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WO2024203741A1 - Film de polyamide à orientation biaxiale - Google Patents

Film de polyamide à orientation biaxiale Download PDF

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Publication number
WO2024203741A1
WO2024203741A1 PCT/JP2024/011079 JP2024011079W WO2024203741A1 WO 2024203741 A1 WO2024203741 A1 WO 2024203741A1 JP 2024011079 W JP2024011079 W JP 2024011079W WO 2024203741 A1 WO2024203741 A1 WO 2024203741A1
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WO
WIPO (PCT)
Prior art keywords
polyamide
film
resin
biaxially oriented
less
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.)
Pending
Application number
PCT/JP2024/011079
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English (en)
Japanese (ja)
Inventor
和茂 上田
考道 後藤
彩芽 永坂
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
Original Assignee
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 JP2024529851A priority Critical patent/JP7619530B1/ja
Publication of WO2024203741A1 publication Critical patent/WO2024203741A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material

Definitions

  • the present invention relates to a biaxially oriented polyamide film suitable for use as a food packaging film and a packaging material for alcohol-evaporating agents.
  • Biaxially stretched films made of aliphatic polyamides, such as polyamide 6, have excellent impact resistance and pinhole resistance due to bending, and are widely used as various packaging film materials.
  • polyamide films generally have high alcohol permeability, and therefore are also used as base films for packaging bags for alcohol evaporative agents and freshness-preserving packaging bags, which require specific gas permeability.
  • Patent Document 3 describes how the desired gas permeability can be obtained by reducing the thickness of the biaxially stretched polyamide film.
  • Patent Document 3 indicates that reducing the thickness of the nylon film is effective in improving ethanol permeability, but the inventors have found that reducing the film thickness leads to problems with reduced pinhole resistance and puncture strength. Patent Document 3 also found that there is room for improvement in the dimensional stability of the film.
  • the object of the present invention is to provide a biaxially oriented polyamide film that has excellent bending pinhole resistance, puncture strength, dimensional stability, and excellent ethanol permeability.
  • the inventors conducted extensive research to achieve the above object, and discovered that by dispersing a resin other than polyamide 6 having a maximum dispersion diameter of 1 ⁇ m or more in a polyamide 6 resin in a biaxially oriented polyamide film and imparting a specific degree of planar orientation and a specific degree of crystallinity, a biaxially oriented polyamide film with good bending pinhole resistance, puncture strength, dimensional stability, and ethanol permeability can be obtained.
  • the inventors continued to conduct further research and improvements, and have now completed the following representative inventions.
  • a biaxially oriented polyamide film containing polyamide 6 as a main component having an ethanol permeability of 6000 to 10000 g ⁇ m/ m2 24 hr (50% RH/40°C), a thickness of 15 ⁇ m or less, a thermal shrinkage rate of 2.0% or less in both the machine direction and the width direction of the film when heat-treated at 160°C for 10 minutes, a surface crystallization parameter of 1.0 to 1.5, and a puncture strength of 6.0 N or more.
  • thermoplastic elastomers such as polyolefins, ionomer polymers, polyester-based elastomers, polyamide-based elastomers, polyolefin-based elastomers, polystyrene-based elastomers, polyurethane-based elastomers, and polyvinyl chloride-based elastomers, aliphatic polyester resins, aliphatic-aromatic polyester resins, aliphatic polyamide resins, and aliphatic-aromatic polyamide resins.
  • a food packaging material comprising the biaxially oriented polyamide film according to any one of [1] to [9] and a sealant film.
  • a packaging material for an ethanol evaporative agent comprising a laminate including at least two layers of the biaxially oriented polyamide film according to any one of [1] to [9] and a breathable resin film or nonwoven fabric.
  • the present invention provides a biaxially oriented polyamide film that is excellent in bending pinhole resistance, puncture strength, dimensional stability, and ethanol permeability, as well as a food packaging material and an ethanol evaporative packaging material that use the biaxially oriented polyamide film.
  • FIG. 1 is a transmission electron microscope photograph showing the dispersion state of polyamide 6 resin (a) and a resin other than polyamide 6 (b) contained in a film.
  • the biaxially stretched polyamide film of the present invention preferably contains, as a main component, polyamide 6.
  • "containing as a main component” means that the content of the component in the polyester resin composition constituting the film is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on 100% by mass of all the components of the polyester resin.
  • the biaxially stretched polyamide film of the present invention is preferably a biaxially stretched polyamide film having a functional layer laminated on at least one side of a substrate layer.
  • the biaxially stretched polyamide film of the present invention is preferably a film having at least two layers, a substrate layer and a functional layer, and may have a two-layer structure of substrate layer/functional layer or a three-layer structure of functional layer/substrate layer/functional layer. Each layer will be described in detail below.
  • the first resin composition forming the base layer contains at least polyamide 6 resin (a).
  • the first resin composition preferably contains 60% by mass or more of polyamide 6, more preferably 80% by mass or more, and even more preferably 85% by mass or more, based on the first resin composition being 100% by mass. If the content of polyamide 6 is less than 60%, the impact resistance may decrease and the gas permeability may increase significantly.
  • a polyamide film having mechanical strength such as impact strength and gas barrier properties can be obtained.
  • the upper limit of the content of polyamide 6 is preferably 98% by mass or less, more preferably 97% by mass or less, based on the first resin composition being 100% by mass.
