WO2020175064A1 - Film de polyester à orientation biaxiale et procédé de production pour film de polyester à orientation biaxiale - Google Patents

Film de polyester à orientation biaxiale et procédé de production pour film de polyester à orientation biaxiale Download PDF

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Publication number
WO2020175064A1
WO2020175064A1 PCT/JP2020/004362 JP2020004362W WO2020175064A1 WO 2020175064 A1 WO2020175064 A1 WO 2020175064A1 JP 2020004362 W JP2020004362 W JP 2020004362W WO 2020175064 A1 WO2020175064 A1 WO 2020175064A1
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WIPO (PCT)
Prior art keywords
biaxially oriented
polyester film
oriented polyester
film
resin
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PCT/JP2020/004362
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English (en)
Japanese (ja)
Inventor
昇 玉利
考道 後藤
雅幸 春田
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東洋紡株式会社
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Priority to JP2020532064A priority Critical patent/JP7365569B2/ja
Publication of WO2020175064A1 publication Critical patent/WO2020175064A1/fr

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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
    • 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
    • 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
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • 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
    • 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

Definitions

  • the present invention relates to a biaxially oriented polyester film and a method for producing a biaxially oriented polyester film.
  • Polyethylene terephthalate (hereinafter, referred to as “polyethylene terephthalate” is abbreviated as “Mita”)
  • Polyethylene terephthalate (hereinafter, abbreviated as “polyethylene terephthalate” is abbreviated as “Mita”) resin.
  • Applications are also being considered in the fields of films, vacuum insulation materials, drawing films, and film for can inner bags.
  • Patent Document 1 For example, in Patent Document 1, 40 to 80% by weight of Mingo resin is used with respect to Mingo resin, and tensile elastic moduli in the longitudinal direction and the width direction are set to 2.3 to 3.503. It is disclosed that it can be suitably used as a polyester film for an inner bag of a can.
  • Patent Document 2 four directions (0° (longitudinal direction), 45°, 90° (width direction)
  • a biaxially stretched film made of Mingko resin, which has a ratio of the maximum value to the minimum value of 1.12 or less, of the tensile rupture strength of ° ) is disclosed. Further, using the biaxially stretched film as a base layer, the packaging material comprising a structure composed of the substrate layer _ gas barrier layer _ sealant layer from the outside is disclosed.
  • Patent Document 3 a Mihinoto resin 6 0 wt% or more, the longitudinal direction and the width direction of the yield stress 7 0 IV!? 3 or more, the breaking strength of 1 6 0 IV!? 3 or more, break It is disclosed that when the elongation is 100% or more, it can be suitably used for nylon film and other flexible film applications.
  • Patent Document 1 Patent No. 6 1 9 5 7 6 5
  • Patent Document 2 Patent No. 6 3 4 7 4 9 9 Publication
  • Patent Document 3 Patent No. 5 9 9 4 8 6 4 Publication
  • the end portion of the film obtained by casting tends to be thicker than the center portion for manufacturing reasons. Therefore, crystallization becomes more remarkable at the edges of the film obtained by casting.
  • an object of the present invention is to provide a biaxially oriented polyester film having good bag breaking resistance and excellent film-forming property.
  • Another object of the present invention is to provide a method for producing a biaxially oriented polyester film capable of obtaining the biaxially oriented polyester film. ⁇ 02020/175064 3 ⁇ (: 171?2020/004362
  • the present inventors have earnestly studied a biaxially oriented polyester film. As a result, they have found that a biaxially oriented polyester film having good bag-breaking resistance and excellent film-forming property can be obtained by adopting the following constitution, and completed the present invention.
  • the puncture strength of the biaxially oriented polyester film measured by the puncture test according to 1 3-7 1 7 0 7 is 0.501 ⁇ 1/1 or more.
  • the intrinsic viscosity of the biaxially oriented polyester film is 0.7 ⁇ / 9 or more.
  • the puncture strength is 0.501 ⁇ 1/1/ or more, the bag puncture resistance can be improved.
  • the density is 1.4 Since it is below, crystallization at the edge is suppressed. As a result, it is possible to suppress excessive stress at the end portion in the stretching step when producing the biaxially oriented polyester film, and it is possible to improve the film forming property.
  • the yield stress at the ends can be prevented from becoming too high. As a result, it can be made difficult to break in the stretching process.
  • the biaxially oriented polyester film of the present invention is assumed to be a film after production (after casting and stretching treatment), that is, a film not subjected to slit treatment (film in a mill roll state). ing.
  • the biaxially oriented polyester film of the present invention contains a polyester resin composition containing 75 to 100% by mass of a polybutylene terephthalate resin (8), and as long as the above requirements (1) to (3) are satisfied,
  • the form of the film is not particularly limited, and includes, for example, a film made into a small film by slitting or the like, and a film of a single sheet.
  • the polyester resin composition contains a polyester resin (Mitsumi) other than the polyethylene terephthalate resin (8).
  • the polyester resin composition contains a polyester resin (Mitsumi) other than the polypropylene terephthalate resin (8), the film formability during biaxial stretching and the mechanical properties of the obtained film can be adjusted.
  • the absorption intensity 8 is the absorption derived from the methylene group of the ⁇ type crystal of Mending, the absorption intensity is the absorption derived from the carbon bond of the benzene ring, and the absorption intensity ratio 8/Mis is The orientation coefficient is shown. The smaller the orientation coefficient is, the lower the crystallinity is. The higher the orientation coefficient is, the higher the crystallinity is.
  • the plane orientation degree is 0.145 or more, the plane orientation is suitably high, the puncture strength is sufficient, and the bag breaking resistance is excellent.
  • a process step of blowing air to the unstretched sheet on the cooling port the process step, when the total width of the unstretched sheet is 100%, the temperature of the wind blown to the center is X, When the temperature blown to both ends is assumed to be less than 1, X is 15 ° or less, and the temperature is lower than X, and the end is at least 1 from the edge. It is characterized by including the area within 0%.
