.
  • aliphatic carboxylate examples include acetates such as sodium acetate, potassium acetate, magnesium acetate, calcium acetate, sodium laurate, potassium laurate, potassium hydrogen laurate, magnesium laurate, calcium laurate, zinc laurate , Laurates such as silver laurate, lithium myristate, sodium myristate, potassium hydrogen myristate, magnesium myristate, calcium myristate, zinc myristate, silver myristate, myristate, lithium palmitate, palmitic acid Palmitates such as potassium, magnesium palmitate, calcium palmitate, zinc palmitate, copper palmitate, lead palmitate, thallium palmitate, cobalt palmitate, etc., sodium oleate Oleates such as potassium oleate, magnesium oleate, calcium oleate, zinc oleate, lead oleate, thallium oleate, copper oleate, nickel oleate, sodium stearate, lithium stearate, magnesium steacetate,
  • stearic acid salts and montanic acid salts are preferably used, and in particular, sodium stearate, potassium stearate, zinc stearate, barium stearate, sodium montanate, and the like are suitably used.
  • aliphatic alcohols include aliphatic monoalcohols such as pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol, and melyl alcohol, 1,6-hexane.
  • aliphatic carboxylic acid ester examples include lauric acid cetyl ester, lauric acid phenacyl ester, myristic acid cetyl ester, myristic acid phenacyl ester, palmitic acid isopropylidene ester, palmitic acid dodecyl ester, palmitic acid tetradodecyl ester, Palmitic acid pentadecyl ester, palmitic acid octadecyl ester, palmitic acid cetyl ester, palmitic acid phenyl ester, palmitic acid phenacyl ester, stearic acid cetyl ester, aliphatic monocarboxylic acid esters such as behenic acid ethyl ester, monolauric acid glycol, Monoesters of ethylene glycol such as glycol monopalmitate and glycol monostearate, glycol dilaurate, dipalmitin Diesters of ethylene glycol such as glycol and
  • aliphatic / aromatic carboxylic acid hydrazides include sebacic acid dibenzoic acid hydrazide
  • specific examples of melamine compounds include melamine cyanurate, melamine polyvinic acid, and phenylphosphonic acid metal salts such as phenyl.
  • a phosphonic acid zinc salt, a phenylphosphonic acid calcium salt, a phenylphosphonic acid magnesium salt, a phenylphosphonic acid magnesium salt, and the like can be used.
  • sorbitol compounds include 1,3-di (P-methylbenzylidene) sorbitol, 2,4-di (P-methylbenzylidene) sorbitol, 1,3-dibenzylidenesorbitol, 2,4-dibenzylidenesorbitol, Examples include 3-di (P-ethyldibenzylidene) sorbitol and 2,4-di (P-ethyldibenzylidene) sorbitol.
  • organic phosphate compound examples include sodium bis (4-t-butylphenyl) phosphate, sodium 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, cyclic organic phosphate basic Examples thereof include a mixture selected from a polyvalent metal salt and an alkali metal carboxylate, an alkali metal ⁇ -diketonate and an alkali metal ⁇ -ketoacetate salt or an organic carboxylic acid metal salt.
  • aliphatic carboxylic acid amides, aliphatic carboxylates and sorbitol compounds are preferably used from the viewpoint of transparency and heat resistance.
  • the polyester film of the present invention has a plane orientation coefficient (fn) of 0.15 or more and 0.28 or less. If the plane orientation coefficient (fn) is less than 0.15, the orientation may be lowered and sufficient thermal expansion may not be achieved. If the plane orientation coefficient (fn) exceeds 0.28, the film is too highly oriented, so that the film forming property is deteriorated and film formation may be difficult. In the present invention, it is important to achieve both low thermal expansion and low thermal shrinkage. In order to achieve low thermal expansion, it is necessary to highly orient the film. However, it is not preferable to reduce the thermal shrinkage rate. Therefore, it is necessary to adjust ⁇ Tcg as described above to lower the thermal shrinkage rate.
  • the plane orientation coefficient (fn) can be controlled by the film forming conditions, the conditions of the heat treatment step and the draw ratio are particularly affected. Since the thermal crystallization is promoted when the heat treatment temperature is increased, the plane orientation coefficient (fn) tends to increase. Further, since the in-plane orientation is increased by increasing the draw ratio, the plane orientation coefficient (fn) tends to increase. In particular, when the polyester is polyethylene terephthalate, the plane orientation coefficient (fn) is preferably from 0.155 to 0.175, more preferably from 0.160 to 0.175.
