WO2021045127A1 - Film barrière, stratifié utilisant ledit film barrière, produit d'emballage utilisant ledit stratifié - Google Patents

Film barrière, stratifié utilisant ledit film barrière, produit d'emballage utilisant ledit stratifié Download PDF

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Publication number
WO2021045127A1
WO2021045127A1 PCT/JP2020/033327 JP2020033327W WO2021045127A1 WO 2021045127 A1 WO2021045127 A1 WO 2021045127A1 JP 2020033327 W JP2020033327 W JP 2020033327W WO 2021045127 A1 WO2021045127 A1 WO 2021045127A1
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Prior art keywords
film
base material
plasma
barrier
barrier film
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PCT/JP2020/033327
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English (en)
Japanese (ja)
Inventor
誠一郎 小柴
岸本　好弘
拓志 義原
正泰 高橋
浩之 岩橋
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大日本印刷株式会社
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Publication of WO2021045127A1 publication Critical patent/WO2021045127A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C14/08—Oxides
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • 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
    • 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
    • C23C14/58—After-treatment

Definitions

  • the present invention relates to a barrier film, a laminate using the barrier film, and a packaged product using the laminate.
  • a barrier laminated film in which a barrier layer made of a thin film such as aluminum oxide is provided on a plastic film to have a barrier function against oxygen and water vapor has also been developed.
  • Patent Document 1 describes aluminum hydroxide by removing water contained in a reaction space in which an oxidation reaction between oxygen gas and evaporated aluminum occurs at the time of vapor deposition. It is disclosed that the formation of substances is suppressed and the heat resistance and water resistance are improved.
  • An object of the present invention is to provide a barrier film provided with an aluminum oxide vapor-deposited film, which has a higher barrier property, and a laminate using the barrier film.
  • the growth of the aluminum oxide vapor-deposited film on the surface of the aluminum hydroxide proceeds in two-dimensional growth, and a more dense aluminum oxide-deposited film is formed. That is, the aluminum oxide film deposited on the surface of the aluminum hydroxide has a feature of exhibiting an excellent barrier property against oxygen and water vapor as compared with aluminum oxide deposited directly on the surface of the plastic film.
  • an alumina hydroxide region is formed in the vicinity of the plastic film and the aluminum vapor deposition interface, and the alumina hydroxide region is mainly oxidized.
  • the aluminum region it is possible to provide a higher barrier property.
  • the structure of such a vapor-deposited film is supported by the presence of a downwardly convex peak derived from the elemental bond OH by TOF-SIMS analysis and the depth position of the peak.
  • the present invention (first invention) provides the following.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the intensity derived from the elemental bond OH has a downwardly convex peak, and the downwardly convex peak is located at a depth of 10% or more and 60% or less from the surface side of the organic coating layer in the aluminum oxide vapor-deposited film.
  • a laminate comprising the barrier film according to any one of (1) to (3) and a sealant layer.
  • the barrier film of the present invention has even higher barrier properties.
  • FIG. 1A is a cross-sectional view showing an example of a barrier film according to the present embodiment.
  • Barrier films produced by using the film deposition apparatus of this embodiment for example, as a barrier film A 1 shown in FIG. 1 (a), a substrate 1, a deposited film 2, and the organic coating layer 3a , Equipped with.
  • the vapor deposition film 2 is located on one surface of the base material 1.
  • the barrier film A is laminated in the order of the base material 1, the vapor-deposited film 2, and the organic coating layer 3a, and the organic coating layer 3a is located on the surface of the barrier film. ..
  • laminated in this order means that the base material, the aluminum oxide vapor deposition film, and the organic coating layer are laminated in this order, and between these layers, For example, layers other than the primer may be laminated.
  • the base material 1 is a layer mainly containing a resin.
  • the resin is not particularly limited, and a known resin film or sheet can be used.
  • a resin film containing a resin or the like can be used.
  • polyester-based resins are preferably used, and further, among polyester-based resins, polyethylene terephthalate-based resins and polybutylene terephthalate-based resins are preferably used.
  • the polyester film used as the base material 1 may be stretched in a predetermined direction.
  • the polyester film may be a uniaxially stretched film stretched in a predetermined unidirectional direction, or may be a biaxially stretched film stretched in a predetermined bidirectional direction.
  • a film made of polyethylene terephthalate is used as the base material 1
  • a biaxially stretched polyethylene terephthalate film can be used.
  • the thickness of the polyester film used as the base material 1 as described above is not particularly limited, and it is possible to perform pretreatment or film formation treatment when the vapor deposition film 2 is formed by a film forming apparatus described later. It may be possible, but from the viewpoint of flexibility and shape retention, a range of 6 ⁇ m or more and 100 ⁇ m or less is preferable. When the thickness of the polyester film is within the above range, it is easy to bend and is not torn during transportation, and is easy to handle in a film forming apparatus used for manufacturing a barrier film having a vapor-deposited film 2 having improved adhesion. ..
  • PET film polyethylene terephthalate film
  • a biomass PET film, a recycled PET film, or a high stiffness PET film may be used as the base material 1.
  • the biomass PET film is a resin film containing a polyester derived from biomass, and the polyester derived from biomass is an ethylene glycol derived from biomass as a diol unit and a dicarboxylic acid derived from a fossil fuel as a dicarboxylic acid unit.
  • biomass-derived ethylene glycol has the same chemical structure as conventional fossil fuel-derived ethylene glycol
  • polyester films synthesized using biomass-derived ethylene glycol are mechanically similar to conventional fossil fuel-derived polyester films. It is not inferior in terms of physical properties such as physical characteristics. Therefore, since the base material using the polyester film derived from biomass has a layer made of carbon-neutral material, the amount of fossil fuel used is reduced as compared with the base material produced from the raw material obtained from the conventional fossil fuel. And can reduce the environmental load.
  • Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass such as sugar cane and corn.
  • biomass-derived ethylene glycol can be obtained from biomass ethanol by a method of producing ethylene glycol via ethylene oxide by a conventionally known method.
  • commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol Co., Ltd. can be preferably used.
  • the dicarboxylic acid unit of polyester uses a fossil fuel-derived dicarboxylic acid.
  • dicarboxylic acid aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and derivatives thereof can be used.
  • aromatic dicarboxylic acid include terephthalic acid and isophthalic acid
  • the derivative of the aromatic dicarboxylic acid include lower alkyl esters of the aromatic dicarboxylic acid, specifically, methyl ester, ethyl ester, propyl ester and butyl. Esters and the like can be mentioned.
  • terephthalic acid is preferable, and dimethyl terephthalate is preferable as the derivative of the aromatic dicarboxylic acid.
  • Biomass-derived polyester can be obtained by a conventionally known method of polycondensing a diol unit and a dicarboxylic acid unit. Specifically, a general method of melt polymerization such as an esterification reaction and / or a transesterification reaction between the above dicarboxylic acid component and a diol component and then a polycondensation reaction under reduced pressure, or an organic solvent. It can be produced by a known solution heating dehydration condensation method using.
  • the resin composition constituting the resin film containing the biomass-derived polyester may be composed of only the biomass-derived polyester, or may contain a fossil fuel-derived polyester in addition to the biomass-derived polyester.
  • Polyester derived from fossil fuel is composed of diol unit and dicarboxylic acid unit, and is obtained by polycondensation reaction using ethylene glycol of fossil fuel-derived diol as diol unit and dicarboxylic acid derived from fossil fuel as dicarboxylic acid unit. It is a thing.
  • the resin in the resin composition constituting the resin film containing the biomass-derived polyester may contain recycled polyester in addition to the biomass-derived polyester.
  • the recycled polyester may be a recycled polyester derived from biomass or a recycled polyester derived from fossil fuel.
  • the resin composition constituting the resin film containing biomass-derived polyester can contain various additives.
  • Additives include, for example, plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, friction reducing agents, mold release agents, antioxidants, ion exchange. Agents, coloring pigments and the like can be mentioned.
  • the additive is preferably contained in the entire resin composition containing PET in the range of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less.
  • a resin film containing a biomass-derived polyester can be formed, for example, by forming a film by the T-die method. Specifically, after the above-mentioned PET is dried, it is supplied to a melt extruder heated to a temperature (Tm) to Tm + 70 ° C. above the melting point of PET to melt the resin composition, for example, a T die.
  • the film can be formed by extruding the extruded sheet-like material into a sheet from a die such as, and quenching and solidifying the extruded sheet-like material with a rotating cooling drum or the like.
  • melt extruder a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder and the like can be used depending on the purpose.
  • Tm melting point
  • Tg glass transition point
  • the 14C content in a plant that grows by taking in the carbon dioxide in the atmosphere, for example, corn is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no 14C. Therefore, the proportion of biomass-derived carbon can be calculated by measuring the proportion of 14C contained in all carbon atoms in polyester. In the present invention, the "biomass degree" indicates the mass ratio of biomass-derived components.
  • PET polyethylene terephthalate
  • PET is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms at a molar ratio of 1: 1 and is derived from biomass as ethylene glycol.
  • the mass ratio of the biomass-derived component of the fossil fuel-derived polyester is 0%, and the biomass degree of the fossil fuel-derived polyester is 0%.
  • the degree of biomass in the resin film containing the polyester derived from biomass is preferably 5.0% or more, more preferably 10.0% or more, and preferably 30.0% or less.
  • the resin film containing the biomass-derived polyester is biaxially stretched.
  • Biaxial stretching can be performed by a conventionally known method.
  • the film extruded onto the cooling drum as described above is subsequently heated by roll heating, infrared heating, or the like, and stretched in the vertical direction to obtain a vertically stretched film.
  • This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls.
  • the longitudinal stretching is usually carried out in a temperature range of 50 to 100 ° C.
  • the magnification of longitudinal stretching depends on the required characteristics of the film application, but is preferably 2.5 times or more and 4.2 times or less. When the draw ratio is less than 2.5 times, the thickness unevenness of the polyester film becomes large, and it is difficult to obtain a good film.
  • the vertically stretched film is subsequently subjected to each of the treatment steps of lateral stretching, heat fixing, and heat relaxation to become a biaxially stretched film.
  • the transverse stretching is usually carried out in a temperature range of 50 to 100 ° C.
  • the lateral stretching ratio depends on the required characteristics of this application, but is preferably 2.5 times or more and 5.0 times or less. If it is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage is likely to occur during film formation.
  • the heat fixing treatment is subsequently performed, and the preferable temperature range of the heat fixing is Tg + 70 to Tm-10 ° C. of polyester.
  • the heat fixing time is preferably 1 to 60 seconds. Further, for applications that require a reduction in the heat shrinkage rate, heat relaxation treatment may be performed as necessary.
  • the thickness of the resin film containing the biomass-derived polyester is arbitrary depending on its use, but is usually about 5 to 500 ⁇ m.
  • Breaking strength of a resin film comprising a polyester derived from biomass is 5 ⁇ 35kgf / mm 2 at 5 ⁇ 40kgf / mm 2, TD direction MD direction, elongation at break, 50 to 350% in MD direction, It is 50 to 300% in the TD direction.
  • the shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1 to 5%.
  • the resin film containing polyester derived from biomass can be suitably used for applications such as bags, lid materials, packaging products such as Lami tubes, various label materials, and sheet molded products.
  • the thickness of the stretched film is preferably 5 to 30 ⁇ m.
  • the recycled PET film is a resin film containing recycled PET, and includes PET recycled by mechanical recycling. Specifically, it contains PET in which a PET bottle is recycled by mechanical recycling, and this PET contains ethylene glycol as a diol component and terephthalic acid and isophthalic acid as a dicarboxylic acid component.