  • polyamide 6 is preferably 60 to 98% by mass, more preferably 80 to 98% by mass, and even more preferably 85 to 97% by mass.
  • the upper and lower limits of the numerical range may be appropriately combined to form a suitable numerical range (hereinafter the same applies to the numerical range).
  • the first resin composition forming the base layer contains at least one type of resin (b) other than polyamide 6.
  • Resin (b) is a substance that has the effect of imparting flexibility to the base layer, and is not particularly limited as long as it is incompatible with polyamide 6, but is preferably at least one type selected from the group consisting of thermoplastic elastomers such as polyolefins, ionomer polymers, polyester-based elastomers, polyamide-based elastomers, polyolefin-based elastomers, polystyrene-based elastomers, polyurethane-based elastomers, and polyvinyl chloride-based elastomers, aliphatic polyester resins, aliphatic aromatic polyester resins, aliphatic polyamide resins, and aliphatic aromatic polyamide resins.
  • Polyolefins include olefin homopolymers, copolymers of olefins with other monomers, mixtures of these, and polyolefins grafted with unsaturated carboxylic acids.
  • Olefin homopolymers include polyethylene (high density, low density) and polypropylene.
  • Copolymers of olefins with other monomers include ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer.
  • Unsaturated carboxylic acids used in grafting polyolefins with unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and other carboxylic acids, as well as acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride. Unsaturated carboxylic acids may be used alone or in combination.
  • An ionomeric polymer is a polymer composed of a polyolefin and an ⁇ , ⁇ -ethylenically unsaturated monomer having a carboxyl moiety, the carboxyl moiety being neutralized with a metal ion having a valence of 1 to 3.
  • polyolefins include copolymers of polyethylene or ethylene with at least one ⁇ -olefin having usually 3 to 8 carbon atoms and a diolefin, such as 1,4-hexadiene.
  • Examples of ⁇ , ⁇ -ethylenically unsaturated monomers having a carboxyl moiety include methacrylic acid, acrylic acid, maleic acid, maleic anhydride, and fumaric acid.
  • Ionomeric polymers are produced by a direct synthesis method in which an ⁇ -olefin and an olefin monomer having a carboxyl moiety are polymerized, or by a grafting method in which a monomer having a carboxyl moiety is added to the olefin skeleton.
  • Thermoplastic elastomers include polyolefins, ionomer polymers, polyester-based elastomers, polyamide-based elastomers, polyolefin-based elastomers, polystyrene-based elastomers, polyurethane-based elastomers, polyvinyl chloride-based elastomers, and other thermoplastic elastomers, aliphatic polyester resins, aliphatic aromatic polyester resins, aliphatic polyamide resins, and aliphatic aromatic polyamide resins.
  • polyamide-based elastomers for example, polyamide-based elastomers, polyester-based elastomers, polyurethane-based elastomers, acrylic thermoplastic elastomers, polystyrene-based elastomers, and hydrogenated products thereof may also be used.
  • Polyamide-based elastomers include polyetheramides, polyetheresteramides, and polyesteramides.
  • polyamide-based elastomers may be copolymerized with dicarboxylic acids such as dodecanedicarboxylic acid, adipic acid, and terephthalic acid as optional components.
  • Polyester-based elastomers refer to block copolymers composed of crystalline hard segments and flexible soft segments. Among these, block copolymers having hard segments made of cyclic polyester and soft segments made of polyalkylene ether, and block copolymers having hard segments made of cyclic polyester and soft segments made of linear aliphatic polyester are preferred, with cyclic polyester-polyalkylene ether block copolymers being even more preferred.
  • cyclic polyester refers to a material in which the dicarboxylic acid or its alkyl ester, which is the raw material, contains a dicarboxylic acid or its alkyl ester having a cyclic structure.
  • examples of polyurethane-based thermoplastic elastomers include those having a hard segment consisting of a diisocyanate compound and a glycol with a molecular weight of about 50 to 500, and a soft segment consisting of a diisocyanate compound and a long-chain glycol.
  • the long-chain glycol may be a polyether-based one such as a polyalkylene glycol with a molecular weight of about 500 to 10,000, or a polyester-based one such as polyalkylene adipate, polycaprolactone, or polycarbonate.
  • diisocyanate compounds include phenylene diisocyanate, trigen diisocyanate, xylene diisocyanate, 4,4-diphenylmethane diisocyanate, and hexamethylene diisocyanate.
  • the diisocyanate compounds in the soft segment and the hard segment may be the same or different.
  • Acrylic thermoplastic elastomers include ethylene-acrylic ester copolymer elastomers, ethylene-methacrylic ester copolymer elastomers, and acrylic ABA triblock copolymers consisting of acrylic esters and methacrylic esters.
  • Polystyrene-based elastomers include styrene-butadiene copolymer rubber and styrene-isoprene copolymer rubber.
  • polybutylene succinate and polybutylene succinate adipate are preferably used.
  • an aliphatic aromatic polyester resin containing an adipic acid component is preferable, and polybutylene adipate terephthalate is particularly preferable.
  • More preferable is an aliphatic or aliphatic aromatic polyester resin with a glass transition temperature (Tg) of -30°C or less.
  • polyamide 11 polyamide 610, polyamide 1010 and polyamide 410 are preferably used.
  • the polyamide resin may be at least partly derived from biomass as a raw material.
  • the bending pinhole resistance can be further improved.