  • the polyester film of the present invention has a crystallinity ( ⁇ c (%)) of 35% or less. If it is larger than 35%, the crystal grows, so that the orientation in the in-plane direction is lowered, and sufficient low thermal expansion may not be achieved.
  • the crystallinity ( ⁇ c (%)) is preferably 30% or less.
  • the degree of crystallinity ( ⁇ c (%)) is greatly influenced by ⁇ Tcg and the conditions of the heat treatment step and the relaxation annealing step. For example, the crystallinity can be lowered by lowering the heat setting temperature in the heat treatment step.
  • the polyester film of the present invention has a heat shrinkage rate at 180 ° C. in the longitudinal direction and the width direction of 0 to 1.5%, more preferably 0 to 1.2%, still more preferably 0 to 1.0%, particularly Preferably it is 0 to 0.7%, and most preferably 0 to 0.4%.
  • the thermal shrinkage rate at 180 ° C. in the longitudinal direction and the width direction is within the above range, curling due to heat in various processes when forming the device layer can be reduced, and dimensional change is reduced, so that peeling from the device layer is suppressed. It is more preferable because it is possible.
  • the heat shrinkage rate at 180 ° C. in the longitudinal direction and the width direction can be controlled by predetermined film forming conditions described later, but it is particularly preferable to control the conditions of the relaxation annealing process.
  • the thermal contraction rate of the film of the present invention increases when the thermal contraction rate of the film before the annealing step is large. In order to make the thermal shrinkage rate 1.5% or less, it is preferable that the thermal shrinkage rate at 180 ° C. of the film before the annealing step is 0 to 8.0%. If the heat shrinkage rate at 180 ° C. of the film before the annealing step exceeds 8.0%, the heat shrinkage rate is too large, and thus the heat shrinkage rate may not be reduced to the specified range even after the relaxation annealing treatment step.
  • the thermal dimensional stability in the high temperature range is not sufficient, and the shrinkage increases in the relaxation annealing process, and wrinkles, undulations, and curls may occur, resulting in poor planarity.
  • the heat shrinkage rate of the film before relaxation annealing at 180 ° C. is more preferably 0 to 7.0%, and still more preferably 0 to 5.0%.
  • the heat shrinkage ratio of the film before the annealing process is affected by the draw ratio and the heat treatment process. However, by setting ⁇ Tcg within the specified range, the heat shrinkage ratio of the film before the relaxation annealing process is reduced even when highly oriented.
  • the thermal shrinkage rate at 180 ° C. can be 0 to 1.5%, and the flatness in the relaxation annealing process can be maintained.
  • the polyester film of the present invention preferably has a thermal expansion coefficient of 0 to 25 ppm / ° C. at a temperature of 50 to 150 ° C. in both the longitudinal direction and the width direction.
  • the thermal expansion coefficient at a temperature of 50 to 150 ° C. in the longitudinal direction and the width direction is within the above range, the dimensional change in the relaxation annealing process can be reduced and the planarity can be maintained, and the device layer is formed when the device layer is formed. It is preferable because cracks due to peeling and deformation can be suppressed.
  • the thermal expansion coefficient has a correlation with the plane orientation coefficient and crystallinity, and the thermal expansion coefficient of the present invention can be obtained by the film forming conditions described later, but is obtained by controlling the stretching ratio and the heat treatment conditions. It becomes possible.
  • the polyester used in the present invention is a polymer containing at least 80% by mass of a polymer obtained by condensation polymerization of a diol and a dicarboxylic acid.
  • the dicarboxylic acid is represented by terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, and the like
  • the diol is ethylene glycol, trimethylene glycol, tetramethylene glycol, It is represented by cyclohexanedimethanol.
  • Specific polymers include, for example, polymethylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene isophthalate, polytetramethylene terephthalate, poly-p-oxybenzoate, poly-1,4-cyclohexylenedimethylene terephthalate, polyethylene-2. , 6-naphthalate and the like can be used.
  • polyesters may be a homopolymer or a copolymer.
  • the copolymer component include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, adipic acid, and sebatin.
  • Dicarboxylic acid components such as acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and hydroxycarboxylic acid components such as hydroxybenzoic acid and 6-hydroxy-2naphthoic acid may be contained.
  • polyethylene terephthalate, polyethylene-2,6-naphthalate, and copolymers thereof are preferable, and blends with other polymers, and composites such as laminates may be used.
  • a polyester mainly composed of polyethylene terephthalate hereinafter sometimes referred to as PET
  • PET polyethylene terephthalate
  • Various additives such as an antioxidant, a heat stabilizer, a slipping agent, an antiblocking agent, an antistatic agent, inorganic particles, and organic particles may be added to the polyester.
