WO2022168702A1 - 二軸配向ポリエステルフィルム及びその製造方法 - Google Patents

二軸配向ポリエステルフィルム及びその製造方法 Download PDF

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Publication number
WO2022168702A1
WO2022168702A1 PCT/JP2022/002851 JP2022002851W WO2022168702A1 WO 2022168702 A1 WO2022168702 A1 WO 2022168702A1 JP 2022002851 W JP2022002851 W JP 2022002851W WO 2022168702 A1 WO2022168702 A1 WO 2022168702A1
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WIPO (PCT)
Prior art keywords
film
biaxially oriented
less
polyester film
oriented polyester
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Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2022/002851
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English (en)
French (fr)
Japanese (ja)
Inventor
信之 真鍋
雅幸 春田
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Toyobo Co Ltd
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Toyobo Co Ltd
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Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to EP22749576.9A priority Critical patent/EP4289598A4/en
Priority to US18/262,163 priority patent/US12479992B2/en
Priority to KR1020237023756A priority patent/KR20230137888A/ko
Priority to JP2022579482A priority patent/JPWO2022168702A1/ja
Priority to CN202280012113.6A priority patent/CN116745347A/zh
Publication of WO2022168702A1 publication Critical patent/WO2022168702A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • 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
    • B29C48/0013—Extrusion moulding in several steps, i.e. components merging outside the die
    • B29C48/0014—Extrusion moulding in several steps, i.e. components merging outside the die producing flat articles having components brought in contact outside the extrusion die
    • 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
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
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    • B29C48/08—Flat, e.g. panels flexible, e.g. films
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    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/911—Cooling
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    • B29C48/914—Cooling drums
    • 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
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    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
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    • B29C48/286—Raw material dosing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/287—Raw material pre-treatment while feeding
    • 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
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    • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0026—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C—CHEMISTRY; METALLURGY
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Definitions

  • the present invention relates to a biaxially oriented polyester film and a method for producing the same. More specifically, the present invention relates to a biaxially oriented polyester film, which is suitable for secondary processing such as coating and vapor deposition for further enhancing the function of the biaxially oriented polyester film.
  • a biaxially oriented polyester film that is an environmentally friendly polyester film by using a carbon-neutral polyester resin using glycol and has little variation in physical properties in the longitudinal direction even if it is a long film roll with a long winding length; It relates to the manufacturing method thereof.
  • biaxially oriented polyester films have been widely used in a wide range of fields such as packaging materials and industrial materials due to their excellent mechanical strength, thermal properties and optical properties.
  • Biaxially oriented polyester film has excellent oxygen barrier properties, and in packaging applications such as general food, retort food, and pharmaceuticals, there is a growing demand for oxygen barrier properties and water vapor barrier properties related to deterioration and deterioration of contents. There is a problem that the quality of the contents is changed and deteriorated.
  • biaxially oriented polyester films used for packaging of general foods, retort foods, pharmaceuticals, etc. are required to further improve adhesion to printing ink and gas barrier properties against oxygen and water vapor. measures are taken.
  • a method for improving the gas barrier property a method of laminating a film made of a resin having a good gas barrier property such as polyvinylidene chloride or polyethylene vinyl alcohol copolymer on a biaxially oriented polyester film, or a solution in which these resins are dissolved. and laminating a thin film, or vapor-depositing a metal such as aluminum or a metal oxide such as aluminum oxide to form a thin film on the surface of the film.
  • a vapor-deposited polyester film having a metal oxide on the film surface is often used because it is excellent in heat resistance and transparency in addition to gas barrier properties.
  • a metal oxide thin film such as a silicon oxide or aluminum oxide film having good gas barrier properties on the film surface.
  • Biomass is an organic compound that is photosynthesised from carbon dioxide and water, and is a so-called carbon-neutral renewable energy that is regenerated into carbon dioxide and water by using it.
  • biomass plastics using these biomass as raw materials has progressed rapidly, and attempts have been made to produce polyesters, which are general-purpose polymer materials, from these biomass raw materials.
  • Patent Document 4 discloses a resin composition containing a polyester composed of a diol unit and a dicarboxylic acid unit, wherein the diol component unit is biomass-derived ethylene glycol, and the dicarboxylic acid component unit is petroleum-derived dicarboxylic acid.
  • a resin composition and a film are disclosed which are characterized by comprising 50 to 95% by mass of a polyester with respect to the entire resin composition.
  • the polyester that uses plant-derived ethylene glycol as a raw material instead of the ethylene glycol obtained from conventional fossil fuels is a polyester produced using ethylene glycol obtained from conventional fossil fuels.
  • mechanical properties equivalent to those obtained using conventional fossil fuel-derived ethylene glycol can be obtained.
  • a vapor-deposited polyester film having a metal oxide thin film such as a silicon oxide or aluminum oxide film on the film surface which has good gas barrier properties, and uses porous silica with an average particle size of 0.9 ⁇ m.
  • the maximum peak height Sp tends to be small, and the film roll is not sufficiently ventilated, resulting in wrinkles and blocking.
  • it has excellent transparency, is easy to perform secondary processing such as coating and vapor deposition, has excellent properties after secondary processing, and is environmentally friendly by using a carbon-neutral polyester resin that uses biomass-derived ethylene glycol.
  • a polyester film that has been developed has not yet been realized.
  • a carbon-neutral polyester resin that has excellent transparency as described above is easy to perform secondary processing such as coating and vapor deposition, has excellent properties after secondary processing, and uses biomass-derived ethylene glycol.
  • As a means of obtaining an environmentally friendly polyester film it can be obtained by biaxially stretching a polyester resin composition in which a polyester resin containing particles is blended with a carbon-neutral polyester resin using biomass-derived ethylene glycol. Therefore, it is common to mix resin chips with a normal specific gravity and resin chips with a large specific gravity containing particles to form a film.
  • the object of the present invention is to improve such problems of the conventional technology, to have excellent transparency, to be easy to perform secondary processing such as coating and vapor deposition, to have excellent properties after secondary processing, and to use biomass-derived ethylene glycol. It is to provide an environmentally friendly biaxially oriented polyester film and a method for producing the same by using the carbon-neutral polyester resin used, and more preferably a long film roll with a long winding length, even in the longitudinal direction To provide a biaxially oriented polyester film roll with little variation in physical properties and a method for producing the same.
  • the inventors of the present invention have investigated the cause of the deterioration of the properties after secondary processing. Static marks, which are locally charged parts, and static mark discharge traces caused by the discharge of accumulated static electricity, are likely to occur in this part. It was found that it is difficult for molecules to form a thin film on the surface of the film regularly and uniformly without defects.
  • a biaxially oriented polyester obtained by biaxially stretching a polyester resin composition in which a polyester resin containing particles is blended with a carbon-neutral polyester resin using biomass-derived ethylene glycol
  • resin chips which are raw materials for film, polyester resin chips recycled from the market and society, including PET bottles
  • a pipe with an outlet in the hopper and directly above the extruder polyester resin chips containing particles are supplied through a pipe (hereinafter sometimes referred to as an inner pipe), and both chips are mixed and melt-extruded to form a uniform film with little variation in physical properties in the longitudinal direction of the film.
  • a biaxially oriented polyester film made of a polyester resin composition containing particles and containing 50% by weight or more of a polyester resin composed of biomass-derived ethylene glycol and a fossil fuel-derived dicarboxylic acid unit, wherein at least one surface has the following A biaxially oriented polyester film that satisfies all requirements (1) to (3).
  • the number of fine protrusions having a height of less than 3 nm per area of 4 ⁇ 10 ⁇ 12 m 2 is 250 or more and 600 or less.
  • the number of fine projections with a height of 3 nm or more per area of 4 ⁇ 10 ⁇ 12 m 2 is 300 or more and 600 or less.
  • the arithmetic mean height Sa is 0.010 ⁇ m or more and 0.025 ⁇ m or less.
  • the surface of the biaxially oriented polyester film that satisfies all of the requirements (1) to (3) and the surface opposite thereto have dynamic friction coefficients of 0.20 or more and 0.60 or less1. ⁇ 2.
  • the wetting tension of the surface of the biaxially oriented polyester film that satisfies all of the requirements (1) to (3) is 50 mN/m or more1. ⁇ 3.