  • the unstretched sheet on the cooling port is blown with a wind of not more than 15°, and the unstretched sheet has a mound surface (a surface opposite to the surface in contact with the cooling port). ) Is rapidly cooled, the crystallinity can be reduced and the film-forming property can be improved. In addition, the thickness of the end portion of the unstretched sheet is often thicker than that of the central portion. Then, by quenching the edge (at least the area within 10% from the edge) more strongly than the center, crystallization of the edge is suppressed to the center and the film forming property is improved. You can
  • the temperature is 10 ° or less.
  • the crystallinity of the edge of the unstretched sheet at the edge of the facet does not necessarily become high, and the film formability becomes better.
  • the present invention it is possible to provide a biaxially oriented polyester film having good bag-breaking resistance and excellent film-forming properties.
  • the biaxially oriented poly ⁇ 02020/175064 6 ⁇ (: 171-12020/004362
  • Fig. 1 is a schematic front view for explaining a method of blowing cooling air from a multi-duct onto a mound surface of an unstretched sheet on a cooling port.
  • Fig. 2 is a side view of Fig. 1.
  • FIG. 3 is a bottom view showing an example of a multi-duct.
  • a biaxially oriented polyester film which satisfies the following requirements (1) to (3).
  • the puncture strength of the biaxially oriented polyester film measured by the puncture test according to 1 3-7 1 7 0 7 is 0.501 ⁇ 1/1 or more.
  • the intrinsic viscosity of the biaxially oriented polyester film is 0.7 ⁇ / 9 or more.
  • the polyester resin composition has a minor resin () as a main constituent, and the content of the minor resin (8) in the polyester resin composition is 75% by mass or more. It is preferably 85% by mass or more, and more preferably 90% by mass or more. When the content is 75% by mass or more, the puncture strength can be made sufficient and the bag puncture resistance can be improved.
  • Mingpo resin (8) which is used as the main component, is a dicarboxylic acid component. ⁇ 02020/175064 7 ⁇ (: 171-12020/004362
  • the content of terephthalic acid is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and most preferably 100 mol%.
  • 1,4-butanediol is preferably 90 mol% or more, more preferably 95 mol% or more.
  • the lower limit of the intrinsic viscosity of Mihinoto resin (eight) is preferably ⁇ . 8 0 ⁇ / 9, more preferably ⁇ . 9 5 ⁇ / 9, more preferably 1. 0 I / 9 Is.
  • the upper limit of the intrinsic viscosity of the Mouto resin () is preferably 1.3 ⁇ / 9 . 1 With ⁇ / 9 or less, to suppress a high stress during film stretching Risugiru, the film-forming property can be improved. Furthermore, when using Mending resin with a high intrinsic viscosity, the melting temperature of the resin increases, so it is necessary to raise the extrusion temperature.However, the Mending resin with an intrinsic viscosity of 1.3 I/9 or less ( By using (8), it is not necessary to perform high temperature extrusion, and the generation of decomposition products can be suppressed.
  • the polyester resin composition contains a polyester resin (M) other than the Ming resin (8) for the purpose of adjusting film-forming properties during biaxial stretching and mechanical properties of the obtained film. Is preferred.
  • polyester resin examples include polyester, polyethylene naphthalate, polypropylene naphthalate, polypropylene terephthalate and the like, or isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, cyclohexanedicarboxylic acid.
  • the resin mainly composed of mitoba has a high melting point, is excellent in heat resistance, has good compatibility with mitoba resin and is excellent in transparency. Therefore, mitoba resin or copolymerized mitoba resin is preferable, Mingko resin is particularly preferable.
  • the addition amount of the polyester resin (Mitsumi) is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass with respect to the entire polyester resin composition. % Or less, particularly preferably 10% by mass or less.
  • the amount of the polyester resin (Mitsumi) added is 25% by mass or less, the puncture strength can be further increased and the bag breaking resistance is excellent. In addition, the transparency can be kept high.
  • the amount of the polyester resin (Mitsumi) added may be 0% by mass or more, 5% by mass or more, 10% by mass or more based on the whole polyester resin composition.
  • the lower limit of the intrinsic viscosity of the polyester resin (Mitsumi) is preferably 0.5 I/
  • the upper limit of the intrinsic viscosity of the polyester resin (Mitsumi) is preferably 1.3 ⁇ / 9 .
  • the intrinsic viscosity of the polyester resin (Mitsumi) is the above value. ⁇ 02020/175064 9 ⁇ (: 171-12020/004362
  • the biaxially oriented polyester film contains, in addition to the polyester resin composition, a conventionally known additive, for example, a lubricant, a stabilizer, a colorant, an antioxidant, an antistatic agent, an ultraviolet absorber and the like. It may be contained.
  • a conventionally known additive for example, a lubricant, a stabilizer, a colorant, an antioxidant, an antistatic agent, an ultraviolet absorber and the like. It may be contained.
  • the content of the polyester resin composition is preferably 99.5% by mass or more, and more preferably 99.6% by mass or more. , 99.7 mass% or more is more preferable.
  • the content of the polyester resin composition is preferably 100% by mass or less, when the total amount of the biaxially oriented polyester film is 100% by mass, and 99.
  • the lubricant is one that can adjust the dynamic friction coefficient of the film, and examples thereof include inorganic lubricants such as silica, calcium carbonate, and alumina, and organic lubricants. Silica and calcium carbonate are more preferable, and silica is particularly preferable because it reduces haze. By these, transparency and slipperiness can be exhibited.
  • the lower limit of the content of the lubricant in the biaxially oriented polyester film is preferably 100 mass, and more preferably 800 mass 111. When the amount is 100 mass or more, the slipperiness can be improved.
  • the upper limit of the lubricant content is preferably 2000 mass 111, more preferably 100 mass, and particularly preferably 180 mass 111. By setting the amount to be 200 mass% or less, transparency can be maintained.
  • the biaxially oriented polyester film satisfies the following requirement (1).