  • the film of the present invention may be a single film, but other polymer layers such as polyester, polyamide, polyvinylidene chloride polymer and the like may be laminated thereon. Moreover, it is good also as a film which surface-modified by attaching the coating layer of resin represented by polyurethane, polyacryl, polyester, polyamide etc. to the film surface.
  • the film surface may be subjected to surface activation treatment such as corona discharge treatment.
  • a value (fn / ⁇ c) obtained by dividing the plane orientation coefficient (fn) by the crystallinity ( ⁇ c) is preferably 0.50 or more.
  • a value (fn / ⁇ c) obtained by dividing the plane orientation coefficient (fn) by the crystallinity ( ⁇ c) is in the above range, which is preferable because the thermal expansion coefficient can be reduced and the thermal dimensional stability is improved. More preferably, it is 0.55 or more.
  • (Fn / ⁇ c) of the present invention can be obtained by the film forming conditions described later, but can be obtained by controlling the draw ratio, heat treatment conditions, and relaxation annealing temperature.
  • the polyester film of the present invention preferably has a film haze value of 0 to 5%. If the film haze value exceeds 5%, the transparency is low and the performance of the organic EL or thin film solar cell may not be sufficient.
  • the film haze value is more preferably 0 to 3%, still more preferably 0 to 1%.
  • the film haze value may be increased when polyester having a high crystallization index ( ⁇ Tcg) is used. Moreover, it can control by the addition density
  • the particle concentration of the particles to be added is preferably 0.0 part by mass to 1.0 part by mass with respect to 100 parts by mass of the polyester. Further, two or more kinds of particles having different particle diameters may be mixed and used as long as the particle diameter and particle concentration are within the above ranges.
  • the biaxially oriented polyester film of the present invention preferably has a change in film haze value of 0.0 to 3.0% when heat treated at 180 ° C. for 30 minutes.
  • the amount of change in the film haze value is within the above range, it is preferable that transparency can be maintained in the device layer forming process.
  • the amount of change in the film haze value exceeds 3.0%, transparency is deteriorated in the device layer forming process, leading to deterioration of power generation efficiency and light emission efficiency.
  • the change amount of the film haze value is more preferably 0 to 1.5%.
  • the biaxially oriented polyester film of the present invention preferably uses a polyester resin from which an oligomer component has been removed as a raw material.
  • a method for producing a polyester resin from which the oligomer component has been removed for example, the technology described in Japanese Patent Application Laid-Open No. 2005-53968 can be employed.
  • the polyester film of the present invention preferably has a film thickness of 25 to 150 ⁇ m. If the thickness is less than 25 ⁇ m, the film is lowered, and when it is made into an organic EL or solar cell, it may be easily wrinkled. When it exceeds 150 ⁇ m, the film may not be flexible and the flexibility may be impaired.
  • the film thickness is more preferably 75 to 125 ⁇ m. The film thickness can be controlled by the film forming conditions.
  • PET is described as a specific example, it is not limited thereto.
  • PET is manufactured by one of the following processes. That is, (1) A process of obtaining terephthalic acid and ethylene glycol as raw materials, obtaining a low molecular weight PET or oligomer by direct esterification, and then obtaining a polymer by polycondensation reaction using antimony trioxide or a titanium compound as a catalyst. Or (2) A process in which dimethyl terephthalate and ethylene glycol are used as raw materials, a low molecular weight product is obtained by transesterification, and then a polymer is obtained by polycondensation reaction using antimony trioxide or a titanium compound as a catalyst.
  • the reaction proceeds even without a catalyst, but in the transesterification reaction, a compound such as manganese, calcium, magnesium, zinc, lithium and titanium is usually used as a catalyst. Further, after the transesterification reaction is substantially completed, a phosphorus compound may be added for the purpose of inactivating the catalyst used in the reaction.
  • lithium acetate, magnesium acetate, potassium acetate, phosphorous acid, phosphonic acid, phosphinic acid or their derivatives, antimony oxide, and germanium oxide are present during transesterification and polymerization. It is preferable to keep it.
  • a crystal nucleating agent other than the above compounds it is necessary to knead the crystal nucleating agent and PET resin in advance using a bent type biaxial kneading extruder into PET to make a master pellet. This is preferable.
  • a method for setting ⁇ Tcg within a predetermined range a method of adjusting the crystal nucleating agent content by mixing the crystal nucleating agent-containing PET pellets prepared by the above method and a PET resin substantially not containing a crystal nucleating agent is preferably used. It is done.
