WO2025084406A1 - ガスバリアフィルムおよび製造方法 - Google Patents

ガスバリアフィルムおよび製造方法 Download PDF

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WO2025084406A1
WO2025084406A1 PCT/JP2024/037206 JP2024037206W WO2025084406A1 WO 2025084406 A1 WO2025084406 A1 WO 2025084406A1 JP 2024037206 W JP2024037206 W JP 2024037206W WO 2025084406 A1 WO2025084406 A1 WO 2025084406A1
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Prior art keywords
gas barrier
layer
barrier layer
barrier film
film
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English (en)
French (fr)
Japanese (ja)
Inventor
友輔 鍬形
健司 松久
卓行 谷
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Toppan Holdings Inc
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Toppan Holdings Inc
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    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation

Definitions

  • the present invention relates to a gas barrier film, and more particularly to a gas barrier film suitable for packaging foods, medicines, precision electronic parts, etc. A method for producing this gas barrier film will also be mentioned.
  • This application claims priority based on Japanese Patent Application No. 2023-180257, filed on October 19, 2023, the contents of which are incorporated herein by reference.
  • Packaging materials used for food and pharmaceuticals are often required to have gas barrier properties that prevent the contents from deteriorating and to preserve their functions and properties, preventing oxygen, water vapor, and other gases that can degrade the contents and permeate the packaging material.
  • Gas barrier films that use metal foils such as aluminum as a gas barrier layer, which are less affected by temperature and humidity, are known as packaging materials with gas barrier properties.
  • gas barrier film is one in which a vapor-deposited film of inorganic oxides such as silicon oxide and aluminum oxide is formed by vacuum deposition or sputtering on a base film made of a polymeric material (see, for example, Patent Document 1). These gas barrier films are transparent and have the ability to block gases such as oxygen and water vapor.
  • the inventors discovered that when the gas barrier layer is made of a vapor-deposited film of silicon oxide, there is a tendency for the water vapor barrier properties to vary relatively widely. The inventors conducted extensive research to reduce this tendency, and completed the present invention.
  • the objective is to provide a gas barrier film that has a gas barrier layer containing silicon oxide and has stable water vapor barrier properties.
  • a first aspect of the present invention is a gas barrier film comprising a base layer and a gas barrier layer formed on the base layer and containing silicon oxide.
  • the ratio of the peak area of an absorption peak from 3100 cm -1 to 3700 cm -1 attributable to OH bonds to the peak area of an absorption peak from 720 cm -1 to 1320 cm -1 attributable to Si-O-Si bonds is 0.25 or less.
  • the overcoat layer contains at least one of a metal alkoxide, a hydrolysate of a metal alkoxide, a reaction product of a metal alkoxide, and a reaction product of a hydrolysate of a metal alkoxide, and a water-soluble polymer.
  • the overcoat layer contains at least one of a silane coupling agent, a hydrolysate of a silane coupling agent, a reaction product of a silane coupling agent, and a reaction product of a hydrolysate of a silane coupling agent.
  • a second aspect of the present invention is a method for producing the gas barrier film according to the first aspect.
  • a film formation apparatus is prepared that includes a film formation chamber and an unwinding/winding chamber, and has gas adsorption devices (devices that condense and adsorb gas (water vapor)) in the film formation chamber and the unwinding/winding chamber.
  • a roll-shaped base layer is attached to an unwinding roll arranged in the unwinding/winding chamber, and the gas adsorption devices in the film formation chamber and the unwinding/winding chamber are operated to set the partial pressure value of m/z18 in the film formation chamber to 0.05 Pa or less.
  • a gas barrier layer is formed on the base layer passing through the film formation chamber using a deposition material that is a mixture of a Si material and a SiO2 material.
  • the present invention provides a gas barrier film that has a gas barrier layer containing silicon oxide and has stable water vapor barrier properties.
  • FIG. 1 is a schematic cross-sectional view of a gas barrier film according to a first embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing an example of a manufacturing apparatus for the gas barrier film.
  • FIG. 2 is a schematic cross-sectional view of a gas barrier film according to a second embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a modified example of the gas barrier film.
  • FIG. 1 is a schematic cross-sectional view of a gas barrier film 1 according to this embodiment.
  • the gas barrier film 1 includes a base layer 10 and a gas barrier layer 20 provided on one surface of the base layer 10.
  • materials that themselves have high gas barrier properties such as polyethylene naphthalate, polyimides, and polyethersulfone.
  • polyethylene terephthalate polyethylene
  • polypropylene polypropylene
  • the thickness of the base material layer 10 is preferably flexible and rigid enough to withstand processing, particularly when used as a packaging material, and can be about 9 ⁇ m to 100 ⁇ m. More preferably, it is 9 ⁇ m to 90 ⁇ m, 9 ⁇ m to 70 ⁇ m, 9 ⁇ m to 50 ⁇ m, or 9 ⁇ m to 30 ⁇ m. A base material layer 10 with a thickness within this range has appropriate flexibility and can be wound into a roll, making it easy to handle.
  • the base material layer 10 may be in the form of a long material or a sheet material, but a long material is preferably used.
