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WO2019142781A1 - Film de polyester à orientation biaxiale - Google Patents

Film de polyester à orientation biaxiale Download PDF

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Publication number
WO2019142781A1
WO2019142781A1 PCT/JP2019/000918 JP2019000918W WO2019142781A1 WO 2019142781 A1 WO2019142781 A1 WO 2019142781A1 JP 2019000918 W JP2019000918 W JP 2019000918W WO 2019142781 A1 WO2019142781 A1 WO 2019142781A1
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WO
WIPO (PCT)
Prior art keywords
film
layer
gas barrier
resin
biaxially oriented
Prior art date
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/JP2019/000918
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English (en)
Japanese (ja)
Inventor
昇 玉利
考道 後藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
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Toyobo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to JP2019566466A priority Critical patent/JPWO2019142781A1/ja
Publication of WO2019142781A1 publication Critical patent/WO2019142781A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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 polyester film used in the field of packaging of food, medicine, industrial products and the like. More specifically, it is mainly composed of polybutylene terephthalate resin which is excellent in pinhole resistance, bag-proof resistance after boiling treatment and retorting treatment, and is excellent in gas-barrier property with little cracking of the gas barrier layer in the protective layer forming step.
  • the present invention relates to a biaxially oriented polyester film.
  • polybutylene terephthalate (hereinafter, polybutylene terephthalate is abbreviated as PBT) resin is more excellent in impact resistance, gas barrier property and chemical resistance than polyethylene terephthalate (hereinafter, polyethylene terephthalate is abbreviated as PET) resin, it is a film for food packaging Applications are also being considered in the field of films such as draw forming films.
  • PBT polybutylene terephthalate
  • PET polyethylene terephthalate
  • a biaxially oriented PBT-based film comprising a polyester-based resin composition in which a polyester resin other than PBT resin is blended in a range of 40% by weight or less with respect to PBT resin
  • the angle between the molecular chain main axes is 30 ° or less
  • the thermal shrinkage at 150 ° C. is 4.0% or less in both the width direction and the longitudinal direction
  • the intrinsic viscosity of the film is 0.80 dl / g or more, 1.2 dl / g It is disclosed that it can be suitably used for retort pouch packaging and water packaging by setting it to g or less.
  • the thermal contraction rate in the longitudinal direction is suppressed to a low value, it is considered that the film is easily stretched in the longitudinal direction in the protective layer forming step, and the gas barrier property is lowered.
  • Patent Document 2 a film mainly composed of PET resin is used as a base material layer, and in a laminated film having at least one metal oxide layer, the thermal shrinkage at 150 ° C. is 0.6 to 3.0%.
  • a packaging member having sufficient impact strength even after hot water treatment such as retort treatment and boiling treatment, and having excellent gas barrier properties.
  • the present invention has been made on the background of the problems of the prior art. That is, the object of the present invention relates to a polyester film used in the field of packaging of food, medicine, industrial products and the like. More specifically, it is possible to obtain a laminated polyester film which is excellent in pinhole resistance, tear resistance after boiling treatment and retort treatment, and is excellent in gas barrier properties with less cracking of the gas barrier layer in the protective layer forming step. is there.
  • the present invention is pin resistant by setting the dimensional change rate and heat shrinkage rate at 120 ° C. of a biaxially oriented stretched film mainly composed of PBT resin as a specific range.
  • the present inventors have found that a laminated polyester film excellent in hole property, bag-proof resistance after being subjected to boiling treatment and retort treatment, and having few cracks in the gas barrier layer in the protective layer forming step and excellent in gas barrier properties can be obtained.
  • the present invention has the following configuration.
  • a polyester resin composition comprising 60 to 100% by weight of polybutylene terephthalate resin (A) and 0 to 40% by weight of polyester resin (B) other than polybutylene terephthalate resin (A), (a) and (b) A biaxially oriented polyester film that simultaneously satisfies
  • A) The dimensional change at 120 ° C. with respect to the film original length of the temperature dimensional change curve measured using TMA (thermal mechanical analyzer) is ⁇ 2.0% to 4.0% in the longitudinal direction of the film.
  • TMA thermo mechanical analyzer
  • the thermal shrinkage at 150 ° C. in the longitudinal direction of the film is 1.0% to 5.0%.
  • the value of piercing strength measured by a piercing strength test according to JIS-Z1707 is 8.0 N or more.
  • the thickness accuracy of the entire width of the film is 1 to 20%. Or 2.
  • the inventor of the present invention is a laminated polyester excellent in pinhole resistance, bag-proof resistance after boiling treatment and retorting treatment by such a technology, and is excellent in gas barrier properties with less cracking of the gas barrier layer in the protective layer forming step. It became possible to obtain a film.