  • inorganic particles and organic particles such as clay, mica, titanium oxide, calcium carbonate, carion, talc, wet silica, dry silica , Colloidal silica, calcium phosphate, barium sulfate, inorganic particles such as alumina and zirconia, organic particles containing acrylic acid, styrene resin, thermosetting resin, silicone and imide compound as constituents, and added during PET polymerization reaction It is also a preferred embodiment to add particles (so-called internal particles) that are precipitated by a catalyst or the like.
  • the inert particles are contained in the PET which is a constituent component of the PET film of the present invention
  • a method in which the inert particles are dispersed in a predetermined proportion in the form of a slurry in ethylene glycol and this ethylene glycol is added during polymerization is preferable.
  • inert particles for example, water sol or alcohol sol particles obtained at the time of synthesis of the inert particles are added without drying once, the dispersibility of the particles is good. It is also effective to mix an aqueous slurry of inert particles directly with PET pellets and knead them into PET using a vented biaxial kneading extruder.
  • a master pellet of a high concentration of inert particles is prepared by the above method, and this is diluted with PET that does not substantially contain inert particles during film formation.
  • a method for adjusting the content of the active particles is effective.
  • the intrinsic viscosity decreases.
  • supply to an extruder heated to a temperature of 270 to 320 ° C. under a nitrogen stream or under reduced pressure so that the desired film composition is obtained, melt-extrude from a slit-shaped die, and cool and solidify on a casting roll
  • an unstretched film is obtained.
  • filters for example, filters made of materials such as sintered metal, porous ceramic, sand and wire mesh, in order to remove foreign substances and denatured polymers.
  • laminating films a plurality of different polymers are melt laminated using two or more extruders and manifolds or merging blocks.
  • the intrinsic viscosity of the PET pellet containing the crystal nucleating agent and the PET resin chip not containing the crystal nucleating agent should be 0.5 to 1.5 dl / g so that the intrinsic viscosity of the polyester constituting the film falls within a preferable range. preferable.
  • additives such as compatibilizers, plasticizers, weathering agents, antioxidants, thermal stabilizers, lubricants, antistatic agents, whitening agents, coloring, as long as the effects of the present invention are not impaired.
  • Agents, conductive agents, ultraviolet absorbers, flame retardants, flame retardant aids, pigments and dyes may be added.
  • the sheet-like material molded as described above is biaxially stretched.
  • the film is stretched biaxially in the longitudinal direction and the width direction and heat-treated.
  • a sequential biaxial stretching method such as stretching in the width direction after stretching in the longitudinal direction, a simultaneous biaxial stretching method in which the longitudinal direction and the width direction are simultaneously stretched using a simultaneous biaxial tenter, etc.
  • Examples include a method in which the sequential biaxial stretching method and the simultaneous biaxial stretching method are combined.
  • it is desirable that the heat treatment after the stretching process is effectively performed without causing relaxation of molecular chain orientation due to excessive heat treatment.
  • An unstretched film is stretched in the machine direction by utilizing the difference in peripheral speed of the rolls (MD stretching) using a longitudinal stretching machine in which several rolls are arranged, and then laterally stretched by a stenter (TD stretching). ) Will be described in more detail.
  • the unstretched film is MD stretched.
  • the stretching temperature is preferably in the range of (glass transition temperature (Tg) to (Tg + 40) ° C., more preferably in the range of (Tg + 5) to (Tg + 30) ° C., and further preferably in the range of (Tg + 10) to (Tg + 20) ° C. Heated by a heating roll group, preferably 3.0 to 4.0 times in the longitudinal direction (MD), more preferably 3.2 to 4.0 times, still more preferably 3.5 to 4.0 times It is preferable that the film is stretched and then cooled with a cooling roll group having a temperature of 20 to 50 ° C. Among them, when stretched at 3.2 to 4.0 times, the stretching orientation can be improved, and it is effective in the next step. It becomes possible to stretch.
  • the specific preheating temperature is preferably 90 ° C. to 110 ° C., more preferably 95 ° C. to 100 ° C.
  • the stretching temperature is in the range of (preheating temperature ⁇ 5) to (preheating temperature + 5) ° C., and more preferably, stretching is performed at the same temperature as the preheating temperature.
  • the draw ratio is preferably 3.5 to 6.0 times, more preferably 4.0 to 6.0 times, and even more preferably 4.5 to 6.0 times.
  • the heat setting temperature (hereinafter sometimes abbreviated as “Ths”) is preferably 180 to 220 ° C., more preferably 195 to 210 ° C., and particularly preferably 200 to 210 ° C. If Ths is less than 180 ° C., the structure is not sufficiently fixed, fn increases, and the heat shrinkage rate increases and the film-forming property deteriorates. When Ths exceeds 220 ° C., crystal growth is promoted, the in-plane orientation is relaxed, and the thermal expansion coefficient may be deteriorated.