  • the aliphatic aromatic polyamide resin include polymetaxylylene adipamide (MXD6), polyamide 6T, polyamide 6I, polyamide 6T6I, and polyamide 9T.
  • MXD6 is suitable from the viewpoint of improving stretchability and adhesiveness.
  • the content of the resin (b) other than polyamide 6 contained in the first resin composition forming the base layer is preferably 2% by mass to 40% by mass or less, or 20% by mass or less, and more preferably 4% by mass to 15% by mass, based on 100% by mass of the first resin composition.
  • the first resin composition forming the base layer may contain a thermoplastic resin other than polyamide 6 resin, provided that the object of the present invention is not impaired.
  • a thermoplastic resin other than polyamide 6 resin examples include polyamide-based resins such as polyamide 12 resin, polyamide 66 resin, polyamide 6-12 copolymer resin, polyamide 6-66 copolymer resin, polyamide MXD6 resin, polyamide MXD10 resin, and polyamide 11-6T copolymer resin.
  • it may contain a thermoplastic resin other than polyamide-based, for example, a polyester-based polymer such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene-2,6-naphthalate, or a polyolefin-based polymer such as polyethylene or polypropylene.
  • the base layer can contain various additives such as other thermoplastic resins, lubricants, heat stabilizers, antioxidants, antistatic agents, anti-fogging agents, UV absorbers, dyes, pigments, etc. as needed.
  • the second resin composition forming the functional layer preferably contains at least polyamide 6.
  • the second resin composition preferably contains 70% by mass or more of polyamide 6, more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on 100% by mass of the second resin composition.
  • a polyamide film having mechanical strength such as impact strength and gas barrier properties can be obtained.
  • the upper limit of the content of polyamide 6 is preferably 99% by mass or less, more preferably 96% by mass or less, based on 100% by mass of the first resin composition. That is, the content of polyamide 6 is preferably 70 to 99% by mass, more preferably 80 to 96% by mass, and even more preferably 90 to 96% by mass.
  • the polyamide 6 can be the same polyamide 6 as the polyamide 6 used in the first resin composition.
  • the second resin composition forming the functional layer may contain a polyamide resin other than polyamide 6.
  • polyamide resins other than polyamide 6 include polyamide MXD6 resin, polyamide 11, polyamide 12, and polyamide 66.
  • the content is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 20% by mass, and particularly preferably 5% by mass to 10% by mass, based on 100% by mass of the second resin composition.
  • polyamide MXD6 resin is preferably used as a polyamide resin other than polyamide 6, polyamide MXD6 resin is preferably used.
  • the second resin composition that forms the functional layer can contain microparticles or organic lubricants as lubricants to improve the film's slipperiness. By improving the slipperiness, the film becomes easier to handle and the risk of packaging bags breaking due to friction can be reduced.
  • the fine particles can be appropriately selected from inorganic fine particles such as silica, kaolin, and zeolite, and polymeric organic fine particles such as acrylic and polystyrene fine particles. From the standpoint of transparency and slipperiness, it is preferable to use silica fine particles.
  • the preferred average particle size of the fine particles is 0.5 ⁇ m or more and 5.0 ⁇ m or less, and more preferably 1.0 ⁇ m or more and 3.0 ⁇ m or less. With an average particle size of 0.5 ⁇ m or more, good slip properties can be expected, and with an average particle size of 5.0 ⁇ m or less, it is expected that poor appearance due to increased surface roughness of the film can be prevented.
  • the range of the pore volume of the silica is preferably 0.5 ml/g or more and 2.0 ml/g or less, and more preferably 0.8 ml/g or more and 1.6 ml/g or less.
  • fatty acid amides and/or fatty acid bisamides can be used as the organic lubricant.
  • fatty acid amides and/or fatty acid bisamides include erucic acid amide, stearic acid amide, ethylene bisstearic acid amide, ethylene bisbehenic acid amide, and ethylene bisoleic acid amide.
  • the content of fatty acid amides and/or fatty acid bisamides contained in the second resin composition forming the functional layer is preferably 0.01% by mass or more and 0.40% by mass or less, and more preferably 0.05% by mass or more and 0.30% by mass or less, based on 100% by mass of the second resin composition. By being 0.01% by mass or more, a slip effect can be expected. By being 0.40% by mass or less, the wettability of the printing ink can be ensured when a printing layer is provided on the functional layer side.
  • the functional layer can contain various additives such as other thermoplastic resins, lubricants, heat stabilizers, antioxidants, antistatic agents, anti-fogging agents, UV absorbers, dyes, pigments, etc.
  • the biaxially stretched polyamide film of the present invention is preferably a film having at least two layers, a substrate layer and a functional layer, and may have a two-layer structure of substrate layer/functional layer or a three-layer structure of functional layer/substrate layer/functional layer.
  • the ethanol permeability of the biaxially stretched polyamide film of the present invention is preferably 6000 g ⁇ m/m 2 24 hr (50% RH/40° C.) or more.
  • the biaxially stretched polyamide film of the present invention is used as a packaging material for an ethanol transpiration agent, the ethanol impregnated into the nonwoven fabric as an ethanol transpiration agent slowly transpires, and a sufficient ethanol gas concentration for maintaining the freshness of the food in the food packaging can be obtained.
  • the ethanol permeability is less than 6000 g ⁇ m/m 2 24 hr (50% RH/40° C.), the permeation of the alcohol gas transpired from the alcohol transpiration agent is inhibited, and it is undesirable that a sufficient alcohol gas concentration for maintaining the freshness of the food in the food packaging cannot be obtained.