  • the biaxially oriented polyester film has an external haze of 1.8% or less and an internal haze of 2.0% or less. ⁇ 4.
  • Variation in arithmetic mean height Sa when sampled every 1000 m from the surface of the film roll to the winding core in the longitudinal direction of the film is 40% or less.
  • a method for producing a biaxially oriented polyester film comprising a melt extrusion step of a polyester raw material resin and a biaxial stretching step, wherein in the melt extrusion step of the polyester raw material resin, the biomass-derived Supplying raw resin chips of a carbon-neutral polyester resin using ethylene glycol, and supplying raw resin chips of a polyester resin composition containing the particles through a pipe having an outlet in a hopper and directly above the extruder, It is characterized by having a step of mixing both chips and melt-extruding them.
  • ⁇ 5 A method for producing a polyester film according to any one of the above.
  • a method for producing a biaxially oriented polyester film roll comprising a step of melt extruding a polyester raw resin, a biaxial stretching step, and a step of winding the film after biaxial stretching into a roll, wherein the polyester raw resin
  • raw material resin chips of a carbon-neutral polyester resin using the biomass-derived ethylene glycol are supplied from above to the hopper, and the particles are contained through a pipe having an outlet in the hopper and directly above the extruder. 6.
  • the process comprises a step of supplying raw material resin chips for the polyester resin composition, mixing the two chips, and melt extruding. or 7.
  • the transparency is excellent, the film roll is less likely to wrinkle when wound on a film roll after film production, and there is little adhesion between films in the film roll (so-called blocking phenomenon), so secondary coatings such as coating and vapor deposition are possible.
  • It is a polyester film that is easy to process, has excellent performance after secondary processing, and is environmentally friendly by using a carbon-neutral polyester resin that uses biomass-derived ethylene glycol. A long film with a long winding length. It is possible to provide a biaxially oriented polyester film with little variation in physical properties in the longitudinal direction even when rolled, and a method for producing the same.
  • the length in the width direction and the length in the longitudinal direction of the biaxially oriented polyester film roll (hereinafter referred to as the master roll) that is first wound after the stretching process has been increased.
  • the master roll the biaxially oriented polyester film roll
  • a biaxially oriented polyester film can be obtained. The same is true for film rolls obtained by slitting the master roll into subdivisions.
  • FIG. 3 is a diagram of the arrangement of the biaxially oriented polyester film, the film roll, the neutralization brush, and the meandering prevention device during unwinding.
  • the biaxially oriented polyester film in the present invention is preferably composed of the following biomass-derived ethylene glycol and fossil fuel-derived dicarboxylic acid units.
  • biomass degree the content of biomass-derived carbon in the film. It is possible to obtain a carbon-neutral and environmentally friendly film.
  • Biomass-derived ethylene glycol is made from ethanol produced from biomass (biomass ethanol).
  • biomass-derived ethylene glycol can be obtained by a method in which biomass ethanol is converted into ethylene glycol via ethylene oxide by a conventionally known method.
  • commercially available biomass ethylene glycol may be used.
  • Dicarboxylic acid derived from fossil fuels is used for polyester dicarboxylic acid units.
  • dicarboxylic acids aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation.
  • aromatic dicarboxylic acids include terephthalic acid and isophthalic acid.
  • derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters and butyl esters. and esters. Among these, terephthalic acid is preferred, and dimethyl terephthalate is preferred as the aromatic dicarboxylic acid derivative.
  • aliphatic dicarboxylic acid specifically, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, etc., usually having 2 to 40 carbon atoms. chain or alicyclic dicarboxylic acids.
  • lower alkyl esters such as methyl esters, ethyl esters, propyl esters and butyl esters of the above aliphatic dicarboxylic acids and cyclic acid anhydrides of the above aliphatic dicarboxylic acids such as succinic anhydride are used.
  • succinic anhydride adipic acid, succinic acid, dimer acid, or mixtures thereof are preferred, and those containing succinic acid as a main component are particularly preferred.
  • More preferred derivatives of aliphatic dicarboxylic acids are methyl esters of adipic acid and succinic acid, or mixtures thereof.
  • dicarboxylic acids can be used alone or in combination of two or more.
  • the carbon-neutral polyester resin using biomass-derived ethylene glycol used in the present invention can be obtained by a conventionally known method of polycondensing the diol units and dicarboxylic acid units described above. Specifically, after performing the esterification reaction and / or transesterification reaction of the dicarboxylic acid component and the diol component, a general method of melt polymerization such as performing a polycondensation reaction under reduced pressure, or an organic solvent can be produced by a known solution heating dehydration condensation method using
  • a deodorant a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducing agent, a releasing agent, an antioxidant, an ion exchange agent, a coloring pigment, and the like can be added.
  • the biaxially oriented polyester film in the present invention comprises a polyester resin composition containing the following polyester resin as a main component.
  • the polyester resin constituting the biaxially oriented polyester film of the present invention is a polymer synthesized from a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative. Examples thereof include polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate, and polyethylene terephthalate is preferred from the viewpoint of mechanical properties, heat resistance, cost, and the like.
  • the main component here means that the content in the polyester resin composition is 80% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more, and 98% by weight or more Most preferred.
  • polyester resins may be copolymerized with other components as long as the object of the present invention is not impaired.
  • copolymerization components include dicarboxylic acid components such as isophthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, adipic acid, sebacic acid and ester-forming derivatives thereof.
  • Diol components include diethylene glycol, hexamethylene glycol, neopentyl glycol, and cyclohexanedimethanol.
  • polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol.
  • the amount of copolymerization is preferably 10 mol % or less, more preferably 5 mol % or less, most preferably 3 mol % or less per constituent repeating unit.
  • polyester resin that constitutes the biaxially oriented polyester film of the present invention first, using the dicarboxylic acid or its ester-forming derivative and the diol or its ester-forming derivative as main starting materials, according to a conventional method, Examples include a method of producing by conducting an esterification or transesterification reaction, and then conducting a polycondensation reaction at high temperature and under reduced pressure.
  • the intrinsic viscosity of the polyester resin constituting the biaxially oriented polyester film of the present invention is preferably in the range of 0.50 to 0.9 dl/g, more preferably 0.55, from the viewpoint of film-forming properties and re-recoverability. ⁇ 0.8 dl/g.
  • the number of fine protrusions having a height of less than 3 nm per area of 4 ⁇ 10 ⁇ 12 m 2 is 250 or more.
  • the number of fine projections with a height of 3 nm or more per area of 4 ⁇ 10 ⁇ 12 m 2 is 300 or more and 600 or less.
  • the arithmetic mean height Sa is 0.010 ⁇ m or more and 0.025 ⁇ m or less.
  • inorganic particles to be used include particles made of silica (silicon oxide), alumina (aluminum oxide), titanium dioxide, calcium carbonate, kaolin, and barium sulfate.
  • organic particles include acrylic resin particles, melamine resin particles, silicone resin particles, and particles made of crosslinked polystyrene. Among them, particles made of silica (silicon oxide), calcium carbonate, or alumina (aluminum oxide), or particles made of polymethacrylate, polymethyl acrylate, or derivatives thereof are preferred, and particles made of silica (silicon oxide) or calcium carbonate are preferred. More preferred are inorganic particles made of silica (silicon oxide).
  • the particle size distribution of the particles used in the present invention is preferably monodisperse.
  • the shape of the inorganic fine particles is not particularly limited, but the closer to a spherical shape, the greater the number of fine protrusions with a height of 3 nm or more, and the number of fine protrusions with a height of less than 3 nm can be increased without significantly changing the arithmetic mean height Sa. .
  • the weight-average particle size of the particles in the present invention as measured by a Coulter counter is preferably in the range of 0.8 to 1.8 ⁇ m.
  • the weight-average particle size of the particles is 0.8 ⁇ m or more, the number of fine protrusions having a height of less than 3 nm and the arithmetic mean height Sa are easily made to be the lower limits of (1) and (3) above, respectively.
  • the weight average particle diameter of the particles is 1.8 ⁇ m or less, the arithmetic mean height Sa is easily made equal to or less than the upper limit of (3) above, and the number of fine projections having a height of less than 3 nm is equal to or more than the lower limit of (1) above. It's a good choice.