  • mechanical recycling generally refers to crushing a recovered polyethylene terephthalate resin product such as a PET bottle, cleaning it with an alkali to remove stains and foreign substances on the surface of the PET resin product, and then drying it at a high temperature and under reduced pressure for a certain period of time.
  • This is a method in which the pollutants remaining inside the PET resin are diffused and decontaminated to remove stains on the resin product made of the PET resin, and the resin product is returned to the PET resin again.
  • polyethylene terephthalate obtained by recycling PET bottles will be referred to as "recycled polyethylene terephthalate (hereinafter, also referred to as recycled PET)", and non-recycled polyethylene terephthalate shall be referred to as “virgin polyethylene terephthalate (hereinafter, also referred to as virgin PET)”. ..
  • the content of the isophthalic acid component in the PET contained in the base material is preferably 0.5 mol% or more and 5 mol% or less, and 1.0 mol% or more, in the total dicarboxylic acid component constituting the PET. More preferably, it is 2.5 mol% or less. If the content of the isophthalic acid component is less than 0.5 mol%, the flexibility may not be improved, while if it exceeds 5 mol%, the melting point of PET may be lowered and the heat resistance may be insufficient.
  • the PET may be a biomass-derived PET as well as a normal fossil fuel-derived PET.
  • This biomass-derived PET is a PET containing ethylene glycol derived from biomass as a diol component and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid component.
  • the PET used in the PET bottle can be obtained by a conventionally known method of polycondensing the above-mentioned diol component and dicarboxylic acid component. Specifically, a general method of melt polymerization such as an esterification reaction and / or an ester exchange reaction between the above diol component and a dicarboxylic acid component and then a polycondensation reaction under reduced pressure, or an organic solvent. It can be produced by a known solution heating dehydration condensation method or the like using the above.
  • the amount of the diol component used in producing the PET is substantially equimolar to 100 mol of the dicarboxylic acid or its derivative, but generally, esterification and / or transesterification reaction and / or polycondensation.
  • the polycondensation reaction is preferably carried out in the presence of a polymerization catalyst.
  • the timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added at the time of raw material preparation or at the start of reduced pressure.
  • PET bottles made from recycled PET bottles are polymerized and solidified as described above, and then solid-phase polymerization is performed as necessary in order to further increase the degree of polymerization and remove oligomers such as cyclic trimers. You may go. Specifically, in solid-phase polymerization, PET is chipped and dried, and then heated at a temperature of 100 ° C. or higher and 180 ° C. or lower for about 1 to 8 hours to pre-crystallize the PET, followed by 190 ° C. It is carried out by heating at a temperature of 230 ° C. or lower for 1 hour to several tens of hours in an inert gas atmosphere or under reduced pressure.
  • the ultimate viscosity of PET contained in recycled PET is preferably 0.58 dl / g or more and 0.80 dl / g or less. If the ultimate viscosity is less than 0.58 dl / g, the mechanical properties required for the PET film as a resin base material may be insufficient. On the other hand, if the ultimate viscosity exceeds 0.80 dl / g, the productivity in the film forming process may be impaired. The ultimate viscosity is measured with an orthochlorophenol solution at 35 ° C.
  • the recycled PET preferably contains recycled PET in a proportion of 50% by mass or more and 95% by mass or less, and may contain virgin PET in addition to recycled PET.
  • the diol component as described above may be ethylene glycol
  • the dicarboxylic acid component may be PET containing terephthalic acid and isophthalic acid
  • the dicarboxylic acid component may be PET containing no isophthalic acid. May be good.
  • an aliphatic dicarboxylic acid or the like may be contained in addition to the aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid.
  • the aliphatic dicarboxylic acid include chains having 2 to 40 carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid.
  • the shape or alicyclic dicarboxylic acid can be mentioned.
  • the derivative of the aliphatic dicarboxylic acid include lower alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of the aliphatic dicarboxylic acid, and cyclic acid anhydride of the aliphatic dicarboxylic acid such as succinic anhydride.
  • aliphatic dicarboxylic acid adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and one containing succinic acid as a main component is particularly preferable.
  • succinic acid a methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable.
  • the resin in the resin composition constituting the resin film containing recycled PET may be composed of only recycled PET, or may contain virgin PET in addition to recycled PET. Further, the recycled PET film may be a single layer or a multilayer.
  • the intermediate layer is a layer composed of only recycled PET or a mixed layer of recycled PET and virgin PET, and the innermost layers on both sides and the outermost layer.
  • the outermost layer is preferably a layer composed of only virgin PET. As described above, by using only virgin PET for the innermost layer and the outermost layer, it is possible to prevent the recycled PET from being exposed from the front surface or the back surface of the resin film. Therefore, the hygiene of the laminated body can be ensured.
  • one layer is a layer composed of only recycled PET or a mixed layer of recycled PET and virgin PET, and the other layer is composed of only virgin PET. It is preferable to use a layer.
  • a resin film containing recycled PET is formed by mixing recycled PET and virgin PET in a single layer, there are a method of separately supplying the resin film to a molding machine, a method of supplying the resin film after mixing with a dry blend or the like, and the like. Above all, the method of mixing by dry blend is preferable from the viewpoint of easy operation.
  • the resin composition constituting the resin film containing recycled polyethylene PET can contain various additives in the manufacturing process thereof or after the manufacturing thereof as long as the characteristics are not impaired.
  • Additives include, for example, plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, friction reducing agents, mold release agents, antioxidants, ion exchange. Agents, coloring pigments and the like can be mentioned.
  • the additive is preferably contained in the entire resin composition containing PET in the range of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less.
  • the resin film containing recycled PET can be formed, for example, by forming a film by the T-die method. Specifically, after the above-mentioned PET is dried, it is supplied to a melt extruder heated to a temperature (Tm) to Tm + 70 ° C. above the melting point of PET to melt the resin composition, for example, a T die.
  • the film can be formed by extruding the extruded sheet-like material into a sheet from a die such as, and quenching and solidifying the extruded sheet-like material with a rotating cooling drum or the like.
  • a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder and the like can be used depending on the purpose.
  • the resin film containing recycled PET is biaxially stretched.
  • Biaxial stretching can be performed by a conventionally known method.
  • the film extruded onto the cooling drum as described above is subsequently heated by roll heating, infrared heating, or the like, and stretched in the vertical direction to obtain a vertically stretched film.
  • This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls.
  • the longitudinal stretching is usually carried out in a temperature range of 50 ° C. or higher and 100 ° C. or lower. Further, the magnification of longitudinal stretching depends on the required characteristics of the film application, but is preferably 2.5 times or more and 4.2 times or less.
  • the thickness unevenness of the PET film becomes large and it is difficult to obtain a good film.
  • the vertically stretched film is subsequently subjected to each of the treatment steps of transverse stretching, heat fixing, and heat relaxation to obtain a biaxially stretched film.
  • the transverse stretching is usually carried out in a temperature range of 50 ° C. or higher and 100 ° C. or lower.
  • the lateral stretching ratio depends on the required characteristics of this application, but is preferably 2.5 times or more and 5.0 times or less. If it is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage is likely to occur during film formation.
  • the heat fixing treatment is subsequently performed, and the preferable temperature range of the heat fixing is Tg + 70 to Tm-10 ° C. of PET.
  • the heat fixing time is preferably 1 second or more and 60 seconds or less. Further, for applications that require a reduction in the heat shrinkage rate, heat relaxation treatment may be performed as necessary.
  • the thickness of the resin film containing recycled PET is arbitrary depending on the intended use, but is usually about 5 to 500 ⁇ m.
  • Breaking strength of the resin film containing the recycled PET is a MD direction 5 kgf / mm 2 or more 40 kgf / mm 2 or less, at 35 kgf / mm 2 or less 5 kgf / mm 2 or more in the TD direction, elongation at break, MD direction Is 50% or more and 350% or less, and 50% or more and 300% or less in the TD direction.
  • the shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1% or more and 5% or less.
  • the virgin PET may be fossil fuel polyethylene terephthalate (hereinafter, also referred to as fossil fuel PET) or biomass PET.
  • the "fossil fuel PET” has a diol derived from fossil fuel as a diol component and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid component.
  • the recycled PET may be obtained by recycling a PET resin product formed by using fossil fuel PET, or may be obtained by recycling a PET resin product formed by using biomass PET. There may be.
  • the resin film containing recycled PET can be suitably used for applications such as bags, lid materials, packaging products such as Lami tubes, various label materials, and sheet molded products.
  • the thickness of the stretched film is preferably 5 to 30 ⁇ m.
  • the high-stiffness PET film contains polyester as a main component and has a loop stiffness of 0.0017 N / 15 mm or more in at least one direction.
  • the high stiffness film has a loop stiffness of 0.0017 N or more in at least one of the flow direction (MD) and the vertical direction (TD), for example.
  • the high stiffness film may have a loop stiffness of 0.0017 N or more in both the flow direction (MD) and the vertical direction (TD), for example.
  • Loop stiffness is a parameter that indicates the strength of the film.
  • a method for measuring loop stiffness will be described with reference to FIGS. 15 to 20.
  • the measuring method described below can be used not only for a single-layer film such as a stretched plastic film but also for a film containing a plurality of layers such as a vapor-deposited film and a laminated film.
  • the thin-film film is a film including a single-layer film such as a stretched plastic film and a thin-film film formed on the single-layer film.
  • the laminated film is a film containing a plurality of laminated films.
  • FIG. 15 is a plan view showing the test piece 40 and the loop stiffness measuring instrument 45
  • FIG. 16 is a cross-sectional view of the test piece 40 and the loop stiffness measuring instrument 45 of FIG. 15 along lines IV-IV.
  • the test piece 40 is a rectangular film having a long side and a short side.
  • the length L1 of the long side of the test piece 40 is 150 mm
  • the length L2 of the short side is 15 mm.
  • the loop stiffness measuring instrument 45 for example, No. 1 manufactured by Toyo Seiki Co., Ltd. 581 Loop Steph NESSA (registered trademark) LOOP STIFFNESS TESTER DA type can be used.
  • the length L1 of the long side of the test piece 40 can be adjusted as long as the test piece 40 can be gripped by the pair of chuck portions 46 described later.
  • the loop stiffness measuring instrument 45 has a pair of chuck portions 46 for gripping a pair of end portions in the long side direction of the test piece 40, and a support member 47 for supporting the chuck portions 46.
  • the chuck portion 46 includes a first chuck 461 and a second chuck 462.
  • the test piece 40 is arranged on the pair of first chucks 461, and the second chuck 462 still grips the test piece 40 with the first chuck 461.
  • the test piece 40 is gripped between the first chuck 461 and the second chuck 462 of the chuck portion 46.
  • the second chuck 462 may be connected to the first chuck 461 via a hinge mechanism.
  • the test piece 40 is manufactured by cutting the film to be measured. You may. Further, the test piece 40 may be manufactured by cutting a packaged product manufactured from a packaging material such as a packaging bag and taking out a film to be measured.
  • the test piece 40 is placed on the first chuck 461 of the pair of chuck portions 46 arranged at intervals L3.
  • the interval L3 is set so that the length of the loop portion 41 (hereinafter, also referred to as the loop length) described later is 60 mm.
  • the test piece 40 includes an inner surface 40x located on the side of the first chuck 461 and an outer surface 40y located on the opposite side of the inner surface 40x.
  • the inner surface 40x and the outer surface 40y of the test piece 40 correspond to the inner surface and the outer surface of the packaging material.