  • the ethanol permeability is preferably 10000 g ⁇ m/m 2 24 hr (50% RH/40° C.) or less. By keeping the resistance to 10,000 g ⁇ m/m 2 ⁇ 24 hr (50% RH/40° C.) or less, it is possible to prevent condensation of ethanol inside the package that would occur due to a large amount of ethanol permeating through the package.
  • the thickness of the biaxially oriented polyamide film of the present invention is preferably 15 ⁇ m or less, and more preferably 5 to 12 ⁇ m.
  • a thickness of 15 ⁇ m or less provides excellent alcohol permeability and contributes to resource conservation and waste reduction.
  • a thickness of 5 ⁇ m or more is preferable because it provides sufficient mechanical strength required for secondary processing such as lamination, coating, and slitting.
  • the thickness of the substrate layer is preferably 50% to 90%, and particularly preferably 60% to 80%, of the total thickness of the substrate layer and the functional layer (if there are multiple substrate layers and functional layers, the total thickness of each), taken as 100%.
  • the thickness of the substrate layer 50% or more bending pinhole resistance can be imparted.
  • the biaxially stretched polyamide film of the present invention preferably has a stress at 5% elongation obtained by a tensile test in the machine direction and width direction of the film, i.e., F5 value, of 70 MPa or less. More preferably, it is 60 MPa or less, and even more preferably, it is 50 MPa or less.
  • F5 value a stress at 5% elongation obtained by a tensile test in the machine direction and width direction of the film
  • F5 value a stress at 5% elongation obtained by a tensile test in the machine direction and width direction of the film. More preferably, it is 60 MPa or less, and even more preferably, it is 50 MPa or less.
  • the lower limit of the F5 value is preferably 20 MPa or more. Setting the F5 value to 20 MPa or more is preferable in terms of preventing printing pitch deviation due to film elongation during secondary processing.
  • the F5 value is preferably 20 to 70 MPa, more preferably 20 to 60 MPa, and even more preferably 20 to 50 MPa.
  • Methods for setting the F5 value to 20 MPa or more and 70 MPa or less include low-fold stretching, high-temperature stretching, and the addition of resins other than nylon 6, but the addition of resins other than nylon 6 is preferable from the viewpoint of productivity.
  • the biaxially stretched polyamide film of the present invention has excellent pinhole resistance when subjected to a twist bending test using a Gelbo flex tester 1000 times at a temperature of 1°C, and has 1520 or less pinhole defects, more preferably 15 or less, and even more preferably 10 or less pinhole defects when subjected to a twist bending test.
  • the biaxially stretched polyamide film of the present invention preferably has a crystallization parameter (1200 cm -1 /1370 cm -1 ) of 1.0 or more, which is calculated from the intensity ratio of the peaks around 1200 cm -1 and 1370 cm -1 in the spectrum obtained by ATR measurement of FT-IR.
  • the peak at 1200 cm -1 is an absorption derived from the ⁇ -crystal of nylon 6, and the peak at 1370 cm -1 is an absorption unrelated to crystals.
  • the biaxially stretched polyamide film of the present invention preferably has a heat shrinkage rate at 160°C for 10 minutes in the range of 0.6% to 3.0% in both the machine direction (hereinafter sometimes abbreviated as MD direction) and the width direction (hereinafter sometimes abbreviated as TD direction), more preferably 0.5% to 2.0%.
  • a heat shrinkage rate of 3.0% or less can suppress the occurrence of curling or shrinkage when heat is applied in the next process, such as lamination or printing.
  • a heat shrinkage rate of 0.6% or more is preferable in terms of excellent impact resistance.
  • the planar orientation ( ⁇ P) of the biaxially stretched polyamide film in the present invention is preferably 0.050 to 0.070.
  • the planar orientation is determined by measuring the birefringence with a refractometer and calculating it from the following formula, where Nx is the refractive index in the longitudinal direction, Ny is the refractive index in the width direction, and Nz is the refractive index in the thickness direction.
  • ⁇ P (Nx+Ny)/2-Nz
  • the plane orientation can be increased by increasing the biaxial stretch ratio, particularly the stretch ratio in the TD direction, and a plane orientation of 0.05 or more can provide the film with mechanical strength such as puncture strength, while a plane orientation of 0.07 or less can suppress a decrease in productivity.
  • the impact strength of the biaxially oriented polyamide film of the present invention is preferably 0.6 J or more, and more preferably 0.7 J or more.
  • the puncture strength of the film of the present invention is preferably 6.0 N or more.
  • the puncture strength is preferably 6.0 N or more.
  • it may be 100 N or less, or 50 N or less.
  • the maximum dispersion diameter of the resin (b) other than polyamide 6 contained in the base layer is preferably 1.0 ⁇ m or more.
  • the maximum dispersion diameter refers to the maximum length in the long axis length of the resin (b) dispersed in the base layer when the base layer is observed with a transmission electron microscope (TEM): unit ⁇ m.
  • TEM transmission electron microscope
  • FIG. 1 is a photograph of a cross section of the film in the machine direction observed with a transmission electron microscope at a magnification of 2000 times, and the darkly dyed domain is the resin (b).
  • the reason why good pinhole resistance is obtained is believed to be that the flexibility of the entire film is improved and destruction due to bending fatigue is less likely to occur due to the dispersion of the flexible resin (b), which is incompatible with polyamide 6.