  • the lower limit of the content of particles in the polyester resin composition (masterbatch) containing particles in the present invention is 1000 ppm by weight, more preferably 1300 ppm by weight, and particularly preferably 1400 ppm by weight.
  • the upper limit of the content of particles is preferably 3000 ppm by weight, more preferably 2500 ppm by weight, still more preferably 2200 ppm by weight, and particularly preferably 1800 ppm by weight.
  • the concentration of inorganic particles in the masterbatch is preferably 7,000 to 100,000 ppm, more preferably 8,000 to 80,000 ppm, and particularly preferably 9,000 to 50,000 ppm.
  • concentration of the inorganic particles in the masterbatch is less than 7000 ppm, the addition ratio of the masterbatch containing the inorganic particles increases, and is composed of ethylene glycol derived from biomass as the main raw material and dicarboxylic acid units derived from fossil fuel.
  • the ratio of the polyester resin is reduced, and it becomes impossible to effectively obtain resin characteristics such as low-cost resin and environmental friendliness.
  • the concentration of the inorganic particles in the masterbatch is more than 100,000 ppm, the segregation of the raw materials causes large fluctuations in the raw material ratio in the longitudinal direction, and thus the obtained film tends to have large variations in the longitudinal direction.
  • the step of esterification for producing the polyester resin for example, the step of esterification for producing the polyester resin, after the transesterification reaction, or before the start of the polycondensation reaction.
  • it can be added in stages, it is preferable to add it as a slurry dispersed in ethylene glycol or the like to proceed with the polycondensation reaction.
  • a method of blending a slurry of particles dispersed in ethylene glycol or water or the like with a polyester resin raw material using a kneading extruder with a vent, or using a kneading extruder, dried particles and the polyester resin raw material It is also preferable to carry out by a method of blending and the like.
  • the step of mixing the particles with the polyester resin raw material it is preferable to reduce the aggregates of the particles as much as possible in order to stably obtain the desired surface state, but the formation of the biaxially oriented polyester film after the mixing step The influence can be reduced by adjusting the process conditions.
  • polyester resin composition of the present invention a small amount of other polymers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, plasticizers, pigments or Other additives and the like may be contained.
  • the lower limit of the content of the carbon-neutral polyester resin using biomass-derived ethylene glycol with respect to the total amount is preferably 50% by weight, more preferably 70% by weight, and still more preferably 90% by weight. %, particularly preferably 100% by weight. If the content is less than 50% by weight, the content is poor in terms of utilization of the carbon-neutral polyester resin, and it is not so preferable from the viewpoint of contribution to environmental protection.
  • a carbon-neutral polyester resin using biomass-derived ethylene glycol can be used as a masterbatch (high-concentration content resin) used when adding lubricants and additives such as inorganic particles to improve the function of the film. .
  • the lower limit of the biomass degree by radiocarbon (C14) measurement is preferably 10%, more preferably, from the viewpoint of reducing the environmental load. is 13%. If it is less than the above, the effect as a carbon offset material may be small in terms of reducing the environmental load.
  • the upper limit of the biomass degree is preferably 100%, more preferably 20%.
  • polyethylene terephthalate can theoretically have a biomass content of 20% by using only plant-derived ethylene glycol, but in order to increase the biomass content beyond that, terephthalic acid must also be plant-derived, which increases the cost.
  • the ratio of biomass-derived carbon can be calculated.
  • polyethylene terephthalate polyethylene terephthalate is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms at a molar ratio of 1:1, so only ethylene glycol derived from biomass is used. In this case, the biomass degree in the polyester is 20%.
  • the biaxially oriented polyester film of the present invention is produced by extruding a carbon-neutral polyester resin chip using ethylene glycol derived from biomass and a chip of a polyester resin composition containing a polyester resin as a main component in a hopper. It can be obtained by feeding and mixing, melt extruding with an extruder to form an unstretched sheet, and stretching the unstretched sheet. Preferred examples are described below, but are not limited to these.
  • the film of the present invention may have a single layer structure of at least one layer, or may have a laminated structure of two or more layers. It may be two layers, three layers, four layers, or five layers.
  • the laminate part/base layer part in the case of three layers, the laminate part (A)/base layer part/laminate part (B), and in the case of three layers, the laminate part (A) and the laminate part (B) They may have the same composition and structure, or may have different compositions, for example, a structure of particle-free layer/base layer portion/particle-containing layer. Also, they may have substantially the same thickness, or they may have different thicknesses.
  • the laminated part (A) and the laminated part (B) are designed to have the same composition for easy production.
  • the film of the present invention it is preferable that at least one of the layers constituting the film is biaxially oriented. It is particularly preferable that all the layers in the laminated structure of two or more layers are biaxially oriented. If all the layers are non-oriented or uniaxially oriented, it is difficult to use the label as a wraparound label, which is not very preferable.
  • FIG. 4 shows an example of a specific mixing procedure.
  • FIG. 4 is a schematic diagram showing an example of the relationship between the extruder 2 having the hopper 1 and the inner pipe 3.
  • resins other than carbon-neutral polyester resin chips using biomass-derived ethylene glycol which is the main raw material of the polyester film of the present invention, are supplied through an inner pipe 3, and the chips of the polyester resin composition are fed into a hopper. 1 from the top. Since the outlet 4 of the inner pipe 3 is located directly above the extruder (more precisely, directly above the resin supply port 5 of the extruder 2), the raw material mixing ratio can be kept constant.
  • melt extruding a carbon-neutral polyester resin and a polyester resin composition using ethylene glycol derived from biomass it is preferable to dry using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer.
  • a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer.
  • an extruder is used to melt at a temperature above the melting point of the polyester resin and at a temperature of 200 to 300 ° C. and extruded into a film.
  • the polyester resin, the particles and, if necessary, the additives may be sent out by separate extruders, mixed, melted, and extruded into a sheet.
  • any existing method such as a T-die method, a tubular method, or the like can be employed.
  • the unstretched sheet can be obtained by rapidly cooling the extruded sheet-shaped molten polyester resin.
  • a method for rapidly cooling the molten polyester resin a method of obtaining a substantially non-oriented resin sheet by casting the molten polyester resin from a die onto a rotating drum and rapidly solidifying it can be adopted. It is preferable to set the temperature of the rotating drum to 40° C. or lower.
  • the biaxially oriented polyester film of the present invention can be obtained by combining the obtained unstretched sheet with the following processes such as the stretching process in the longitudinal direction and the width direction, the heat setting process, and the heat relaxation process. It becomes possible. Details will be described below.
  • the longitudinal direction means the direction in which the unstretched sheet runs
  • the width direction means the direction perpendicular thereto.
  • the stretching method can be simultaneous biaxial stretching in which the longitudinal direction and the width direction are stretched at the same time, or sequential biaxial stretching in which one of the longitudinal direction and the width direction is stretched first. Sequential biaxial stretching is most preferable from the viewpoint of high elasticity and excellent thickness uniformity of the finally obtained biaxially oriented polyester film.
  • the film-forming speed as used herein means the traveling speed (m/min) of the biaxially oriented polyester film when it is wound up on a master roll through the stretching process.
  • the temperature during stretching in the longitudinal direction of the unstretched sheet is in the range of (Tg + 15) to (Tg + 55) ° C., with the glass transition temperature (hereinafter referred to as Tg) of the polyester resin as an index, and the stretching ratio is 4.2 to 4.
  • Tg glass transition temperature
  • a range of 0.7 is preferred.
  • the obtained biaxially stretched polyester film has good planarity, which is preferable.
  • the stretching temperature in the longitudinal direction is (Tg+15)° C. or higher and the stretching ratio is 4.7 times or less, the arithmetic mean height Sa is easily made equal to or less than the upper limit of (3) above. It is preferable because the tensile stress (bowing phenomenon) generated in the direction opposite to the running direction of the film in the thermal relaxation step does not become too large.
  • a method of stretching in two stages, three stages, or four or more stages between a plurality of rolls may be used without increasing the stretching speed too much. Since the stretch ratio of the film can be increased, the difference in physical properties in the film width direction can be further reduced, which is preferable. Two-stage or three-stage stretching is preferable from the viewpoint of effects, facilities, and cost.
