WO2023157930A1 - Rouleau de film de polyamide - Google Patents

Rouleau de film de polyamide Download PDF

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Publication number
WO2023157930A1
WO2023157930A1 PCT/JP2023/005522 JP2023005522W WO2023157930A1 WO 2023157930 A1 WO2023157930 A1 WO 2023157930A1 JP 2023005522 W JP2023005522 W JP 2023005522W WO 2023157930 A1 WO2023157930 A1 WO 2023157930A1
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Prior art keywords
polyamide
layer
film roll
resin
film
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PCT/JP2023/005522
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English (en)
Japanese (ja)
Inventor
彩芽 鳥居
考道 後藤
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東洋紡株式会社
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Priority to JP2024501436A priority Critical patent/JPWO2023157930A1/ja
Publication of WO2023157930A1 publication Critical patent/WO2023157930A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • 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
    • B29C48/285—Feeding the extrusion material to the extruder
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H18/00—Winding webs
    • B65H18/28—Wound package of webs

Definitions

  • the present invention relates to a carbon-neutral biaxially stretched polyamide film roll that is suitably used for packaging films and the like and that uses biomass-derived raw materials, and a method for producing the same.
  • a biaxially stretched film made of an aliphatic polyamide represented by polyamide 6 is excellent in impact resistance and bending pinhole resistance, and is widely used as various packaging materials.
  • Biomass is an organic compound that is photosynthesised from carbon dioxide and water, and is a so-called carbon-neutral raw material that regenerates carbon dioxide and water by utilizing it. Carbon neutrality means reducing emissions of carbon dioxide, a greenhouse gas, to virtually zero by balancing the amount of carbon dioxide emitted and absorbed in the environment. Biomass plastics made from these biomass materials have been rapidly put to practical use, and a biaxially oriented polyamide film containing a polyamide 6 resin and a polyamide resin at least part of which is derived from biomass has been proposed (Patent Document 1). ).
  • Polyamide 6 resin and polyamide resin, at least part of which is derived from biomass, may differ in specific gravity and shape of resin chips, so the segregation of these raw resin chips causes variation in the ratio of raw materials in the mixing and extrusion process.
  • the difference in biomass degree occurs in the MD (Machine Direction) direction of the film.
  • the object of the present invention is to provide a biaxially oriented polyamide film using a raw material derived from biomass, and a film roll of a biaxially oriented polyamide film that has little variation in the degree of biomass in the MD direction even if it is a long film roll with a long winding length. and to provide a method for producing the same.
  • the present invention consists of the following configurations.
  • (Section 1) It consists of a biaxially stretched polyamide film containing at least two layers, an A layer and a B layer, and the A layer contains 99 to 70% by mass of a polyamide 6 resin containing ⁇ -caprolactam derived from fossil fuel as a lactam unit, and a raw material derived from biomass.
  • (Section 6) A laminated film roll obtained by laminating a sealant film on the biaxially stretched polyamide film roll according to any one of Items 1 to 5.
  • (Section 7) The raw material resins for the A layer and the B layer are supplied to and mixed with different extruders, and the raw material resins for the A layer and the B layer are melt-extruded into sheets from the extruder and laminated.
  • the A layer is formed in the first hopper
  • the raw resin chips of polyamide 6 are supplied to the second hopper, the raw resin chips of polyamide whose raw material is at least partly derived from biomass are supplied to the second hopper, and the raw resin chips supplied from the first hopper and the second
  • a method for producing a biaxially oriented polyamide film roll comprising mixing raw resin chips supplied from a hopper directly above an extruder, and then melt extruding the raw resin from the extruder.
  • the raw resin chips of the second hopper are supplied through a pipe having an outlet in the first hopper and directly above the extruder, and the raw resin chips of the first hopper and Item 8.
  • FIG. 2 is a schematic diagram showing an example of a method of mixing two or more resins in a film roll manufacturing process.
  • the biaxially stretched polyamide film in the present invention is a biaxially stretched polyamide film in which a layer B (surface layer) is laminated on at least one side of a layer A (base layer).
  • the A layer is made of a polyamide resin composition containing 99 to 70% by mass of polyamide 6 resin and 1 to 30% by mass of polyamide whose raw material is at least partly derived from biomass.