  • the inner surface 40x is located inside the loop portion 41 and the outer surface 40y is located outside the loop portion 41.
  • the second chuck 462 is arranged on the test piece 40 so as to grip the end portion of the test piece 40 in the long side direction with the first chuck 461.
  • the test piece 40 shown in FIG. 18 has a loop portion 41, a pair of intermediate portions 42, and a pair of fixing portions 43.
  • the pair of fixing portions 43 are portions of the test piece 40 that are gripped by the pair of chuck portions 46.
  • the pair of intermediate portions 42 are portions of the test piece 40 located between the loop portion 41 and the pair of intermediate portions 42.
  • the chuck portion 46 is slid on the support member 47 until the inner surfaces 40x of the pair of intermediate portions 42 come into contact with each other.
  • the loop portion 41 having a loop length of 60 mm can be formed.
  • the loop length of the loop portion 41 is the position P1 at which the surface of one second chuck 462 on the loop portion 41 side and the test piece 40 intersect, and the surface of the other second chuck 462 on the loop portion 41 side and the test piece 40. It is the length of the test piece 40 with respect to the position P2 where the test pieces intersect.
  • the above-mentioned interval L3 is a value obtained by adding 2 ⁇ t to the length of the loop portion 41 when the thickness of the test piece 40 is ignored. t is the thickness of the second chuck 462 of the chuck portion 46.
  • the posture of the chuck portion 46 is adjusted so that the protruding direction Y of the loop portion 41 with respect to the chuck portion 46 is in the horizontal direction.
  • the posture of the chuck portion 46 supported by the support member 47 is adjusted by moving the support member 47 so that the normal direction of the support member 47 faces the horizontal direction.
  • the protruding direction Y of the loop portion 41 coincides with the thickness direction of the chuck portion.
  • the load cell 48 is prepared at a position separated from the second chuck 462 by a distance Z1 in the protruding direction Y of the loop portion 41. In the present application, the distance Z1 is set to 50 mm.
  • the load cell 48 is moved toward the loop portion 41 of the test piece 40 at a speed V by the distance Z2 shown in FIG.
  • the distance Z2 is set so that the load cell 48 comes into contact with the loop portion 41 and then the load cell 48 pushes the loop portion 41 toward the chuck portion 46, as shown in FIGS. 19 and 20.
  • the distance Z2 is set to 40 mm.
  • the distance Z3 between the load cell 48 and the second chuck 462 of the chuck portion 46 in the state where the load cell 48 is pushing the loop portion 41 toward the chuck portion 46 is 10 mm.
  • the speed V for moving the load cell 48 was set to 3.3 mm / sec.
  • the load cell 48 is moved toward the chuck portion 46 by a distance Z2, and is added to the load cell 48 from the loop portion 41 in a state where the load cell 48 is pushing the loop portion 41 of the test piece 40. After the load value stabilizes, record the load value.
  • the value of the load thus obtained is adopted as the loop stiffness of the film constituting the test piece 40.
  • the environment at the time of measuring the loop stiffness is a temperature of 23 ° C. and a relative humidity of 50%.
  • the piercing strength of the stretched plastic film can be increased.
  • the puncture strength of the laminated film can be made, for example, 13 N or more, more preferably 14 N or more, and further preferably 15 N or more or 16 N or more. it can.
  • a high-stiffness film is a high-stiffness PET film containing 51% by mass or more of PET.
  • the content of PET in the high-stiffness PET film may be 80% by mass or more, 90% by mass or more, or 95% by mass or more.
  • the thickness of the high stiffness film is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more.
  • the thickness of the high stiffness film may be 10 ⁇ m or more, or 14 ⁇ m or more.
  • the thickness of the high stiffness film is preferably 30 ⁇ m or less, 25 ⁇ m or less, or 20 ⁇ m or less.
  • the preferable mechanical properties of the high stiffness film will be further described.
  • the piercing strength of the high stiffness film is preferably 10 N or more, more preferably 11 N or more.
  • the tensile strength of the high stiffness film in at least one direction is preferably 250 MPa or more, more preferably 280 MPa or more.
  • the tensile strength of the high stiffness film in the flow direction is preferably 250 MPa or more, more preferably 280 MPa or more.
  • the tensile strength of the high stiffness film in the vertical direction is preferably 250 MPa or more, more preferably 280 MPa or more.
  • the tensile elongation of the high stiffness film in at least one direction is preferably 130% or less, more preferably 120% or less.
  • the tensile elongation of the high stiffness film in the flow direction is preferably 130% or less, more preferably 120% or less.
  • the tensile elongation of the high stiffness film in the vertical direction is preferably 120% or less, more preferably 110% or less.
  • the tensile strength of the high stiffness film divided by the tensile elongation is 2.0 [MPa /%] or more.
  • the value obtained by dividing the tensile strength of the high stiffness film in the vertical direction (TD) by the tensile elongation is preferably 2.0 [MPa /%] or more, and more preferably 2.2 [MPa /%] or more. Is.
  • the value obtained by dividing the tensile strength of the high stiffness film in the flow direction (MD) by the tensile elongation is preferably 1.8 [MPa /%] or more, and more preferably 2.0 [MPa /%] or more. ..
  • the heat shrinkage of the high stiffness film in at least one direction is preferably 0.7% or less, more preferably 0.5% or less.
  • the heat shrinkage rate of the high stiffness film in the flow direction is preferably 0.7% or less, and more preferably 0.5% or less.
  • the heat shrinkage of the high stiffness film in the vertical direction is preferably 0.7% or less, more preferably 0.5% or less.
  • the heating temperature when measuring the heat shrinkage rate is 100 ° C., and the heating time is 40 minutes.
  • the Young's modulus of the high stiffness film in at least one direction is preferably 4.0 GPa or more, more preferably 4.5 GPa or more.
  • the Young's modulus of a high-stiffness film in the flow direction is preferably 4.0 GPa or more, and more preferably 4.5 GPa or more.
  • the Young's modulus of the high stiffness film in the vertical direction is preferably 4.0 GPa or more, and more preferably 4.5 GPa or more.
  • Young's modulus can be measured in accordance with JIS K7127 as well as tensile strength and tensile elongation.
  • a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used.
  • As the test piece a high-stiffness film cut out into a rectangular film having a width of 15 mm and a length of 150 mm can be used.
  • the distance at the start of measurement between the pair of chucks holding the test piece is 100 mm, and the tensile speed is 300 mm / min.
  • the length of the test piece can be adjusted as long as the test piece can be gripped by a pair of chucks.
  • the environment at the time of measuring Young's modulus is a temperature of 25 ° C. and a relative humidity of 50%.
  • the high-stiffness film has the same mechanical properties as a single high-stiffness film even when a vapor-deposited film is provided.
  • the high stiffness film provided with the aluminum oxide vapor deposition film 3 has a loop stiffness of 0.0017 N or more in at least one direction.
  • the organic coating layer is further provided on the vapor-deposited film, it has the same mechanical properties as a single high-stiffness film.
  • a high-stiffness film provided with an aluminum oxide vapor-deposited film and an organic coating layer has a loop stiffness of 0.0017 N or more in at least one direction.
  • a plastic film obtained by melting and molding polyester is tripled to 4.5 times at 90 ° C. to 145 ° C. in the flow direction and the vertical direction, respectively.
  • the first stretching step of stretching is carried out.
  • a second stretching step of stretching the plastic film 1.1 to 3.0 times at 100 ° C. to 145 ° C. in the flow direction and the vertical direction is carried out.
  • heat fixing is performed at a temperature of 190 ° C. to 220 ° C.
  • a relaxation treatment (a treatment for reducing the film width) of about 0.2% to 2.5% is carried out at a temperature of 100 ° C. to 190 ° C.
  • the high stiffness film As a specific example of the high stiffness film, XP-55 manufactured by Toray Industries, Inc. can be used. This high stiffness film is biaxially stretched, contains 90% by mass or more of PET, and has a thickness of 16 ⁇ m. The measured value of the loop stiffness of this high-stiffness PET film was 0.0021N in both the flow direction and the vertical direction. The Young's modulus of the high-stiffness PET film in the flow direction was 4.8 GPa, and the Young's modulus of the high-stiffness PET film in the vertical direction was 4.7 GPa.
  • the tensile strength of the high-stiffness PET film in the flow direction was 292 MPa, and the tensile strength of the high-stiffness PET film in the vertical direction was 257 MPa.
  • the tensile elongation of the high-stiffness PET film in the flow direction was 107%, and the tensile elongation of the high-stiffness PET film in the vertical direction was 102%.
  • the value obtained by dividing the tensile strength of the high-stiffness PET film in the flow direction by the tensile elongation is 2.73 [MPa /%]
  • the tensile strength of the high-stiffness PET film in the vertical direction is divided by the tensile elongation.
  • the value is 2.52 [MPa /%].
  • the heat shrinkage of the high-stiffness PET film in the flow direction and the vertical direction was 0.4%.
  • the base material 1 may have a single layer or a multi-layer structure of two or more layers, and in the case of a multi-layer structure, it may be a layer having the same composition or a layer having a different composition. Further, in the case of a multi-layer structure, each layer may be bonded with an adhesive layer or the like interposed therebetween.
  • the vapor-deposited film 2 contains aluminum oxide.
  • Aluminum exists in the vapor-deposited film 2 in a state where, for example, an element bond Al 2 O 3 is formed.
  • the vapor deposition film 2 further includes metal oxides such as silicon oxide, silicon nitride, silicon oxide nitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, and zirconium oxide, or metals thereof. It may contain nitrides and carbides.
  • the thickness of the vapor-deposited film 2 is preferably 3 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less, and particularly preferably 5 nm or more and 15 nm or less.
  • the "aluminum oxide vapor-deposited film” in the present invention means "aluminum oxide-containing vapor-deposited film” as described above, and in addition to aluminum oxide Al 2 O 3 , aluminum hydroxide Al 2 O 4 H and the like are used. It may be included.
  • FIG. 9 shows the elements contained in the barrier film A by etching the barrier film A shown in FIG. 1 from the surface side of the organic coating layer 3a using a time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • TOF-SIMS Time-of-Flight Secondary Ion Mass Spectrometry
  • TOF-SIMS Time-of-Flight Secondary Ion Mass Spectrometry
  • the transition time with respect to the data of the time transition of the ionic strength of the secondary ion, that is, the element to be detected or the molecular ion bonded to the element to be detected. Is converted into the depth, so that the concentration distribution of the element to be detected in the depth direction of the sample surface can be known.
  • the depth of the dent formed on the sample surface by the irradiation of the primary ion is measured in advance using a surface roughness meter, and the average sputter rate is calculated from the depth of the dent and the transition time. It is possible to calculate the depth (spatter amount) from the irradiation time (that is, transition time) or the number of irradiation cycles under the assumption that the sputter rate is constant.
  • the vapor deposition film 2 and the base material 1 are used by using a flight time type secondary ion mass spectrometer while repeating soft etching from the outermost surface of the organic coating layer 3a with a Cs (cesium) ion gun at a constant speed.
  • a Cs cesium
  • each graph can be obtained for the measured elements and elemental bonds.
  • FIG. 9 from the barrier film according to the present embodiment, the strength derived from OH, the strength derived from Si, the strength derived from Al 2 O 3 , and AL 2 O are shown. At least the intensity derived from 4H and the intensity derived from C6 are detected. In the example shown in FIG. 9, an example in which the strength of these five types of elemental bonds is measured is shown.
  • the position of Et time T 1 at which the intensity of strength derived from C6 is halved (the strongest strength) is defined as the interface between the plastic base material and aluminum oxide.