  • the polyester resin composition used for the film of the present invention contains the PBT resin (A) as a main component, and the content of the PBT resin (A) is preferably 60% by weight or more, and preferably 75% by weight or more. Furthermore, 85 weight% or more is preferable. If it is less than 60% by weight, the pinhole resistance and the bag resistance will be reduced.
  • the PBT resin (A) used as the main component preferably contains 90 mol% or more, more preferably 95 mol% or more, and still more preferably 98 mol% or more of terephthalic acid as a dicarboxylic acid component. Preferably it is 100 mol%.
  • 1,4-butanediol is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more, and most preferably 1,4-butane at the time of polymerization. It is not included except by-products generated by the ether bond of diol.
  • polyester resin composition used for the film of the present invention contains a polyester resin (B) other than PBT resin (A) for the purpose of adjusting film forming property when performing biaxial stretching and mechanical properties of the obtained film.
  • Polyester resins (B) other than PBT resin (A) are polyester resins such as PET, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, or isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, cyclohexane dicarboxylic acid , PBT resin copolymerized with at least one dicarboxylic acid selected from the group consisting of adipic acid, azelaic acid and sebacic acid, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol , 1,5-pentanediol, 1,6-hexanediol
  • PET resin is high in melting point and excellent in heat resistance, so dimensional change is difficult, and compatibility with PBT resin is also excellent, and transparency is excellent, and polyester resin (B) other than PBT resin (A) is copolymerized PET resins are preferred, and PET is particularly preferred.
  • the lower limit of the intrinsic viscosity of the PBT resin (A) used in the film of the present invention is preferably 0.8 dl / g, more preferably 0.95 dl / g, and still more preferably 1.0 dl / g.
  • the upper limit of the intrinsic viscosity of PBT resin (A) is preferably 1.3 dl / g.
  • the upper limit of the addition amount of the polyester resin (B) other than the PBT resin (A) is preferably 40% by weight or less, more preferably 35% by weight or less, and particularly preferably 15% by weight or less.
  • the addition amount of the polyester resin (B) other than the PBT resin (A) exceeds 40% by weight, the pinhole resistance and the bag resistance may be impaired, and the transparency and the gas barrier properties may be deteriorated.
  • the polyester resin composition may contain, if necessary, conventionally known additives such as a lubricant, a stabilizer, a colorant, an antioxidant, an antistatic agent, an ultraviolet absorber and the like.
  • a lubricant for adjusting the dynamic friction coefficient of the film of the present invention in addition to inorganic lubricants such as silica, calcium carbonate and alumina, organic lubricants are preferable, silica and calcium carbonate are more preferable, and silica reduces haze It is particularly preferable in that By these, transparency and slipperiness can be expressed.
  • inorganic lubricants such as silica, calcium carbonate and alumina
  • organic lubricants are preferable, silica and calcium carbonate are more preferable, and silica reduces haze It is particularly preferable in that By these, transparency and slipperiness can be expressed.
  • the lower limit of the content of the lubricant in the polyester resin composition is preferably 100 ppm by weight, more preferably 800 ppm by weight, and if it is less than 100 ppm by weight, slipperiness may be lowered.
  • the upper limit of the content of the lubricant is preferably 20000 ppm by weight, more preferably 1000 ppm by weight, and particularly preferably 1800 ppm by weight. If it exceeds 20000 ppm by weight, the transparency may be reduced.
  • a T-die system is preferable from the viewpoint of thickness accuracy in the width direction.
  • the inflation method it is difficult to increase the draw ratio due to the manufacturing method, and thickness defects in the width direction may occur.
  • a suitable method for obtaining the biaxially oriented polyester film of the present invention when casting a molten polyester resin composition on a cooling roll, it is possible to cite a polyester resin composition raw material of the same composition and cast. Since the PBT resin has a high crystallization rate, crystallization also proceeds during casting.
  • the method for producing a biaxially oriented PBT film of the present invention comprises the molten fluid formed in the step (1) of melting a polyester resin composition containing 60% by weight or more of PBT resin to form a molten fluid
  • the laminated fluid formed in the step (2) of forming a laminated fluid having a lamination number of 60 or more is discharged from a die, brought into contact with a cooling roll and solidified to form a laminated body (3); It has at least the step (4) of axial stretching.
  • Other steps may be inserted between the step (1) and the step (2) and between the step (2) and the step (3).
  • a filtration step, a temperature change step and the like may be inserted between the step (1) and the step (2).
  • a temperature change step, a charge addition step and the like may be inserted between the step (2) and the step (3).