  • the A layer can provide excellent mechanical strength such as impact strength and gas barrier properties such as oxygen, which are inherent to a biaxially stretched polyamide film made of polyamide 6.
  • the A layer contains 1 to 30% by mass of polyamide, at least part of which is derived from biomass. improve sexuality.
  • Polyamide 6 used in the present invention is usually produced by ring-opening polymerization of ⁇ -caprolactam.
  • Polyamide 6 obtained by ring-opening polymerization is usually melt-extruded by an extruder after removing the lactam monomer with hot water and then drying.
  • the relative viscosity of polyamide 6 is preferably 1.8-4.5, more preferably 2.6-3.2. If the relative viscosity is less than 1.8, the impact strength of the film may be insufficient. If it is more than 4.5, the load on the extruder increases, and it may be difficult to obtain an unstretched film before stretching.
  • polyamide 6 in addition to those polymerized from commonly used fossil fuel-derived monomers, polyamide 6 chemically recycled from waste polyamide 6 products such as waste plastic products, waste tire rubber, fibers, and fishing nets can also be used.
  • waste polyamide 6 products such as waste plastic products, waste tire rubber, fibers, and fishing nets
  • depolymerization is performed to obtain ⁇ -caprolactam, which is purified and then polyamide 6 is obtained.
  • a method of polymerization can be used.
  • polyamide 6 obtained by mechanically recycling waste material from the production process of the polyamide film can be used together.
  • Mechanically recycled polyamide 6 is, for example, a non-standard film that cannot be shipped when manufacturing a biaxially stretched polyamide film, and waste materials generated as cut ends (edge trim) are collected and melted extrusion or compression molding. It is a raw material pelletized by
  • Polyamide at least part of which is derived from biomass examples include polyamide 11, polyamide 410, polyamide 610, polyamide 1010, polyamide MXD10, and polyamide 11/6T copolymer resin.
  • Polyamide 11 is a polyamide resin having a structure in which monomers having 11 carbon atoms are bonded via amide bonds.
  • Polyamide 11 is usually obtained using aminoundecanoic acid or undecanelactam as a monomer.
  • aminoundecanoic acid is desirable from the viewpoint of carbon neutrality because it is a monomer obtained from castor oil.
  • These structural units derived from monomers having 11 carbon atoms account for preferably 50 mol% or more, more preferably 80% mol or more, more preferably 80% mol or more, and 100 mol% of all structural units in polyamide 11. good too.
  • Polyamide 11 is usually produced by the ring-opening polymerization of undecanelactam described above.
  • Polyamide 11 obtained by ring-opening polymerization is usually melt-extruded by an extruder after removing the lactam monomer with hot water and then drying.
  • the relative viscosity of polyamide 11 is preferably 1.8 to 4.5, more preferably 2.4 to 3.2.
  • Polyamide 410 is a polyamide resin having a structure in which a monomer having 4 carbon atoms and a diamine having 10 carbon atoms are copolymerized. Polyamide 410 typically utilizes sebacic acid and tetramethylene diamine. Sebacic acid is preferably made from castor oil, which is a vegetable oil, from an environmental point of view. Sebacic acid used here is preferably obtained from castor oil from the viewpoint of environmental protection, particularly from the viewpoint of carbon neutrality.
  • Polyamide 610 is a polyamide resin having a structure in which a diamine having 6 carbon atoms and a dicarboxylic acid having 10 carbon atoms are polymerized. Hexamethylenediamine and sebacic acid are commonly used. Of these, sebacic acid is a monomer obtained from castor oil, and is desirable from the viewpoint of carbon neutrality. Structural units derived from these monomers having 6 carbon atoms and structural units derived from monomers having 10 carbon atoms, the total in PA610 is 50 mol of all structural units % or more, more preferably 80 mol % or more, and may be 100 mol %.
  • Polyamide 1010 is a polyamide resin having a structure in which a diamine having 10 carbon atoms and a dicarboxylic acid having 10 carbon atoms are polymerized.
  • Polyamide 1010 typically utilizes 1,10-decanediamine (decamethylenediamine) and sebacic acid. Decamethylenediamine and sebacic acid are monomers obtained from castor oil, and thus are desirable from the carbon neutral point of view.