  • a film obtained by stretching an unstretched sheet in the longitudinal direction is given surface treatment such as corona treatment or plasma treatment as necessary, and then imparted with functions such as lubricity, easy adhesion, and antistatic properties.
  • a resin dispersion or resin solution can also be applied to at least one surface of the film for this purpose.
  • the unstretched sheet is guided to a tenter device, the both ends of the film stretched in the longitudinal direction are held with clips, and the film is stretched by hot air. After heating to a predetermined temperature, the film can be stretched in the width direction by widening the distance between the clips while conveying it in the longitudinal direction.
  • the temperature during stretching in the width direction is Tg+5° C. or higher, the arithmetic mean height Sa is easily made equal to or less than the upper limit of (3) above, and breakage is less likely to occur during stretching, which is preferable. Further, when the temperature during stretching is Tg + 40 ° C.
  • the number of fine protrusions having a height of less than 3 nm is easily made equal to or greater than the lower limit of (1) above, and uniform width direction stretching is easily performed, resulting in uneven thickness in the width direction. is less likely to increase, it is preferable because variation in the roll hardness of the surface of the film roll in the width direction is less likely to increase. It is more preferably Tg+8° C. or higher and Tg+37° C. or lower, and still more preferably Tg+11° C. or higher and Tg+34° C. or lower.
  • the stretch ratio in the width direction of the film obtained by stretching the unstretched sheet in the longitudinal direction is preferably 4.0 times or more and 6 times or less.
  • the stretch ratio in the width direction is 4.0 times or more, the number of fine projections having a height of less than 3 nm is easily made equal to or greater than the lower limit of the above (1), and a high yield is easily obtained in terms of material balance. It is preferable because the strength is not lowered, thickness unevenness in the width direction is less likely to increase, and variation in winding hardness in the width direction of the film roll is less likely to occur.
  • the width direction draw ratio is more preferably 4.1 times or more, more preferably 4.2 times or more. Further, when the stretch ratio in the width direction is 6 times or less, the arithmetic mean height Sa can easily be made equal to or less than the upper limit value of (3) above, and the film is less likely to break during stretching film formation, which is preferable.
  • the heat setting process is performed following the stretching process in the width direction, and the heat setting temperature of the film obtained by stretching the film obtained by stretching the unstretched sheet in the longitudinal direction is preferably 240° C. or more and 250° C. or less.
  • the heat setting temperature is 240 ° C. or higher, the number of fine protrusions with a height of less than 3 nm is easily made equal to or higher than the lower limit of (1) above, and the heat shrinkage rate in both the longitudinal direction and the width direction does not become too high. It is preferable because thermal dimensional stability is improved.
  • the heat setting temperature is 250° C. or lower, bowing is less likely to increase, which is preferable.
  • a heat relaxation treatment step is performed, but it may be performed separately from the heat setting step after the heat setting step, or may be performed simultaneously with the heat setting step.
  • the relaxation rate in the film width direction in the heat relaxation treatment step is preferably 4% or more and 8% or less.
  • the relaxation rate is 4% or more, the heat shrinkage rate in the width direction of the obtained biaxially oriented polyester film does not become too high, and the dimensional stability during vapor deposition processing is improved, which is preferable.
  • the relaxation rate is 8% or less, the tensile stress (bowing phenomenon) generated in the direction opposite to the running direction of the film at the center in the width direction of the film does not become too large, and the film thickness variation rate in the width direction does not increase. preferred.
  • the film obtained by stretching the unstretched sheet in the longitudinal direction is shrunk by heat relaxation, the restraining force in the width direction is reduced and the film is stretched by its own weight.
  • the film may swell due to the accompanying air currents of the hot air blown out from the nozzles installed above and below the film, so the film is in a situation where it is very easy to move up and down, resulting in biaxial stretching.
  • the amount of change in the orientation angle of the polyester film and the difference in the oblique heat shrinkage rate tends to fluctuate greatly.
  • the film can be kept parallel by adjusting the wind speed of the hot air blown out from the upper and lower nozzles.
  • the biaxially oriented polyester film for vapor deposition of the present invention may be subjected to corona discharge treatment, glow discharge treatment, flame treatment or surface roughening treatment as long as the object of the invention is not impaired.
  • Anchor coat treatment, printing, decoration, and the like may be applied.
  • the wide biaxially oriented polyester film stretched and formed by the above method is wound up by a winder to produce a master roll.
  • the width of the master roll is preferably 5000 mm or more and 10000 mm or less. When the width of the roll is 5000 mm or more, the cost per film area in the subsequent slitting process, vapor deposition process and printing process is low, which is preferable.
  • the winding length of the master roll is preferably 10000 m or more and 100000 m or less. If the length of the roll is 5000 m or more, the cost per film area in the subsequent slitting process, vapor deposition process and printing process will be low, which is preferable.
  • the winding width of the film roll slit from the master roll is preferably 400 mm or more and 3000 mm or less.
  • the winding width is 400 mm or more, it is preferable from the viewpoint of cost because it reduces the trouble of frequently exchanging film rolls in the printing process.
  • a longer winding width is preferable, but a roll width of 3000 mm or less is preferable because the roll width does not become too large, the roll weight does not become too heavy, and the handling property does not deteriorate.
  • the winding length of the film roll is preferably 2000 m or more and 65000 m or less. When the winding length is 2000 m or more, the trouble of frequently replacing the film roll in the printing process is reduced, which is preferable in terms of cost.
  • a longer winding length is preferable, but a length of 65,000 m or less is preferable because the diameter of the roll does not become too large, the weight of the roll does not become too heavy, and the handling property does not deteriorate.
  • At least one surface of the biaxially oriented polyester film made of a polyester resin composition containing carbon-neutral polyester resin using biomass-derived ethylene glycol and particles of the present invention satisfies all of the following (1) to (3). preferable.
  • the number of fine protrusions having a height of less than 3 nm per area of 4 ⁇ 10 ⁇ 12 m 2 is 250 or more and 600 or less.
  • the number of fine projections with a height of 3 nm or more per area of 4 ⁇ 10 ⁇ 12 m 2 is 300 or more and 600 or less.
  • the arithmetic mean height Sa is 0.010 ⁇ m or more and 0.025 ⁇ m or less.
  • the number of fine protrusions with a height of less than 3 nm does not further improve the film's slipperiness or reduce the blocking property, and has the characteristic that the gas barrier property of the inorganic thin film layer formed on the film surface is less likely to be adversely affected. In addition, even if the number of fine protrusions with a height of less than 3 nm is in the range of 600 or less, static marks and static mark discharge traces are sufficiently small.
  • the arithmetic mean height Sa of at least one surface of the biaxially oriented polyester film of the present invention is preferably 0.010 or more and 0.025 ⁇ m or less.
  • adhesion blocking phenomenon
  • adhesion between films in the film roll in recesses between films and between projections formed on the film surface is less likely to occur, and two films are formed. This is preferable because the subsequent processing can be performed smoothly. It is more preferably 0.013 ⁇ m or more, and more preferably 0.015 ⁇ m or more.
  • the arithmetic mean height Sa is 0.025 ⁇ m or less, the haze of the biaxially oriented polyester film, particularly the external haze, is lowered, and the transparency is excellent, which is preferable. It is more preferably 0.023 ⁇ m or less, more preferably 0.020 ⁇ m or less, and particularly preferably 0.017 ⁇ m or less. The same range is preferable for the arithmetic mean height Sa of the surface of the other film.
  • the coefficient of dynamic friction between one surface and the opposite surface of the biaxially oriented polyester film of the present invention is preferably 0.20 or more and 0.60 or less.
  • it is 0.20 or more, the films do not slide too much, and when the film roll is wound by a winder during film production or slitting, wrinkles are less likely to occur in the film roll, and secondary workability is less likely to deteriorate. More preferably, it is 0.30 or more.
  • the value is 0.60 or less, the films slide against each other, so that the film roll is less likely to be displaced when the film roll is wound by a winder during film production or slitting, and the secondary workability is less likely to deteriorate. It is more preferably 0.50 or less, and most preferably 0.45 or less.
  • the coefficient of static friction between one side and the opposite side of the biaxially oriented polyester film of the present invention is preferably 0.20 or more and 0.60 or less.