  • the method for melting the polyester resin composition to form a molten fluid is not particularly limited, but a suitable method is to cite a method of heating and melting using a single screw extruder or a twin screw extruder. Can.
  • the method for forming the laminated fluid in step (2) is not particularly limited, but a static mixer and / or a multilayer feed block is more preferable from the viewpoint of facility simplicity and maintainability. Further, from the viewpoint of uniformity in the sheet width direction, one having a rectangular melt line is more preferable. It is further preferred to use a static mixer or multilayer feed block with rectangular melt lines.
  • the resin composition comprising a plurality of layers formed by combining a plurality of polyester resin compositions may be passed through one or more of a static mixer, a multilayer feed block and a multilayer manifold.
  • the theoretical number of layers in step (2) needs to be 60 or more.
  • the lower limit of the theoretical stacking number is preferably 200, and more preferably 500. If the theoretical number of layers is too small, the distance between layer interfaces will be long and the crystal size will be too large, resulting in breakage at the time of stretching, reduction in mechanical strength and reduction in thickness accuracy. In addition, the degree of crystallinity in the vicinity of both ends of the sheet may be increased, the film formation may be unstable, and the transparency after molding may be reduced.
  • the upper limit of the theoretical number of layers in step (2) is not particularly limited, but is preferably 100,000, more preferably 10,000, and still more preferably 7,000. Even if the theoretical stacking number is extremely increased, the effect may be saturated.
  • the number of theoretical laminations can be adjusted by selecting the number of elements of the static mixer.
  • a static mixer is generally known as a static mixer without a drive (line mixer), and the fluid entering the mixer is sequentially stirred and mixed by the elements.
  • line mixer line mixer
  • the high viscosity fluid is passed through a static mixer, division and lamination of the high viscosity fluid occur to form a laminated fluid.
  • a typical static mixer element has a structure in which a rectangular plate is twisted 180 degrees, and depending on the direction of twist, there are right and left elements, and the dimension of each element is 1.5 times the length of the diameter Is based on
  • the static mixer that can be used in the present invention is not limited to such.
  • the number of theoretical laminations can be adjusted by selecting the number of divisions / laminations of the multilayer feed block.
  • a plurality of multilayer feed blocks can be installed in series. Further, it is also possible to use the high viscosity fluid itself supplied to the multilayer feed block as a laminated fluid.
  • the above-mentioned multilayering apparatus can also be introduce
  • step (3) the laminated fluid is discharged from the die and brought into contact with the cooling roll to solidify.
  • the lower limit of the die temperature is preferably 255 ° C., more preferably 260 ° C., particularly preferably 265 ° C. If the temperature is lower than the above range, the discharge may not be stable and the thickness may be uneven. In addition, the PET resin retained in the melt extrusion process of the resin may become unmelted and be mixed in the film, which may deteriorate the quality of the film.
  • the upper limit of the resin melting temperature is preferably 285 ° C, more preferably 280 ° C, and most preferably 275 ° C. If the above is exceeded, decomposition of the resin proceeds and the film becomes brittle.
  • the upper limit of the die temperature is preferably 320 ° C., more preferably 300 ° C. or less, still more preferably 280 ° C. or less. If the thickness exceeds the above range, the thickness may not be uniform, and the resin may be deteriorated to cause appearance defects due to die lip stains and the like.
  • the upper limit of the cooling roll temperature is preferably 40 ° C, more preferably 20 ° C or less. When it exceeds the above, the degree of crystallization at the time of cooling and solidification of the molten polyester resin composition may become too high, which may make stretching difficult.
  • the lower limit of the temperature of the cooling roll is preferably 0 ° C., and if it is less than the above, the effect of suppressing crystallization when the molten polyester resin composition is solidified by cooling may be saturated. When the temperature of the cooling roll is in the above range, it is preferable to lower the humidity of the environment near the cooling roll to prevent condensation.
  • the thickness of the unstretched sheet is preferably in the range of 15 to 2500 ⁇ m. More preferably, it is 500 micrometers or less, More preferably, it is 300 micrometers or less.
  • the casting in the multilayer structure described above is performed with at least 60 layers, preferably 250 layers or more, and more preferably 1000 layers or more.
  • the number of layers is small, the spherulite size of the unstretched sheet becomes large, and the effect of improving the stretchability is small, and in addition, the mechanical strength and the thickness accuracy of the obtained biaxially stretched film decrease.
  • the stretching method can be either simultaneous biaxial stretching or sequential biaxial stretching, but it is easy to increase the plane orientation coefficient from the viewpoint of pinhole resistance and tear resistance, and it is easy to improve the uniformity of the film thickness in the width direction Sequential biaxial stretching is most preferable from the viewpoint of high film formation speed and high productivity.