  • These structural units derived from a diamine having 10 carbon atoms and structural units derived from a dicarboxylic acid having 10 carbon atoms account for 50 mol% or more of all structural units in PA1010. It is preferably 80 mol % or more, more preferably 100 mol %.
  • the lower limit of the content of the polyamide, at least part of which is derived from biomass, in the A layer is not particularly limited, but is preferably 1% by mass, more preferably 3% by mass or more.
  • the upper limit of the content is 30% by mass, more preferably 20% by mass. If the content of the polyamide, at least part of which is derived from biomass, exceeds 30% by mass, the melt film may become unstable during casting, making it difficult to obtain a homogeneous unstretched film.
  • additives Various additives such as other thermoplastic resins, lubricants, heat stabilizers, antioxidants, antistatic agents, antifogging agents, ultraviolet absorbers, dyes, and pigments may be added to the A layer as necessary. can be done.
  • the A layer may contain a thermoplastic resin in addition to the polyamide 6 and the polyamide resin at least partially derived from biomass as long as the object of the present invention is not impaired.
  • a thermoplastic resin such as polyamide 12 resin, polyamide 66 resin, polyamide 6/12 copolymer resin, polyamide 6/66 copolymer resin, and polyamide MXD6 resin.
  • Thermoplastic resins other than polyamides for example, polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate, and polyolefin polymers such as polyethylene and polypropylene, may be added as necessary. good. It is preferable that the raw materials for these thermoplastic resins are biomass-derived, since they do not affect the increase or decrease of carbon dioxide on the ground, thereby reducing the burden on the environment.
  • Layer B is a layer containing 70% by mass or more of polyamide 6 resin.
  • the B layer contains 80% by mass or more of polyamide 6 resin, and more preferably, the B layer is a layer containing 90% by mass or more of polyamide 6 resin.
  • a biaxially stretched polyamide film having excellent mechanical strength such as impact strength and gas barrier properties such as oxygen can be obtained.
  • the polyamide 6 resin the same polyamide 6 resin as used in the layer A can be used.
  • the upper limit of the polyamide 6 resin content is 100% by mass, preferably 97% by mass, more preferably 95% by mass.
  • the B layer has various additives such as other thermoplastic resins, lubricants, heat stabilizers, antioxidants, antistatic agents, antifogging agents, ultraviolet absorbers, dyes, and pigments on the surface of the B layer. It can be contained depending on the function. When the B layer is used on the outside of the packaging bag, it is necessary to have friction pinhole resistance, so it is not preferable to contain a soft resin such as a polyamide elastomer or a polyolefin elastomer or a substance that generates a large amount of voids.
  • a soft resin such as a polyamide elastomer or a polyolefin elastomer or a substance that generates a large amount of voids.
  • the B layer can contain a thermoplastic resin in addition to the polyamide 6 as long as it does not impair the purpose of the present invention.
  • a thermoplastic resin such as polyamide MXD6 resin, polyamide 11 resin, polyamide 12 resin, polyamide 66 resin, polyamide 6/12 copolymer resin, and polyamide 6/66 copolymer resin.
  • Thermoplastic resins other than polyamides for example, polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate, and polyolefin polymers such as polyethylene and polypropylene, may be added as necessary. good.
  • the B layer contains a thermoplastic resin other than polyamide 6, the content of the thermoplastic resin is 30% by mass or less, preferably 20% by mass or less, relative to the resin composition forming the B layer, More preferably, it is 10% by mass or less.
  • the layer B preferably contains fine particles or an organic lubricant such as a fatty acid amide as a lubricant in order to improve the lubricity and facilitate handling.
  • an organic lubricant such as a fatty acid amide
  • the fine particles inorganic fine particles such as silica, kaolin, and zeolite, and polymer-based organic fine particles such as acryl-based and polystyrene-based organic fine particles can be appropriately selected and used. From the viewpoint of transparency and slipperiness, it is preferable to use fine silica particles.
  • the fine particles preferably have an average particle size of 0.5 to 5.0 ⁇ m, more preferably 1.0 to 3.0 ⁇ m.
  • the B layer may contain a fatty acid amide and/or a fatty acid bisamide for the purpose of improving slipperiness.
  • Fatty acid amides and/or fatty acid bisamides include erucic acid amide, stearic acid amide, ethylene bis stearic acid amide, ethylene bis behenic acid amide, ethylene bis oleic acid amide and the like.