  • the position of Et time T 2 at which the intensity of Si-derived strength constituting the organic coating layer is halved (the strongest strength) is defined as the interface between the organic coating film and aluminum oxide.
  • T 1 to T 2 are formed as an aluminum oxide vapor-deposited film (X in FIG. 9).
  • the intensity derived from OH exists in the aluminum oxide vapor deposition film, that is, within the range of X in FIG. 9, and the intensity derived from OH is mainly present in the region of the organic coating layer on the left side of X in the figure. It is the strength derived from the organic coating layer, and in the region of the base material on the right side of X in the figure, it is the strength mainly derived from the base material (moisture).
  • the intensity derived from OH is a peak mainly derived from aluminum hydroxide. That is, in the region of X, the change in strength derived from OH reflects the change in the abundance of aluminum hydroxide. Then, according to FIG. 9, there is a downwardly convex peak Tp in the region of X.
  • the peak (Tp) depth position (corresponding to Y / X in FIG. 9) at X is preferably 10% or more and 60% or less from the surface side (organic coating layer side) of the vapor-deposited film. Is present in 10% or more and 50% or less, more preferably 10% or more and 40% or less.
  • Tp is present on the organic coating layer side of the vapor-deposited film. That is, while the main region of Al 2 O 4 H exists on the substrate side of the vapor deposition film, the ratio of Al 2 O 4 H is small in the region on the organic coating side of the vapor deposition film, and mainly of Al 2 O 3 It means that there is a region of state. As a result, the barrier performance can be improved.
  • the presence of the downwardly convex peak Tp derived from OH and the depth position of Tp are determined by the conditions of pretreatment, especially oxygen plasma treatment, plasma assist treatment during vapor deposition, and the formation of an aluminum oxide vapor deposition film. It can be adjusted by controlling the combination of the oxygen concentration at the time of vapor deposition in.
  • the intensity derived from Al 2 O 4 H (mass number 118.93) in FIG. 9 has two peaks in the vicinity of 3100 cycles and in the vicinity of 3600 cycles. Since the former peak is the intensity that may contain the derivative AlSiO 4 generated at the interface between the organic coating layer and the aluminum oxide layer, the intensity of Al2O4H can be determined by separating the two from each other and observing only the latter peak. Although it can be supplemented directly, according to the present invention, the distribution of the intensity of Al 2 O 4 H in the vapor-deposited film can be known by measuring the intensity derived from OH regardless of this.
  • a profile with a mass number of 118.93 obtained by TOF-SIMS is subjected to non-linear curve fitting using a Gaussian function, and overlapping peaks are separated using a least squares Levenberg-Marquardt algorithm. Just do.
  • Organic coating layer 3a laminated on the surface of the aluminum oxide vapor-deposited film 2 mechanically and chemically protects the aluminum oxide-deposited film and improves the barrier performance of the laminated film having a barrier property.
  • the organic coating layer 3a coated to form a barrier laminated film having retort resistance having excellent barrier properties will be described.
  • the organic coating layer 3a is formed by applying a barrier coating agent on an aluminum oxide vapor deposition film and solidifying it.
  • the barrier coating agent is composed of a metal alkoxide, a water-soluble polymer, a silane coupling agent added as needed, a sol-gel method catalyst, an acid and the like.
  • the general formula R1 n M (OR 2 ) m (where R 1 and R 2 represent organic groups having 1 to 8 carbon atoms, M represents a metal atom, and n represents a metal atom. Represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M.)
  • At least one kind of metal alkoxide represented by M, and a metal atom represented by M of the metal alkoxide include silicon, zirconium, titanium, aluminum, and the like.
  • the above alkoxysilane is represented by, for example, the general formula Si (ORa) 4 (where Ra represents a lower alkyl group in the formula).
  • Ra a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc. are used.
  • Specific examples of the above alkoxysilane include tetramethoxysilane Si (OCH 3 ) 4 , tetraethoxysilane Si (OC 2 H 5 ) 4 , tetrapropoxysilane Si (OC 3 H 7 ) 4, and tetrabutoxysilane Si. (OC 4 H 9 ) 4 , etc. can be used. Two or more kinds of the above alkoxides may be used in combination.
  • silane coupling agent one having a reactive group such as a vinyl group, an epoxy group, a methacryl group and an amino group can be used.
  • organoalkoxysilane having an epoxy group is preferable, for example, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropyldimethylmethoxysilane, ⁇ -glycidoxy.
  • Propyltriethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -glycidoxypropyldimethylethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be used.
  • the above-mentioned silane coupling agent may be used alone or in combination of two or more.
  • the cross-linking density of the cured film of the organic coating layer using bifunctionality such as ⁇ -glycidoxypropylmethyldimethoxysilane and ⁇ -glycidoxypropylmethyldiethoxysilane was determined in the system using trialkoxysilane. It is lower than the crosslink density. Therefore, while being excellent as a film having gas barrier properties and heat-resistant water treatment properties, it becomes a flexible cured film and also has excellent bending resistance. Therefore, the packaging material using the barrier film has gas barrier properties even after the Gelboflex test. Hard to deteriorate.
  • a polyvinyl alcohol-based resin or an ethylene / vinyl alcohol copolymer can be used alone, or a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer can be used in combination. can do.
  • a polyvinyl alcohol-based resin is suitable.
  • the polyvinyl alcohol-based resin generally, one obtained by saponifying polyvinyl acetate can be used.
  • the polyvinyl alcohol-based resin may be a partially saponified polyvinyl alcohol-based resin in which several tens of percent of acetic acid groups remain, a completely saponified polyvinyl alcohol in which no acetic acid groups remain, or a modified polyvinyl alcohol-based resin in which OH groups are modified.
  • the degree of saponification it is necessary to use at least a polyvinyl alcohol-based resin that is crystallized to improve the film hardness of the gas barrier coating film, and the degree of saponification is preferably 70% or more.
  • the degree of polymerization can be used as long as it is in the range (about 100 to 5000) used in the conventional sol-gel method.
  • a saponified product of a copolymer of ethylene and vinyl acetate that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer
  • it includes, and is not particularly limited, from a partially saponified product in which several tens of mol% of acetic acid groups remain to a completely saponified product in which only a few mol% of acetic acid groups remain or no acetic acid groups remain.
  • the degree of saponification is preferably 80% or more, more preferably 90% or more, further preferably 95% or more and 100% or less, and particularly preferably 99% or more and 100% or less. It is preferable to do so.
  • an acid or amine compound is suitable.
  • the acid for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid can be used.
  • the acid content is preferably 0.001 to 0.05 mol%, more preferably 0.01 to 0.03 mol%, based on the total molar amount of the alkoxy groups of the metal alkoxide. If it is less than 0.001% mol, the catalytic effect is too small, and if it is more than 0.05 mol%, the catalytic effect is too strong and the reaction rate becomes too fast, which tends to cause non-uniformity.
  • amine compound a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is preferable.
  • N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used.
  • N, N-dimethylbenzylamine is preferable.
  • the content of the amine compound is preferably 0.01 to 1.0 parts by mass, particularly 0.03 to 0.3 parts by mass, per 100 parts by mass of the metal alkoxide. If it is less than 0.01 part by mass, the catalytic effect is too small, and if it is more than 1.0 part by mass, the catalytic effect is too strong and the reaction rate becomes too fast, which tends to cause non-uniformity.
  • the solvent it is preferable to use water, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropanol and n-butanol.
  • alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropanol and n-butanol.
  • the barrier coating layer formed as described above has a layer thickness of 100 to 500 nm. This range is preferable because the coating film does not crack and sufficiently covers the surface of the vapor-deposited film.
  • the composition of the barrier coating agent is 5 to 10 parts by mass of a water-soluble polymer such as a polyvinyl alcohol resin and 1 part by mass of the silane coupling agent with respect to 100 parts by mass of alkoxysilane. It can be used within the range of ⁇ 10 mass parts. As a result, the flexibility of the film can be maintained and the retort resistance can be enhanced. In the above, when the silane coupling agent is used in an amount of more than 20 parts by mass, the rigidity and brittleness of the formed barrier coating film are increased, which is not preferable.
  • the silane coupling agent When the silane coupling agent is not contained, the amount ratio of the metal alkoxide is lowered by using 10 to 20 parts by mass of a water-soluble polymer such as a polyvinyl alcohol resin with respect to 100 parts by mass of alkoxysilane. Therefore, the barrier property can be enhanced.
  • the film forming apparatus 10 includes a base material transport mechanism 11A for transporting the base material 1, a plasma pretreatment mechanism 11B for performing plasma pretreatment on the surface of the base material 1, and a thin-film deposition film 2.
  • a film forming mechanism 11C for forming a film is provided.
  • the film forming apparatus 10 further includes a pressure reducing chamber 12.
  • the decompression chamber 12 has a decompression mechanism such as a vacuum pump described later that adjusts the atmosphere of at least a part of the space inside the decompression chamber 12 to atmospheric pressure or less.
  • the decompression chamber 12 is composed of a base material transfer chamber 12A in which the base material transfer mechanism 11A is located, a plasma pretreatment chamber 12B in which the plasma pretreatment mechanism 11B is located, and a film forming mechanism 11C. Membrane chamber 12C and.
  • the decompression chamber 12 is preferably configured to prevent the atmosphere inside each chamber from mixing with each other.
  • the decompression chamber 12 is formed between the base material transfer chamber 12A and the plasma pretreatment chamber 12B, between the plasma pretreatment chamber 12B and the film formation chamber 12C, and between the base material transfer chamber 12A and the film formation. It may have partition walls 35a to 35c that are located between the chambers 12C and separate the chambers.
  • the base material transfer chamber 12A, the plasma pretreatment chamber 12B, and the film formation chamber 12C will be described.
  • the plasma pretreatment chamber 12B and the film forming chamber 12C are each provided in contact with the base material transfer chamber 12A, and each has a portion connected to the base material transfer chamber 12A.
  • the base material 1 can be transported between the base material transport chamber 12A and the plasma pretreatment chamber 12B and between the base material transport chamber 12A and the film forming chamber 12C without being exposed to the atmosphere.
  • the base material 1 can be transported through the opening provided in the partition wall 35a.
  • the base material transport chamber 12A and the film forming chamber 12C have the same structure, and the base material 1 can be transported between the base material transport chamber 12A and the film forming chamber 12C.
  • the decompression mechanism of the decompression chamber 12 is configured to be able to depressurize the atmosphere of the space in which at least the plasma pretreatment mechanism 11B or the film forming mechanism 11C of the film forming apparatus 10 is arranged to be below atmospheric pressure.
  • the decompression mechanism may be configured so that each of the base material transport chamber 12A, the plasma pretreatment chamber 12B, and the film forming chamber 12C, which are partitioned by the partition walls 35a to 35c, can be depressurized to atmospheric pressure or lower.
  • the decompression chamber 12 may have, for example, a vacuum pump connected to the plasma pretreatment chamber 12B.
  • a vacuum pump By adjusting the vacuum pump, the pressure in the plasma pretreatment chamber 12B when performing the plasma pretreatment described later can be appropriately controlled. Further, it is possible to suppress the diffusion of the plasma supplied into the plasma pretreatment chamber 12B to another chamber by the method described later.
  • the decompression mechanism of the decompression chamber 12 may have a vacuum pump connected to the film forming chamber 12C as well as a vacuum pump connected to the plasma pretreatment chamber 12B.
  • a vacuum pump a dry pump, a turbo molecular pump, a cryopump, a rotary pump, a diffusion pump and the like can be used.