  • the heat setting time is preferably in the range of 0.5 to 10 seconds.
  • the relaxation rate in the heat setting treatment (hereinafter sometimes abbreviated as Rxhs) is preferably within 3 times the relaxation rate in the subsequent relaxation annealing treatment (hereinafter sometimes abbreviated as Rxa).
  • the relaxation rate is a value of the ratio with respect to the difference from the width after the processing on the basis of the width before the treatment. For example, when the relaxation rate is 2 mm, 2% of 2% is relaxed when the width before the treatment is 100 mm. It shows that it becomes 98 mm after processing.
  • Rxhs with respect to Rxa exceeds 3 times, orientation relaxation proceeds too much, and the thermal expansion coefficient may deteriorate.
  • Rxhs is preferably 0 to 9%.
  • the relaxation annealing temperature (hereinafter sometimes abbreviated as Ta) is preferably lower than the heat setting temperature (Ths), preferably (Ths-25) to (Ths-5) ° C., more preferably (Ths ⁇ 20) to (Ths-10) ° C., particularly preferably (Ths-20) to (Ths-10) ° C.
  • the relaxation annealing treatment time is preferably 1 to 120 seconds, more preferably 5 to 90 seconds, and further preferably 20 to 60 seconds.
  • the relaxation rate (Rxa) in the relaxation annealing treatment is preferably 0.1 to 3%.
  • Rxa can be set by the stretching tension and the clip width in the relaxation annealing process. The film is annealed while being conveyed at a speed of 10 to 300 m / min, and the biaxially stretched PET film of the present invention can be obtained.
  • the PET film and the PET film roll may be subjected to arbitrary processing such as molding, surface treatment, laminating, coating, printing, embossing and etching as necessary.
  • the inside of the chamber is evacuated to 5 ⁇ 10 ⁇ 4 Pa before plasma discharge, and then argon and oxygen are introduced into the chamber to a pressure of 0.3 Pa (oxygen).
  • the partial pressure was 3.7 mPa), and power was applied at a power density of 2 W / cm 2 using indium oxide containing 36% by mass of tin oxide as a target (made by Sumitomo Metal Mining Co., Ltd., density 6.9 g / cm 3 ).
  • a transparent conductive layer made of ITO having a film thickness of 250 nm by a direct current magnetron sputtering method and further forming an organic EL light emitting layer it can be used as an organic EL display substrate and an organic EL lighting substrate. Moreover, it can be used as a flexible solar cell substrate by forming a power generation layer.
  • the characteristic value measurement method and the effect evaluation method in the present invention are as follows.
  • Crystallization index ( ⁇ Tcg (° C.)), crystallinity ( ⁇ c (%)) In accordance with JIS K7121-1987, a differential scanning calorimeter was used as a differential scanning calorimeter DSC (RDC6220), and a data analysis device was used as a disk analyzer (SSC / 5200). The mixture was sealed and heated in a nitrogen atmosphere from 25 ° C. to 300 ° C. at a heating rate of 10 ° C./min. Then, it cools rapidly using liquid nitrogen, and it heats up again at a speed
  • the crystallization index ( ⁇ Tcg) was calculated from the glass transition temperature (Tg) and the cold crystallization temperature (Tcc) in the second temperature raising process using the following formula.
  • ⁇ Tcg Tcc ⁇ Tg
  • the crystallinity ( ⁇ c (%)) was calculated from the following formula.
  • ⁇ c (%) ⁇ ( ⁇ H m ⁇ H c ) / ⁇ H m 0 ⁇ ⁇ 100
  • ⁇ H m 0 is the heat of fusion of the complete crystal, and is calculated using, for example, 140.1 J / g for PET and 103.3 J / g for PEN (reference document Wunderlich B “Thermal analysis of Polymeric Materials”). did.
  • Plane orientation coefficient (fn) According to JIS-K7142 (2008), measurement was performed using the following measuring instrument. The number of samples was cut to 25 mm in width and 30 mm in length, measured in the film longitudinal direction, film width direction, and film thickness direction, and the average value was taken as the refractive index in each direction. Using the result, the plane orientation coefficient was calculated by the following formula. When the longitudinal direction and the width direction of the film are not known, the direction having the maximum refractive index in the film is regarded as the longitudinal direction, and the direction perpendicular to the longitudinal direction is regarded as the width direction.