  • it is 0.20 or more, the films do not slide too much, and when the film roll is wound by a winder during film production or slitting, wrinkles are less likely to occur in the film roll, and secondary workability is less likely to deteriorate. More preferably, it is 0.30 or more.
  • the value is 0.60 or less, the films slide against each other, so that the film roll is less likely to be displaced when the film roll is wound by a winder during film production or slitting, and the secondary workability is less likely to deteriorate. It is more preferably 0.50 or less, and most preferably 0.45 or less.
  • the maximum height Sz of the surface satisfying all of the above (1) to (3) of the biaxially oriented polyester film of the present invention is preferably 0.5 ⁇ m or more and 2.0 ⁇ m or less.
  • the maximum height Sz is 0.5 ⁇ m or more, a large amount of air is entrapped between the films in contact with each other when the master roll is wound or when the master roll is slit and the biaxially oriented polyester film is wound around the core. It is hard to become, and there is little elongation and deformation of the film. In addition, the film in the roll is less likely to sag after the air in the film roll is removed.
  • the maximum height Sz is easily made 0.5 ⁇ m or more.
  • the coating film and the inorganic thin film layer after secondary processing on the surface of the biaxially oriented polyester film are reduced in omissions and defects.
  • the temperature during stretching in the longitudinal direction is Tg+40° C. or less, or the stretching ratio is 4.2 times or more, the maximum height Sz is easily made 2.0 ⁇ m or less. The same applies to the maximum height Sz of the other film surface.
  • the external haze of the biaxially oriented polyester film of the present invention is 1.8% or less.
  • the smoothness of the film surface is less likely to be impaired. This is preferable because quality defects due to electrification are less likely to occur. It is more preferably 1.6% or less, more preferably 1.4% or less, particularly preferably 1.2% or less, and most preferably 1.0% or less.
  • the internal haze of the biaxially oriented polyester film of the present invention is preferably 2.5% or less.
  • the transparency is less likely to deteriorate, which is preferable. It is more preferably 2.0% or less, more preferably 1.8% or less, and particularly preferably 1.6% or less.
  • the wetting tension of the surface of the biaxially oriented polyester film of the present invention is preferably 50 mN/m or more, more preferably 52 mN/m or more. There is no particular upper limit, but even if it is in the range of 55 mN/m or less, it is sufficient for the performance after the secondary coating or vapor deposition thin film is performed.
  • the film thickness of the biaxially oriented polyester film of the present invention is preferably 5 to 40 ⁇ m. When the thickness is 5 ⁇ m or more, the strength and stiffness of the film do not decrease, and the film roll is less likely to wrinkle when wound with a winder, which is preferable. On the other hand, if the film thickness is in the range of 40 ⁇ m or less, sufficient strength and stiffness can be obtained, and it is preferable to reduce the thickness from the viewpoint of cost.
  • the thickness of the film is more preferably 8-30 ⁇ m, particularly preferably 9-20 ⁇ m.
  • the biaxially oriented polyester film of the present invention preferably contains 10 to 18% biomass-derived carbon based on radioactive carbon (C14) measurement with respect to the total carbon in the polyester film. If the degree of biomass in the environmentally friendly polyester film is less than 10% by using a carbon-neutral polyester resin using biomass-derived ethylene glycol, the effect as a carbon offset material will be poor.
  • the biomass degree in a carbon-neutral polyester resin using biomass-derived ethylene glycol is preferably close to 20%, but the actual upper limit is 19% due to problems in the film manufacturing process, physical properties, and costs. .
  • a gas barrier layer such as an inorganic thin film layer or a metal foil such as an aluminum foil can be provided on at least one side of the biaxially oriented polyester film of the present invention that satisfies all of the following (1) to (3).
  • the number of fine protrusions having a height of less than 3 nm per area of 4 ⁇ 10 ⁇ 12 m 2 is 250 or more and 600 or less.
  • the number of fine projections with a height of 3 nm or more per area of 4 ⁇ 10 ⁇ 12 m 2 is 300 or more and 600 or less.
  • the arithmetic mean height Sa is 0.010 ⁇ m or more and 0.025 ⁇ m or less.
  • the inorganic thin film layer is a thin film made of metal or inorganic oxide.
  • the material for forming the inorganic thin film layer is not particularly limited as long as it can be made into a thin film. things are preferred. In particular, a composite oxide of silicon oxide and aluminum oxide is preferable from the viewpoint of transparency and flexibility of the thin film layer.
  • the mixing ratio of silicon oxide and aluminum oxide is preferably in the range of 20 to 70% by weight of Al in terms of metal content. If the Al concentration is less than 20%, the water vapor gas barrier properties may deteriorate. On the other hand, if it exceeds 70%, the inorganic thin film layer tends to become hard, and there is a risk that the film will be destroyed during secondary processing such as printing and lamination, resulting in a decrease in gas barrier properties.
  • silicon oxide means various silicon oxides such as SiO and SiO 2 or mixtures thereof
  • aluminum oxide means various aluminum oxides such as AlO and Al 2 O 3 or mixtures thereof.
  • the film thickness of the inorganic thin film layer is usually 1 to 100 nm, preferably 5 to 50 nm. If the thickness of the inorganic thin film layer is less than 1 nm, it may be difficult to obtain satisfactory gas barrier properties. It is rather disadvantageous in terms of bending resistance and manufacturing cost.
  • the method for forming the inorganic thin film layer is not particularly limited, and known vapor deposition methods such as physical vapor deposition (PVD method) such as vacuum vapor deposition, sputtering, and ion plating, or chemical vapor deposition (CVD method). Laws should be adopted accordingly.
  • PVD method physical vapor deposition
  • CVD method chemical vapor deposition
  • a typical method for forming an inorganic thin film layer will be described below using a silicon oxide/aluminum oxide thin film as an example.
  • a vacuum deposition method a mixture of SiO 2 and Al 2 O 3 or a mixture of SiO 2 and Al is preferably used as the deposition raw material.
  • Particles are usually used as these vapor deposition raw materials, and in this case, the size of each particle is desirably such that the pressure during vapor deposition does not change, and the preferred particle diameter is 1 mm to 5 mm.
  • heating methods such as resistance heating, high-frequency induction heating, electron beam heating, and laser heating can be employed. It is also possible to introduce oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor, etc. as reaction gases, or adopt reactive vapor deposition using means such as addition of ozone and ion assist.
  • film formation conditions can be arbitrarily changed, such as applying a bias to the object to be vapor-deposited (laminated film to be vapor-deposited), heating or cooling the object to be vapor-deposited.
  • Such vapor deposition material, reaction gas, bias of the object to be vapor-deposited, heating/cooling, etc. can be similarly changed when adopting the sputtering method or the CVD method.
  • a printed layer may be laminated on the inorganic thin film layer.
  • a gas barrier layer made of a metal oxide is not a completely dense film, and is dotted with minute defects.
  • the resin in the resin composition for protective layer permeates into the defective portions of the metal oxide layer, As a result, the effect of stabilizing the gas barrier property is obtained.
  • the gas barrier properties of the laminated film are greatly improved.
  • Examples of the protective layer include resins such as urethane, polyester, acrylic, titanium, isocyanate, imine, and polybutadiene with addition of curing agents such as epoxy, isocyanate, and melamine.
  • Examples of the solvent (solvent) used for forming the protective layer include aromatic solvents such as benzene and toluene; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate and acetic acid. ester solvents such as butyl; and polyhydric alcohol derivatives such as ethylene glycol monomethyl ether.
  • the polar group of the urethane bond interacts with the inorganic thin film layer, and the presence of the amorphous part also provides flexibility, so even when a bending load is applied, damage to the inorganic thin film layer is suppressed. It is preferable because it can
  • the acid value of the urethane resin is preferably within the range of 10-60 mgKOH/g. It is more preferably in the range of 15 to 55 mgKOH/g, still more preferably in the range of 20 to 50 mgKOH/g.
  • the acid value of the urethane resin is within the above range, the liquid stability is improved when it is made into an aqueous dispersion, and the protective layer can be uniformly deposited on the highly polar inorganic thin film, so that the coat appearance is good. becomes.
  • the urethane resin preferably has a glass transition temperature (Tg) of 80° C. or higher, more preferably 90° C. or higher. By setting the Tg to 80° C. or higher, it is possible to reduce swelling of the protective layer due to molecular movement during the wet heat treatment process (temperature increase, heat retention, and temperature decrease).