  • the reason why good ethanol permeability is obtained is believed to be that the dispersion of the incompatible resin (b) in polyamide 6 forms an interface with weak adhesion between polyamide 6 and resin (b), and ethanol permeates the film through this interface.
  • the maximum dispersion diameter of the resin (b) is less than 1.0 ⁇ m, compatibility is promoted and the characteristics of the base material, polyamide 6, become apparent, resulting in a decrease in pinhole resistance and ethanol permeability.
  • the raw resin is melt-extruded using an extruder, extruded from a T-die into a film, cast onto a cooling roll and cooled to obtain an unstretched film in which at least a substrate layer and a functional layer are laminated.
  • a co-extrusion method using a feed block or a multi-manifold is preferred.
  • a dry lamination method, an extrusion lamination method, etc. can also be selected.
  • the melting temperature of the resin is preferably 220°C or higher and 350°C or lower. If the temperature is lower than the above, unmelted material may occur, resulting in defects and other poor appearance, while if the temperature exceeds the above, deterioration of the resin may be observed, resulting in a decrease in molecular weight and a decrease in appearance.
  • the die temperature is preferably 250°C or higher and 350°C or lower.
  • the cooling roll temperature is preferably -30°C or higher and 80°C or lower, and more preferably 0°C or higher and 50°C or lower.
  • an unstretched film by casting the film-like molten material extruded from the T-die onto a rotating cooling drum and cooling it, for example, a method using an air knife or an electrostatic adhesion method in which a static charge is applied can be preferably applied. It is also preferable to cool the opposite side of the cooling roll of the cast unstretched film. For example, it is preferable to use a combination of a method of contacting the opposite side of the cooling roll of the unstretched film with a cooling liquid in a tank, a method of applying a liquid that evaporates with a spray nozzle, and a method of cooling by spraying a high-speed fluid. The unstretched film obtained in this manner is stretched in a biaxial direction to obtain the biaxially stretched polyamide film of the present invention.
  • the stretching method may be either a simultaneous biaxial stretching method or a sequential biaxial stretching method.
  • the sequential biaxial stretching method is preferable because it has the advantages of increasing the degree of planar orientation and making it easier to obtain puncture strength, adjusting the crystallization parameters to obtain the desired dimensional stability, and increasing the film-forming speed, making it easier to reduce production costs.
  • multi-stage stretching such as one-stage stretching or two-stage stretching can be used as the MD stretching method.
  • multi-stage MD stretching such as two-stage stretching is preferable in terms of physical properties and uniformity of physical properties in the MD and TD directions (isotropy) rather than one-stage stretching.
  • Roll stretching is preferable for MD stretching in the sequential biaxial stretching method.
  • the lower limit of the MD stretching temperature is preferably 50°C, more preferably 55°C, and even more preferably 60°C. If it is less than 50°C, the resin does not soften and stretching may be difficult.
  • the upper limit of the MD stretching temperature is preferably 120°C, more preferably 115°C, and even more preferably 110°C. If it exceeds 120°C, the resin may become too soft and stable stretching may not be possible. Stretching at 120°C or less is preferable in terms of preventing sticking to the roll and breakage. In other words, the MD stretching temperature is preferably 50 to 120°C, more preferably 55 to 115°C, and even more preferably 60 to 110°C.
  • the lower limit of the stretch ratio in the MD direction (when stretching in multiple stages, the total stretch ratio multiplied by each stretch ratio) is preferably 2.2 times, more preferably 2.5 times, and even more preferably 2.8 times. If it is less than 2.2 times, the thickness accuracy in the MD direction decreases, and the crystallinity may become too low, resulting in a decrease in impact strength.
  • the upper limit of the stretch ratio in the MD direction is preferably 5.0 times, more preferably 4.5 times, and most preferably 4.0 times. A stretch ratio of 5.0 times or less is preferable from the viewpoint of achieving both productivity and film formation stability. In other words, the stretch ratio in the MD direction is preferably 2.2 to 5.0 times, more preferably 2.5 to 4.5 times, and even more preferably 2.8 to 4.0 times.
  • the above-mentioned stretching is possible for each stretching, but it is preferable to adjust the stretching ratio so that the product of all stretching ratios in the MD direction is 5.0 or less.
  • the film stretched in the MD direction is stretched in the TD direction using a tenter, heat-set, and relaxed (also called relaxation).
  • the lower limit of the TD stretching temperature is preferably 50°C, more preferably 55°C, and even more preferably 60°C. If the temperature is less than 50°C, the resin does not soften and stretching may be difficult.
  • the upper limit of the TD stretching temperature is preferably 190°C, more preferably 185°C, and even more preferably 180°C.
  • a TD stretching temperature of 190°C or less is preferable from the viewpoint of suppressing film crystallization and preventing breakage. In other words, the TD stretching temperature is preferably 50 to 190°C, more preferably 55 to 185°C, and even more preferably 60 to 180°C.
  • the lower limit of the stretch ratio in the TD direction (when stretching in multiple stages, the total stretch ratio multiplied by each stretch ratio) is preferably 2.8 times, more preferably 3.2 times, even more preferably 3.5 times, and particularly preferably 3.8 times. If it is less than 2.8 times, the thickness accuracy in the TD direction decreases, and the crystallinity may become too low, resulting in a decrease in impact strength.