  • the direction of the maximum refractive index in the film may be obtained by measuring the refractive index in all directions of the film with an Abbe refractometer, for example, by using a phase difference measuring device (birefringence measuring device) or the like. You may obtain
  • ⁇ Device Abbe refractometer 4T (manufactured by Atago Co., Ltd.)
  • Light source Sodium D line
  • Mount solution: methylene iodide (n D 20 1.74), sulfur methylene iodide (n D 20 ⁇ 1.74 to 1.78).
  • -Planar orientation coefficient (fn) fn (nMD + nTD) / 2 ⁇ nZD nMD: Refractive index in the film longitudinal direction nTD: Refractive index in the film width direction nZD: Refractive index in the film thickness direction.
  • HGM-2DP fully automatic direct reading haze computer
  • the reaction was carried out for 2 hours (3 hours after the start of polymerization), and the stirring torque of the polymerization apparatus was a predetermined value (the specific value differs depending on the specifications of the polymerization apparatus, but this polymerization apparatus The value indicated by polyethylene terephthalate having an intrinsic viscosity of 0.65 was a predetermined value). Therefore, the reaction system was purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, discharged into cold water in the form of a strand, and immediately cut to obtain polyethylene terephthalate PET pellets X having an intrinsic viscosity of 0.65.
  • Reference Example 2 A transesterification reaction and a polymerization reaction were performed in the same manner as in Reference Example 1 except that 0.35 parts by mass of dimethylphenylphosphonate (DPPO) was added as a crystal nucleating agent instead of trimethyl phosphate, and the intrinsic viscosity was 0.62. PET pellet Y with adjusted crystallization speed was obtained.
  • DPPO dimethylphenylphosphonate
  • Reference Example 3 PET pellets obtained in Reference Example 1 and sodium montanate (manufactured by Nitto Kasei Co., Ltd.) as a crystal nucleating agent were mixed at a mass ratio of 90:10 and kneaded at 280 ° C. using a vent type twin screw extruder. A PET master pellet Z containing 10 parts by mass of sodium montanate was obtained.
  • the reaction product is transferred to a polymerization apparatus, heated to a temperature of 290 ° C., subjected to a polycondensation reaction under a high vacuum of 30 Pa, and the stirring torque of the polymerization apparatus is a predetermined value (specifically depending on the specifications of the polymerization apparatus).
  • the value indicated by polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.65 in this polymerization apparatus was a predetermined value). Therefore, the reaction system was purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, discharged into cold water in the form of a strand, and immediately cut to obtain a PEN pellet X having an intrinsic viscosity of 0.65.
  • Example 1 90 parts by mass of the PET pellet X obtained in Reference Example 1 and 10 parts by mass of the PET pellet Y adjusted in crystallization speed obtained in Reference Example 2 were mixed, and after evacuation at 180 ° C. for 3 hours, 280 It was supplied to an extruder heated to a temperature of 0 ° C. and introduced into a T-die die under a nitrogen atmosphere. Subsequently, it was extruded into a sheet from the inside of the T die die to obtain a molten single layer sheet, which was closely cooled and solidified by an electrostatic application method on a drum kept at a surface temperature of 25 ° C. to obtain an unstretched single layer film. It was 78 degreeC when the glass transition temperature (Tg) of the unstretched single layer film was measured.
  • Tg glass transition temperature
  • the obtained unstretched single layer film was preheated with a heated roll group, and then stretched 3.5 times MD at a temperature of 93 ° C., and cooled with a roll group at a temperature of 25 ° C. to form a uniaxially stretched film. Obtained. It was 90 degreeC when the cold crystallization temperature of the obtained uniaxially stretched film was measured. While holding both ends of the obtained uniaxially stretched film with clips, it is guided to a preheating zone at a temperature of 95 ° C. in the tenter, and then continuously in the heating zone at a temperature of 90 ° C. in the width direction (TD direction) perpendicular to the longitudinal direction. The film was stretched 4.6 times.
  • a heat treatment for 5 seconds was performed at a temperature of 210 ° C. in a heat treatment zone in the tenter as a heat setting treatment, and a relaxation treatment was further performed in the 2% width direction at the same temperature.
  • a heat treatment for 5 seconds was performed at a temperature of 210 ° C. in a heat treatment zone in the tenter as a heat setting treatment, and a relaxation treatment was further performed in the 2% width direction at the same temperature.
  • the film edge was removed, and the film was wound on a core to obtain a biaxially stretched film having a thickness of 100 ⁇ m.
  • a relaxation annealing treatment was performed at a relaxation rate of 1% while transporting for 30 seconds at a film speed of 30 m / min at a temperature of 190 ° C. to obtain a polyester film.