  • Tg glass transition temperature
  • the proportion of the aromatic or araliphatic diisocyanate in the urethane resin is preferably in the range of 50 mol% or more (50 to 100 mol%) in 100 mol% of the polyisocyanate component (F).
  • the proportion of the total amount of aromatic or araliphatic diisocyanates is preferably 60-100 mol %, more preferably 70-100 mol %, still more preferably 80-100 mol %.
  • the "Takelac (registered trademark) WPB” series commercially available from Mitsui Chemicals, Inc. can be suitably used. If the total amount of aromatic or araliphatic diisocyanates is less than 50 mol %, good gas barrier properties may not be obtained.
  • the urethane resin preferably has a carboxylic acid group (carboxyl group).
  • a carboxylic acid (salt) group for example, a polyol compound having a carboxylic acid group such as dimethylolpropionic acid or dimethylolbutanoic acid may be introduced as a copolymerization component.
  • neutralization with a salt-forming agent makes it possible to obtain an aqueous dispersion of the urethane resin.
  • salt-forming agents include ammonia, trialkylamines such as trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine and tri-n-butylamine; -alkylmorpholines, N-dialkylalkanolamines such as N-dimethylethanolamine and N-diethylethanolamine. These may be used alone or in combination of two or more.
  • the biaxially oriented polyester film of the present invention may be used as a base film and layers of other materials may be laminated to form a laminate.
  • the biaxially oriented polyester film can be laminated after being produced, or laminated during film formation.
  • the biaxially oriented polyester film of the present invention may be used as a packaging material by further forming a heat-sealable resin layer called a sealant. can.
  • Formation of the heat-sealable resin layer is usually carried out by an extrusion lamination method or a dry lamination method.
  • the thermoplastic polymer forming the heat-sealable resin layer may be any polymer capable of exhibiting sufficient sealant adhesiveness, such as polyethylene resins such as HDPE, LDPE, and LLDPE, and polypropylene resins. Ethylene-vinyl acetate copolymers, ethylene- ⁇ -olefin random copolymers, ionomer resins and the like can be used.
  • the sealant layer may be a single layer film or a multilayer film, and may be selected according to the required functions.
  • a multilayer film in which a resin such as an ethylene-cyclic olefin copolymer or polymethylpentene is interposed can be used.
  • the sealant layer may contain various additives such as flame retardants, slip agents, antiblocking agents, antioxidants, light stabilizers and tackifiers.
  • the thickness of the sealant layer is preferably 10-100 ⁇ m, more preferably 20-60 ⁇ m.
  • Examples of the layer structure of a laminate for packaging materials using the biaxially oriented polyester film of the present invention as a base film include base film/gas barrier layer/protective layer and base film/gas barrier layer/protective layer/adhesive.
  • a laminate using the biaxially oriented polyester film of the present invention can be suitably used for applications such as packaging products, various label materials, lid materials, sheet molded products, and laminated tubes.
  • it is used for packaging bags (for example, pouches such as pillow bags, standing pouches and four-sided pouches).
  • the thickness of the laminate can be appropriately determined according to its use. For example, it is used in the form of a film or sheet having a thickness of about 5 to 500 ⁇ m, preferably about 10 to 300 ⁇ m.
  • polyester resin Evaluation methods for the polyester resin are as follows. [Glass transition (Tg)] Using a differential scanning calorimeter (DSC6220, manufactured by SII Nanotechnology Co., Ltd.), 5 mg of a resin sample was melted to 280°C under a nitrogen atmosphere, held for 5 minutes, then quenched with liquid nitrogen and cooled to room temperature. Measurement was performed under the condition of a temperature increase rate of 20°C/min.
  • the degree of biomass was calculated from the ratio of plant-derived carbon to the total carbon number measured according to the radiocarbon (C14) measurement shown in ASTM D6866-16 Method B (AMS).
  • the evaluation method of the polyester film is as follows. [Film thickness] It was measured using a dial gauge in accordance with JIS K7130-1999 A method.
  • haze H2 The haze (hereinafter referred to as "haze H2") of the laminate sandwiched between two sheets was measured.
  • the internal haze is obtained according to the following formula.
  • Internal Haze Haze (H2) - Haze (H1) Equation 1
  • the external haze is a value obtained by subtracting the internal haze from the total haze. All of the total haze, internal haze, and external haze refer to haze for all wavelengths of visible light.
  • Measurements were taken at 10 arbitrary points on a 10 cm x 10 cm sample, and the average values were taken as the arithmetic mean height Sa and the maximum height Sz, respectively.
  • the variation (%) of the arithmetic mean height Sa was sampled every 1000 m from the surface layer of the film roll to the winding core in the longitudinal direction of the obtained polyester film roll (width 2080 mm, winding length 63,000 m). Each sampled film was measured under the above conditions.
  • the maximum value of the obtained arithmetic mean height Sa was Xmax(N), the minimum value was Xmin(N), and the average value was Xave.
  • a sample film was prepared by cutting the obtained film into an area of 400 mm in the longitudinal direction ⁇ 100 mm in the width direction. This was aged for 12 hours in an atmosphere of 23° C. and 65% RH, and divided into a test piece of 300 mm in the vertical direction ⁇ 100 mm in the horizontal direction for the test table and a test piece of 100 mm in the vertical direction ⁇ 100 mm in the width direction for the sliding piece. .
  • the test piece for the test table is set on the test table, and the test piece for the sliding piece is cast on the bottom surface of the sliding piece (area size is 39.7 mm 2 , square) with a metal load of 1.5 kg.
  • test piece It was pasted with double-sided tape so that the surface in contact with the drum faced each other.
  • the sliding speed of the test piece is 200 mm / min, 23 ° C., 65% RH, and other conditions conform to JIS K-7125, and the dynamic friction coefficient and static friction coefficient are measured, and the average of three measurements is used. board.
  • the number of particles of 3 nm or more (number of protrusions) and the number of particles of less than 3 nm (number of protrusions), with the threshold value of particles to be extracted under the following particle analysis conditions being 3 nm, is calculated as the area Counted within 4 ⁇ 10 ⁇ 12 m 2 (2 ⁇ m ⁇ 2 ⁇ m square).
  • the number of particles (number of projections) of less than 3 nm particles of 0.01 nm or more were counted. The measurement was performed 5 times at different locations, and the average value of 3 times excluding the highest and lowest counts was calculated as the number of fine protrusions.
  • Frictional electrification voltage was measured using a triboelectrification voltage measuring machine (RST-300a) manufactured by Daiei Kagaku Seiki Seisakusho. The sample was fixed to a rotating device, and static electricity generated by friction with a metal plate was measured for 60 seconds at a drum rotation speed of 400 rpm, and the maximum value was taken as the triboelectric voltage. Evaluation was made according to the following criteria based on the measured frictional electrification voltage.
  • V triboelectric charge voltage ⁇ 200 V or more and less than 500 V tribo electrification voltage ⁇ : 500 V or more and less than 1000 V tribo electrification voltage: ⁇ : Friction electrification voltage of 1000 V or more:
  • the film was unwound from the end of the film on the outermost surface of the resulting film roll, and after removing 2 m from the end of the film, the film was sampled at a length of 10 cm in the center in the width direction and 10 cm in the longitudinal direction. was used to visualize the charging state of the film surface.
  • the chargeability of the film roll was evaluated according to the following criteria. ⁇ : No static marks, static mark discharge traces, or toner adhesion. ⁇ : No static marks or static mark discharge traces were observed, but toner adhered. x: Static marks and static mark discharge traces are observed.
  • the wetting tension is determined by observing the liquid film of the mixed liquid for testing in a bright place and observing the state of the liquid film after 3 seconds. If the applied state is maintained for 3 seconds or more without breaking the liquid film, it means that the liquid is wet. If the wetting persists for more than 3 seconds, proceed further to the next higher surface tension mixture. Conversely, if the liquid film is broken in 3 seconds or less, the next mixed liquid having a lower surface tension is used. This operation is repeated to select a mixed solution that can wet the surface of the test piece accurately in 3 seconds. Use a new swab for each test. Brushes or wire bars are cleaned with methanol and dried between uses, as residual liquid changes composition and surface tension upon evaporation. The operation of selecting a mixture that can wet the surface of the corona-treated surface in 3 seconds is performed at least 3 times. The surface tension of the mixture thus selected is reported as the wetting tension of the film.