  • the upper limit of the stretch ratio in the TD direction is preferably 5.5 times, more preferably 5.0 times, even more preferably 4.7 times, especially preferably 4.5 times, and most preferably 4.3 times. It is preferable to set the stretch ratio in the TD direction to 5.5 times or less from the viewpoint of preventing breakage.
  • the stretch ratio in the TD direction is preferably 2.8 to 5.5 times, more preferably 3.2 to 5.0 times, even more preferably 3.5 to 4.7 times, especially preferably 3.8 to 4.5 times, and most preferably 3.8 to 4.3 times.
  • the lower limit of the heat setting temperature is preferably 210°C, more preferably 212°C. If the heat setting temperature is low, the heat shrinkage rate becomes too large, which deteriorates the appearance after lamination and tends to reduce the laminate strength.
  • the upper limit of the heat setting temperature is preferably 220°C, more preferably 218°C. If the heat setting temperature is too high, the impact strength tends to decrease.
  • the heat setting time is preferably 0.5 to 20 seconds. It is further preferably 1 to 15 seconds. The heat setting time can be set appropriately depending on the heat setting temperature and the wind speed in the heat setting zone. A heat setting temperature of 220°C or less is preferable from the viewpoint of preventing embrittlement of the film. A heat setting temperature of 210°C or more is preferable from the viewpoint of improving dimensional stability and laminate strength. In other words, the heat setting temperature is preferably 210 to 220°C, more preferably 212 to 218°C.
  • the temperature for the relaxation process can be selected in the range from the heat setting temperature to the Tg of the resin, but it is preferably (heat setting temperature (°C) - 10) °C or higher (Tg (°C) + 10) °C or lower. If the relaxation temperature is too high, the shrinkage rate will be too fast, which is not preferable as it can cause distortion. Conversely, if the relaxation temperature is too low, the film will not be relaxed, but will simply slacken, and the heat shrinkage rate will not decrease, resulting in poor dimensional stability.
  • the lower limit of the relaxation rate for the relaxation process is preferably 0.5%, more preferably 1%.
  • the heat shrinkage rate may not decrease sufficiently.
  • the upper limit of the relaxation rate is preferably 20%, more preferably 15%, and even more preferably 10%. If it exceeds 20%, sagging may occur in the tenter, making production difficult.
  • a relaxation rate of 0.5% or higher is preferable in terms of reducing the heat shrinkage rate.
  • a relaxation rate of 20% or lower is preferable in terms of preventing film sagging. That is, the relaxation rate is preferably 0.5 to 20%, more preferably 1 to 15%, and even more preferably 1 to 10%.
  • the biaxially oriented polyamide film of the present invention can be subjected to heat treatment or humidity conditioning treatment to improve dimensional stability depending on the application.
  • heat treatment or humidity conditioning treatment to improve dimensional stability depending on the application.
  • the biaxially oriented polyamide film of the present invention is processed into a laminated film by laminating a sealant film to provide a packaging material.
  • the sealant film include unstretched linear low density polyethylene (LLDPE) film, unstretched polypropylene (CPP) film, and ethylene-vinyl alcohol copolymer resin (EVOH) film.
  • LLDPE linear low density polyethylene
  • CPP unstretched polypropylene
  • EVOH ethylene-vinyl alcohol copolymer resin
  • the sealant film may be laminated so as to be in direct contact with the biaxially oriented polyamide film, or may be laminated via another layer such as an adhesive layer.
  • the packaging material may include a printing layer.
  • the packaging material of the present invention is made into a bag and processed into a packaging bag.
  • Another embodiment of the present invention provides a packaging material for ethanol evaporative agents, which is composed of a laminate including at least two layers of the biaxially oriented polyamide film of the present invention and a breathable resin film or nonwoven fabric.
  • the breathable resin film is not particularly limited as long as it is a film having breathability or ethanol permeability, and examples thereof include unstretched linear low density polyethylene (LLDPE) film, unstretched polypropylene (CPP) film, ethylene-vinyl alcohol copolymer resin (EVOH) film, and ethylene-vinyl acetate copolymer resin (EVA) film.
  • LLDPE unstretched linear low density polyethylene
  • CPP unstretched polypropylene
  • EVOH ethylene-vinyl alcohol copolymer resin
  • EVA ethylene-vinyl acetate copolymer resin
  • polyester, polypropylene, rayon, nylon, biodegradable fiber, pulp, cotton, etc. may be used as the nonwoven fabric substrate, and polypropylene is preferably used.
  • Either a short fiber nonwoven fabric or a long fiber nonwoven fabric can be used as the nonwoven fabric.
  • the nonwoven fabric may be a paper substrate.
  • the films were evaluated using the following measurement methods. Unless otherwise specified, measurements were performed in a measurement room with an environment of 23°C and a relative humidity of 65%.
  • Film Thickness Divide the film into 10 equal parts in the TD direction (for narrow films, divide them so that the width is sufficient to measure the thickness), cut out 10 pieces of 100 mm film in the MD direction, and condition them for 2 hours or more in an environment of 23°C and 65% relative humidity.
  • the thickness of the center of each sample was measured using a thickness measuring device manufactured by Tester Sangyo, and the average value was taken as the thickness.