  • the longitudinal length of the long base material layer 10 is not particularly limited, but a resin film of, for example, 10 m or more is preferably used. There is no upper limit to the length, and it may be, for example, about 10 km.
  • the surface of the base layer 10 may contain additives such as antistatic agents, UV absorbers, plasticizers, and slip agents as necessary. Furthermore, in order to enhance adhesion, the surface of the base layer 10 may be subjected to physical treatments such as corona treatment, frame treatment, plasma treatment, and easy-adhesion treatment, or chemical treatment modification treatments such as chemical treatment with acids or alkalis.
  • the surface of the base layer 10 contributes to the density in the initial growth stage of vacuum film deposition when forming the gas barrier layer, and from this viewpoint it is preferable that it is as smooth as possible.
  • the gas barrier layer 20 plays a major role in the gas barrier properties exhibited by the gas barrier film 1, and is a film made of an inorganic oxide that contains at least silicon oxide (SiOx).
  • the ratio (O/Si) of the number of oxygen (O) atoms to the number of silicon (Si) atoms is 1.0 or more and 1.9 or less at least on the surface of the gas barrier layer 20.
  • O/Si is more preferably 1.3 or more.
  • O/Si is preferably 1.3 or more and 1.9 or less, more preferably 1.4 or more and 1.9 or less, 1.41 or more and 1.9 or less, 1.45 or more and 1.9 or less, 1.5 or more and 1.9 or less, 1.6 or more and 1.9 or less, 1.7 or more and 1.9 or less, 1.41 or more and 1.85 or less, 1.41 or more and 1.8 or less, 1.45 or more and 1.85 or less, or 1.45 or more and 1.8 or less.
  • the O/Si of the gas barrier layer 20 can be evaluated by an analysis device such as an XPS (X-ray photoelectron spectroscopy).
  • sputter etching with argon (Ar) ions is sometimes used for analysis inside the film, but since a transparent oxide film layer containing silicon (Si) is reduced and the correct ratio of the number of silicon (Si) atoms to the number of oxygen (O) atoms (O/Si) cannot be obtained, it is preferable to analyze the surface of the layer.
  • the method for forming the gas barrier layer 20 there are no limitations on the method for forming the gas barrier layer 20, and known film formation methods such as vacuum deposition, ion plating, sputtering, and plasma enhanced chemical vapor deposition (PECVD) can be used, but vacuum deposition is particularly preferred due to its excellent productivity.
  • vacuum deposition is particularly preferred due to its excellent productivity.
  • As a means for heating the material in the vacuum deposition method resistance heating, high frequency induction heating, electron beam heating, etc. can be used.
  • the gas barrier layer 20 can be formed densely, improving the barrier properties.
  • the partial pressure value of m/z 18 measured by a partial pressure meter (a quadrupole mass spectrometer using a Faraday cup) during film formation is set to be equal to or less than 0.05 Pa. If the partial pressure of m/z 18 measured by a mass spectrometer during film formation exceeds 0.09 Pa, the amount of water molecules in the deposition atmosphere increases, which undesirably increases the amount of OH in the inorganic oxide film and the amount of OH and H bonded to Si.
  • m/z in italics, to be precise is a value defined as a dimensionless quantity obtained by dividing the mass of an ion by the unified atomic mass unit, and further dividing it by the absolute value of the charge number of the ion, and is the value adopted on the horizontal axis of the mass spectrum measured by a mass spectrometer.
  • m/z is defined as an academic term by the International Union of Pure and Applied Sciences (IUPAC).
  • m/z18 is an m/z derived from H 2 O + ions related to water.
  • a typical method for adjusting the partial pressure of m/z18 during film formation is to provide a mechanism for adsorbing gas in the film formation environment.
  • a device for condensing and adsorbing gas water vapor
  • the effect of reducing water vapor in the film formation chamber can be obtained. This makes it possible to suppress the partial pressure of m/z18 during film formation to 0.05 Pa or less.
  • the effect of reducing water vapor derived from moisture released from the substrate can be obtained.
  • Moisture released from the substrate may inhibit the initial film growth of the gas barrier layer.
  • a dense gas barrier layer can be formed in the initial film growth, and stable water vapor barrier properties can be obtained not only in the initially formed film but also in the entire gas barrier layer.
  • a Meissner coil, a cryopanel, a cryopump, a sorption pump, an ion pump, or a getter pump is preferably used, and a Meissner coil or a cryopanel is more preferably used because it can increase the adsorption area.
  • the cooling temperature is preferably ⁇ 100° C. or less, and more preferably ⁇ 110° C. or less, from the viewpoint of obtaining sufficient performance of condensing and adsorbing gas.
  • the inventors discovered that by adjusting the above-mentioned O/Si value and the partial pressure of m/z18 during film formation to a predetermined range, the gaps between molecules in the inorganic oxide film formed are smaller than in a typical deposition process. In such an inorganic oxide film, there is less room for adsorbed water to enter, and the amount of OH in the inorganic oxide film is reduced. Furthermore, the reduction in dangling bonds also reduces the amount of OH and H that can bond with Si, so by using this as the gas barrier layer 20, the stability of the water vapor barrier properties exhibited can be improved.