  • the puncture strength is preferably ⁇ .551 ⁇ 1/ or more, and more preferably ⁇ .601 ⁇ 1/ or more. Since the puncture strength is at least .501 ⁇ 1/, the bag puncture resistance can be improved.
  • the puncture strength is preferably ⁇ .901 ⁇ 1/ or less, more preferably ⁇ .851 ⁇ 1/ or less, and further preferably ⁇ .801 ⁇ 1/ or less. ⁇ If it is less than 91/1/, the heat shrinkage rate is suppressed and the thermal stability is superior.
  • piercing strength is ⁇ .501 ⁇ 1/111 or more
  • "piercing strength is 0.5.501 ⁇ 1/111 or more” in any part of the biaxially oriented polyester film. ..
  • the biaxially oriented polyester film has the following requirements.
  • the density (the highest value of the density) is preferably 1.39 9 /
  • the density is 1.
  • the density is preferably 1.28. 3 or more, and more preferably 1. And more preferably 1.
  • the biaxially oriented polyester film has the following requirements.
  • the intrinsic viscosity of the biaxially oriented polyester film is 0.7 ⁇ / 9 or more.
  • the intrinsic viscosity is preferably 0.75 / 9 or more, more preferably 0.80 / 9 or more.
  • the unstretched sheet is crystallized because the intrinsic viscosity is 0.7 0.7 / 9 or more. Can be suppressed, and the yield stress at the thick end can be prevented from becoming too high. As a result, it can be made difficult to break in the stretching process.
  • the intrinsic viscosity is preferably 1.20 I/or less, more preferably 1.15 I/. It is below, and more preferably 1.10 / 9 or below. When the intrinsic viscosity is 1.20 / 9 or less, the stress during stretching does not become too high, and the film-forming property becomes better.
  • the biaxially oriented polyester film has a width direction of the biaxially oriented polyester film, which extends from the left and right ends toward the center, respectively. Sampling at the positions of and the respective peaks of the absorption intensity of 1 450 ⁇ 100 obtained by using the total reflection method in the Fourier transform infrared spectroscopy spectrum intensity. It is preferable that the highest value is 0.62 or less when calculating the value.
  • the ratio/min (the highest value of the ratio/min) is more preferably 0.61 or less, still more preferably 0.60 or less.
  • the ratio 8/M is less than or equal to 0.62, the crystallinity does not become too high, so the stress during stretching is suppressed and it becomes difficult to break.
  • the ratio/min is preferably 0.52 or more, more preferably 0.53 or more, and still more preferably 0.54 or more. ⁇ When it is 0.52 or more, the crystallinity is not too low and the mechanical strength is better.
  • the biaxially oriented polyester film has a face-to-face ratio of 8/min or less than 0.62. ⁇ 02020/175064 12 ((171?2020/004362
  • the aspect ratio/Mitsumi will also be less than 0.62.
  • the biaxially oriented polyester film has a degree of plane orientation of 8 0.145 to 0.
  • the plane orientation degree is more preferably at least 0.1455 and even more preferably at least 0.146. ⁇ When it is 45 or more, the plane orientation is suitably high, the puncture strength is sufficient, and the bag breaking resistance is excellent.
  • the degree of plane orientation 8 is more preferably 0.157 or less, and further preferably 0.154 or less. When it is less than 0.160, the heat shrinkage can be kept low, and the thermal stability can be improved.
  • the lower limit of the heat shrinkage rate of the biaxially oriented polyester film after heating at 150° in the IV!0 direction at 150° for 15 minutes is preferably 0.5%. It is more preferably 0.8% and even more preferably 1.2%. ⁇ If it is 0.5% or more, the puncture strength can be increased and the bag puncture resistance can be maintained high.
  • the upper limit of the heat shrinkage rate of the biaxially oriented polyester film after heating at 150° for 15 minutes in the IV!0 direction for 15 minutes is preferably 3.5%. It is more preferably 3.0% and even more preferably 2.5%. When it is 3.5% or less, it is possible to prevent the film from being greatly shrunk when heat is applied in the post-processing, and the processing becomes easier.
  • the lower limit of the thickness of the biaxially oriented polyester film is preferably 5. It is more preferably 7, and even more preferably 90! When it is at least 50!, the strength as a film can be made sufficient.
  • the upper limit of the thickness of the biaxially oriented polyester film is preferably 40. It is more preferably 30, and even more preferably 20.
  • the biaxially oriented polyester film preferably has the same composition over the entire area of the film.
  • a printing layer may be laminated on the biaxially oriented polyester film.
  • the printing ink for forming the printing layer water-based and solvent-based resin-containing printing inks can be preferably used.
  • the resin used in the printing ink ⁇ 02020/175064 13 ⁇ (:171?2020/004362
  • Printing inks include known antistatic agents, light blocking agents, UV absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, defoamers, cross-linking agents, anti-blocking agents, antioxidants, etc.
  • the additive may be included.
  • the printing method for providing the printing layer is not particularly limited, and known printing methods such as an offset printing method, a gravure printing method, and a screen printing method can be used.
  • known drying methods such as hot air drying, hot air drying, and infrared drying can be used.
  • the biaxially oriented polyester film may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, and surface roughening treatment, as long as the object of the present invention is not impaired.
  • Known anchor coat treatment, printing, decoration and the like may be applied.
  • 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 surface of the biaxially oriented polyester film.
  • 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 form a thin film, but from the viewpoint of gas barrier properties, inorganic oxides such as silicon oxide (silica), aluminum oxide (alumina), and a mixture of silicon oxide and aluminum oxide. The thing is preferably mentioned. In particular, a composite oxide of silicon oxide and aluminum oxide is preferable from the viewpoint of achieving both flexibility and denseness 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 in terms of metal content. If the Hachijo concentration is 20% or more, the water vapor gas barrier property can be further enhanced. On the other hand, when the content is 70% or less, the inorganic thin film layer can be softened, and it is possible to prevent the film from being destroyed during the secondary processing such as printing or laminating, thereby lowering the gas barrier property.