  • the lower limit of the stretching temperature in the longitudinal direction is preferably 55 ° C., more preferably 60 ° C. If the temperature is less than 55 ° C., breakage may easily occur, and stretching at a low temperature strengthens the longitudinal orientation, so that the shrinkage stress in the heat setting process becomes large, so molecular orientation in the width direction Distortion may increase, resulting in a decrease in straight straight tearability in the longitudinal direction.
  • the upper limit of the MD stretching temperature is preferably 100 ° C., more preferably 95 ° C. If the temperature exceeds 100 ° C., the mechanical properties may be deteriorated since the orientation is not applied.
  • the lower limit of the MD stretching ratio is preferably 2.5 times, particularly preferably 2.7 times. If it is less than the above, the mechanical properties may be reduced because orientation is unlikely to take place.
  • the upper limit of the MD stretching ratio is preferably 3.8 times, more preferably 3.4 times, and particularly preferably 3.0 times. If the above is exceeded, the effect of mechanical strength and thickness unevenness improvement may be saturated.
  • the lower limit of the stretching temperature in the width direction (hereinafter referred to as TD) is preferably 60 ° C. When the stretching temperature is less than the above, breakage may easily occur.
  • the upper limit of the TD stretching temperature is preferably 100 ° C. If the temperature exceeds the above range, the mechanical properties may be deteriorated since no orientation is applied.
  • the lower limit of the TD stretch ratio is preferably 3.5 times, more preferably 3.6 times, and particularly preferably 3.7 times. If it is less than the above, the degree of orientation in the width direction is reduced, so that the mechanical strength and the thickness unevenness may be deteriorated.
  • the upper limit of the TD stretching ratio is preferably 5 times, more preferably 4.6 times, and particularly preferably 4.2 times. If the above is exceeded, the effect of mechanical strength and thickness unevenness improvement may be saturated.
  • the lower limit of the TD heat setting temperature is preferably 185 ° C, more preferably 190 ° C. If it is less than the above, the thermal contraction rate becomes large, the film shrinks in the protective layer forming step, and the laminated gas barrier layer may be cracked, which may result in the deterioration of the gas barrier property.
  • the upper limit of the TD heat setting temperature is preferably 210 ° C. When the temperature exceeds the above range, the film melts, and may not be extremely brittle even if it does not melt, and the thermal shrinkage in the MD direction decreases and the protective layer In the forming step, the film may be stretched, and the laminated gas barrier layer may be cracked, which may lead to a decrease in the gas barrier property.
  • the lower limit of the TD relaxation rate is preferably 0.5%, and if it is less than the above, breakage may easily occur during heat setting.
  • the upper limit of the TD relaxation rate is preferably 10%, and if it exceeds the above, not only sag may occur to cause thickness unevenness, but also shrinkage in the longitudinal direction at the time of heat setting may be increased.
  • the distortion of molecular orientation may be large, and dimensional stability may be uneven in the width direction.
  • the lower limit of the film thickness is preferably 3 ⁇ m, more preferably 5 ⁇ m, and still more preferably 8 ⁇ m. If it is less than 3 ⁇ m, the strength as a film may be insufficient.
  • the upper limit of the film thickness is preferably 100 ⁇ m, more preferably 75 ⁇ m, and still more preferably 50 ⁇ m. If it exceeds 100 ⁇ m, it becomes too thick and processing for the purpose of the present invention may become difficult.
  • the lower limit of the intrinsic viscosity of the biaxially oriented PBT film of the present invention is preferably 0.80 dl / g, more preferably 0.85 dl / g, still more preferably 0.90 dl / g, particularly preferably 0 It is .95 dl / g. Impact strength, puncture resistance, etc. will be improved as it is more than the above.
  • the upper limit of the intrinsic viscosity of the biaxially oriented PBT film is preferably 1.2 dl / g, more preferably 1.1 dl / g. When it exceeds the above, the stress at the time of stretching becomes too high, and the film forming property is deteriorated.
  • the biaxially oriented PBT film of the present invention preferably has a resin of the same composition throughout the entire film.
  • the lower limit of the degree of plane orientation ( ⁇ P) of the biaxially oriented polyester film of the present invention is preferably 0.145, more preferably 0.148, still more preferably 0.151. If it is less than the above range, the plane orientation may be weak, the puncture strength may be reduced, and the resistance to breakage may be reduced.
  • the upper limit of ⁇ P of the biaxially oriented polyester film of the present invention is preferably 0.200. If the above is exceeded, the improvement effect may be saturated.