  • the above-mentioned state of the gas barrier layer 20 can be evaluated by calculating the amount of OH, the amount of Si-OH, the amount of Si-H, and the like using FT-IR (Fourier transform infrared spectrophotometer) analysis.
  • FT-IR Fastier transform infrared spectrophotometer
  • a baseline is drawn connecting plots at both ends of a defined range for each of the peak area derived from Si-O-Si bonds (720 cm -1 to 1320 cm -1 ), the peak area derived from OH bonds ( 3100 -1 to 3700 cm -1 ) , the peak area derived from Si-OH bonds (830 -1 to 910 cm -1 ), and the peak area derived from Si-H bonds (2100 -1 to 2200 cm -1 ), and the area of the part surrounded by the spectrum and the baseline is calculated using software attached to the device. At this time, the area below the baseline is ignored and not included in the area.
  • FT-IR analysis is often measured by the ATR method, but the inventors' investigation has revealed that data before correction such as ATR correction and baseline correction is performed more accurately reflects the properties of the gas barrier layer 20. For this reason, the parameter values mentioned hereinafter are defined as those of uncorrected data obtained by FT-IR analysis.
  • the ratio of the peak area derived from OH bonds (3100 -1 to 3700 cm -1 ) to the peak area derived from Si-O-Si bonds (720 cm -1 to 1320 cm -1 ) is 0.25 or less; the ratio of the peak area derived from Si-OH bonds (830 -1 to 910 cm -1 ) to the peak area derived from Si-O-Si bonds (720 cm -1 to 1320 cm -1 ) is 0.025 or less; and the ratio of the peak area derived from Si-H bonds (2100 -1 to 2200 cm -1 ) to the peak area derived from Si-O-Si bonds (720 cm -1 to 1320 cm -1 ) is 0.003 or less.
  • the OH bond is an index correlating with the amount of moisture adsorbed in the gas barrier layer 20. It is considered that the smaller the ratio of the peak area originating from the OH bond (3100 -1 to 3700 cm -1 ) to the peak area originating from the Si-O-Si bond (720 cm -1 to 1320 cm -1 ), the smaller the amount of moisture adsorbed in the structure of the gas barrier layer 20.
  • the Si—OH bond is an index correlating with the amount of moisture adsorption and the number of dangling Si bonds in the gas barrier layer 20.
  • the Si—H bond is an index correlating with the amount of dangling Si bonds in the gas barrier layer 20.
  • the gas barrier film according to the present invention exhibits stable gas barrier properties by including the gas barrier layer 20 that satisfies at least one of the above-mentioned indices. Furthermore, the gas barrier properties are stable at a high level even in mass production processes, and a high-quality gas barrier film can be efficiently produced.
  • the chemical bond state of the gas barrier layer 20 can also be analyzed using X-ray photoelectron spectroscopy (hereinafter sometimes referred to as "XPS").
  • XPS is a method of irradiating an object to be measured with X-rays and analyzing the energy of photoelectrons emitted from the surface of the object to be measured, and can analyze the composition and chemical bond state of elements in a region several nm deep from the surface of the object to be measured.
  • the chemical bond state related to silicon oxide in the inorganic oxide film layer 13 includes SiO 2 (Si 4+ ), three suboxide components Si 3+ , Si 2+ , and Si + , and five Si.
  • SiO 2 When a narrow spectrum of Si 2p is measured by XPS, SiO 2 is observed near 103.5 to 104.5 eV, and Si 3+ , Si 2+ , Si + , and Si are observed at positions shifted to the lower energy side than SiO 2 , each separated by about 1 eV.
  • the narrow spectrum of Si 2p is measured using XPS with a pass energy of about 10 eV using a commonly used X-ray source of MgK ⁇ or AlK ⁇ , the peaks of each bond are not separated but are observed in a composite form. Therefore, in the narrow spectrum of Si 2p , in the case of a SiO 2 film, the peak top is detected near 103.5 to 104.5 eV, but in the case of a silicon oxide film containing mainly SiO 2 and a plurality of other chemical bond states, the peak top shifts to the range of 101 to 103.5 eV.
  • the full width at half maximum (FWHM) of the Si 2p peak is broadened.
  • the C 1s peak detected due to the surface contamination hydrocarbon is set to 284.6 eV.
  • sputter etching using argon (Ar) ions is sometimes used in XPS for depth analysis. However, reduction and mixing occur due to collisions of argon (Ar) ions, which may cause changes to the chemical bonding state in the original silicon oxide film. Therefore, it is preferable to analyze the surface without using sputter etching.
  • XPS X-ray photoelectron spectroscopy
  • b/a is preferably 0.123 or more and 0.153 or less, more preferably 0.123 or more and 0.148 or less, 0.123 or more and 0.147 or less, 0.123 or more and 0.145 or less, 0.123 or more and 0.143 or less, 0.123 or more and 0.138 or less, 0.123 or more and 0.133 or less, 0.126 or more and 0.147 or less, 0.128 or more and 0.147 or less, 0.128 or more and 0.145 or less, or 0.128 or more and 0.143 or less.