  • the base material transport mechanism 11A of the base material 1 of the film forming apparatus 10 will be described together with the transport path of the base material 1.
  • the base material transport mechanism 11A is a mechanism for transporting the base material 1 arranged in the base material transport chamber 12A.
  • the base material transport mechanism 11A includes a winding roller 13 to which the roll-shaped raw fabric of the base material 1 is attached, a winding roller 15 for winding the base material 1, and guide rolls 14a to 14d.
  • the base material 1 sent out from the base material transfer mechanism 11A is then divided into a pretreatment roller 20 described later arranged in the plasma pretreatment chamber 12B and a film forming roller 25 described later arranged in the film forming chamber 12C. , Transported by.
  • the base material transport mechanism 11A may further have a tension pickup roller. Since the base material transport mechanism 11A has the tension pickup roller, the base material 1 can be transported while adjusting the tension applied to the base material 1.
  • the plasma pretreatment mechanism 11B is a mechanism for applying plasma pretreatment to the surface of the base material 1.
  • the plasma pretreatment mechanism 11B shown in FIG. 2 generates plasma P, and uses the generated plasma P to perform plasma pretreatment on the surface of the base material 1.
  • the plasma pretreatment activates the surface of the base material 1 so that the nitrogen contained inside the base material 1 easily collects on the surface of the base material 1, or the nitrogen contained in the environment surrounding the base material 1 is the base material. It can be easily taken into the surface of 1.
  • the plasma pretreatment mechanism 11B shown in FIG. 2 is between the pretreatment roller 20 arranged in the plasma pretreatment chamber 12B, the electrode portion 21 facing the pretreatment roller 20, and the pretreatment roller 20 and the electrode portion 21. It has a magnetic field forming unit 23 that forms a magnetic field in the.
  • FIG. 3 is an enlarged view of the portion surrounded by the alternate long and short dash line with the reference numeral VI in FIG.
  • the pretreatment roller 20 has a rotation axis X.
  • the pretreatment roller 20 is provided so that at least the rotation axis X is located in the plasma pretreatment chamber 12B partitioned by the partition walls 35a and 35b.
  • a base material 1 having dimensions in the direction of the rotation axis X is wound around the pretreatment roller 20.
  • the dimension of the base material 1 in the direction of the rotation axis X is also referred to as the width of the base material 1.
  • the direction of the rotation axis X is also referred to as the width direction of the base material 1.
  • the pretreatment roller 20 may be provided so that a part thereof is exposed on the base material transport chamber 12A side.
  • the plasma pretreatment chamber 12B and the base material transfer chamber 12A are connected via an opening provided in the partition wall 35a, and a part of the pretreatment roller 20 is connected through the opening. Is exposed on the base material transport chamber 12A side.
  • the base material 1 can be conveyed.
  • the pretreatment roller 20 may be provided so that the entire pretreatment roller 20 is located in the plasma pretreatment chamber 12B.
  • the pretreatment roller 20 may have a temperature adjusting mechanism for adjusting the temperature of the surface of the pretreatment roller 20.
  • the pretreatment roller 20 may have a temperature adjustment mechanism inside the pretreatment roller 20 including a pipe for circulating a temperature adjustment medium such as a refrigerant or a heat medium.
  • the temperature adjusting mechanism adjusts the surface temperature of the pretreatment roller 20 to a target temperature in the range of, for example, ⁇ 20 ° C. or higher and 100 ° C. or lower.
  • the pretreatment roller 20 has a temperature adjusting mechanism, it is possible to suppress shrinkage or breakage of the base material 1 due to heat during plasma pretreatment.
  • the pretreatment roller 20 is formed of a material containing at least one or more of stainless steel, iron, copper and chromium.
  • the surface of the pretreatment roller 20 may be subjected to a hard chrome hard coat treatment or the like in order to prevent scratches. These materials are easy to process. Further, by using the above-mentioned material as the material of the pretreatment roller 20, the thermal conductivity of the pretreatment roller 20 itself is increased, so that the temperature of the pretreatment roller 20 can be easily controlled.
  • the electrode portion 21 will be described.
  • the electrode portion 21 has a first surface 21c facing the pretreatment roller 20 and a second surface 21d located on the opposite side of the first surface 21c.
  • the electrode portion 21 is a plate-shaped member, and both the first surface 21c and the second surface 21d are flat surfaces.
  • the electrode portion 21 generates plasma with the pretreatment roller 20 by applying an AC voltage with the pretreatment roller 20.
  • the electrode portion 21 preferably applies an electric field between the pretreatment roller 20 and the plasma so that the generated plasma moves in a direction perpendicular to the surface of the base material 1 so as to be directed toward the surface of the base material 1. Form. Thereby, the base material 1 can be efficiently pretreated.
  • the peak intensity H1 of the peak of the element-bonded CN formed at the interface between the base material 1 and the vapor-deposited film 2 is increased. It can be made larger.
  • the number of electrode portions 21 is preferably 2 or more.
  • the two or more electrode portions 21 are preferably arranged along the transport direction of the base material 1. In the examples shown in FIGS. 2 and 3, an example in which the film forming apparatus 10 has two electrode portions 21 is shown.
  • the number of electrode portions 21 is, for example, 12 or less.
  • the effect of arranging two or more electrode portions 21 along the transport direction of the base material 1 will be described.
  • plasma is generated between the electrode portion 21 and the pretreatment roller 20.
  • the region where plasma is generated expands as the size of the electrode portion 21 in the transport direction increases.
  • the electrode portion 21 is a flat plate-shaped member, the larger the dimension of the electrode portion 21 in the transport direction, the more the first surface 21c of the electrode portion 21 in the transport direction faces the pretreatment roller 20.
  • the distance from the end of the pretreatment roller 20 to the pretreatment roller 20 becomes large, and the processing capacity by plasma decreases.
  • two or more electrode portions 21 are lined up along the transport direction of the base material 1. Therefore, even when the size of the electrode portion 21 in the transport direction of the base material 1 is small, plasma can be generated over a wide range in the transport direction. Further, by reducing the size of the electrode portion 21, the distance from the end of the first surface 21c of the electrode portion 21 to the pretreatment roller 20 in the transport direction can be reduced, and plasma is uniformly generated in the transport direction. Can be made to.
  • the electrode portion 21 has a first end portion 21e and a second end portion 21f located on the first surface 21c of the electrode portion 21.
  • the first end portion 21e is an upstream end portion in the transport direction of the base material 1
  • the second end portion 21f is a downstream end portion in the transport direction of the base material 1.
  • the angle ⁇ is an angle formed by a straight line passing through the first end portion 21e and the rotation axis X and a straight line passing through the second end portion 21f and the rotation axis X.
  • the angle ⁇ is preferably 20 ° or more and 90 ° or less, more preferably 60 ° or less, and further preferably 45 ° or less.
  • the material of the electrode portion 21 is not particularly limited as long as it has conductivity. Specifically, aluminum, copper, and stainless steel are preferably used as the material of the electrode portion 21.
  • the thickness L3 of the electrode portion 21 when viewed in the direction perpendicular to the first surface 21c of the electrode portion 21 is not particularly limited, but is, for example, 15 mm or less.
  • the magnetic field forming portion 23 can effectively form a magnetic field between the pretreatment roller 20 and the electrode portion 21.
  • the thickness L3 of the electrode portion 21 is, for example, 3 mm or more.
  • the magnetic field forming unit 23 will be described. As shown in FIGS. 2 and 3, the magnetic field forming portion 23 is provided on the side of the electrode portion 21 opposite to the side facing the pretreatment roller 20.
  • the magnetic field forming portion 23 is a member that forms a magnetic field between the pretreatment roller 20 and the electrode portion 21.
  • the magnetic field between the pretreatment roller 20 and the electrode portion 21 contributes to the generation of higher density plasma, for example, when plasma is generated using the plasma pretreatment mechanism 11B.
  • the magnetic field forming portion 23 shown in FIGS. 2 and 3 has a first magnet 231 and a second magnet 232 provided on the second surface 21d of the electrode portion 21.
  • the number of magnetic field forming portions 23 is preferably 2 or more.
  • each of the two or more magnetic field forming portions 23 is a respective of the two or more electrode portions 21.
  • the pretreatment roller 20 is provided on the side opposite to the side facing the pretreatment roller 20. In the examples shown in FIGS. 2 and 3, each of the two magnetic field forming portions 23 is provided on the second surface 21d of each of the two electrode portions 21.
  • the first magnet 231 and the second magnet 232 have an north pole and an south pole, respectively.
  • Reference numeral N shown in FIGS. 2 and 3 indicates the north pole of the first magnet 231 or the second magnet 232.
  • reference numeral S shown in FIGS. 2 and 3 indicates the S pole of the first magnet 231 or the second magnet 232.
  • One of the north pole or the south pole of the first magnet 231 is located closer to the base material 1 than the other.
  • the other of the north pole or the south pole of the second magnet 232 is located closer to the base material 1 than one. In the examples shown in FIGS.
  • the north pole of the first magnet 231 is located closer to the base material 1 than the south pole of the first magnet 231 and the south pole of the second magnet 232 is the second magnet. It is located on the base material 1 side of the north pole.
  • the S pole of the first magnet 231 is located on the base material 1 side of the N pole of the first magnet 231 and the N pole of the second magnet 232 is based on the S pole of the second magnet 232. It may be located on the material 1 side.
  • FIG. 4 is a plan view of the electrode portion 21 and the magnetic field forming portion 23 shown in FIG. 2 as viewed from the magnetic field forming portion 23 side.
  • FIG. 5 is a cross-sectional view showing a cross section taken along the line VIII-VIII of FIG. Further, in FIG. 4, the direction D1 is the direction in which the rotation axis X of the pretreatment roller 20 extends.
  • the first magnet 231 has a first axial portion 231c. As shown in FIG. 4, the first axial portion 231c extends along the direction D1, that is, along the rotation axis X of the pretreatment roller 20.
  • the first magnet 231 provided on one electrode portion 21 may have one first axial portion 231c, or may have two or more first axial portions 231c. In the example shown in FIG. 4, the first magnet 231 provided on one electrode portion 21 has one first axial direction portion 231c.
  • the second magnet 232 has a second axial portion 232c. As shown in FIG. 4, the second axial portion 232c also extends along the direction D1, that is, along the rotation axis X, like the first axial portion 231c.
  • the uniformity of the strength of the magnetic field formed around the base material 1 in the width direction of the base material 1 is enhanced. be able to. Thereby, the uniformity of the distribution density of the plasma formed around the base material 1 in the width direction of the base material 1 can be enhanced.
  • the second magnet 232 provided on one electrode portion 21 may have one second axial portion 232c, or may have two or more second axial portions 232c. In the examples shown in FIGS. 4 and 5, the second magnet 232 provided on one electrode portion 21 has two second axial portions 232c. The two second axial portions 232c may be positioned so as to sandwich the first axial portion 231c in the direction D2 orthogonal to the rotation axis X in the surface direction of the second surface 21d of the electrode portion 21.
  • the dimension L4 of the first axial portion 231c and the dimension L5 of the second axial portion 232c in the transport direction of the base material 1 shown in FIG. 5 are not particularly limited. Further, the ratio of the dimension L4 of the first axial portion 231c and the dimension L5 of the second axial portion 232c in the transport direction of the base material 1 is not particularly limited. The dimension L4 of the first axial portion 231c and the dimension L5 of the second axial portion 232c may be equal to each other, and the dimension L4 of the first axial portion 231c may be larger than the dimension L5 of the second axial portion 232c. ..