  • the content of fatty acid amide and/or fatty acid bisamide is preferably 0.01 to 0.40% by mass, more preferably 0.05 to 0.30% by mass.
  • a polyamide resin such as a polyamide MXD6 resin, a polyamide 12 resin, a polyamide 66 resin, a polyamide 6-12 copolymer resin, or a polyamide 6-66 copolymer resin can be added to the B layer for the purpose of improving slipperiness.
  • the layers A and B of the biaxially stretched polyamide film of the present invention may contain an antioxidant.
  • Phenolic antioxidants are preferred as antioxidants.
  • the phenolic antioxidant is preferably a fully hindered phenolic compound or a partially hindered phenolic compound.
  • the substrate layer in the present invention is a biaxially stretched polyamide film in which a B layer is laminated on at least one side of an A layer.
  • a B layer is laminated on at least one side of an A layer.
  • Specific examples include a two-layer structure of A layer/B layer and a three-layer structure of B layer/A layer/B layer.
  • the thickness of the biaxially stretched polyamide film in the present invention is not particularly limited. 30 ⁇ m is used.
  • the biaxially stretched polyamide film in the present invention preferably has a heat shrinkage rate of 0.6 to 3.0% in both the MD and TD directions at 160° C. for 10 minutes, more preferably 0.6. ⁇ 2.5%.
  • a heat shrinkage rate of 3.0% or less, it is possible to suppress the occurrence of curling and shrinkage when heat is applied in subsequent processes such as lamination and printing.
  • the impact strength of the biaxially stretched polyamide film in the present invention is preferably 0.7 J/15 ⁇ m or more.
  • a more preferable impact strength is 0.9 J/15 ⁇ m or more.
  • the haze value of the biaxially stretched polyamide film in the invention is preferably 10% or less. More preferably 7% or less, still more preferably 5% or less. If the haze value is small, the transparency and gloss are good, so when used for packaging bags, clear printing can be performed and the product value is increased.
  • the dynamic friction coefficient of the biaxially stretched polyamide film in the invention is preferably 1.0 or less. It is more preferably 0.7 or less, still more preferably 0.5 or less. If the coefficient of dynamic friction of the film is small, the slipperiness is improved and the handling of the film is facilitated. If the coefficient of dynamic friction of the film is too small, the film will be too slippery and difficult to handle.
  • the content of biomass-derived carbon measured by radioactive carbon 14 C of ASTM D6866-18 that is, the degree of biomass is 1 to 30% with respect to the total carbon in the polyamide film. is preferred. Since carbon dioxide in the atmosphere contains 14 C at a certain rate (105.5 pMC), the 14 C content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. is known to be It is also known that fossil fuels contain almost no 14 C. Therefore, by measuring the ratio of 14 C contained in the total carbon atoms in the film, the ratio of biomass-derived carbon can be calculated.
  • the film roll of the present invention is sampled every 1000 m from the surface layer of the film roll to the winding core in the MD direction, and the maximum value of biomass degree when measuring radiocarbon 14 C is Xmax, the minimum value is Xmin, and the average
  • the variation in the degree of biomass represented by the following formula (1) is preferably 15% or less, more preferably 13% or less, and most preferably 10% or less.
  • Variation in biomass degree (%) ⁇ (Xmax-Xmin)/Xave ⁇ ⁇ 100
  • the upper limit of the thickness accuracy of the film roll in the MD direction and the TD direction in the present invention is preferably 30% or less, more preferably 25% or less, and most preferably 20% or less.
  • the thickness accuracy of the film is 30% or less, it is possible to suppress appearance defects of the film roll to be obtained, and to prevent the occurrence of wrinkles and winding misalignment due to meandering.
  • the roll width of the film roll in the present invention is preferably 400 mm or more, may be 1,000 mm or more, or may be 1,500 mm or more, from the viewpoint of improving productivity in the secondary processing step. .
  • the upper limit is not particularly limited, it may be 5,000 mm or less, 4,000 mm or less, or 3,000 mm or less.
  • the winding length of the film roll is preferably 1,000 m or more, may be 2,000 m or more, or may be 3,000 m or more, from the viewpoint of improving productivity in the secondary processing step.
  • the upper limit of the winding length is not particularly limited, it may be 60,000 m or less, 50,000 m or less, or 40,000 m or less.