  • the gas barrier layer 20 is preferably amorphous. In the case of a polycrystalline film, grain boundaries are generated, but since the gas barrier layer 20 is an amorphous film, it is a film without grain boundaries, and therefore it is possible to reduce the permeation paths of gas molecules. Whether the gas barrier layer 20 is amorphous or not can be evaluated by a known method. For example, it can be evaluated by whether or not there is a crystalline diffraction peak in an X-ray diffraction pattern obtained by an analytical device such as an XRD (X-ray diffraction device).
  • an analytical device such as an XRD (X-ray diffraction device).
  • the thickness of the gas barrier layer 20 varies depending on the configuration and deposition method used, but can generally be set appropriately within the range of 1 to 200 nm. If the thickness of the gas barrier layer 20 is less than 1 nm, a uniform film may not be obtained or the film thickness may be insufficient, and the gas barrier layer may not function fully. If the thickness of the gas barrier layer 20 exceeds 200 nm, external factors such as bending and pulling may cause cracks after deposition, resulting in a loss of barrier properties.
  • the thickness is preferably within the range of 5 to 150 nm, and more preferably within the ranges of 10 to 120 nm, 10 to 60 nm, 10 to 50 nm, 10 to 45 nm, and 10 to 40 nm.
  • FIG. 2 is a schematic diagram showing an example of a gas barrier film manufacturing apparatus according to an embodiment of the present invention.
  • a film forming apparatus 100 which includes a vacuum film forming chamber 40 and an unwinding/winding chamber 50 in which a winding roll 42 is arranged.
  • the film forming chamber 40 and the unwinding/winding chamber 50 are separated by a partition wall and have independent exhaust systems.
  • a gas adsorption device 48 is installed in the film forming chamber 40, and a gas adsorption device 49 having a function similar to that of the gas adsorption device 48 is also installed near the unwinding roll 42 in the unwinding/winding chamber 50.
  • the gas adsorption device 49 may be of the same type as the gas adsorption device 48 or a different type as long as it condenses and adsorbs gas.
  • a plastic film 41 to become the base layer 10 is set on a winding roll 42.
  • the plastic film 41 unwound from the winding roll 42 passes through a film-forming roll 43 exposed in the film-forming chamber 40, and is then taken up by a take-up roll 44.
  • a vapor deposition material 45 for forming the gas barrier layer 20 is set in the film-forming chamber 40, and an electron beam gun 46 is installed as a vapor deposition means.
  • the vapor deposition material 45 heated by the electron beam becomes vapor deposition particles 47 and is vapor-deposited on the plastic film.
  • the gas barrier layer 20 is formed on the plastic film 41.
  • the deposition material 45 includes a material obtained by mixing a Si material and a SiO2 material.
  • the Si material includes a material containing a simple Si element and/or a Si element other than SiO2.
  • the O/Si ratio of the gas barrier layer can be adjusted. 2
  • the deposition material 45 is heated by an electron beam deposition method using an electron beam gun 46, but the deposition material 45 may be heated and evaporated by a resistance heating method or a high-frequency induction heating method.
  • the resistance heating method may be a method of directly resistively heating a crucible filled with the material, or may be another method. Either method requires that the device be configured to achieve a high film formation rate.
  • the manufacturing equipment for the gas barrier layer deposition film is not limited to this form, and if necessary, a plasma pretreatment device may be installed in the unwinding/winding chamber, and a reactive gas introduction device may be installed in the deposition chamber. There are also no particular limitations on the arrangement of the rolls.
  • a gas barrier layer is provided on both sides of the base layer 10.
  • the two gas barrier layers may be the same or different.
  • Plasma treatment is performed on the substrate layer 10, and the gas barrier layer 20 is laminated on the plasma-treated surface to improve the adhesion and gas barrier properties between the substrate layer 10 and the gas barrier layer 20.
  • various known plasma treatments such as RIE (Reactive Ion Etching) treatment, corona treatment, hollow anode plasma treatment, and flat plate plasma treatment, as well as various known surface treatments such as ozone treatment and ion beam treatment can be adopted as treatments that have the same effect as the plasma treatment.
  • gas species used for the plasma treatment known discharge gases such as argon, oxygen, nitrogen, and helium can be used.
  • FIG. 3 is a schematic cross-sectional view of the gas barrier film 2 according to this embodiment.
  • the gas barrier film 2 further includes an overcoat layer 30 provided on the gas barrier layer 20.
  • the overcoat layer 30 is a layer containing an organic polymer resin, and has the function of protecting the gas barrier layer 20 and preventing the occurrence of cracks due to friction or bending.
  • the overcoat layer 30 is obtained, for example, by forming a coating film made of a coating agent on the gas barrier layer 20 by a wet coating method and drying the coating film.
  • coating film refers to a wet film
  • film refers to a dry film.
  • the overcoat layer 30 may be a film (hereinafter sometimes referred to as an "organic-inorganic composite film") that contains at least one of a metal alkoxide and its hydrolysate or its reaction product, and a water-soluble polymer. It is preferable that the overcoat layer 30 further contains at least one of a silane coupling agent and its hydrolysate.
  • metal alkoxides and hydrolysates thereof contained in the organic-inorganic composite film include those represented by the general formula M(OR)n, such as tetraethoxysilane [Si( OC2H5 ) 4 ] and triisopropoxyaluminum [Al( OC3H7 ) 3 ], and their hydrolysates.