  • the upper limit of the thermal shrinkage after heating at 150 ° C. for 15 minutes in the MD direction of the biaxially oriented polyester film of the present invention is 5.0%, preferably 4.0%, more preferably 3.3%. is there.
  • the expansion and contraction of the film can be suppressed in the protective layer forming step where tension is applied, and the deterioration of the gas barrier properties due to the cracking of the gas barrier layer can be suppressed.
  • the film may be shrunk in the protective layer forming step to cause cracking of the gas barrier layer and as a result, the gas barrier properties may be lowered.
  • the expansion and contraction of the film can be suppressed in the protective layer forming step where tension is applied, and the deterioration of the gas barrier properties due to the cracking of the gas barrier layer can be suppressed. If it is less than the above, the film may be stretched in the protective layer forming step to cause cracking of the gas barrier layer and as a result, the gas barrier properties may be reduced.
  • the upper limit of the dimensional change rate at 120 ° C. in the MD direction assuming a protective layer forming step measured using TMA of the biaxially oriented polyester film of the present invention is 4.0%, preferably 3.0%. .
  • elongation of the film can be suppressed in the protective layer forming step where tension is applied, and deterioration in gas barrier properties due to cracking of the gas barrier layer can be suppressed.
  • the film may be stretched in the protective layer forming step to cause cracking of the gas barrier layer and as a result, the gas barrier properties may be lowered.
  • contraction of a film is suppressed in the protective layer formation process to which tension
  • the lower limit of the puncture strength of the biaxially oriented polyester film of the present invention is preferably 8N. When it is less than the above, the strength may be insufficient when used as a bag.
  • the upper limit of the piercing strength is preferably 20N. If the above is exceeded, the improvement effect may be saturated.
  • the upper limit of the dynamic friction coefficient of at least one surface of the film is preferably 0.4 or less, preferably 0.39 or less, and most preferably 0.38 or less.
  • the upper limit of the haze per thickness of the biaxially oriented polyester film of the present invention is preferably 0.66% / ⁇ m, more preferably 0.60% / ⁇ m, still more preferably 0.53% / ⁇ m. . If the above is exceeded, the quality of printed characters and images may be impaired when the film is printed.
  • a printing layer may be laminated on the biaxially oriented polyester film of the present invention.
  • water-based and solvent type can use it preferably.
  • the resin used for the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins and mixtures thereof.
  • a printing method for providing a printing layer it does not specifically limit as a printing method for providing a printing layer.
  • Well-known printing methods such as an offset printing method, a gravure printing method, the screen-printing method, can be used.
  • known drying methods such as hot air drying, hot roll drying, infrared drying and the like can be used.
  • the biaxially oriented polyester film of the present invention may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, surface roughening treatment, as long as the object of the present invention is not impaired.
  • Anchor coating treatment, printing, decoration, etc. may be given.
  • An inorganic thin film layer or a gas barrier layer such as a metal foil such as aluminum foil can be provided on at least one side of the biaxially oriented polyester film of the present invention.
  • 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, but from the viewpoint of gas barrier properties, inorganic oxide such as silicon oxide (silica), aluminum oxide (alumina), and a mixture of silicon oxide and aluminum oxide Are preferably mentioned.
  • inorganic oxide such as silicon oxide (silica), aluminum oxide (alumina), and a mixture of silicon oxide and aluminum oxide are preferably mentioned.
  • a composite oxide of silicon oxide and aluminum oxide is preferable from the viewpoint of achieving both the flexibility and the compactness of the thin film layer.
  • the mixing ratio of silicon oxide and aluminum oxide is preferably in the range of 20 to 70% of Al by weight ratio of metal components.
  • the Al concentration is less than 20%, the water vapor gas barrier properties may be lowered.
  • the inorganic thin film layer tends to be hard, and the film may be broken during secondary processing such as printing or laminating, and the gas barrier properties may be lowered.
  • silicon oxide refers to various silicon oxides such as SiO and SiO 2 or a mixture thereof
  • aluminum oxide refers to various aluminum oxides such as AlO and Al 2 O 3 or a mixture thereof.
  • the thickness of the inorganic thin film layer is usually 1 to 100 nm, preferably 5 to 50 nm. If the film thickness of the inorganic thin film layer is less than 1 nm, satisfactory gas barrier properties may not be obtained in some cases. On the other hand, even if it exceeds 100 nm and is excessively thick, the corresponding improvement effect of gas barrier properties is obtained It is rather disadvantageous in terms of bending resistance and manufacturing cost.