  • the production method for obtaining the polyamide film roll of the present invention includes (1) supplying and mixing polyamide 6 resin chips and polyamide resin chips at least part of which is derived from biomass to an extruder equipped with a hopper, A step of melt extruding the polyamide raw material resin from the extruder into a sheet and cooling it on a casting drum to form an unstretched sheet; , (3) a preheating step of preheating to a temperature at which TD stretching is possible after the MD stretching, (4) a TD stretching step of stretching in the TD direction orthogonal to the MD direction, and (5) the MD stretching and the TD stretching. (6) a thermal relaxation step of relaxing tension in the width direction of the heat-set polyamide film to remove residual strain of the film, and and (7) a cooling step of cooling the polyamide film after thermal relaxation.
  • layer A as a method of mixing polyamide 6 resin chips and polyamide resin chips at least part of which is derived from biomass, raw material resin chips of polyamide 6 are supplied to the first hopper, and Raw material resin chips of polyamide, at least part of which is derived from biomass, were supplied, and the raw resin chips supplied from the first hopper and the raw resin chips supplied from the second hopper were mixed immediately above the extruder. After that, it is preferable to melt-extrude the raw material resin from an extruder.
  • FIG. 1 is a schematic diagram showing an example of the relationship between an extruder 2 having a hopper 1 and an inner pipe 3.
  • resins other than the polyamide 6 resin chips which are the main raw material of the polyamide film of the present invention, are supplied through the inner pipe 3, and the polyamide 6 resin chips are supplied from the upper part of the hopper 1.
  • the outlet 4 of the inner pipe 3 is directly above the resin supply port 5 of the extruder 2, the mixing ratio of the raw materials can be kept constant.
  • the raw material resin is obtained by melt extruding the resin composition forming the A layer and the resin composition forming the B layer using an extruder, laminating the A layer and B layer using a feed block or multi-manifold, and extruding the T die. It is extruded into a film form from a film, cast on a cooling roll and cooled to obtain an unstretched film.
  • the melting temperature of the resin is preferably 220-350°C. If it is less than the above range, unmelted materials may occur, resulting in appearance defects such as defects.
  • the die temperature is preferably 250-350°C.
  • the cooling roll temperature is preferably -30 to 80°C, more preferably 0 to 50°C.
  • a method using an air knife or an electrostatic adhesion method in which an electrostatic charge is applied is preferably applied. can. Especially the latter is preferably used.
  • the stretching method may be a simultaneous biaxial stretching method or a sequential biaxial stretching method.
  • single-stage stretching or multi-stage stretching such as two-stage stretching can be used as the stretching method in the MD direction.
  • multi-stage stretching in the MD direction such as two-stage stretching is preferable in terms of physical properties and uniformity (isotropy) of physical properties in the MD and TD directions, rather than single-stage stretching.
  • Stretching in the MD direction in the sequential biaxial stretching method is preferably roll stretching.
  • the lower limit of the stretching temperature in the MD direction is preferably 50°C, more preferably 55°C, and still more preferably 60°C.
  • the upper limit of the stretching temperature in the MD direction is preferably 120°C, more preferably 115°C, still more preferably 110°C.
  • the lower limit of the draw ratio in the MD direction is preferably 2.2 times, more preferably 2.5 times, and even more preferably 2.8 times.
  • the upper limit of the draw ratio in the MD direction is preferably 5.0 times. , more preferably 4.5 times, and most preferably 4.0 times.
  • the stretching ratio in the MD direction is the total stretching ratio obtained by multiplying the respective stretching ratios.
  • the above-mentioned stretching is possible in each stretching. is preferably adjusted.
  • the first stage stretching is preferably 1.5 to 2.1 times
  • the second stage stretching is preferably 1.5 to 1.8 times.
  • a film stretched in the MD direction is stretched in the TD direction with a tenter, heat-set, and then subjected to relaxation treatment (also called relaxation treatment).
  • the lower limit of the stretching temperature in the TD direction is preferably 50°C, more preferably 55°C, still more preferably 60°C.
  • the upper limit of the stretching temperature in the TD direction is preferably 190°C, more preferably 185°C, still more preferably 180°C.