  • M(OR)n such as tetraethoxysilane [Si( OC2H5 ) 4 ] and triisopropoxyaluminum [Al( OC3H7 ) 3 ]
  • One of these may be contained alone, or two or more may be contained in combination.
  • the total content of at least one of the metal alkoxides and their hydrolysates, or their reaction products in the organic-inorganic composite film can be, for example, 40 to 70 mass%.
  • the lower limit of the total content of at least one of the metal alkoxides and their hydrolysates, or their reaction products in the organic-inorganic composite film can be 50 mass%.
  • the upper limit of the total content of at least one of the metal alkoxides and their hydrolysates, or their reaction products in the organic-inorganic composite film can be 65 mass%.
  • the water-soluble polymer contained in the organic-inorganic composite film is not particularly limited, and examples include polyvinyl alcohol-based polymers, acrylic polyol-based polymers, and polysaccharides such as starch, methyl cellulose, and carboxymethyl cellulose. From the viewpoint of further improving the gas barrier properties, it is preferable to include a polyvinyl alcohol-based polymer.
  • the number average molecular weight of the water-soluble polymer can be, for example, 40,000 to 180,000.
  • Water-soluble polymers such as polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate (including partial saponification). These water-soluble polymers may have several tens of percent of acetate groups remaining, or may have only a few percent of acetate groups remaining.
  • the content of the water-soluble polymer in the organic-inorganic composite film can be, for example, 15 to 50 mass %. If the content of the water-soluble polymer is 20 to 45 mass %, the gas barrier properties of the organic-inorganic composite film can be further improved, which is preferable.
  • the silane coupling agents and their hydrolysates contained in the organic-inorganic composite film include silane coupling agents having an organic functional group.
  • Such silane coupling agents and their hydrolysates include ethyltrimethoxysilane, vinyltrimethoxysilane, ⁇ -chloropropylmethyldimethoxysilane, ⁇ -chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, and their hydrolysates.
  • One of these may be contained alone, or two or more may be contained in combination.
  • silane coupling agent and its hydrolysate has an epoxy group as an organic functional group.
  • examples of silane coupling agents having an epoxy group include ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
  • Silane coupling agents having an epoxy group and their hydrolysates may have an organic functional group other than the epoxy group, such as a vinyl group, an amino group, a methacryl group, or a ureyl group.
  • a silane coupling agent having an organic functional group and its hydrolysate can further improve the gas barrier properties of the overcoat layer 30 and the adhesion to the gas barrier layer 20 through the interaction between the organic functional group and the hydroxyl group of the water-soluble polymer.
  • the epoxy groups of the silane coupling agent and its hydrolysate and the hydroxyl groups of polyvinyl alcohol can improve the adhesion between the overcoat layer 30 and the gas barrier layer 20 through the interaction.
  • the total content of the silane coupling agent and its hydrolysate, or at least one of its reaction products in the organic-inorganic composite film can be, for example, 1 to 15 mass%. If the total content of the silane coupling agent and its hydrolysate, or at least one of its reaction products is 2 to 12 mass%, the gas barrier properties of the organic-inorganic composite film can be further improved, which is preferable.
  • the thickness of the overcoat layer 30 can be set according to the required gas barrier properties, and can be, for example, 0.05 to 5 ⁇ m.
  • the thickness of the overcoat layer 30 is preferably 0.05 to 1 ⁇ m, and more preferably 0.1 to 0.5 ⁇ m. If the thickness of the overcoat layer 30 is 0.05 ⁇ m or more, sufficient oxygen barrier properties are easily obtained. If the thickness of the overcoat layer 30 is 1 ⁇ m or less, it is easy to form a uniform coating surface, and drying loads and manufacturing costs can be suppressed.
  • a gas barrier film having the above-mentioned organic-inorganic composite coating as the overcoat layer 30 maintains excellent gas barrier properties even after undergoing boiling or retort sterilization.
  • an undercoat layer 15 may be further provided between the base layer 10 and the gas barrier layer 20, for example as in the modified example shown in FIG. 4. That is, FIG. 4 shows a modified gas barrier film 2A according to the second embodiment, but the same modification may be made to the first embodiment shown in FIG. 1.
  • a pair of an undercoat layer 15 and a gas barrier layer 20 may be provided on both sides of the base layer 10.
  • the undercoat layer 15 is provided on the base layer 10 to increase the adhesion between the base layer 10 and the gas barrier layer 20, prevent peeling of the gas barrier layer 20, and provide protection against mechanical damage such as scratches and abrasions.
  • the material of the undercoat layer 15 is not particularly limited, but may be a thermosetting resin, a thermoplastic resin, an ultraviolet-curable resin, an electron beam-curable resin, or the like.
  • Thermosetting resins that form the undercoat layer 15 include thermosetting urethane resins made of acrylic polyol resins and isocyanate prepolymers, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, and the like.
  • the undercoat layer 15 is formed using a composite of an acrylic polyol resin containing hydroxyl groups and/or organic acid groups and an isocyanate compound having at least two NCO groups in the molecule, thereby improving the adhesion between the substrate layer 10 and the gas barrier layer 20.