  • Puncture strength of film The puncture strength was measured in accordance with "2. Test method for strength, etc.” in "Standards and standards for food, additives, etc., Part 3: Apparatus and containers and packaging" (Ministry of Health and Welfare Notification No. 20, 1982) in the Food Sanitation Act. A needle with a tip diameter of 0.7 mm was pierced into the film at a piercing speed of 50 mm/min, and the strength at which the needle penetrated the film was measured and used as the puncture strength. The measurement was performed at room temperature (23°C), and the obtained value was used as the puncture strength of the film (unit: N).
  • FT-IR ATR measurements were performed on the front and back surfaces of the sample under the following conditions.
  • FT-IR device Bio Rad DIGILAB FTS-60A/896 Single reflection ATR attachment: golden gate MKII (SPECAC) Internal reflection element: Diamond Incident angle: 45° Resolution: 4 cm
  • the degree of crystallinity was calculated from the intensity ratio (1200 cm -1 /1370 cm -1 ) of the absorption appearing near 1200 cm -1 and the absorption appearing near 1370 cm -1 .
  • 1200 cm -1 is the absorption of ⁇ -crystals of nylon 6, and 11370 cm -1 is the absorption unrelated to crystals.
  • Planar Orientation Degree of Film For a sample, the refractive index (nx), the refractive index (ny), and the refractive index (nz) in the longitudinal direction, width direction, and thickness direction of the film were measured using an Abbe refractometer with sodium D line as a light source according to JIS K 7142-1996, Method A, and the planar orientation coefficient was calculated according to the formula (1).
  • Planar orientation coefficient ( ⁇ P) (nx+ny)/2-nz
  • Ethanol Permeability Absorbent cotton soaked in ethanol was placed in a cup, the cup was covered with a film, and the cup was left for 24 hours under conditions of a relative humidity of 50% and a temperature of 40° C., after which the ethanol permeability was measured from the weight loss.
  • One end of the cylindrical film was fixed to the fixed head side of the Gelbo Flex Tester, and the other end was fixed to the movable head side, with an initial gripping distance of 7 inches.
  • a bending fatigue test was performed 1000 times at a speed of 40 times/min, in which a 440-degree twist was given in the first 3.5 inches of the stroke, and the entire stroke was completed in a linear horizontal motion for the next 2.5 inches, and the number of pinholes generated in the laminate film was counted.
  • the measurements were carried out in an environment of 1°C.
  • the test film was placed on a filter paper (Advantec, No. 50) with the L-LDPE film side facing down, and the four corners were fixed with Cellophane Tape (registered trademark).
  • Ink (Pilot ink (product number INK-350-Blue) diluted 5 times with pure water) was applied to the test film and spread over the entire surface using a rubber roller. After wiping off unnecessary ink, the test film was removed, and the number of ink dots on the filter paper was counted.
  • Resin composition constituting base layer A Polyamide 6 (manufactured by Toyobo Co., Ltd., relative viscosity 2.8, melting point 220° C.) Resin other than polyamide 6 (b) ⁇ Polybutylene adipate terephthalate PBAT (BASF Ecoflex F-Blend C1200) - Polyester elastomer PEE (Tefabloc TPC A1400N, manufactured by Mitsubishi Chemical Corporation) ⁇ Polyamide elastomer PAE (Arkema PEBAX 4033 SA01) ⁇ Polyolefin elastomer POE (MELSON H6051, manufactured by Tosoh Corporation) Polybutylene succinate PBS (Showa Polymer Co., Ltd., Bionolle 1001) Polyamide 11: (Arkema Rilsan, melting point 186°C)
  • Resin composition constituting functional layer B Polyamide 6 (manufactured by Toyobo Co., Ltd., relative viscosity 2.8, melting point 220° C.) 90% by mass; Polyamide MXD6 (manufactured by Mitsubishi Gas Chemical Co., Inc., relative viscosity 2.1, melting point 237° C.) 10% by mass; Porous silica fine particles (manufactured by Fuji Silysia Chemical Ltd., average particle size 2.0 ⁇ m, pore volume 1.6 ml/g) 0.54% by mass; Fatty acid bisamide (ethylene bis stearic acid amide, manufactured by Kyoeisha Chemical Co., Ltd.) 0.15% by mass
  • Examples 1 to 7 The raw materials for the base layer: A layer and the functional layer: B layer were mixed in the formulation shown in Table 1. Using an apparatus consisting of two extruders and a 380 mm wide co-extrusion T-die, lamination was performed using the feed block method in a configuration of functional layer: B layer/base layer: A layer/functional layer: B layer, and the molten resin of the resin composition shown in Table 1 was extruded from the T-die into a film, which was then cast onto a cooling roll whose temperature was controlled at 20°C and electrostatically adhered to obtain an unstretched film with a thickness of 100 to 200 ⁇ m.
  • the unstretched film obtained was fed to a roll-type stretching machine, where it was stretched 1.73 times in the MD direction at 80°C using the difference in peripheral speed of the rolls, and then further stretched 1.85 times at 70°C.
  • the uniaxially stretched film was then fed to a tenter-type stretching machine, preheated at 60°C, and stretched 1.2 times in the TD direction at 120°C, 1.7 times at 130°C, and 2.0 times at 160°C, heat-set at 218°C, and then relaxed by 7% at 218°C.
  • One surface was then corona discharge-treated to obtain a biaxially stretched polyamide film.
  • the extruder output was adjusted so that the thickness of the base layer was 8 ⁇ m and the thickness of the functional layer was 1 ⁇ m on each side, relative to the thickness of the biaxially stretched polyamide film (10 ⁇ m).