  • polyester resin A As a carbon-neutral PET resin using biomass-derived ethylene glycol used in the production of a biaxially stretched polyester film to be described later, one synthesized using the following method was used. Magnesium acetate tetrahydrate was added to a mixture of terephthalic acid refined from petroleum-derived raw materials and ethylene glycol refined from plant-derived raw materials so that the Mg atom was 70 ppm in the polyester, and esterification was performed at a temperature of 255 ° C. under normal pressure. chemically reacted.
  • polyester resin A When the biomass degree of this polyester resin A was measured, it was 17%.
  • (Polyester resin B) Terephthalic acid // ethylene glycol 100 // 100 (mol%) (manufactured by Toyobo Co., Ltd., intrinsic viscosity 0.62 dl / g) was used as the fossil fuel-derived PET resin used in the production of the biaxially oriented polyester film described later. .
  • silica particles are particles obtained by preparing an ethylene glycol slurry in advance, centrifuging it to remove 35% of the coarse particles, and then filtering it through a metal filter with an opening of 5 ⁇ m. After 15 minutes, the resulting esterification reaction product was transferred to a polycondensation reactor and subjected to a polycondensation reaction at 280°C under reduced pressure to obtain a polyester resin C having an intrinsic viscosity of 0.60 dl/g.
  • Polyester resin D, E, F, G Polyester resins D, E, F, and G were obtained in the same manner as polyester resin C, except that the shape and average particle size of the silica particles were changed.
  • Raw material resin chips are as shown in Table 1.
  • the abbreviations in the table are as follows.
  • TPA terephthalic acid
  • EG ethylene glycol
  • Example 1 A three-layered film was formed using three extruders.
  • the base layer (B) contains 98.7% by weight of polyester resin A and 1.3% by weight of polyester resin C
  • the surface layer (A) contains 93.3% by weight of polyester resin A and 6.7% by weight of polyester resin C.
  • the polyester resin C was introduced using an inner pipe as shown in FIG. 4 so as to be mixed with other raw materials before entering the extruder.
  • the surface layer (A) forming mixed resin is melt extruded from the first and third extruders at a resin temperature of 285 ° C., and the base layer (B) forming mixed resin is extruded by the second extruder.
  • the resin is melted at a resin temperature of 285 ° C., and the thickness ratio is 1/10/ They were merged and laminated so as to have a thickness of 1 ( ⁇ m), discharged from a T-shaped die, and cooled and solidified in a casting drum having a surface temperature of 30° C. to obtain an unstretched polyethylene terephthalate sheet.
  • static electricity was applied using a wire-shaped electrode with a diameter of 0.15 mm, and the film was brought into close contact with a cooling drum to obtain a three-layer unstretched film.
  • the obtained unstretched film was heated to 115° C.
  • a master roll (winding length: 26,000 m, width: 8,000 mm) of a biaxially oriented polyester film with a thickness of 12 ⁇ m was produced by performing corona treatment under conditions of min/m 2 and winding it into a roll with a winder.
  • a biaxially oriented polyester film was unwound from the obtained master roll, and while slitting at a width of 2200 mm on a core of 6 inches in diameter (152.2 mm), the film roll was subjected to surface pressure with a contact roll and a biaxial turret winder. The film roll was wound while tension was applied to the film.
  • Table 2 shows the raw material composition and film-forming conditions of the obtained film, the physical properties of the obtained film, and the evaluation results. Film evaluation was performed on the layer A surface on the side in contact with the chill roll.
  • Example 2 A biaxially stretched film was formed in the same manner as in Example 1, except that the polyester resin A of the surface layer (A) was changed to 95.0% by mass and the polyester resin C was changed to 5.0% by mass as raw materials.
  • a biaxially oriented polyester film with a thickness of 12 ⁇ m was obtained.
  • Table 2 shows the raw material composition and film-forming conditions of the obtained film, the physical properties of the obtained film, and the evaluation results. Film evaluation was performed on the layer A surface on the side in contact with the chill roll.
  • Example 3 As raw materials, the polyester resin A of the surface layer (A) was 96.0% by mass, the polyester resin D was 4.0% by mass, and the polyester resin of the base layer (B) was changed to polyester resin D. A biaxially stretched film was formed in the same manner to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m. Table 2 shows the raw material composition and film-forming conditions of the obtained film, the physical properties of the obtained film, and the evaluation results. Film evaluation was performed on the layer A surface on the side in contact with the chill roll.
  • Example 4 As raw materials, the polyester resin A of the surface layer (A) was 92.0% by mass, the polyester resin E was 8.0% by mass, and the polyester resin of the base layer (B) was changed to polyester resin E. A biaxially stretched film was formed in the same manner to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m. Table 2 shows the raw material composition and film-forming conditions of the obtained film, the physical properties of the obtained film, and the evaluation results. Film evaluation was performed on the layer A surface on the side in contact with the chill roll.
  • Example 1 As a raw material, a biaxially stretched film was formed in the same manner as in Example 1 except that the polyester resin of the surface layer (A) and the base layer (B) was changed to polyester resin B, and a biaxially oriented polyester having a thickness of 12 ⁇ m was prepared. got the film.
  • Table 2 shows the raw material composition and film-forming conditions of the obtained film, the physical properties of the obtained film, and the evaluation results. Film evaluation was performed on the layer A surface on the side in contact with the chill roll.
  • the polyester resin A of the surface layer (A) was 95.0% by mass
  • the polyester resin F was 5.0% by mass
  • the polyester resin of the base layer (B) was changed to polyester resin F.
  • a biaxially stretched film was formed in the same manner to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
  • Table 2 shows the raw material composition and film-forming conditions of the obtained film, the physical properties of the obtained film, and the evaluation results. Film evaluation was performed on the layer A surface on the side in contact with the chill roll.
  • the polyester resin A of the surface layer (A) was 95.0% by mass
  • the polyester resin G was 5.0% by mass
  • the polyester resin of the base layer (B) was changed to polyester resin G.
  • a biaxially stretched film was formed in the same manner to obtain a biaxially oriented polyester film having a thickness of 12 ⁇ m.
  • Table 2 shows the raw material composition and film-forming conditions of the obtained film, the physical properties of the obtained film, and the evaluation results. Film evaluation was performed on the layer A surface on the side in contact with the chill roll.
  • the surface layer (A) forming mixed resin is melt extruded from the first and third extruders at a resin temperature of 285 ° C.
  • the base layer (B) forming mixed resin is extruded by the second extruder.
  • the resin is melted at a resin temperature of 285 ° C., and the thickness ratio is 1/10/ They were merged and laminated so as to have a thickness of 1 ( ⁇ m), discharged from a T-shaped die, and cooled and solidified in a casting drum having a surface temperature of 30° C. to obtain an unstretched polyethylene terephthalate sheet.
  • Corona treatment was performed under the conditions of min/m 2 , followed by stretching in the width direction at a temperature of 140 ° C. and a draw ratio of 4.3 times, heat setting at 245 ° C., and heat relaxation treatment by 5% in the width direction.
  • a master roll (winding length: 26,000 m, width: 8,000 mm) of a biaxially oriented polyester film having a thickness of 12 ⁇ m was produced by winding it into a roll with a winder.
  • a biaxially oriented polyester film was unwound from the obtained master roll, and while slitting at a width of 2200 mm on a core of 6 inches in diameter (152.2 mm), the film roll was subjected to surface pressure with a contact roll and a biaxial turret winder. The film roll was wound while tension was applied to the film.
  • Table 2 shows the raw material composition and film-forming conditions of the obtained film, the physical properties of the obtained film, and the evaluation results. Film evaluation was performed on the layer A surface on the side in contact with the chill roll.
  • the number of fine protrusions having a height of 3 nm or more, the number of fine protrusions having a height of less than 3 nm, and the arithmetic mean height Sa are within the specified ranges.
  • Comparative Example 1 the number of fine protrusions with a height of 3 nm or more, the number of fine protrusions with a height of less than 3 nm, and the arithmetic mean height Sa of the obtained film are within the specified range, so static marks, static mark discharge traces, etc. Although quality defects due to electrification are few and the performance after secondary processing such as coating and vapor deposition is excellent, since it is a conventional polyester resin derived from fossil fuel, it was inferior as an environmentally friendly polyester film. .