  • the term "silicon oxide” used here refers to ⁇ 0 2020/175064 14 ⁇ (: 17 2020 /004362
  • the thickness of the inorganic thin film layer is usually 1 to 100 nm, preferably 5 to 50 n.
  • the thickness of the inorganic thin film layer is 1 nm or more, more satisfactory gas barrier properties are likely to be obtained.
  • it is 100 or less, it is advantageous in terms of bending resistance and manufacturing cost.
  • the method for forming the inorganic thin film layer is not particularly limited, and examples thereof include physical vapor deposition methods such as vacuum vapor deposition method, sputtering method, and ion plating method ( ⁇ method).
  • a known vapor deposition method such as a chemical vapor deposition method ( ⁇ 30 method) may be appropriately adopted.
  • a typical method for forming an inorganic thin film layer will be described by taking a silicon oxide/aluminum oxide thin film as an example.
  • a mixture of 3 ⁇ 2 and eight ⁇ 2 ⁇ 3 as evaporation raw material, or 3 ⁇ 2 and eight ⁇ mixtures are preferably used.
  • Particles are usually used as these vapor deposition raw materials. At that time, it is desirable that the size of each particle is such that the pressure during vapor deposition does not change. Is.
  • resistance heating, high frequency induction heating, electron beam heating, laser heating, and other methods can be adopted.
  • the reaction gas it is also possible to introduce oxygen, nitrogen, hydrogen, argon, carbon dioxide, water vapor or the like as the reaction gas, or employ reactive vapor deposition using means such as ozone addition or ion assist.
  • the deposition conditions can be arbitrarily changed, such as applying a bias to the material to be vapor-deposited (a laminated film to be subjected to vapor deposition) or heating or cooling the material to be vapor-deposited.
  • the vapor deposition material, reaction gas, bias of the object to be vapor-deposited, heating/cooling, etc. can be similarly changed when the sputtering method or the zero method is adopted.
  • a printing layer may be laminated on the inorganic thin film layer.
  • the gas barrier layer made of metal oxide is not a completely dense film, but has small defects.
  • the resin in the protective layer resin composition permeates the defective portion of the metal oxide layer, and as a result, the gas barrier property is stabilized.
  • the gas barrier performance of the laminated film will be greatly improved.
  • the protective layer is a urethane-based, polyester-based, acrylic-based, titanium-based, isocyanate-based, imine-based, polybutadiene-based resin, etc. to which a curing agent such as an epoxy-based, isocyanate-based, or melamine-based resin is added. Can be mentioned.
  • solvent (solvent) used when forming the protective layer examples 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; Ester solvents such as butyl acetate; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether, etc. may be mentioned.
  • the urethane resin has a polar group of a urethane bond that interacts with the inorganic thin film layer, and also has flexibility due to the presence of an amorphous portion, so that the inorganic thin film layer is also subjected to bending load. It is preferable because damage to the can be suppressed.
  • the acid value of urethane resin is 10 to 6 And more preferably within the range of When the acid value of the fat 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, resulting in a good coat appearance. Becomes
  • the urethane resin preferably has a glass transition temperature (Ding 9) is 8 0 ° ⁇ As, more preferably 9 0 ° ⁇ As.
  • Ding 9 glass transition temperature
  • urethane resin it is more preferable to use a urethane resin containing an aromatic or araliphatic diisocyanate component as a main constituent from the viewpoint of improving gas barrier properties. ⁇ 02020/175064 16 ⁇ (: 171?2020/004362
  • the metaxylylene diisocyanate component it is particularly preferable to contain the metaxylylene diisocyanate component.
  • the proportion of the aromatic or araliphatic diisocyanate in the urethane resin is not less than 50 mol% in 100 mol% of the polyisocyanate component (50 to 100 mol%). ) It is preferable to set it as the range of.
  • the proportion of the total amount of the aromatic or aromatic aliphatic diisocyanate is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and further preferably 80 to 100 mol%. is there.
  • “Yukerack (registered trademark) ⁇ ZV P B” series commercially available from Mitsui Chemicals, Inc. can be preferably used.
  • the proportion of the total amount of aromatic or araliphatic diisocyanate is 50 mol% or more, better gas barrier properties can be obtained.
  • the urethane resin preferably has a carboxylic acid group (carboxyl group).
  • carboxylic acid (salt) group for example, a polyol component having a carboxylic acid group such as dimethylolpropionic acid or dimethylolbutanoic acid may be introduced as a copolymerization component. ..
  • a urethane resin of an aqueous dispersion can be obtained by synthesizing a carboxylic acid group-containing urethane resin and then neutralizing it with a salt forming agent.
  • the salt forming agent include ammonia, trimethylamine, triethylamine, triisopropylamine, tree 11-propylamine, tree 1!-trialkylamines such as butylamine, 1 ⁇ 1-methylmorpholine, 1 ⁇ 1.
  • Examples include 1 ⁇ 1-alkylmorpholines such as ethylmorpholine, 1 ⁇ 1-dimethylethanolamine, and 1 ⁇ 1-dialkylalkanolamines such as 1 ⁇ 1_diethylethanolamine. These may be used alone or in combination of two or more.
  • the biaxially oriented polyester film may be laminated with a layer of another material.
  • the biaxially oriented polyester film may be laminated after being produced, ⁇ 02020/175064 17 ⁇ (:171?2020/004362 Can be attached during film formation.
  • the biaxially oriented polyester film is used as a packaging material, for example, by providing an inorganic vapor deposition layer on the biaxially oriented polyester film, and further forming a heat-sealable resin layer (also referred to as a sealant layer) called a sealant. be able to.
  • the heat-sealable resin layer is usually formed by an extrusion laminating method or a dry laminating method.
  • the thermoplastic polymer forming the heat-sealable resin layer may be any one as long as it can sufficiently exhibit sealant adhesiveness, Polyethylene resin such as Mami and polypropylene resin. Ethylene-vinyl acetate copolymer, ethylene-olefin-random copolymer, ionomer resin and the like can be used.