  • the distance L6 between the first axial portion 231c and the second axial portion 232c in the direction D2 is such that the magnetic field generated by the first axial portion 231c and the second axial portion 232c is between the pretreatment roller 20 and the electrode portion 21. Is set to be formed in.
  • the second magnet 232 may surround the first magnet 231 when the magnetic field forming portion 23 is viewed along the normal direction of the second surface 21d of the electrode portion 21.
  • the second magnet 232 has two second axial portions 232c and two connecting portions 232d provided to connect the two second axial portions 232c. May be good.
  • the magnetic flux density of the magnets of the magnetic field forming unit 23 such as the first magnet 231 and the second magnet 232 is, for example, 100 gauss or more and 10,000 gauss or less.
  • the magnetic flux density is 100 gauss or more, a sufficiently high density plasma can be generated by forming a sufficiently strong magnetic field between the pretreatment roller 20 and the electrode portion 21, and a good pretreatment surface can be generated. Can be formed at high speed.
  • an expensive magnet or a magnetic field generation mechanism is required.
  • the plasma pretreatment mechanism 11B may have a plasma raw material gas supply unit.
  • the plasma raw material gas supply unit supplies the plasma raw material gas into the plasma pretreatment chamber 12B.
  • the configuration of the plasma raw material gas supply unit is not particularly limited.
  • the plasma raw material gas supply unit is provided on the wall surface of the plasma pretreatment chamber 12B and includes a hole for ejecting a gas as a raw material for plasma.
  • the plasma raw material gas supply unit may have a nozzle for discharging the plasma raw material gas at a position closer to the base material 1 than the wall surface of the plasma pretreatment chamber 12B.
  • the plasma raw material gas supplied by the plasma raw material gas supply unit for example, an inert gas such as argon, an active gas such as oxygen, nitrogen, carbon dioxide gas, or ethylene, or a mixed gas of these gases is supplied.
  • an inert gas such as argon
  • an active gas such as oxygen, nitrogen, carbon dioxide gas, or ethylene
  • a mixed gas of these gases is supplied.
  • the plasma raw material gas regardless of whether one of the inert gases is used alone or one of the active gases is used alone, the inert gas or two or more kinds of gases contained in the active gas You may use the mixed gas of.
  • the plasma raw material gas it is preferable to use a mixed gas of an inert gas such as argon and an active gas.
  • the plasma raw material gas supply unit supplies a mixed gas of argon (Ar) and oxygen (O 2).
  • Plasma pretreatment mechanism 11B is, for example, supplied between the pretreatment roller 20 and the electrode portion 21 of the plasma density 100W ⁇ sec / m 2 or more 8000W ⁇ sec / m 2 or less of the plasma.
  • the plasma pretreatment mechanism 11B is arranged in the plasma pretreatment chamber 12B separated from the base material transport chamber 12A and the film forming chamber 12C by a partition wall.
  • the atmosphere of the plasma pretreatment chamber 12B can be easily adjusted independently. As a result, for example, it becomes easy to control the plasma raw material gas concentration in the space where the pretreatment roller 20 and the electrode portion 21 face each other, and the productivity of the laminated film is improved.
  • the voltage applied between the pretreatment roller 20 of the plasma pretreatment mechanism 11B and the electrode portion 21 is an AC voltage.
  • an AC voltage By applying an AC voltage, plasma is generated between the pretreatment roller 20 and the electrode portion 21.
  • an electric field is formed so that the generated plasma moves toward the surface of the base material 1 in a direction perpendicular to the surface of the base material 1.
  • the value of the AC voltage applied between the pretreatment roller 20 and the electrode portion 21 is preferably 250 V or more and 1000 V or less.
  • the value of the AC voltage means the effective value Ve.
  • the effective value Ve of the AC voltage is calculated by the following formula when the maximum value of the AC voltage is Vm.
  • the AC voltage applied between the pretreatment roller 20 and the electrode portion 21 has, for example, a frequency of 20 kHz or more and 500 kHz or less.
  • the film forming mechanism 11C (Film formation mechanism) Next, the film forming mechanism 11C will be described.
  • the film forming mechanism 11C has a film forming roller 25 arranged in the film forming chamber 12C and an evaporation mechanism 24.
  • the film forming roller 25 will be described.
  • the film forming roller 25 is a roller that winds and conveys the base material 1 with the treatment surface of the base material 1 pretreated by the plasma pretreatment mechanism 11B on the outside.
  • the material of the film forming roller 25 will be described.
  • the film forming roller 25 is preferably formed of a material containing at least one or more of stainless steel, iron, copper and chromium.
  • the surface of the film forming roller 25 may be subjected to a hard chrome hard coat treatment or the like in order to prevent scratches. These materials are easy to process. Further, by using the above-mentioned material as the material of the film forming roller 25, the thermal conductivity of the film forming roller 25 itself is increased, so that the temperature controllability is excellent when the temperature is controlled.
  • the surface average roughness Ra of the surface of the film forming roller 25 is, for example, 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the film forming roller 25 may have a temperature adjusting mechanism for adjusting the temperature of the surface of the film forming roller 25.
  • the temperature adjusting mechanism has, for example, a circulation path for circulating the cooling medium or the heat source medium inside the film forming roller 25.
  • the cooling medium (refrigerant) is, for example, an ethylene glycol aqueous solution
  • the heat source medium heat medium
  • the temperature adjusting mechanism may have a heater installed at a position facing the film forming roller 25.
  • the temperature adjusting mechanism preferably sets the temperature of the surface of the film forming roller 25 to ⁇ 20 from the viewpoint of heat resistance restrictions and versatility of related mechanical parts. Adjust to the target temperature within the range of ° C or higher and 200 ° C or lower. Since the film forming roller 25 has a temperature adjusting mechanism, it is possible to suppress fluctuations in the temperature of the base material 1 due to heat generated during film formation.
  • FIG. 6 is an enlargement of the portion surrounded by the alternate long and short dash line in FIG. 2, showing a specific form of the evaporation mechanism 24 which was omitted in FIG. 5, and was omitted in FIG. It is a figure which showed the vapor deposition material supply part 61 which supplies the vapor deposition material.
  • the evaporation mechanism 24 is a mechanism for evaporating a vaporized material containing aluminum. When the evaporated vaporized material adheres to the base material 1, a thin-film vapor-deposited film containing aluminum is formed on the surface of the base material 1.
  • the evaporation mechanism 24 in this embodiment adopts a resistance heating type.
  • the evaporation mechanism 24 has a boat 24b.
  • the boat 24b has a power source (not shown) and a resistor (not shown) electrically connected to the power source.
  • a plurality of boats 24b may be arranged in the width direction of the base material 1.
  • the film forming mechanism 11C may have a vapor deposition material supply unit 61 that supplies the vapor deposition material to the evaporation mechanism 24.
  • FIG. 6 shows an example in which the thin-film deposition material supply unit 61 continuously sends out a metal wire rod made of aluminum.
  • the film forming mechanism 11C has a gas supply mechanism.
  • the gas supply mechanism is a mechanism for supplying gas between the evaporation mechanism 24 and the film forming roller 25.
  • the gas supply mechanism supplies at least oxygen gas.
  • the oxygen gas evaporates from the evaporation mechanism 24 and reacts with or combines with an evaporative material such as aluminum heading toward the base material 1 on the film forming roller 25. As a result, a vapor-deposited film containing aluminum oxide can be formed on the surface of the base material 1.
  • the film forming mechanism 11C includes a plasma supply mechanism 50 that supplies plasma between the surface of the base material 1 and the evaporation mechanism 24.
  • the plasma supply mechanism 50 has a hollow cathode 51.
  • the hollow cathode 51 is a cathode having a hollow portion that is partially open.
  • the hollow cathode 51 can generate plasma in the cavity.
  • the hollow cathode 51 is provided so that the opening of the cavity of the hollow cathode 51 is located obliquely above the boat 24b.
  • the plasma supply mechanism 50 according to the present embodiment has an anode facing the opening that draws plasma from the opening of the hollow portion of the hollow cathode 51.
  • the plasma supply mechanism 50 generates plasma in the cavity of the hollow cathode 51, and pulls the plasma between the surface of the base material 1 and the evaporation mechanism 24 by the opposing anodes, thereby causing the base material.
  • a strong plasma can be generated between the surface of 1 and the evaporation mechanism 24.
  • the position of the facing anode is not particularly limited as long as the facing anode can draw plasma from the opening of the hollow portion of the hollow cathode 51 and supply the plasma between the surface of the base material 1 and the evaporation mechanism 24. ..
  • the opposing anodes are arranged on both sides of the boat 24b in the width direction of the base material 1 will be described.
  • the film forming mechanism 11C has a plurality of boats 24b and a plurality of opposing anodes, and even if the plurality of boats 24b and the plurality of facing anodes are alternately arranged in the width direction of the base material 1.
  • the plasma supply mechanism 50 may have a raw material supply device that supplies plasma raw material gas at least in the cavity of the hollow cathode 51.
  • a gas similar to the gas that can be used as the plasma raw material gas supplied by the plasma raw material gas supply unit of the plasma pretreatment mechanism 11B can be used.
  • the plasma supply mechanism 50 supplies plasma between the surface of the base material 1 and the evaporation mechanism 24.
  • the aluminum and oxygen gas evaporated in the evaporation mechanism 24 are activated.
  • the reaction or bond between aluminum and oxygen gas can be promoted.
  • the ratio of aluminum in the vapor-deposited film 2 formed on the surface of the base material 1 as aluminum oxide can be increased, and the characteristics of the vapor-deposited film 2 can be stabilized.
  • the film forming apparatus 10 is caused by the film formation by the film forming mechanism 11C in the portion of the base material conveying chamber 12A located on the downstream side in the conveying direction of the base material 1 with respect to the film forming chamber 12C.
  • a base material charge removing portion for performing post-treatment for removing the charge generated on the base material 1 may be provided.
  • the base material charge removing portion may be provided so as to remove the charge on one side of the base material 1, or may be provided so as to remove the charge on both sides of the base material 1.
  • the device used as the base material charge removing unit for post-treating the base material 1 is not particularly limited, and examples thereof include a plasma discharge device, an electron beam irradiation device, an ultraviolet irradiation device, a static elimination bar, a glow discharge device, and a corona treatment device. Can be used.
  • post-treatment When post-treatment is performed by forming a discharge using a plasma treatment device or a glow discharge device, a single discharge gas such as argon, oxygen, nitrogen, or helium, or a mixed gas thereof is supplied in the vicinity of the base material 1.
  • post-processing can be performed using any discharge method such as AC (AC) plasma, DC (DC) plasma, arc discharge, microwave, and surface wave plasma.
  • AC AC
  • DC DC
  • arc discharge arc discharge
  • microwave and surface wave plasma
  • the base material charge removing portion is installed in a portion of the base material transport chamber 12A located downstream of the film forming chamber 12C in the transport direction of the base material 1, and the base material 1 is removed from the charge.
  • the material 1 can be quickly separated from the film forming roller 25 at a predetermined position and conveyed. Therefore, stable transfer of the base material is possible, damage to the base material 1 and deterioration of quality due to charging can be prevented, and the wettability of the front and back surfaces of the base material can be improved to improve post-processing suitability.
  • the film forming apparatus 10 further includes a power supply 32 electrically connected to the pretreatment roller 20 and the electrode portion 21.
  • the power supply 32 is electrically connected to the pretreatment roller 20 and the electrode portion 21 via the power supply wiring 31.
  • the power supply 32 is, for example, an AC power supply.
  • the power supply 32 can apply an AC voltage having a frequency of, for example, 20 kHz or more and 500 kHz or less between the pretreatment roller 20 and the electrode portion 21.