  • Example 8 A biaxially oriented polyamide film was obtained in the same manner as in Examples 1 to 7, except that the feed block configuration and the extrusion rate of the extruder were adjusted so that the total thickness of the biaxially oriented polyamide film was 15 ⁇ m, the thickness of the base layer was 12 ⁇ m, and the thickness of the functional layer was 1.5 ⁇ m on each side with the composition shown in Table 1.
  • the films described in Examples 1 to 9 had good pinhole resistance, dimensional stability, puncture strength, and ethanol permeability, making them suitable for use as alcohol evaporative agents.
  • the plane orientation degree was 0.5 or more, indicating high orientation
  • the crystallization parameter was 1.0 or more, indicating high crystallization.
  • the resin (b) was dispersed with a dispersion diameter of 1 ⁇ m or more, forming an interface with relatively low adhesion strength with the polyamide resin, and it is believed that this interface was utilized to improve ethanol permeability.
  • the flexibility of the base layer A itself was improved by the dispersion of resin (b), which is believed to have improved pinhole resistance.
  • the film described in Comparative Example 1 had excellent dimensional stability and puncture strength, but poor pinhole resistance and ethanol permeability.
  • the plane orientation ⁇ P was 0.05 or more and the crystallization parameter was in the range of 1 to 1.5, the dimensional stability and puncture strength were good, but it is believed that the brittleness of the film increased due to the progress of crystallization, causing pinhole resistance and ethanol permeability to decrease.
  • Comparative Example 2 has a thickness of 15 ⁇ m, since the base layer does not contain any resin other than polyamide 6, no dispersion structure due to phase separation occurs, and ethanol does not permeate through the dispersion interface, so the ethanol permeability is not satisfactory for use as an alcohol evaporant.
  • the film described in Comparative Example 3 was thick at 25 ⁇ m, and the base layer contained no resin other than polyamide 6, so the pinhole resistance and ethanol permeability were not satisfactory for use as an alcohol vaporizer.
  • the film described in Comparative Example 4 had a small amount of PBAT added as resin (b), and the interface between polyamide 6 and PBAT was small, resulting in insufficient ethanol permeability.
  • the film described in Comparative Example 6 was added with 40% PBAT, and as a result, the ethanol permeability increased to 16000 g ⁇ m/ m2 ⁇ 24 hr (50% RH/40°C). As an ethanol transpiration agent, the ethanol transpiration was rapid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Le but de la présente invention est de fournir un film de polyamide à orientation biaxiale ayant une excellente résistance des perforations au pliage, une excellente résistance au perçage, une excellente stabilité dimensionnelle et ayant également une excellente perméabilité à l'éthanol. La présente invention concerne un film de polyamide à orientation biaxiale contenant du polyamide en tant que constituant principal. Le film de polyamide à orientation biaxiale présente un taux de perméation à l'éthanol de 6000 à 10 000g·μm/m2·24hr (50%RH/40°C), une épaisseur de 15 µm ou moins, un rapport de retrait thermique de 2,0% ou moins dans chacun des sens de déplacement de film et de largeur de film, un paramètre de cristallisation de surface de 1,0 à 1,5, et une résistance au perçage de 6,0 N ou plus.
PCT/JP2024/011079 2023-03-30 2024-03-21 Film de polyamide à orientation biaxiale Pending WO2024203741A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010158775A (ja) * 2008-12-12 2010-07-22 Kohjin Co Ltd 延伸ポリアミドフィルム及びその製造方法
JP2010167652A (ja) * 2009-01-22 2010-08-05 Kohjin Co Ltd 水蒸気及びアルコール透過性に優れたポリアミド系積層フィルム
JP2010241901A (ja) * 2009-04-02 2010-10-28 Kohjin Co Ltd アルコール透過性ポリアミドフィルム
JP2021130770A (ja) * 2020-02-19 2021-09-09 三菱ケミカル株式会社 ポリアミド系樹脂フィルムおよび該フィルムを用いた包装体
JP2022077210A (ja) * 2020-11-11 2022-05-23 三菱ケミカル株式会社 ポリアミド系二軸延伸フィルムおよび包装体
JP2022169513A (ja) * 2017-09-28 2022-11-09 東洋紡株式会社 ラミネートフィルム
WO2023026593A1 (fr) * 2021-08-23 2023-03-02 三菱瓦斯化学株式会社 Film étiré, film multicouche et matériau d'emballage

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010158775A (ja) * 2008-12-12 2010-07-22 Kohjin Co Ltd 延伸ポリアミドフィルム及びその製造方法
JP2010167652A (ja) * 2009-01-22 2010-08-05 Kohjin Co Ltd 水蒸気及びアルコール透過性に優れたポリアミド系積層フィルム
JP2010241901A (ja) * 2009-04-02 2010-10-28 Kohjin Co Ltd アルコール透過性ポリアミドフィルム
JP2022169513A (ja) * 2017-09-28 2022-11-09 東洋紡株式会社 ラミネートフィルム
JP2021130770A (ja) * 2020-02-19 2021-09-09 三菱ケミカル株式会社 ポリアミド系樹脂フィルムおよび該フィルムを用いた包装体
JP2022077210A (ja) * 2020-11-11 2022-05-23 三菱ケミカル株式会社 ポリアミド系二軸延伸フィルムおよび包装体
WO2023026593A1 (fr) * 2021-08-23 2023-03-02 三菱瓦斯化学株式会社 Film étiré, film multicouche et matériau d'emballage

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