  • the sealant layer may be a monolayer film or a multilayer film, and may be selected according to the required function.
  • 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 be mixed with various additives such as a flame retardant, a slip agent, an anti-blocking agent, an antioxidant, a light stabilizer and a tackifier.
  • the thickness of the sealant layer is preferably from 10 to 1001 and more preferably from 20 to 600!.
  • the biaxially oriented polyester film can be used in the field of packaging foods, pharmaceuticals, industrial products and the like.
  • the biaxially oriented polyester film can be used as a base film (base layer) of a packaging laminate.
  • base material layer/gas barrier layer/protective layer when the layer boundary is represented by /, for example, base material layer/gas barrier layer/protective layer, base material layer/gas barrier layer/protective layer/adhesive layer/sea run layer, Base material layer/gas barrier layer/protective layer/adhesive layer/resin layer/adhesive layer/sealant layer, base material layer/adhesive layer/resin layer/gas barrier layer/protective layer/adhesive layer/sealant layer, base Material layer/gas barrier layer/protective layer/printing layer/adhesive layer/sealant layer, base material layer/printing layer/gas barrier layer/protective layer/adhesive layer/sealant layer, base material layer/
  • Sealant layer base material layer/adhesive layer/resin layer/printing layer/gas barrier layer/protective layer/adhesive layer/sealant layer, base material layer/printing layer/gas barrier layer/protective layer/adhesive layer/resin layer/ Adhesive layer/sealant layer, base material layer/printing layer/adhesive layer/resin layer/gas barrier layer/protective layer/adhesive layer/sealant layer, base material layer/adhesive layer/resin layer/gas barrier layer/protective layer /Printing layer/adhesive layer/sealant layer, etc.
  • the laminate using the biaxially oriented polyester film 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 (eg pillow bags, standing pouches and ashameds such as 4-way pouches).
  • the thickness of the laminate can be appropriately determined according to its application. For example, it is used in the form of a film or sheet having a thickness of about 5 to 500, preferably about 10 to 300.
  • the die method is preferable from the viewpoint of thickness accuracy in the width direction.
  • the draw ratio is difficult to increase due to the manufacturing method, and thickness defects in the width direction are likely to occur.
  • a resin having the same composition is multilayered into eight layers or more by a static mixer or the like. Therefore, a method for obtaining a uniform unstretched sheet by suppressing crystallization has been proposed.However, from the viewpoint of facility simplicity and maintainability, the following casting method for obtaining a homogeneous unstretched sheet is used.
  • melt-extruding it is preferable to form a laminate of less than 8 layers. The number of laminated layers is more preferably 3 or less. In terms of equipment maintenance, single layer is the most preferable.
  • a layer structure of 2 types 2 layers, 2 types 3 layers, or 3 types 3 layers is preferable.
  • the lower limit is preferably 0.70 ⁇ /9, more preferably ⁇ .75 ⁇ /9, even more preferably ⁇ .80 ⁇ / 9 , and particularly preferably ⁇ .
  • the upper limit of the intrinsic viscosity of the obtained unstretched sheet is preferably 1.2 ⁇ / 9 , more preferably 1.1 ⁇ / 9 . ...! .2 ⁇ / 9 or less
  • the stress during stretching does not become too high, and the film-forming property becomes better.
  • the lower limit of the die temperature is preferably 240°, more preferably 245°, and particularly preferably 250°. If it is 240° or more, the discharge is more stable and the thickness can be made more uniform.
  • the temperature is 240° or more, it is possible to prevent the resin remaining in the resin melt extrusion step from becoming an unmelted substance and being mixed into the film, thereby impairing the quality of the film.
  • the upper limit of the resin melting temperature is preferably 280 ° , more preferably 275°, and most preferably 270°.
  • the temperature is 2 80 ° or less, the decomposition of the resin can be suppressed and the film can be prevented from becoming brittle. Further, it is possible to suppress the progress of crystallization during casting, and it is possible to further improve the film forming property.
  • the upper limit of the die temperature is preferably 280 ° ⁇ , more preferably 275 ° ⁇ or less, more preferably 270 ° ⁇ below.
  • it is 280°° or less, it is possible to prevent the thickness from becoming uneven. Further, it is possible to prevent the appearance of the resin from being deteriorated due to stains on the die lip or the like. Further, it is possible to prevent the intrinsic viscosity of the obtained film from decreasing. Further, the progress of crystallization at the time of casting is suppressed, and the film forming property becomes better.
  • the lower limit of the rotation number of the screw in the resin melt extrusion step is preferably 7
  • the discharge becomes more stable and the thickness becomes more uniform. Further, the mixing of the resin is more sufficient. And further suppress the appearance defect ⁇ 02020/175064 20 units (:171?2020/004362
  • the upper limit of the number of rotations of the screw in the resin melt extrusion step is preferably 150 0 "01, more preferably 1 3 0 "01, and particularly preferably 1 1 0 ". If so, it is possible to prevent the decomposition of the molten resin from progressing due to shearing heat generation, to suppress the decrease in the intrinsic viscosity of the obtained film, and to suppress the progress of crystallization during casting, thereby forming a film. The property becomes better.
  • the upper limit of the cooling port temperature is preferably 40°, and more preferably 10° or less. When it is 40° or less, the crystallinity of the molten polyester resin composition upon cooling and solidification does not become too high, and the stretching becomes easier. In addition, the laminating strength can be increased, and the bag breaking resistance can be further improved.
  • the lower limit of the cooling port temperature is preferably 0°. When it is 0° or more, the effect of suppressing crystallization when the molten polyester resin composition is cooled and solidified can be sufficiently exhibited. When the temperature of the cooling port is within the above range, it is preferable to reduce the humidity of the environment near the cooling port to prevent dew condensation.
  • the temperature of the surface of the cooling port rises because the high temperature resin comes into contact with the surface.