  • the film had excellent thermal dimensional stability and film forming properties.
  • Example 2 A polyester film was obtained in the same manner as in Example 1 except that 98 parts by mass of PET pellet X obtained in Reference Example 1 and 2 parts by mass of PET pellet Y adjusted in crystallization speed obtained in Reference Example 2 were mixed. It was. When the obtained polyester film was evaluated, it had the characteristics which were excellent in thermal dimensional stability and film forming property.
  • Example 3 A polyester film was obtained in the same manner as in Example 1 except that 80 parts by mass of the PET pellet X obtained in Reference Example 1 and 20 parts by mass of the PET master pellet Z of sodium montanate obtained in Reference Example 3 were mixed. . When the obtained polyester film was evaluated, it had the property which was excellent in thermal dimensional stability.
  • Example 4 95 parts by mass of the PET pellet X obtained in Reference Example 1 and 5 parts by mass of the PET master pellet Z of sodium montanate obtained in Reference Example 3 were mixed, the MD stretch ratio was 3.0 times, and the TD stretch ratio was 4.
  • a polyester film was obtained in the same manner as in Example 1 except that it was changed to 2 times. When the obtained polyester film was evaluated, it had the property which was excellent in thermal dimensional stability.
  • Example 5 95 parts by mass of the PET pellet X obtained in Reference Example 1 and 5 parts by mass of the PET master pellet Z of sodium montanate obtained in Reference Example 3 were mixed, the MD stretch ratio was 3.2 times, and the TD stretch ratio was 4.
  • a polyester film was obtained in the same manner as in Example 1 except that it was changed to 2 times. When the obtained polyester film was evaluated, it had the property which was excellent in thermal dimensional stability.
  • Example 6 80 parts by mass of the PET pellet X obtained in Reference Example 1 and 20 parts by mass of the PET master pellet Z of sodium montanate obtained in Reference Example 3 were mixed, the MD stretch ratio was 3.2 times, and the TD stretch ratio was 4.
  • a polyester film was obtained in the same manner as in Example 1 except that it was changed to 2 times. When the obtained polyester film was evaluated, it had the property which was excellent in thermal dimensional stability.
  • Example 7 98 parts by mass of the PET pellet X obtained in Reference Example 1 and 2 parts by mass of the PET pellet Y adjusted in crystallization speed obtained in Reference Example 2 were mixed, the MD stretch ratio was 3.0 times, and the TD stretch ratio was 4 A polyester film was obtained in the same manner as in Example 1 except that the ratio was changed to 2 times. When the obtained polyester film was evaluated, it had the characteristics which were excellent in thermal dimensional stability and film forming property.
  • Example 8 A polyester film was obtained in the same manner as in Example 1 except that the heat setting temperature Ths was changed to 190 ° C. and the relaxation annealing temperature Ta was changed to 170 ° C. When the obtained polyester film was evaluated, it had the property which was excellent in thermal dimensional stability.
  • Example 9 A polyester film was obtained in the same manner as in Example 1 except that the relaxation annealing temperature Ta was changed to 200 ° C. When the obtained polyester film was evaluated, it had the characteristics which were excellent in thermal dimensional stability and film forming property.
  • Example 10 A polyester film was prepared in the same manner as in Example 1 except that 95 parts by mass of PEN pellet X obtained in Reference Example 4 and 5 parts by mass of PEN master pellet Y of sodium montanate obtained in Reference Example 5 were used. Obtained. When the obtained polyester film was evaluated, it had the property which was excellent in thermal dimensional stability.
  • Example 11 A polyester film was formed in the same manner as in Example 1 except that the MD draw ratio was 3.4 times, the TD draw ratio was 3.7 times, the heat setting temperature Ths was changed to 215 ° C., and the relaxation annealing temperature Ta was changed to 205 ° C. Obtained. When the obtained polyester film was evaluated, it had the characteristics which were excellent in thermal dimensional stability and film forming property.
  • Example 1 A polyester film was obtained in the same manner as in Example 1 using only the PET pellet X obtained in Reference Example 1. When the obtained polyester film was evaluated, the heat shrinkage ratio was increased and the thermal dimensional stability was poor.
  • Example 2 A polyester film was obtained in the same manner as in Example 1 except that only the PET pellet X obtained in Reference Example 1 was used and the MD stretch ratio was set to 3.0 times and the TD stretch ratio was set to 4.2 times. When the obtained polyester film was evaluated, the thermal shrinkage rate was increased and the thermal dimensional stability was poor (Comparative Example 3). As shown in Table 1, a polyester film was obtained in the same manner as in Example 1 except that the relaxation annealing process was not performed. When the obtained polyester film was evaluated, it had the characteristic that thermal contraction was large and thermal dimensional stability was inferior.