  • An acrylic polyol resin is a polymeric compound obtained by polymerizing a (meth)acrylic acid derivative monomer, or a polymeric compound obtained by copolymerizing a (meth)acrylic acid derivative monomer with other monomers, which has hydroxy groups at the ends and side chains and reacts with the NCO groups of isocyanate compounds.
  • (Meth)acrylic acid derivative monomers have hydroxy groups at the ends and side chains. Examples of (meth)acrylic acid derivative monomers include hydroxyethyl (meth)acrylate and hydroxybutyl (meth)acrylate.
  • the above other monomers can be copolymerized with (meth)acrylic acid derivative monomers having hydroxy groups at the end and at the side chain.
  • examples of the above other monomers include (meth)acrylic acid derivative monomers having an alkyl group at the side chain, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and t-butyl (meth)acrylate, (meth)acrylic acid derivative monomers having a carboxy group at the side chain, such as (meth)acrylic acid, and (meth)acrylic acid derivative monomers having an aromatic ring or a cyclic structure at the side chain, such as benzyl (meth)acrylate and cyclohexyl (meth)acrylate.
  • (meth)acrylic acid derivative monomers styrene monomers, cyclohexylmaleimide monomers, and phenylmaleimide monomers are possible.
  • the above other monomers may themselves have hydroxy groups at the end and at the side chain.
  • the acrylic polyol resin is preferably a polymeric compound obtained by polymerizing a (meth)acrylic acid derivative monomer having a carboxy group on the side chain, such as (meth)acrylic acid.
  • a gas barrier laminate film with higher water vapor barrier properties can be obtained by forming the layer using a composite of an acrylic polyol resin obtained by polymerizing a monomer having a carboxy group and an isocyanate compound.
  • the hydroxyl group-containing acrylic polyol resin that can be used for the undercoat layer 15, but it is desirable for the hydroxyl group value to be 50 mgKOH/g or more and 250 mgKOH/g or less.
  • the hydroxyl group value (mgKOH/g) is an index of the amount of hydroxyl groups in the acrylic polyol resin, and indicates the number of mg of potassium hydroxide required to acetylate the hydroxyl groups in 1 g of the acrylic polyol resin.
  • the weight average molecular weight of the acrylic polyol resin but specifically, it is preferably 3,000 or more and 200,000 or less. In particular, it is preferably 5,000 or more and 100,000 or less. Furthermore, it is more preferably 5,000 or more and 40,000 or less.
  • the isocyanate compound used has two or more NCO groups in its molecule.
  • monomeric isocyanates include aromatic isocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), and tetramethylxylylene diisocyanate (TMXDI), and aliphatic isocyanates such as hexamethylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H12MDI). Polymers or derivatives of these monomeric isocyanates can also be used. For example, there are trimer nurate types, adduct types reacted with 1,1,1-trimethylolpropane, and biuret types reacted with biuret.
  • the isocyanate compound can be selected from the above-mentioned isocyanate compounds or their polymers and derivatives, and one or a combination of two or more types can be used.
  • One example of the undercoat layer 15 is formed by applying a solution consisting of a composite of the above-mentioned acrylic polyol resin and the above-mentioned isocyanate compound, and a solvent onto the substrate layer 10, and then reacting and curing the solution.
  • the equivalent ratio (NCO/OH) of the NCO group of the isocyanate compound to the hydroxy group of the acrylic polyol resin is preferably 0.3 or more and 2.5 or less.
  • the solvent used here may be any solvent that dissolves the above-mentioned acrylic polyol resin and the isocyanate compound.
  • solvent examples include methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, dioxolane, tetrahydrofuran, etc. In practice, one or more of these solvents can be used in combination.
  • the thermoplastic resin forming the undercoat layer 15 is appropriately selected from polyols having two or more hydroxyl groups, such as acrylic polyol, polyester polyol, polycarbonate polyol, polyether polyol, polycaprolactone polyol, and epoxy polyol, polyvinyl resins such as polyvinyl acetate and polyvinyl chloride, polyvinylidene chloride resin, polystyrene resin, polyethylene resin, polypropylene resin, and polyurethane resin. Furthermore, these may be mixed in any ratio.
  • the hydroxyl value of the polyol is not particularly limited, but is preferably 10 mgKOH/g or more and 250 mgKOH/g or less.
  • the ultraviolet-curable resin or electron-beam-curable resin forming the undercoat layer 15 is not particularly limited, but it is desirable to include at least a resin having a hydroxyl value in the range of 10 to 100 mgKOH/g as an organic polymer resin. Also, it is not particularly limited, but it is desirable to include at least a resin having an acid value in the range of 10 to 100 mgKOH/g as an organic polymer resin.
  • the acid value indicates the number of mg of potassium hydroxide required to neutralize the free fatty acid, resin acid, etc. contained in 1 g of sample. Also, it is desirable to include at least a thermoplastic resin as an organic polymer resin.
  • the hydroxyl value or acid value is less than 10 mgKOH/g, the chemical bonding strength between the functional group and the surface of the gas barrier layer 20 becomes weak, and the adhesion with the gas barrier layer 20 tends to be low. If the hydroxyl value or acid value exceeds 100 mgKOH/g, the precipitate containing the hydroxyl group generated by the decomposition of the undercoat layer 15 in a durability test such as a moist heat resistance test tends to hinder the adhesion between the undercoat layer 15 and the gas barrier layer 20.