  • the chill roll is cooled by injecting cooling water through the pipe inside, but to ensure a sufficient amount of cooling water, devise the arrangement of the pipe, and maintain the pipe so that sludge does not adhere to it. It is necessary to reduce the temperature difference across the width of the chill roll surface. In particular, unless a method for obtaining a uniform unstretched sheet by forming multiple layers (for example, 8 layers or more) is used, crystallization of the unstretched sheet is likely to proceed, so care must be taken.
  • the thickness of the unstretched sheet is preferably in the range of 15 to 2500. It is more preferably 500 or less, and further preferably 300 or less.
  • the time until contact (hereinafter also referred to as contact time) is preferably in the range of 0.1 to 1.0 seconds, and more preferably in the range of 0.2 to 0.5 seconds.
  • the contact time is a value obtained by (air gap)/(ejection speed).
  • the air gap is the distance between the discharge port 12 and the surface of the cooling port 20.
  • the end portion of the non-stretched sheet's face is quenched more strongly than the center portion.
  • the total width of the unstretched sheet is 100%
  • X is 15 ° It is below, and it is preferable that the temperature is lower than the temperature X. If the thickness of the edge of the unstretched sheet is thicker than the center,
  • the thickness of the end portion of the unstretched sheet is often thicker than that of the central portion. Then, by quenching the edge portion more strongly than the central portion, crystallization can be suppressed to the central portion and the film forming property can be improved.
  • the method of quenching is not particularly limited, but a method of blowing cooling air through a multi-duct is preferable from the viewpoint of facility simplicity and maintainability.
  • the X is more preferably 5° or less.
  • the X is preferably _ 5 ° ⁇ or more.
  • the above X is not less than 150°, a sufficient effect of suppressing crystallization of the face of the unstretched sheet can be obtained.
  • the end portion is a region at least within 10% from the edge.
  • the end portion is more preferably an area within 15% from the edge, more preferably an area within 20% from the edge, and particularly preferably an area within 25% from the edge. Is.
  • the temperature is preferably 10° or less, and more preferably 5° or less.
  • the degree of crystallinity of the unstretched sheet at the edge of the mound face is 10 or less.
  • the temperature is _ 5 ° ⁇ or more.
  • the temperature is not less than 15°, a sufficient effect of suppressing the crystallization of the face of the unstretched sheet can be obtained.
  • Fig. 1 is a schematic front view for explaining a method of blowing cooling air from a multi-duct onto the wall surface of an unstretched sheet on a cooling port
  • Fig. 2 is a side view thereof.
  • the die 10 is arranged so that the discharge port 12 faces the surface of the cooling port 20.
  • the distance (shortest distance) between the discharge port 12 and the surface of the cooling port 20 is not particularly limited, but is generally about 20 to 100.
  • a multi-duct 30 is arranged on the outer peripheral surface of the cooling port 20.
  • the position of the multi-duct 30 is the rotation of the cooling port 20 when the position of the die 10 is 0 ° with respect to the center of the cooling port 20. with respect to the direction ( Figure 2, right rotation direction), preferably Rukoto been installed in a range of ⁇ _ ⁇ 4 5 °, 1 0 ⁇ 3 5 ° and more preferred arbitrarily installed in the range of.
  • the multi-duct 30 is arranged within the above range, it is possible to cool the mound surface of the unstretched sheet 40 cast on the cooling port 20 immediately after casting.
  • the time from the time when the resin composition for producing the biaxially oriented polyester film is cast into the cooling port (the time when it is touched) to the time when the air is blown to the relevant part is within 2.0 seconds.
  • the time is preferably within 1.0 second, more preferably within 0.5 second.
  • the width of the multi-duct 30 (horizontal length in Fig. 1) is ⁇ 02020/175064 23 ⁇ (: 171-12020/004362
  • the width of the unstretched sheet 40 is not less than that of the unstretched sheet 40.
  • the multi-duct 30 is blown to the temperature of the wind blown to the central part and the 20% left end and 20% right end. It is preferable that the temperature is different from that of the temperature.
  • the outlet of the multi-duct 30 is divided into a plurality of parts by a partition plate or the like, and air of different temperatures is blown out from each outlet.
  • the mode of dividing the air outlets is not particularly limited, and the air outlets may be evenly divided or may have different widths for the respective air outlets.
  • FIG. 3 shows an example of the multi-duct.
  • Figure 3 is a bottom view (viewed from the side of the cooling port) showing an example of a multi-duct.
  • the width is set so as to be the same width as the unstretched sheet 40 (Fig. 2), and as shown in Fig. 3, the outlet of the multi-duct 30 is partitioned. It is divided into 5 by the plate 3 2. Specifically, the outlets of the multi-duct 30 are divided into outlets 3 1 — 1 to outlets 3 1 — 5 in order from the left side to the right side in FIG.
  • the vertical width (length in the vertical direction in Fig. 1) of the multi-duct 30 is preferably 3001 or more and 80000 or less, The following is more preferable.
  • the speed at which the unstretched sheet 40 moves on the cooling port 20 is preferably 20
  • a suitable amount of cooling air can be blown to the bottom surface of the unstretched sheet 40. it can.
  • the upper limit of the height of the multi-duct 30 from the cooling port 20 is 200 or less. ⁇ 0 2020/175064 24 ⁇ (: 171? 2020 /004362
  • the lower limit of the height of the multi-duct 30 from the cooling port 20 is not particularly limited, but is preferably within a range where it does not come into contact with the unstretched sheet 40.
  • the upper limit of the wind speed of the cooling air from the multi-duct 30 is preferably 2 It is 1 n, and more preferably 1800 1 /
  • the lower limit of the cooling air velocity is preferably 5 0 111 /111 ⁇ . If it is at least 5 01/
  • a step for blowing air to the unstretched sheet on the cooling port wherein the step width is, when the unstretched sheet total width is 100%, the temperature of the wind blown to the center is X, When the temperature sprayed on both ends is assumed to be low, X is 15 ° or less, and the temperature is lower than X, and the end is at least 1 from the edge. It is preferable to include the area within 0%
  • the stretching method may be simultaneous biaxial stretching or sequential biaxial stretching, and is not particularly limited.