  • vapor deposition such as a physical vapor deposition method (PVD method), such as a vacuum evaporation method, sputtering method, ion plating method, or a chemical vapor deposition method (CVD method)
  • PVD method physical vapor deposition method
  • CVD method chemical vapor deposition method
  • a typical method of forming an inorganic thin film layer will be described by taking a silicon oxide / aluminum oxide based thin film as an example.
  • a vacuum evaporation method a mixture of SiO 2 and Al 2 O 3 or a mixture of SiO 2 and Al is preferably used as an evaporation raw material.
  • the size of each particle is preferably such that the pressure at the time of vapor deposition does not change, and the preferred particle diameter is 1 mm to 5 mm.
  • a method such as resistance heating, high frequency induction heating, electron beam heating, or laser heating can be adopted.
  • reactive vapor deposition using means such as introduction of oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor or the like as a reaction gas, or addition of ozone or ion assist may be employed.
  • film forming conditions can be arbitrarily changed, such as applying a bias to the deposition target (laminated film to be deposited) or heating or cooling the deposition target.
  • Such vapor deposition material, reaction gas, bias of the vapor-deposited body, heating / cooling, etc. can be similarly changed also in the case of employing the sputtering method or the CVD method.
  • the printing layer may be laminated on the above-mentioned inorganic thin film layer.
  • the gas barrier layer made of a metal oxide is not a completely dense film, but minute defects are scattered.
  • the resin in the resin composition for the protective layer penetrates into the defect portion of the metal oxide layer, As a result, the effect of stabilizing the gas barrier properties can be obtained.
  • the gas barrier performance of the laminated film is also greatly improved by using a material having gas barrier properties for the protective layer itself.
  • Examples of the protective layer include those obtained by adding an epoxy-based, isocyanate-based or melamine-based curing agent to a urethane-based, polyester-based, acrylic-based, titanium-based, isocyanate-based, imine-based, or polybutadiene-based resin.
  • Examples of the solvent (solvent) used when 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; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether; and the like.
  • the polar group of the urethane bond interacts with the inorganic thin film layer and also has flexibility due to the presence of the noncrystalline portion, so that the damage to the inorganic thin film layer is suppressed even when a bending load is applied. It is preferable because it can be
  • the acid value of the urethane resin is preferably in the range of 10 to 60 mg KOH / g. More preferably, it is in the range of 15 to 55 mg KOH / g, further preferably in the range of 20 to 50 mg KOH / g.
  • the liquid stability is improved when the aqueous dispersion is prepared, and the protective layer can be uniformly deposited on the high polarity inorganic thin film, so the coat appearance is good. It becomes.
  • the urethane resin preferably has a glass transition temperature (Tg) of 80 ° C. or more, more preferably 90 ° C. or more.
  • Tg glass transition temperature
  • a urethane resin containing an aromatic or aromatic aliphatic diisocyanate component as a main component.
  • 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 to 100 mol%, more preferably 70 to 100 mol%, and still more preferably 80 to 100 mol%.
  • "Takelac (registered trademark) WPB" series commercially available from Mitsui Chemicals, Inc. can be suitably used. If the proportion of the total amount of aromatic or araliphatic diisocyanates is less than 50 mol%, good gas barrier properties may not be obtained.
  • the said urethane resin has a carboxylic acid group (carboxyl group) from a viewpoint of affinity improvement with an inorganic thin film layer.
  • a carboxylic acid (salt) group for example, a polyol compound having a carboxylic acid group such as dimethylol propionic acid or dimethylol butanoic acid may be introduced as a copolymerization component as a polyol component.
  • the urethane resin of a water dispersion can be obtained.
  • the salt forming agent include ammonia, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, trialkylamines such as tri-n-butylamine, N-methylmorpholine, N-ethylmorpholine, etc.
  • N-dialkylalkanolamines such as -alkyl morpholines, N-dimethyl ethanolamine, N-diethyl ethanolamine and the like. These may be used alone or in combination of two or more.
  • Layers of other materials may be laminated on the biaxially oriented polyester film of the present invention, and as the method, the biaxially oriented polyester film can be laminated after preparation or laminated during film formation.
  • the biaxially oriented polyester film of the present invention can be used as a packaging material, for example, by providing an inorganic deposition layer on the biaxially oriented polyester film of the present invention, and further forming a heat sealable resin layer called a sealant.
  • the formation of the heat sealable resin layer is usually carried out by an extrusion laminating method or a dry laminating method.
  • a thermoplastic polymer which forms a heat sealable resin layer polyethylene resins, such as HDPE, LDPE, LLDPE, and polypropylene resin should just be sufficient to express sealant adhesiveness.