  • the lower limit of the draw ratio in the TD direction is preferably 2.8, more preferably 3.2 times, still more preferably 3.5 times, and particularly preferably 3.8 times. is preferably 5.5 times, more preferably 5.0 times, still more preferably 4.7 times, particularly preferably 4.5 times, and most preferably 4.3 times.
  • the above draw ratio in the TD direction is the total draw ratio obtained by multiplying each ratio.
  • the lower limit of the heat setting temperature is preferably 210°C, more preferably 212°C.
  • the upper limit of the heat setting temperature is preferably 220°C, more preferably 218°C.
  • the heat setting time is preferably 0.5 to 20 seconds. Furthermore, it is 1 to 15 seconds.
  • the heat setting time can be set to an appropriate time in consideration of the heat setting temperature and the wind speed in the heat setting zone.
  • the temperature for the relaxation treatment can be selected in the range from the heat setting temperature to the glass transition temperature Tg of the resin, but [heat setting temperature -10°C] to [Tg + 10°C] is preferable.
  • the lower limit of the relaxation rate of relaxation processing is preferably 0.5%, more preferably 1%.
  • the upper limit of the relaxation rate is preferably 20%, more preferably 15%, still more preferably 10%
  • a vapor deposition film formed by the vapor deposition process a vapor deposition film of aluminum, a vapor deposition film of a single substance or a mixture of silicon oxide or aluminum oxide is preferably used. Furthermore, by coating a protective layer or the like on these vapor-deposited films, the oxygen barrier properties and the like can be improved.
  • Heat-sealable laminated film roll When the polyamide film roll of the present invention is used as a packaging material, it is preferable to laminate a heat-sealable film called a sealant film.
  • a laminated film roll can also be constructed by interposing an adhesive layer, a printed layer, a metal layer, or the like between the biaxially stretched polyamide film and the sealant film.
  • a lamination method known methods such as dry lamination and extrusion lamination can be used, but any lamination method may be used. Specific examples are shown below.
  • Example of layer structure of the laminated film roll of the present invention ONY/adhesive/CPP, ONY/adhesive/Al/adhesive/CPP, PET/adhesive/ONY/adhesive/CPP, PET/adhesive/ONY/ Adhesive/Al/Adhesive/CPP, PET/Adhesive/Al/Adhesive/ONY/Adhesive/CPP, ONY/Adhesive/PET/Adhesive/CPP, ONY/PE/CPP, ONY/Adhesive/ EVOH/adhesive/CPP, ONY/adhesive/aluminum-deposited PET/adhesive/CPP, CPP/adhesive/ONY/adhesive/LLDPE, ONY/adhesive/aluminum-deposited CPP.
  • Film evaluation was performed by the following measurement methods. Unless otherwise specified, measurements were carried out in a measurement room at 23° C. and a relative humidity of 65%.
  • MD direction Tv (%) ⁇ (Tmax-Tmin)/Tave ⁇ x 100 [Thickness accuracy of film in TD direction]
  • a film test piece having a width of 5 cm and a length of 100 cm was cut out in the TD direction of the film roll, and measured at a pitch of 5 cm using a dial gauge (thickness measuring device manufactured by Tester Sangyo Co., Ltd.). The test piece was cut out so that the center in the length direction of the film test piece was the central portion in the width direction of the film roll.
  • Tmax being the maximum thickness
  • Tmin being the minimum thickness
  • Tave the average thickness
  • the thickness accuracy (Tv) was obtained from the following equation (3).
  • Formula (3) TD direction Tv (%) ⁇ (Tmax-Tmin)/Tave ⁇ x 100 When the width of the film roll is less than 100 cm, the length of the film in the width direction is taken as the length of the film test piece.
  • Thermal shrinkage rate (%) [(length before treatment - length after treatment) / length before treatment] ⁇ 100
  • Example 1 Using an apparatus consisting of two extruders and a co-extrusion T die with a width of 380 mm, a layer B/layer/B layer is laminated by the feed block method, and the molten resin is extruded into a film form from the T die and heated to 20°C. The film was cast on a cooling roll whose temperature was controlled to 200 ⁇ m and electrostatically adhered to obtain an unstretched film having a thickness of 200 ⁇ m.
  • the resin composition b was introduced using an inner pipe as shown in FIG. 1 so as to be mixed with the resin composition a directly above the extruder.
  • the resin compositions of the A layer and the B layer are as follows.