  • Monomers that can be used in the UV-curable resin or electron beam-curable resin that forms the undercoat layer 15 include, for example, monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, and N-vinylpyrrolidone, as well as polyfunctional monomers such as trimethylolpropane (meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol (meth)acrylate.
  • Oligomers that can be used in this UV-curable resin or electron beam-curable resin include
  • the blending ratio is not particularly limited.
  • the undercoat layer 15 may further contain additives other than the organic polymer resin, as necessary.
  • additives include antioxidants, weathering agents, heat stabilizers, lubricants, crystal nucleating agents, UV absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, and silane coupling agents.
  • the thickness of the undercoat layer 15 is preferably 0.05 ⁇ m or more and 10.0 ⁇ m or less. In particular, it is preferably 0.05 ⁇ m or more and 5.0 ⁇ m or less. If it is thinner than 0.05 ⁇ m, the adhesion between the base layer 10 and the gas barrier layer 20 will be insufficient. If it is thicker than 10.0 ⁇ m, the effect of internal stress will be large, the gas barrier layer 20 will not be laminated neatly, the barrier properties will not be expressed sufficiently, and the transparency and coating accuracy will also be insufficient.
  • the undercoat layer 15 can be formed by a conventional coating method.
  • a conventional coating method for example, well-known methods such as dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset, and organic deposition can be used.
  • the drying method one or more methods of applying heat, such as hot air drying, heat roll drying, high frequency irradiation, infrared irradiation, UV irradiation, and electron beam irradiation, can be used in combination.
  • a film that has been coated in advance on another resin substrate by the above forming method can be transferred to the substrate layer 10 by a transfer method such as adhesive transfer, heat transfer, and UV transfer.
  • gas barrier film according to each embodiment of the present invention will be further described using examples and comparative examples.
  • the technical scope of the present invention is not limited solely by the specific content of the examples and comparative examples.
  • Example 1 A biaxially oriented polypropylene film with a thickness of 20 ⁇ m was used as the substrate layer.
  • Meissner coils cooling temperature: ⁇ 120° C. in both cases
  • the partial pressure of m/z18 in the deposition chamber measured with a partial pressure meter during deposition was adjusted to 0.02 Pa.
  • a SiOx deposition material in which the ratio of Si material and SiO2 material was appropriately adjusted was sublimated, and a gas barrier layer (film thickness 40 nm, O/Si 1.7) made of silicon oxide (SiOx) was formed on the substrate layer by electron beam deposition. In this manner, a gas barrier film according to Example 1 was produced.
  • Example 2 A gas barrier film according to Example 2 was produced in the same manner as in Example 1, except that the partial pressure of m/z 18 was adjusted to 0.01 Pa, and the ratio of the Si material and the SiO2 material was appropriately adjusted to set the O/Si of the gas barrier layer to 1.3.
  • Example 3 A gas barrier film according to Example 3 was produced in the same manner as in Example 1, except that the partial pressure of m/z 18 was adjusted to 0.04 Pa, and the ratio of the Si material and the SiO2 material was appropriately adjusted to set the O/Si of the gas barrier layer to 1.8.
  • Example 4 A gas barrier film according to Example 4 was produced in the same manner as in Example 1, except that the partial pressure of m/z 18 was adjusted to 0.01 Pa.
  • Example 5 A gas barrier film according to Example 5 was produced in the same manner as in Example 1, except that the partial pressure of m/z 18 was adjusted to 0.04 Pa.
  • Example 6 A gas barrier film according to Example 6 was produced in the same manner as in Example 1, except that the thickness of the gas barrier layer was adjusted to 10 nm.
  • Example 7 A gas barrier film according to Example 7 was produced in the same manner as in Example 1, except that the thickness of the gas barrier layer was adjusted to 120 nm.
  • Example 8 A coating agent obtained by mixing the following (1) liquid and (2) liquid in a weight ratio of 6:4 was applied onto the gas barrier layer of the gas barrier film of Example 1 by a gravure coating method, and then dried to form an overcoat layer having a thickness of 0.4 ⁇ m.
  • Example 9 On the gas barrier layer of the gas barrier film of Example 1, a coating agent having a solid content of 5 wt % was applied by a gravure coating method, the coating agent being prepared by mixing an aqueous solution of polyvinyl alcohol, a hydrolyzed solution of tetraethoxysilane, and a hydrolyzed solution of 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate silane coupling agent such that the solid content weight ratio after drying was 30:60:10, and then dried to form an overcoat layer having a thickness of 0.4 ⁇ m. In this manner, a gas barrier film according to Example 9 was produced.
  • Example 10 A mixed solution of acrylic polyol and isocyanate was applied onto the base layer by gravure coating and dried to form an undercoat layer having a thickness of 0.2 ⁇ m.
  • a gas barrier layer 20 was formed on the undercoat layer in the same manner as in Example 1 to produce a gas barrier film according to Example 10.
  • Comparative Example 1 A gas barrier film according to Comparative Example 1 was produced in the same manner as in Example 1, except that neither of the Meissner coils installed in the film formation chamber nor the unwinding/winding chamber was used, the partial pressure of m/z18 in the film formation chamber measured with a partial pressure meter during film formation was set to 0.10 Pa, and the ratio of Si material to SiO2 material was appropriately adjusted to set the O/Si of the gas barrier layer to 1.9.