  • Ethylene-vinyl acetate copolymer, ethylene- ⁇ -olefin random copolymer, ionomer resin 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 function. For example, in terms of imparting moisture resistance, a multilayer film in which a resin such as an ethylene-cyclic olefin copolymer or polymethylpentene is interposed can be used. Further, the sealant layer may be blended with various additives such as a flame retardant, a slip agent, an antiblocking agent, an antioxidant, a light stabilizer, and a tackifier. The thickness of the sealant layer is preferably 10 to 100 ⁇ m, and more preferably 20 to 60 ⁇ m.
  • the biaxially oriented polyester film of the present invention can be used as a base film of a laminate for a packaging material.
  • the layer configuration of the laminate includes, for example, a base layer / gas barrier layer / protective layer, a base layer / gas barrier layer / protective layer / sealant layer, a base layer / gas barrier layer / BR> ⁇ protective layer / resin layer / sealant Layer, substrate layer / resin layer / gas barrier layer / protective layer / sealant layer, substrate layer / gas barrier layer / protective layer / printed layer / sealant layer, substrate layer / printed layer / gas barrier layer / protective layer / sealant layer, Base material layer / gas barrier layer / protective layer / resin layer / printing layer / sealing layer, base material layer / resin layer / printing layer / gas barrier layer / protective layer / sealant layer, base material layer / printing layer / gas barrier layer / protective layer / Resin layer / sealant layer, base material layer / printing layer /
  • the laminate using the biaxially oriented polyester film of the present invention can be suitably used for applications such as packaged products, various label materials, lid materials, sheet molded articles, laminate tubes and the like.
  • it is used for packaging bags (for example, pouches, such as a pillow bag, a standing pouch, and a 4-way pouch).
  • the thickness of the laminate can be appropriately determined depending on the application. 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.
  • Thermal contraction rate The thermal shrinkage of the polyester film was measured by the dimensional change test method described in JIS-C-2151-2006.21 except that the test temperature was 150 ° C. and the heating time was 15 minutes. The test pieces were used as described in 21.1 (a).
  • Aluminum oxide was vapor-deposited on the substrate layers shown in Examples and Comparative Examples described later.
  • the film is set on the unwinding side of a continuous vacuum deposition machine and is run through a cooling metal drum to wind up the film.
  • the pressure in the continuous vacuum deposition machine is reduced to 10 -4 Torr or less, metal aluminum of 99.99% purity is loaded into the alumina crucible from the lower part of the cooling drum, metal aluminum is heated and vapor-deposited,
  • the film was deposited and deposited on the film while supplying oxygen for oxidation reaction to form an aluminum oxide film having a thickness of 30 nm.
  • urethane resin A solution of 60% by weight water, 30% by weight isopropanol and 10% by weight urethane resin is applied onto the inorganic vapor deposited thin film layer of the gas barrier layer deposited and formed as described above by a wire bar coating method, for 30 seconds at 150 ° C. It dried and obtained the protective layer. The applied amount after drying was 0.190 g / m 2 (as solid content).
  • Urethane resin A dispersion of a commercially available metaxylylene group-containing urethane resin ("Takelac (registered trademark) WPB 341"; solid content: 30%, manufactured by Mitsui Chemicals, Inc.) was prepared as the urethane resin.
  • the oxidation of this urethane resin was 25 mg KOH / g, and the glass transition temperature measured by DSC was 130 ° C. Further, the ratio of aromatic or araliphatic diisocyanate to the entire polyisocyanate component measured by 1 H-NMR was 85 mol%.
  • a urethane-based two-component curable adhesive (Takelac (registered trademark) A525S manufactured by Mitsui Chemicals, Inc.) and Takenate (registered trademark) on the protective layer of the laminated film provided with the gas barrier layer / protective layer on the aforementioned base film A)
  • A50 "is blended at a ratio of 13.5: 1 (weight ratio) by a dry laminating method to obtain a 70 ⁇ m thick non-stretched polypropylene film (" P1147 “manufactured by Toyobo Co., Ltd.) as a heat sealable resin layer
  • a laminate gas barrier laminate for evaluation was obtained.
  • the thickness after drying of the adhesive bond layer formed with urethane type 2 liquid curing adhesive agent was about 4 micrometers in all.
  • a melt of 0.22 dl / g of PET resin, silica particles with an average particle diameter of 2.4 ⁇ m as inert particles blended at 0.16% by weight as silica concentration is melted at 290 ° C and then the melt line is 12
  • the melt was divided and laminated to obtain a multilayer melt made of the same raw material, cast from a T-die at 270 ° C., and electrostatically applied to a 15 ° C.
  • Example 1 was carried out in the same manner as Example 1 except that the raw material composition and the film forming conditions were changed to the biaxially stretched film described in Table 1.