  • the lower limit of the stretching temperature in the longitudinal direction (hereinafter, also referred to as IV! 0 direction) is preferably 55°, and more preferably 60°. If it is at least 55°, fracture can be further suppressed. Further, it is possible to prevent the orientation in the vertical direction from becoming too strong, and to suppress an increase in the thermal shrinkage in the IV! IV! 0 direction of the upper limit of the extension Shin temperature is preferably 1 hundred ° ⁇ , more preferably 9 5 ° ⁇ .
  • the lower limit of the draw ratio in the IV! 0 direction is preferably 2.5 times, and particularly preferably.
  • the ratio is 2.5 times or more, the orientation can be sufficiently provided and the mechanical properties can be further enhanced. Further, when it is 2.5 times or more, uneven thickness can be suppressed and slack of the film roll can be prevented.
  • the upper limit of the stretching ratio in the IV! 0 direction is preferably 3.8 times, and more preferably
  • the lower limit of the stretching temperature in the width direction (hereinafter, also referred to as the 0 direction) is preferably 55° ⁇ , more preferably 60 ° ⁇ . If it is 55 ° or more, it is possible to make it difficult for fracture to occur. It also prevents the lateral orientation from becoming too strong,
  • the upper limit of the stretching temperature Ding 0 direction is preferably 1 00 ° ⁇ , more preferably 95 ° ⁇ . When it is 100 ° or less, the orientation can be sufficiently provided, and the mechanical properties can be further enhanced.
  • the lower limit of the draw ratio in the 0-direction is preferably 3.5 times, and more preferably
  • the upper limit of the draw ratio in the 0-direction is preferably 5.0 times, and more preferably
  • the lower limit of the heat setting temperature is preferably 170 ° ⁇ , more preferably 180 ° ⁇ . When it is 1 70° or more, the heat shrinkage rate can be further reduced.
  • the upper limit of the heat setting temperature is preferably 220° ⁇ . When it is 220° or less, it is possible to prevent the film from melting and the puncture strength from decreasing.
  • the lower limit of the relaxation rate is preferably 0.5%. ⁇ 0.5% or more ⁇ 02020/175064 26 ⁇ (: 171?2020/004362
  • the upper limit of the relaxation rate is preferably 10%. When it is 10% or less, slack and the like can be prevented from occurring, and the flatness can be improved.
  • the lower limit of the temperature for the relaxation process is preferably 130°°, and more preferably 150°°. When it is at least 30°°, the film will be sufficiently shrunk when relaxing and the heat shrinkage reduction effect can be sufficiently obtained.
  • the upper limit of the relaxation temperature is preferably 190 ° ⁇ , more preferably 170° ⁇ . When it is 1 90° or less, it is possible to prevent the flatness of the film from being deteriorated due to wrinkles and the like.
  • the puncture strength of the polyester film was calculated by converting the value measured by the test method described in "1 3-71 707" into 1 by the following formula.
  • the medium crystal was brought into close contact with the film surface layer as diamond, and the spectral intensity was measured by the total reflection method while light was incident parallel to the IV!0 direction.
  • the resolution of the spectrometer 4_Rei - 1 spectrum accumulation number was measured as 64 times.
  • the spectral intensity is the absorbance at each wave number. It was calculated by the following formula. The measurement was performed on the Mitsumi surface.
  • Absorbance ratio (8/M) Absorbance 8 Peak of the scan Bae-vector strength) / absorbance Snake (1 4 1 0 ⁇ 1 0_Rei 01- 1 of the scan Bae spectrum intensity of the peak) [0092] [planar orientation of the film ⁇ ]
  • the film was measured at the center position in the film width direction and from the left and right edges toward the center, respectively. Centered on Each sample was cut out.
  • the film was measured at the center position in the film width direction and from the left and right edges toward the center, respectively. Centered on Each sample was cut out.
  • the intrinsic viscosity of the sample was measured using an automatic viscosity measuring device “33_600_1_1” manufactured by Shiyama Scientific Instruments Co., Ltd.
  • the density of the sample was measured by the 0 method (density gradient method) of “3 ⁇ 7 1 1 2 ”.
  • the measurement conditions were as follows. Table 1 shows the highest measured value of the left and right samples.
  • Urethane-based two-component effect adhesive (“Takelac (registered trademark) 5 2 5 3” and “Takenate (registered trademark) 8 50” manufactured by Mitsui Chemicals, Inc. on the surface of the polyester film.
  • a blending ratio of 1 (mass ratio) a non-stretched polypropylene film (“1 1 4 7” manufactured by Toyobo Co., Ltd.) with a thickness of 70 was bonded as a heat-sealable resin layer by a dry lamination method.
  • a laminated laminate was obtained by aging at 40° for 4 days.
  • the thickness of the adhesive layer formed of the urethane-based two-component curing type adhesive after drying was about 4 times.
  • the obtained four-side sealed bag filled with water was immersed in hot water at 1300° for 30 minutes to obtain a retort-treated bag.
  • the bag filled with the retort-treated water was placed at a room temperature of 5° and a relative humidity of 35% at a height of 100 From the position of, the bag surface was dropped horizontally 10 times on the concrete plate, and then the bag surface was dropped vertically 10 times, and the percentage of bags that did not tear was calculated. ..
  • the number of bags used in the test was 20 in each of the horizontal and vertical directions.
  • the width of the obtained non-stretched sheet was 1,600.
  • the multi-duct has a structure as shown in Fig. 1, and cool air of 10° ⁇ is blown from the outlets 3 1-1 and 3 1 -5 (hereinafter also referred to as outlets 1 and 5), and the outlet 3 1 Cold wind of 15 ° was blown from -2 to 3 1-4 (hereinafter also referred to as blow-out ports 2 to 4).
  • the widths of the outlets 1 and 5 are respectively The widths of the outlets 2 to 4 were set respectively. ⁇ 02020/175064 30 box (: 171?2020/004362
  • the vertical width of the multi-duct is 5
  • the moving speed of the unstretched sheet was 60/min.