  • Example 4 A polyester film was obtained in the same manner as in Example 1 except that the MD stretch ratio was 3.0 times and the TD stretch ratio was 3.35 times. When the obtained polyester film was evaluated, the coefficient of thermal expansion was deteriorated because the plane orientation coefficient was decreased, and the thermal dimensional stability was inferior.
  • Comparative Example 5 As shown in Table 1, 75 parts by mass of PET pellet X obtained in Reference Example 1 and 25 parts by mass of PET master pellet Z of sodium montanate obtained in Reference Example 3 were mixed, and the MD draw ratio was 3.2 times. A polyester film was produced in the same manner as in Example 1 except that the TD stretch ratio was 4.2 times and the relaxation annealing treatment was not performed. The crystallization index ( ⁇ Tcg) was small, the film formation stability was deteriorated, and continuous film formation was difficult.
  • Example 6 A polyester film was obtained in the same manner as in Example 1 except that the heat setting temperature Ths was changed to 175 ° C. and the relaxation annealing temperature Ta was changed to 160 ° C. When the obtained polyester film was evaluated, it had the characteristic that thermal contraction was large and thermal dimensional stability was inferior.
  • Example 7 A polyester film was obtained in the same manner as in Example 1 except that the heat setting temperature Ths was changed to 230 ° C and the relaxation annealing temperature Ta was changed to 210 ° C. When the obtained polyester film was evaluated, the thermal expansion coefficient was deteriorated due to the increased crystallinity, and the thermal dimensional stability was poor.
  • Example 8 A polyester film was obtained in the same manner as in Example 1 except that the relaxation annealing temperature Ta was changed to 180 ° C. When the obtained polyester film was evaluated, it had the characteristic that thermal contraction was large and thermal dimensional stability was inferior.
  • Example 9 A polyester film was obtained in the same manner as in Example 1 except that the relaxation annealing temperature Ta was changed to 210 ° C. When the obtained polyester film was evaluated, the thermal expansion coefficient was deteriorated due to the increased crystallinity, and the thermal dimensional stability was poor.
  • the polyester film of the present invention can be applied to a base film for flexible devices having excellent thermal dimensional stability and curling properties. Therefore, there is a possibility of being used to obtain organic EL displays, electronic paper, organic EL lighting, organic solar cells, dye-sensitized solar cells, and the like.

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Abstract

La présente invention concerne un film de polyester approprié comme film de substrat. Lorsqu'Il est utilisé sous la forme d'un film de substrat pour un dispositif souple, le film de polyester présente des changements dimensionnels réduits dans diverses étapes, s'enroule rarement, et présente une excellente aptitude au traitement. Le film de polyester est obtenu à l'aide d'un polyester ayant un indice de cristallisation (ΔTcg) de 10 à 60 °C, et présente un coefficient d'orientation planaire (fn) de 0,15 à 0,28, un degré de cristallinité (Xc (%)) de 35 % ou moins, et des retraits thermiques de 0 à 1,5 % à 180 °C respectivement dans le sens de la longueur et dans le sens de la largeur.
PCT/JP2013/050620 2012-01-24 2013-01-16 Film de polyester et procédé de fabrication associé Ceased WO2013111641A1 (fr)

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JP2023184450A (ja) * 2022-06-17 2023-12-28 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それを含むフォルダブルディスプレイ装置
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JP2023014732A (ja) * 2021-07-19 2023-01-31 三菱ケミカル株式会社 ポリエステルフィルム
JP7775588B2 (ja) 2021-07-19 2025-11-26 三菱ケミカル株式会社 ポリエステルフィルム
JP2023184450A (ja) * 2022-06-17 2023-12-28 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それを含むフォルダブルディスプレイ装置
JP7671804B2 (ja) 2022-06-17 2025-05-02 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それを含むフォルダブルディスプレイ装置
US12344719B2 (en) 2022-06-17 2025-07-01 Sk Microworks Co., Ltd. Polyester film and foldable display device comprising the same
JP2024055258A (ja) * 2022-10-07 2024-04-18 三菱ケミカル株式会社 ポリエステルフィルム

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CN104053535A (zh) 2014-09-17
KR102002798B1 (ko) 2019-07-23
TWI577721B (zh) 2017-04-11
CN104053535B (zh) 2016-08-24
JPWO2013111641A1 (ja) 2015-05-11
TW201335259A (zh) 2013-09-01

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