  • the input power that can be applied by the power source 32 (the power that can be applied per 1 m width of the electrode portion 21 in the width direction of the base material 1) is not particularly limited, but is, for example, 0.5 kW / m or more and 20 kW / m or less. is there.
  • the pretreatment roller 20 may be electrically installed at the ground level or electrically at the floating level.
  • a method for producing the barrier film shown in FIG. 1 will be described using the film forming apparatus 10 described above.
  • a film forming method for forming the vapor deposition film 2 on the surface of the base material 1 will be described.
  • the substrate 1 is transported along the above-mentioned transport path of the base material 1, and the surface of the base material 1 is subjected to plasma pretreatment using the plasma pretreatment mechanism 11B.
  • a plasma pretreatment step and a film forming step of forming a vapor-deposited film on the surface of the base material 1 are performed using the film-forming mechanism 11C.
  • the transport speed of the base material 1 is preferably 200 m / min or more, more preferably 400 m / min or more and 1000 m / min or less.
  • the plasma pretreatment step is performed by, for example, the following method. First, the plasma raw material gas is supplied into the plasma pretreatment chamber 12B. Next, the above-mentioned AC voltage is applied between the pretreatment roller 20 and the electrode portion 21. When applying the AC voltage, input power control, impedance control, or the like may be performed.
  • oxygen alone or a mixed gas of oxygen gas and an inert gas is supplied from the gas storage unit via a flow rate controller while measuring the gas flow rate.
  • the inert gas include one or more mixed gases selected from the group of argon, helium, and nitrogen.
  • the mixing ratio of the oxygen gas and the inert gas and the oxygen gas / inert gas are preferably 6/1 to 1/1, more preferably 5/2 to 3 / 2.5.
  • the mixing ratio By setting the mixing ratio to 6/1 to 1/1, the film forming energy of the vapor-deposited aluminum on the resin base material increases, and by further setting it to 5/2 to 3/2, the oxide of the aluminum oxide-deposited film is oxidized. It is possible to increase the degree and secure the adhesion between the aluminum oxide vapor deposition film and the base material.
  • Plasma is generated at the same time as glow discharge by applying an AC voltage, and the plasma P becomes denser between the pretreatment roller 20 and the magnetic field forming unit 23. In this way, the plasma P can be supplied between the pretreatment roller 20 and the magnetic field forming unit 23. With this plasma P, the surface of the base material 1 can be subjected to plasma (ion) pretreatment.
  • the plasma intensity of the plasma pretreatment is preferably 100 W ⁇ sec / m 2 or more and 1000 W ⁇ sec / m 2 or less in order to form an aluminum oxide layer.
  • the pressure in the plasma pretreatment chamber 12B when an AC voltage is applied between the pretreatment roller 20 and the electrode portion 21 is reduced to atmospheric pressure or less by the pressure reducing chamber 12.
  • the atmospheric pressure in the plasma pretreatment chamber 12B is adjusted so that a glow discharge can be generated between the pretreatment roller 20 and the electrode portion 21 by applying an AC voltage, for example.
  • the degree of vacuum in the plasma pretreatment chamber 12B when an AC voltage is applied between the pretreatment roller 20 and the electrode portion 21 can be set and maintained at about 0.1 Pa or more and 100 Pa or less, and in particular, 1 Pa or more. 20 Pa or less is preferable.
  • the magnetic field forming portion 23 forms a magnetic field between the pretreatment roller 20 and the electrode portion 21.
  • the magnetic field can act to capture and accelerate the electrons present between the pretreatment roller 20 and the electrode section 21. Therefore, in the region where the magnetic field is formed, the frequency of collision between the electrons and the plasma raw material gas can be increased, the density of the plasma can be increased, and the plasma can be localized, so that the efficiency of the plasma pretreatment can be improved. it can.
  • the film forming mechanism 11C is used to form a film on the surface of the base material 1.
  • the film forming process a case where the aluminum oxide vapor deposition film is formed by using the film forming mechanism 11C having the evaporation mechanism 24 shown in FIG. 6 will be described.
  • a vapor deposition material containing aluminum is supplied into the boat 24b of the evaporation mechanism 24 so as to face the film forming roller 25.
  • the vapor deposition material an aluminum metal wire can be used.
  • the vapor deposition material is supplied to the boat 24b by continuously sending the aluminum metal wire into the boat 24b by the vapor deposition material supply unit 61.
  • Aluminum is evaporated in the boat 24b by heating.
  • FIG. 6 illustrates the evaporated aluminum vapor 63 for convenience.
  • the oxygen gas that oxidizes aluminum may be supplied as a simple substance of oxygen or a mixed gas with an inert gas such as argon, but by controlling the amount of oxygen, both barrier property and transparency can be achieved.
  • the degree of vacuum at this time is preferably 0.05 Pa or more and 8.00 Pa or less.
  • a method of supplying plasma between the surface of the base material 1 and the evaporation mechanism 24 by the plasma supply mechanism 50 that is, plasma assist at the time of vapor deposition will be described.
  • plasma is generated in the cavity of the hollow cathode 51 of the plasma supply mechanism 50.
  • a discharge is generated between the hollow cathode 51 and the anode facing the hollow cathode 51, and the plasma in the cavity of the hollow cathode 51 is drawn out between the surface of the base material 1 and the evaporation mechanism 24.
  • the discharge generated between the hollow cathode 51 and the anode facing the hollow cathode 51 is an arc discharge.
  • the arc discharge means for example, a discharge in which the value of the current is 10 A or more.
  • Plasma is supplied to the aluminum vapor 63 by evaporating aluminum while supplying plasma between the surface of the base material 1 and the evaporation mechanism 24.
  • the supply of plasma can promote the reaction or bond between the aluminum vapor 63 and the oxygen gas.
  • the aluminum vapor 63 can be oxidized before reaching the surface of the base material 1.
  • an aluminum oxide vapor-deposited film can be formed on the surface of the base material 1 to produce the barrier film shown in FIG.
  • the plasma raw material gas supplied by the plasma supply mechanism 50 is preferably oxygen alone or a mixed gas of oxygen gas and an inert gas.
  • a plasma pretreatment step of supplying plasma to the surface of the base material 1 is carried out before the film forming step.
  • an AC voltage is applied between the electrode portion 21 and the pretreatment roller 20.
  • the space between the electrode portion 21 and the pretreatment roller 20 is utilized by using the magnetic field forming portion 23 located on the side of the surface of the electrode portion 21 opposite to the surface facing the pretreatment roller 20. Generates a magnetic field in. Therefore, plasma can be efficiently generated in the space between the electrode portion 21 and the pretreatment roller 20, or the plasma can be made to enter perpendicularly to the surface of the base material 1 wound around the pretreatment roller 20. can do. Therefore, it is possible to improve the adhesion between the film formed by the film forming step and the base material 1.
  • the organic coating layer 3a can be produced by the following method. First, the above metal alkoxide, a water-soluble polymer, a silane coupling agent added as needed, a sol-gel method catalyst, an acid, and an organic solvent such as water as a solvent, an alcohol such as methyl alcohol, ethyl alcohol, or isopropanol are mixed. And prepare a barrier coating agent. Next, the above barrier coating agent is applied onto the aluminum oxide vapor deposition film by a conventional method and dried. By this drying step, polycondensation of the metal alkoxide, the silane coupling agent and the water-soluble polymer further proceeds, and a coating film is formed.
  • the above coating operation may be repeated to form a plurality of coating films composed of two or more layers. Further, the heat treatment is carried out at a temperature of 20 to 200 ° C. and lower than the melting point of the plastic substrate, preferably in the temperature range of 50 to 180 ° C. for 3 seconds to 10 minutes. As a result, the organic coating layer 3a made of the barrier coating agent can be formed on the aluminum oxide vapor deposition film.
  • FIG. 7A is a diagram showing an example of a laminated body 40a formed by using the barrier film according to the present embodiment.
  • the laminated body 40a includes the barrier film shown in FIG. 1 and the sealant layer 7. Specifically, the laminated body 40a is further formed on the organic coating layer of the barrier film shown in FIG. 1, an adhesive layer 4, a second base material 5 composed of polyamide or the like, an adhesive layer 6, and a sealant. Layers 7 are provided in this order.
  • the laminate of the present invention is obtained by laminating at least one heat-sealable layer on a barrier film, and the heat-sealable thermoplastic resin is used as the innermost layer with or without an adhesive layer. It is laminated and has a sealing property such as a heat seal.
  • thermoplastic resin constituting the sealant layer 7 examples include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, polymethylpentene, polystyrene, and ethylene-vinyl acetate. Contains one or more resins such as polymers, ionomer resins, ethylene-acrylic acid copolymers, ethyl ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, and elastomers. A film can be exemplified.
  • the thickness of the sealant layer 7 is preferably 3 to 100 ⁇ m, more preferably 15 to 70 ⁇ m.
  • the above-mentioned laminate is useful when used as a packaging material for producing a packaging bag for containing contents such as food.
  • a barrier film that maintains high adhesion even after heat treatment can be suitably used as a material for packaging bags.
  • the above-mentioned barrier film can suppress peeling of the layers constituting the barrier film in the packaged product when the packaged product is produced using the barrier film as a material.
  • a packaging bag made of a barrier film is subjected to a heat sterilization treatment using hot water, for example, a retort treatment or a boil treatment
  • the layers constituting the barrier film are peeled off, particularly the vapor deposition film 2.
  • the peeling from the base material 1 can be suppressed.
  • the retort treatment is a treatment in which the contents are filled in the packaging bag, the packaging bag is sealed, and then the packaging bag is heated in a pressurized state using steam or heated hot water.
  • the temperature of the retort treatment is, for example, 120 ° C. or higher.
  • the boil treatment is a treatment in which the contents are filled in a packaging bag, the packaging bag is sealed, and then the packaging bag is boiled in hot water under atmospheric pressure.
  • the temperature of the boiling treatment is, for example, 90 ° C. or higher and 100 ° C. or lower.
  • the barrier films according to Examples 1 and 2, Reference Examples 1 and 2, and Comparative Example 1 were produced by using the film forming apparatus 1 which is the film forming apparatus according to the present embodiment and the film forming method. .. Table 1 summarizes the pretreatment conditions, vapor deposition conditions, and the like.
  • " ⁇ " in the evaluation of "presence or absence of plasma pretreatment” means that plasma pretreatment is present
  • "x” means that there is no plasma pretreatment.
  • " ⁇ ” in the evaluation of "presence or absence of plasma assist during vapor deposition” means that plasma assist is present during vapor deposition
  • "x" means that there is no plasma assist during vapor deposition.
  • Example 1 A biaxially stretched polyethylene terephthalate film (PET film) having a thickness of 12 ⁇ m was used as the base material 1, and a plasma pretreatment step and a film forming step were performed using the film forming apparatus 10 shown in FIG.
  • PET film polyethylene terephthalate film
  • the vapor deposition film 2 containing aluminum oxide was deposited by the vacuum vapor deposition method using the evaporation mechanism 24 as shown in FIG. Specifically, after adjusting the degree of vacuum in the film forming chamber 12C to 1.5 Pa, the boat uses a resistance heating type evaporation mechanism 24 while supplying an aluminum metal wire as a vapor deposition material into the boat 24b. The vapor-deposited material in 24b was heated to evaporate the aluminum so as to reach the surface of the base material 1, and the vapor-deposited film 2 was formed on the surface of the base material 1 while supplying oxygen at 12500 sccm.