  • Resin composition b Polyamide resin containing raw materials derived from biomass-polyamide 11 (manufactured by Arkema, relative viscosity 2.5, melting point 186 ° C.) 3.0 parts by mass
  • Layer B Polyamide 6 (manufactured by Toyobo Co., Ltd., relative viscosity 2.8, melting point 220 ° C.) 95 parts by mass
  • Polyamide MXD6 Mitsubishi Gas Chemical Co., Ltd., relative viscosity 2.1, melting point 237 ° C.) 5.0 parts by mass; Porous silica fine particles (Fuji Silysia Chemical Co., Ltd., average particle diameter 2.0 ⁇ m, pore volume 1.6 ml / g) 0.54 parts by mass; 0.15 parts by mass
  • the final total thickness of the biaxially stretched polyamide film was 15 ⁇ m, the thickness of the substrate layer (A layer) was 12 ⁇ m, and the thickness of each of the front and back surface layers (B layer) was 1.5 ⁇ m.
  • the composition of the extruder and the discharge rate of the extruder were adjusted.
  • the obtained unstretched film was guided to a roll type stretching machine, and after being stretched 1.73 times in the MD direction at 80°C by utilizing the peripheral speed difference of the rolls, it was further stretched 1.85 times at 70°C. Subsequently, this uniaxially stretched film was continuously guided to a tenter type stretching machine, preheated at 110°C, and stretched in the TD direction at 120°C for 1.2 times, 130°C for 1.7 times, and 160°C for 2.0 times. After being stretched and heat-set at 218°C, a 7% relaxation treatment was performed at 218°C. Then, one surface was corona discharge treated to obtain a jumbo roll of biaxially oriented polyamide film. The obtained jumbo roll was slit to obtain a biaxially stretched polyamide film roll having a width of 1,000 mm and a winding length of 4,000 m. Table 1 shows the evaluation results of the obtained biaxially stretched polyamide film roll.
  • Example 2 to Example 9 A biaxially oriented polyamide film roll was obtained in the same manner as in Example 1, except that the film forming conditions such as the raw material resin composition and the heat setting temperature were changed as shown in Table 1. Table 1 shows the evaluation results of the obtained biaxially stretched polyamide film roll.
  • ⁇ Comparative Example 1> Using an apparatus consisting of two extruders and a co-extrusion T die with a width of 380 mm, a layer B/layer/B layer is laminated by the feed block method, and the molten resin is extruded into a film form from the T die and heated to 20°C. The film was cast on a cooling roll whose temperature was controlled to 200 ⁇ m and electrostatically adhered to obtain an unstretched film having a thickness of 200 ⁇ m. In the A layer, the same resin composition a and resin composition b as in Example 1 were used, but the inner pipe was not used for mixing the resin composition b. and fed the resin composition to the extruder. A biaxially oriented polyamide film roll was obtained under the same film-forming conditions as in Example 1, except that the mixing method of the resin composition was changed. Table 2 shows the evaluation results of the obtained biaxially stretched polyamide film roll.
  • polyamide 410, polyamide 610, and polyamide 1010 which are polyamide resins containing raw materials derived from biomass, were as follows.
  • the biaxially stretched polyamide film rolls of the Examples used an inner pipe to supply the raw material, thereby reducing the variation in the degree of biomass when measuring radiocarbon 14 C in the MD direction.
  • the comparative example does not use an inner pipe to supply raw materials, and the raw material segregation causes large fluctuations in the raw material ratio in the MD direction. There was a lot of variation in the degree of biomass when the measurements were taken.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème à résoudre dans le cadre de la présente invention consiste à fournir un rouleau de film de polyamide étiré biaxialement comprenant une matière première dérivée de biomasse, le rouleau de film de polyamide étiré biaxialement présentant une excellente résistance à la chaleur, une excellente résistance aux chocs et une excellente résistance aux piqûres de flexion, la variation du niveau de biomasse dans la direction MD étant supprimée. La solution selon l'invention porte sur un rouleau de film de polyamide étiré biaxialement qui est formé à partir d'un film de polyamide étiré biaxialement comprenant au moins deux couches, à savoir la couche A et la couche B, la couche A comprenant 99 à 70 % en masse de résine de polyamide 6 dans laquelle l'ε-caprolactame dérivé d'un combustible fossile est pris en tant qu'unité de lactame, et 1 à 30 % en masse de résine de polyamide comprenant une matière première dérivée de biomasse ; la couche B comprenant 70 à 100 % en masse de résine de polyamide 6 dans laquelle l'ε-caprolactame dérivé d'un combustible fossile est pris en tant qu'unité de lactame ; lorsque le rouleau de film est échantillonné tous les 1 000 m dans la direction MD de la couche de surface au noyau de rouleau et que le carbone radioactif 14C est mesuré, la variation du niveau de biomasse dans la direction MD étant égale ou inférieure à 15 % ; la longueur de rouleau étant 1 000 à 60 000 m ; et la largeur de rouleau étant 400 à 3 000 mm.