  • Example 1 It implemented by the method similar to Example 1 except having changed the heat setting temperature into the value of Table 2. Although the pinhole resistance of the obtained film was good, the puncture strength was 6.5 N and the tear resistance was poor at 60%. Moreover, since the dimensional change rate was as large as 4.10%, the gas barrier properties were poor. The results are shown in Table 2.
  • Example 3 It implemented by the method similar to Example 1 except having changed the polyester resin composition into the value of Table 2.
  • the gas barrier properties of the obtained film were good, but because the content of PBT was small, the puncture strength of the obtained film was 7.2 N, and the resistance to puncture and the resistance to puncture were poor. .
  • Example 1 (Reference Example 1) In Example 1, others were similarly film-formed, without introduce
  • the thickness accuracy was measured for a biaxially oriented film (total thickness 15 ⁇ m, width 840 mm) mainly composed of PBT produced by a commercially available inflation method. The thickness accuracy was 28%, which was inferior to the film of the present invention.
  • the present invention it is possible to obtain a laminated polyester film which is excellent in pinhole resistance, bag-proof resistance after boiling treatment and retorting treatment, and which is excellent in gas barrier properties with less cracking of the gas barrier layer in the protective layer forming step. It can be expected to greatly contribute to the industry because it can be widely applied as food packaging and pharmaceutical packaging materials.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Le problème décrit par la présente invention est d'obtenir un film de polyester qui présente une excellente résistance aux piqûres et une excellente résistance à la rupture de sac après un traitement d'ébullition ou un traitement en autoclave, tout en n'étant pas sensible à la fissuration d'une couche de barrière contre les gaz pendant une étape de formation de couche de protection et présentant ainsi d'excellentes propriétés de barrière contre les gaz. La solution selon l'invention concerne un film de polyester à orientation biaxiale qui est formé à partir d'une composition de résine de polyester qui contient 60 à 100 % en poids d'une résine de téréphtalate de polybutylène (A) et 0 à 40 % en poids d'une résine de polyester (B) autre que la résine de téréphtalate de polybutylène (A), et qui satisfait les exigences (a) et (b) en même temps. (A) Le taux de variation dimensionnelle de la courbe de changement dimensionnelle en fonction de la température par rapport à la longueur de départ du film à 120 °C tel que déterminé avec l'utilisation de TMA est compris entre 2,0 % et 4,0 % dans la direction longitudinale du film. (B) Le taux de retrait thermique du film à 150 °C dans la direction longitudinale est compris entre 1,0 % et 5,0 %.
PCT/JP2019/000918 2018-01-22 2019-01-15 Film de polyester à orientation biaxiale Ceased WO2019142781A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020031712A1 (fr) * 2018-08-08 2020-02-13 東洋紡株式会社 Film multicouche formant barrière aux gaz et procédé de production de celui-ci
CN116261520A (zh) * 2020-10-07 2023-06-13 东洋纺株式会社 双轴取向聚酯膜及层叠体

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004250624A (ja) * 2003-02-21 2004-09-09 Teijin Dupont Films Japan Ltd 透明ポリエステルフィルム
WO2005017007A1 (fr) * 2003-08-19 2005-02-24 Toyo Boseki Kabushiki Kaisya Film polyester
WO2016171172A1 (fr) * 2015-04-24 2016-10-27 東洋紡株式会社 Film polyester étiré bi-axialement, et procédé de fabrication de celui-ci
WO2018159157A1 (fr) * 2017-02-28 2018-09-07 東洋紡株式会社 Film stratifié

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004250624A (ja) * 2003-02-21 2004-09-09 Teijin Dupont Films Japan Ltd 透明ポリエステルフィルム
WO2005017007A1 (fr) * 2003-08-19 2005-02-24 Toyo Boseki Kabushiki Kaisya Film polyester
WO2016171172A1 (fr) * 2015-04-24 2016-10-27 東洋紡株式会社 Film polyester étiré bi-axialement, et procédé de fabrication de celui-ci
WO2018159157A1 (fr) * 2017-02-28 2018-09-07 東洋紡株式会社 Film stratifié

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020031712A1 (fr) * 2018-08-08 2020-02-13 東洋紡株式会社 Film multicouche formant barrière aux gaz et procédé de production de celui-ci
JPWO2020031712A1 (ja) * 2018-08-08 2020-08-20 東洋紡株式会社 ガスバリア性積層フィルムおよびその製造方法
CN116261520A (zh) * 2020-10-07 2023-06-13 东洋纺株式会社 双轴取向聚酯膜及层叠体

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