  • Comparative Example 2 Although the number of fine protrusions having a height of 3 nm or more in the obtained film was within the range, the number of fine protrusions having a height of less than 3 nm was small, so the triboelectrification voltage was high and the static mark evaluation was unsatisfactory. rice field. Moreover, since the arithmetic mean height Sa is too large, the external haze is large and the transparency is poor.
  • Comparative Example 3 Although the number of fine protrusions with a height of 3 nm or more in the obtained film was within the range, the number of fine protrusions with a height of less than 3 nm was small, so the triboelectrification voltage was high and the static mark evaluation was unsatisfactory. rice field.
  • Reference Example 1 does not use an inner pipe to supply raw materials, and the segregation of raw materials causes large fluctuations in the ratio of raw materials in the longitudinal direction.
  • the number of fine protrusions of less than 3 nm varies greatly in the longitudinal direction, and although a good film having physical properties partially equivalent to those of Examples 1 to 4 can be obtained in the film roll, it is inferior as a film roll. there were.
  • the biaxially oriented polyester film of the present invention has excellent transparency, and wrinkles are less likely to occur on the film roll when the film is produced or wound around the film roll after frilling, and the film is easily unwound from the film roll. It is easy to perform secondary processing such as In addition, since there are few quality defects due to charging such as static marks and static mark discharge traces, it is excellent in performance after secondary processing such as coating and vapor deposition, and carbon-neutral polyester resin using biomass-derived ethylene glycol should be used. It is possible to provide a biaxially oriented polyester film that is an environmentally friendly polyester film and has little variation in physical properties in the longitudinal direction even if it is a long film roll with a long winding length, and a method for producing the same. Therefore, it is expected to be useful in food packaging applications, particularly in applications to films having gas barrier properties, and to greatly contribute to the industrial world.

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12473408B2 (en) 2019-07-31 2025-11-18 Toyobo Co., Ltd. Biaxially oriented polyester film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7581050B2 (ja) * 2018-10-30 2024-11-12 東洋紡株式会社 二軸配向ポリエステルフィルムロール

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10119172A (ja) 1996-08-27 1998-05-12 Toray Ind Inc 蒸着２軸配向ポリエステルフイルム
JPH1110725A (ja) 1997-06-27 1999-01-19 Toray Ind Inc 透明蒸着用ポリエステルフィルム
JP4834923B2 (ja) 2001-06-18 2011-12-14 東レ株式会社 蒸着用ポリエステルフィルム及び蒸着ポリエステルフィルム
JP2012097163A (ja) 2010-10-29 2012-05-24 Dainippon Printing Co Ltd ポリエステル樹脂組成物
CN106142794A (zh) * 2016-06-29 2016-11-23 安徽国风塑业股份有限公司 一种电子胶带用双向拉伸聚酯薄膜的制备方法及其薄膜
JP2017100446A (ja) * 2015-11-30 2017-06-08 ミツビシ ポリエステル フィルム ジーエムビーエイチ 平滑な表面を有し、巻取性良好な透明二軸延伸ポリエステルフィルム
WO2020031197A1 (en) * 2018-08-09 2020-02-13 Polyplex Corporation Limited Biaxially oriented formable polyester film
WO2020095725A1 (ja) * 2018-11-07 2020-05-14 東洋紡株式会社 二軸配向ポリエステルフィルム及びその製造方法
WO2020195742A1 (ja) * 2019-03-26 2020-10-01 東洋紡株式会社 ポリエステルフィルム及びその製造方法
WO2021019965A1 (ja) * 2019-07-31 2021-02-04 東洋紡株式会社 二軸配向ポリエステルフィルム

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1600625A (https=) 1968-05-18 1970-07-27
US4761327A (en) * 1986-01-17 1988-08-02 Teijin Limited Biaxially oriented aromatic polyester film
JP3146973B2 (ja) * 1996-05-01 2001-03-19 東洋製罐株式会社 ラミネート板及びこれを用いた製缶方法
DE19741878A1 (de) 1997-09-23 1999-03-25 Hoechst Diafoil Gmbh Mehrschichtige, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19930981A1 (de) * 1999-07-05 2001-01-11 Mitsubishi Polyester Film Gmbh Mehrschichtige, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung als Magnetbandfolie ohne Rückseitenbeschichtung
JP3506236B2 (ja) 1999-08-24 2004-03-15 東洋紡績株式会社 ポリエステル重合触媒およびこれを用いて製造されたポリエステルならびにポリエステルの製造方法
US7208565B1 (en) 1999-08-24 2007-04-24 Toyo Boseki Kabushiki Kaisha Polymerization catalyst for polyesters, polyester produced with the same, and process for production of polyester
KR100748289B1 (ko) 2000-09-12 2007-08-09 토요 보세키 가부시기가이샤 폴리에스테르 중합촉매, 이를 사용하여 제조된폴리에스테르 및 폴리에스테르의 제조방법
JP5028713B2 (ja) 2001-02-23 2012-09-19 東洋紡績株式会社 配向ポリエステルフィルム
JP2002249602A (ja) 2001-02-23 2002-09-06 Toyobo Co Ltd 配向ポリエステルフィルム
US20130344345A1 (en) 2011-07-08 2013-12-26 Toray Plastics (America), Inc. Biaxially oriented bio-based polyester window films and laminates
JP6036099B2 (ja) 2012-09-27 2016-11-30 東洋紡株式会社 Ｐｅｔボトル再生原料を使用した二軸配向ポリエステルフィルム
KR102470780B1 (ko) 2014-11-19 2022-11-25 도레이 카부시키가이샤 적층 필름
CN113412184A (zh) * 2019-02-14 2021-09-17 东洋纺株式会社 双轴拉伸聚酯膜
CN113453870B (zh) 2019-02-18 2023-04-18 东洋纺株式会社 双轴拉伸聚酯膜卷
WO2020203105A1 (ja) 2019-03-29 2020-10-08 東洋紡株式会社 ポリエステルフィルム及びその製造方法
KR20220116200A (ko) 2019-12-13 2022-08-22 도요보 가부시키가이샤 2축 배향 폴리에스테르 필름 및 그 제조 방법
EP4289599A4 (en) 2021-02-03 2025-01-01 Toyobo Co., Ltd. BIAXIALLY ORIENTED POLYESTER FILM AND PROCESS FOR PRODUCING THE SAME

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10119172A (ja) 1996-08-27 1998-05-12 Toray Ind Inc 蒸着２軸配向ポリエステルフイルム
JPH1110725A (ja) 1997-06-27 1999-01-19 Toray Ind Inc 透明蒸着用ポリエステルフィルム
JP4834923B2 (ja) 2001-06-18 2011-12-14 東レ株式会社 蒸着用ポリエステルフィルム及び蒸着ポリエステルフィルム
JP2012097163A (ja) 2010-10-29 2012-05-24 Dainippon Printing Co Ltd ポリエステル樹脂組成物
JP2017100446A (ja) * 2015-11-30 2017-06-08 ミツビシ ポリエステル フィルム ジーエムビーエイチ 平滑な表面を有し、巻取性良好な透明二軸延伸ポリエステルフィルム
CN106142794A (zh) * 2016-06-29 2016-11-23 安徽国风塑业股份有限公司 一种电子胶带用双向拉伸聚酯薄膜的制备方法及其薄膜
WO2020031197A1 (en) * 2018-08-09 2020-02-13 Polyplex Corporation Limited Biaxially oriented formable polyester film
WO2020095725A1 (ja) * 2018-11-07 2020-05-14 東洋紡株式会社 二軸配向ポリエステルフィルム及びその製造方法
WO2020195742A1 (ja) * 2019-03-26 2020-10-01 東洋紡株式会社 ポリエステルフィルム及びその製造方法
WO2021019965A1 (ja) * 2019-07-31 2021-02-04 東洋紡株式会社 二軸配向ポリエステルフィルム

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4289598A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12473408B2 (en) 2019-07-31 2025-11-18 Toyobo Co., Ltd. Biaxially oriented polyester film

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CN116745347A (zh) 2023-09-12
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