PCT/JP2023/005522 2022-02-17 2023-02-16 Rouleau de film de polyamide WO2023157930A1 (fr)

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Citations (11)

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Publication number Priority date Publication date Assignee Title
JP2004181777A (ja) * 2002-12-03 2004-07-02 Toyobo Co Ltd ポリアミド系フィルムロールおよびその製造方法
JP2007015354A (ja) * 2005-07-11 2007-01-25 Toyobo Co Ltd ポリアミド系混合樹脂積層フィルムロール、およびその製造方法
JP2010155455A (ja) * 2008-12-03 2010-07-15 Toyobo Co Ltd 層状化合物が高度に面内に配向した熱可塑性樹脂延伸多層フィルム
JP2016120721A (ja) * 2011-03-01 2016-07-07 東洋紡株式会社 延伸ポリアミドフィルム
WO2018062145A1 (fr) * 2016-09-28 2018-04-05 東洋紡株式会社 Rouleau de film blanc à base de polyester thermorétractable
WO2019187694A1 (fr) * 2018-03-30 2019-10-03 東洋紡株式会社 Rouleau de film de polyester
WO2020170714A1 (fr) * 2019-02-18 2020-08-27 東洋紡株式会社 Film de polyamide étiré biaxialement et film stratifié
WO2020195742A1 (fr) * 2019-03-26 2020-10-01 東洋紡株式会社 Film de polyester et son procédé de production
WO2020203106A1 (fr) * 2019-03-29 2020-10-08 東洋紡株式会社 Film de polyester et son procédé de production
CN111763426A (zh) * 2020-07-23 2020-10-13 湖南工业大学 一种生物基聚酰胺双向拉伸薄膜及其制备方法
WO2021117736A1 (fr) * 2019-12-13 2021-06-17 東洋紡株式会社 Film de polyester à orientation biaxiale et son procédé de fabrication

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004181777A (ja) * 2002-12-03 2004-07-02 Toyobo Co Ltd ポリアミド系フィルムロールおよびその製造方法
JP2007015354A (ja) * 2005-07-11 2007-01-25 Toyobo Co Ltd ポリアミド系混合樹脂積層フィルムロール、およびその製造方法
JP2010155455A (ja) * 2008-12-03 2010-07-15 Toyobo Co Ltd 層状化合物が高度に面内に配向した熱可塑性樹脂延伸多層フィルム
JP2016120721A (ja) * 2011-03-01 2016-07-07 東洋紡株式会社 延伸ポリアミドフィルム
WO2018062145A1 (fr) * 2016-09-28 2018-04-05 東洋紡株式会社 Rouleau de film blanc à base de polyester thermorétractable
WO2019187694A1 (fr) * 2018-03-30 2019-10-03 東洋紡株式会社 Rouleau de film de polyester
WO2020170714A1 (fr) * 2019-02-18 2020-08-27 東洋紡株式会社 Film de polyamide étiré biaxialement et film stratifié
WO2020195742A1 (fr) * 2019-03-26 2020-10-01 東洋紡株式会社 Film de polyester et son procédé de production
WO2020203106A1 (fr) * 2019-03-29 2020-10-08 東洋紡株式会社 Film de polyester et son procédé de production
WO2021117736A1 (fr) * 2019-12-13 2021-06-17 東洋紡株式会社 Film de polyester à orientation biaxiale et son procédé de fabrication
CN111763426A (zh) * 2020-07-23 2020-10-13 湖南工业大学 一种生物基聚酰胺双向拉伸薄膜及其制备方法

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