  • the time from the time when the resin composition for producing the biaxially oriented polyester film was cast into the cooling port (the time when it was touched) to the time when the air was blown to the part was 0.5 seconds. ..
  • the content of the silica particles in the resin composition for producing the biaxially oriented polyester film is the silica concentration when the resin composition for producing the biaxially oriented polyester film is the whole (100% by mass). .16% by mass.
  • Table 1 shows the resin composition in the resin composition for producing the biaxially oriented polyester film and the film forming conditions. In addition, Table 1 shows the physical properties and evaluation results of the obtained film.
  • a biaxially oriented polyester film having a thickness of 15 was obtained by forming a film in the same manner as in Example 1 except that the resin composition was changed as shown in Table 1.
  • Table 1 shows the physical properties and evaluation results of the obtained film.
  • a biaxially oriented polyester film having a thickness of 15 was obtained by forming a film in the same manner as in Example 1 except that the die temperature was changed as shown in Table 1.
  • Table 1 shows the physical properties and evaluation results of the obtained film.
  • a film was formed in the same manner as in Example 1 except that the heat treatment temperature was changed as shown in Table 1. ⁇ 02020/175064 31 ⁇ (: 171-12020/004362
  • Table 1 shows the physical properties and evaluation results of the obtained film.
  • a film was formed in the same manner as in Example 6 except that the resin composition was changed as shown in Table 1 to obtain a biaxially oriented polyester film having a thickness of 15.
  • Table 1 shows the physical properties and evaluation results of the obtained film.
  • a film was formed in the same manner as in Example 1 except that the cold air temperatures at the blowout ports 1 and 5 of the multi-duct were changed to the temperatures shown in Table 1 to obtain a biaxially oriented polyester film having a thickness of 15. Since the obtained film had a large density at the film edge and a large difference in crystallinity, the film forming property was poor.
  • a biaxially oriented polyester film with a thickness of 15 was obtained in the same manner as in Example 1 except that the time from the molten resin die to the cooling port was changed to the time shown in Table 1. It was Since the obtained film had a large density at the film edge and a large difference in crystallinity, the film forming property was poor.
  • a film was formed in the same manner as in Example 1 except that the die temperature was changed to the temperature shown in Table 1 to obtain a biaxially oriented polyester film having a thickness of 15.
  • the obtained film had a low intrinsic viscosity, a large density at the edges of the film, and a large difference in crystallinity, resulting in poor film-forming properties and low puncture strength, resulting in poor bag-breaking resistance. ..
  • a film was formed in the same manner as in Example 1 except that the heat treatment temperature was changed to the temperature shown in Table 1 to obtain a biaxially oriented polyester film having a thickness of 15. Since the obtained film had low puncture strength, it had poor bag puncture resistance.
  • Example 1 The procedure of Example 1 was repeated except that the resin composition was changed to the ratio shown in Table 1. ⁇ 0 2020/175064 32 ⁇ (: 171? 2020 /004362
  • the film was formed into a biaxially oriented polyester film having a thickness of 15. Since the obtained film had a low puncture strength, it had poor bag-breaking resistance.
  • a film was formed in the same manner as in Example 1 except that the resin composition was changed to the ratio shown in Table 1 and the cold air temperature at the outlets 1 and 5 of the multi-duct was changed to the temperature shown in Table 1.
  • the resin composition was changed to the ratio shown in Table 1 and the cold air temperature at the outlets 1 and 5 of the multi-duct was changed to the temperature shown in Table 1.
  • a biaxially oriented polyester film having a thickness of 15 was obtained. Since the obtained film had a large density at the edges of the film and a large difference in crystallinity, the film forming property was poor.
  • Example 1 a biaxially stretched film was formed in the same manner as in Example 1 except that the unstretched film face of the unstretched film was not cooled by a multi-duct to obtain a biaxially oriented polyester film having a thickness of 1501. It was Since the obtained film had a large density at the edges of the film and a large difference in crystallinity, the film forming property was poor.

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Abstract

Film de polyester à orientation biaxiale comprenant une composition de résine de polyester qui contient une résine de polytéréphtalate de butylène (A) à une proportion de 75 à 100 % en masse, ledit film de polyester à orientation biaxiale satisfaisant aux exigences suivantes : (1) la résistance à la perforation du film de polyester à orientation biaxiale telle que mesurée par un test de perforation conforme à la norme JIS-Z1707 est de 0,50 N/µm ou plus ; (2) la valeur la plus élevée parmi les densités mesurées conformément à la norme JIS-K7112 pour des échantillons à des positions de 10 mm vers le centre depuis la gauche et l'extrémité droite du film de polyester à orientation biaxiale dans le sens de la largeur est de 1,40 g/cm3 ou moins ; et (3) la viscosité intrinsèque du film de polyester à orientation biaxiale est de 0,7 dl/g ou plus.
PCT/JP2020/004362 2019-02-26 2020-02-05 Film de polyester à orientation biaxiale et procédé de production pour film de polyester à orientation biaxiale WO2020175064A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007185898A (ja) * 2006-01-16 2007-07-26 Toray Ind Inc 二軸延伸ポリエステルフィルムおよびその製造方法
WO2013172214A1 (fr) * 2012-05-14 2013-11-21 東洋紡株式会社 Film de polyester et son procédé de production
WO2018179726A1 (fr) * 2017-03-28 2018-10-04 東洋紡株式会社 Film de polyester orienté biaxialement et procédé pour sa fabrication

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007185898A (ja) * 2006-01-16 2007-07-26 Toray Ind Inc 二軸延伸ポリエステルフィルムおよびその製造方法
WO2013172214A1 (fr) * 2012-05-14 2013-11-21 東洋紡株式会社 Film de polyester et son procédé de production
WO2018179726A1 (fr) * 2017-03-28 2018-10-04 東洋紡株式会社 Film de polyester orienté biaxialement et procédé pour sa fabrication

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