  • Comparative Example 2 A gas barrier film 1 according to Comparative Example 2 was produced in the same manner as in Example 1, except that the partial pressure of m/z 18 was adjusted to 0.04 Pa, and that only SiO2 material was used as the SiOx material without mixing any Si material.
  • the O/Si of the gas barrier layer in Comparative Example 2 was 2.0.
  • Comparative Example 3 A gas barrier film according to Comparative Example 3 was produced in the same manner as in Example 1, except that neither of the Meissner coils installed in the film-forming chamber nor the unwinding/winding chamber was used, and the partial pressure of m/z 18 in the film-forming chamber measured with a partial pressure meter during film formation was set to 0.10 Pa.
  • Comparative Example 4 A gas barrier film according to Comparative Example 4 was produced in the same manner as in Example 1, except that only a Meissner coil was used in the film formation chamber, and the partial pressure of m/z 18 in the film formation chamber measured with a partial pressure meter during film formation was set to 0.07 Pa.
  • the laminates according to the examples and comparative examples were evaluated as follows. The evaluation was carried out on three samples for each example. (FT-IR analysis) The FT-IR analysis was carried out using a Fourier transform infrared spectrophotometer (FT/IR-4600) manufactured by JASCO Corporation under the following measurement conditions.
  • FT/IR-4600 Fourier transform infrared spectrophotometer
  • Measurement method Reflection ATR method (measured from the gas barrier layer side of the barrier film) Measurement atmosphere: air Measurement temperature: room temperature ATR crystal: germanium (wave number range 600-5500 cm -1 ) ⁇ Resolution: 4.0cm -1 Number of integration times: 64
  • a baseline was drawn connecting plots at both ends of a defined range for each of the peak areas attributable to Si-O-Si bonds (720-1320 cm -1 ), OH bonds (3100-3700 cm -1 ), Si-OH bonds (830-910 cm -1 ), and Si-H bonds (2100-2200 cm -1 ), and the area of the part surrounded by the spectrum and the baseline was calculated using the software attached to the device. The area below the baseline was ignored and not included in the area.
  • the FT-IR analysis was measured by the ATR method, but the area ratios shown below are based on uncorrected data without correction such as ATR correction or baseline correction.
  • each narrow spectrum was repeatedly scanned and integrated 30 times or more.
  • the composition of the outermost surface was measured without argon etching.
  • a correction was made so that the C 1s peak detected due to surface contaminating hydrocarbons was 284.6 eV.
  • the water vapor transmission rate (WVTR) of the gas barrier film according to each example was evaluated using a water vapor transmission rate measuring device manufactured by Mocon (product name: PERMATRAN3/34G, measurement conditions: 40°C-90% RH, unit: g/( m2 ⁇ day)). The results are shown in Table 1.
  • the variation in WVTR in the examples was stable, being within ⁇ 0.5 g (standard deviation 0.5 g
  • the gas barrier film according to this embodiment can be stably produced by forming a gas barrier layer on a base material layer passing through a deposition chamber using a vapor deposition material containing a mixture of a Si material and a SiO2 material while keeping the partial pressure value of m/z18 in the deposition chamber at 0.05 Pa or less using a gas adsorption device.
  • the gas barrier film of Example 1 is considered to have improved water vapor barrier properties of the vapor-deposited film initially formed on the base layer due to the gas adsorption device in the unwinding/winding chamber.

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08224825A (ja) * 1994-12-21 1996-09-03 Toyobo Co Ltd ガスバリアフィルム
JP2011194667A (ja) * 2010-03-18 2011-10-06 Fujifilm Corp ガスバリアフィルム
WO2018101084A1 (ja) * 2016-11-29 2018-06-07 住友化学株式会社 ガスバリア性フィルム及びフレキシブル電子デバイス
WO2021176948A1 (ja) * 2020-03-03 2021-09-10 凸版印刷株式会社 ガスバリア積層体及び包装袋
JP2022034746A (ja) * 2020-08-19 2022-03-04 凸版印刷株式会社 ガスバリア積層体
WO2022270490A1 (ja) * 2021-06-21 2022-12-29 凸版印刷株式会社 ガスバリアフィルム、積層体、および包装材料

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08224825A (ja) * 1994-12-21 1996-09-03 Toyobo Co Ltd ガスバリアフィルム
JP2011194667A (ja) * 2010-03-18 2011-10-06 Fujifilm Corp ガスバリアフィルム
WO2018101084A1 (ja) * 2016-11-29 2018-06-07 住友化学株式会社 ガスバリア性フィルム及びフレキシブル電子デバイス
WO2021176948A1 (ja) * 2020-03-03 2021-09-10 凸版印刷株式会社 ガスバリア積層体及び包装袋
JP2022034746A (ja) * 2020-08-19 2022-03-04 凸版印刷株式会社 ガスバリア積層体
WO2022270490A1 (ja) * 2021-06-21 2022-12-29 凸版印刷株式会社 ガスバリアフィルム、積層体、および包装材料

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