  • the plasma by opposing the anode, substrate It was pulled out between the surface of No. 1 and the evaporation mechanism 24 to perform plasma assist during vapor deposition.
  • the vapor deposition film 2 was laminated on the base material 1 by the above method. At this time, the transport speed was 600 m / min, and the thickness of the vapor-deposited film 2 was 8 nm.
  • organic coating layer 3a (organic coating layer A in Tables 1 and 2) was laminated on the vapor-deposited film 2.
  • 307 g of water, 147 g of isopropyl alcohol and 7.3 g of 0.5N hydrochloric acid were mixed, and 175 g of tetraethoxysilane as a metal alkoxide and glycidoxypropyltrimethoxysilane as a silane coupling agent were added to a solution adjusted to pH 2.2.
  • Solution A was prepared by mixing 7 g while cooling to 10 ° C.
  • a solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a degree of polymerization of 2400 with a degree of polymerization of 99% or more, 324 g of water, and 17 g of isopropyl alcohol.
  • the solution obtained by mixing the solution A and the solution B so as to have a mass ratio of 6.5: 3.5 was used as a barrier coating agent.
  • the barrier coating agent prepared above was coated on the aluminum oxide vapor-deposited film of the PET film by a spin coating method. Then, it was heat-treated in an oven at 180 ° C. for 60 seconds to form a barrier coating layer having a thickness of about 400 nm on an aluminum oxide vapor-deposited film to form an organic coating layer A, and the barrier film of Example 1 was formed. Manufactured.
  • Example 2 In Example 1, the barrier film of Example 2 was produced in the same manner as in Example 1 except that the transport speed was 480 m / min and the thickness of the vapor-deposited film 2 was 13 nm.
  • Reference example 1 As shown in Table 1, in Example 1, EB (electron beam) type evaporation mechanism (not shown) was used instead of the resistance heating type evaporation mechanism 24 without performing plasma pretreatment, and plasma during vapor deposition was used.
  • the barrier film of Reference Example 1 was produced in the same manner as in Example 1 except that the oxygen supply amount was 8500 sccm and the vacuum degree at the time of vaporization was 0.15 Pa without performing the assist treatment.
  • Reference example 2 As shown in Table 1, in Example 1, the air pressure in the plasma pretreatment chamber 12B was 3.5 Pa, the plasma assist treatment during vapor deposition was not performed, the oxygen supply amount was 10000 sccm, and the degree of vacuum during vapor deposition was 0.
  • the barrier film of Reference Example 2 was produced in the same manner as in Example 1 except that it was set to .02 Pa.
  • Comparative Example 1 As shown in Table 1, the barrier film of Comparative Example 1 was produced in the same manner as in Reference Example 2 except that the transport speed was 480 m / min and the thickness of the vapor-deposited film 2 was 13 nm in Reference Example 3.
  • Examples 3 to 5, Comparative Example 2 Barrier films of Examples 3 to 5 and Comparative Example 2 were produced under the film-forming conditions shown in Table 2 using a film-forming device 2 different from the above-mentioned film-forming device 1.
  • organic coating layer B 197 g of water, 34 g of isopropyl alcohol and 4.7 g of 0.5N hydrochloric acid were mixed, and 145 g of tetraethoxysilane as a metal alkoxide was cooled to 15 ° C. in a solution adjusted to pH 2.2.
  • Solution A was prepared by mixing with each other.
  • a solution B was prepared by mixing 8.3 g of polyvinyl alcohol having a degree of polymerization of 2400 with a degree of polymerization of 99% or more, 182 g of water, and 9.6 g of isopropyl alcohol.
  • the solution obtained by mixing the solution A and the solution B so as to have a mass ratio of 4.0: 6.0 was used as a barrier coating agent.
  • the barrier coating agent prepared above was coated on the aluminum oxide vapor-deposited film of the PET film by a spin coating method. Then, it was heat-treated in an oven at 180 ° C. for 60 seconds to form a barrier coating layer having a thickness of about 400 nm on an aluminum oxide vapor-deposited film to form an organic coating layer B.
  • TOF-SIMS analysis For the barrier films of Examples 1 to 5 and Comparative Examples 1 and 2, the surface of the vapor-deposited film of the barrier film was subjected to the following measurement conditions using a time-of-flight secondary ion mass spectrometer (TOF.SIMS5 manufactured by ION TOF). From the side, while repeating soft etching at a constant speed with a Cs (cesium) ion gun, C 6 derived from a resin substrate (mass number 72.00) and Al 2 O 3 derived from an aluminum oxide vapor deposition film (mass number 101.
  • TOF.SIMS5 manufactured by ION TOF
  • FIGS. 8 to 10 Graph analysis diagrams of the measurement results of the film forming apparatus 1 are shown in FIGS. 8 to 10.
  • FIG. 8 is the measurement result of Example 1
  • FIG. 9 is the measurement result of Example 2
  • FIG. 10 is the measurement result of Comparative Example 1.
  • FIGS. 11 to 14. 11 is a measurement result of Example 3
  • FIG. 12 is a measurement result of Example 4
  • FIG. 13 is a measurement result of Example 5, and FIG.
  • TOF-SIMS measurement conditions Primary ion type: Bi 3 ++ (0.2 pA, 100 ⁇ s) -Measurement area: 150 x 150 ⁇ m 2 ⁇ Etching gun type: Cs (1keV, 60nA) ⁇ Etching area: 600 ⁇ 600 ⁇ m 2 ⁇ Etching rate: 10 sec / Cycle
  • the position representing the intensity peak of the measured elemental bond OH (mass number 17.00) is determined by the number of etching seconds (peak position Y), and the depth position (peak position Y) from the surface of the vapor-deposited film on the organic coating layer side at that position ( The peak position Y / X in FIG. 9 (unit:%) was determined.
  • the water vapor transmittance was measured using a water vapor transmittance measuring device (manufactured by Mocon Co., Ltd., product name "Permatlan”) under the measurement conditions of 40 ° C. and 100% RH in accordance with the JIS K7129B method.
  • the oxygen permeability is based on JIS K 7126-2 under the measurement conditions of 23 ° C and 90% RH using an oxygen permeability measuring device (manufactured by Mocon, product name "OXTRAN"). It was measured. The results are shown in Tables 5 and 6.
  • a two-component curable polyurethane-based laminating adhesive is applied onto the organic coating layer 3a of the barrier films of Examples 1 and 2, Reference Examples 1 to 3, and Comparative Example 1 produced by the above method, and a gravure roll coating method is applied. It was used to coat a thickness of 4.0 g / m 2 (dry state) to form an adhesive layer 4, and then on the surface of the adhesive layer 4, biaxially stretched nylon having a thickness of 15 ⁇ m as a second base material 5. The 6 films were opposed to each other, dry-laminated and laminated.
  • an adhesive layer 6 for laminating is formed on the surface of the second base material 5 in the same manner as the adhesive layer 4 described above, and then the thickness of the sealant layer 7 is formed on the surface of the adhesive layer 6.
  • a 70 ⁇ m unstretched polypropylene film was dry-laminated and laminated to produce a laminated body having a layer structure as shown in FIG. 7.
  • the laminated body having this layer structure was formed into a pouch by facing the sealant layers so as to face each other and heat-sealing them. After filling the pouch with water, it was retorted at 135 ° C. for 40 minutes. The value of the watering peel strength was measured for each of the laminated bodies in the state after the retort treatment. The results are summarized in Tables 5 and 6.
  • the watering peel strength was measured by the following method. First, each of the laminated bodies in the state after the retort treatment was cut into strips to obtain a rectangular test piece having a width of 15 mm. Next, the vapor-deposited film of the test piece and the base material were partially peeled off in the longitudinal direction of the test piece (the direction orthogonal to the width direction of the test piece). The peeling of the vapor-deposited film and the base material was performed so that the vapor-deposited film and the base material maintained a bond in part.
  • the peel strength at the interface between the vapor-deposited film and the substrate was measured under the conditions of a peeling angle of 180 ° and a peeling speed of 50 mm / min in accordance with JIS Z6854-2.
  • the tensile force required to proceed the peeling over 30 mm was measured, and the average value of the tensile force was calculated.
  • the strength derived from the elemental bond OH has a downwardly convex peak, and the downwardly convex peak is located at a depth of 10% or more and 60% or less from the surface side of the organic coating layer in the vapor deposition film.
  • the barrier property is higher than that of the comparative example.
  • the growth of the aluminum oxide vapor-deposited film on the surface of the aluminum hydroxide proceeds in two-dimensional growth, and a more dense aluminum oxide-deposited film is formed. That is, the aluminum oxide film deposited on the surface of the aluminum hydroxide has a feature of exhibiting an excellent barrier property against oxygen and water vapor as compared with aluminum oxide deposited directly on the surface of the plastic film.
  • an alumina hydroxide region is formed in the vicinity of the plastic film and the aluminum vapor deposition interface, and the alumina hydroxide region is mainly oxidized.
  • the aluminum region it is possible to provide a higher barrier property.
  • the present invention (second invention) provides the following.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the element bond Al 2 O 3 and the element bond Al 2 O 4 H-derived intensity was detected,
  • the intensity ratio of the element bond Al 2 O 4 H to the element bond Al 2 O 3 detected at a depth position of 1/3 in the film thickness direction from the surface of the vapor deposition film (Al 2 O 4).
  • the aluminum oxide vapor-deposited film has an infrared absorption spectrum from the surface side of the thin-film film of the barrier film.
  • the ratio of the absorption intensity of the absorption peak of 3350 cm -1 or more and 3550 cm -1 or less derived from the OH bond to the absorption intensity of the absorption peak of 940 cm -1 or more and 960 cm -1 or less derived from the Al—O bond is 0.
  • the barrier film according to (3) which is 20 or less.
  • a laminate comprising the barrier film according to any one of (1) to (4) and a sealant layer.
  • FIG. 1B is a cross-sectional view showing an example of a barrier film according to the present embodiment.
  • the barrier film produced by using the film forming apparatus according to the present embodiment includes a base material 1 and a vapor-deposited film 2 as in the barrier film A 2 shown in FIG. 1 (b), for example.
  • the vapor deposition film 2 is located on one surface of the base material 1. Further, in the example shown in FIG. 1B, the vapor deposition film 2 is located on the surface of the barrier film.
  • FIG. 22 shows that the barrier film A 2 shown in FIG. 1 (b) is etched into the barrier film from the surface side of the vapor deposition film 2 by using the time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • At least the element bond AL 2 O 3 and the element bond AL 2 O 4 H and the element bond C 6 are detected from the barrier film according to the present embodiment.
  • an example in which the strength of these three types of elemental bonds is measured is shown.
  • the position of Et time T 1 in which the integrity of the graph of the element C6 becomes half of the strongest strength is set as the interface between the plastic base material and aluminum oxide, and the surface of the barrier film (T 0 ) to the interface T 1 is oxidized. It is treated as an aluminum vapor-deposited film (X in FIG. 9), and the position of 1/3 of the Et time from T 0 to T 1 , that is, 1/3 X is T 2.
  • the ratio (I 22 / I 21 ) of the strength I 22 of the element bond Al 2 O 4 H to the strength I 21 of the element bond Al 2 O 3 in T 2 is 0.30 or less, preferably 0. It is 20 or less, more preferably 0.10 or less.
  • the ratio of the element-bonded Al 2 O 4 H is small, and there is a region mainly in the state of Al 2 O 3 , so that the barrier performance can be improved.
  • the maximum peak Tp of the element-bonded Al 2 O 4 H intensity is present in the aluminum oxide vapor-deposited film.
  • the first peak from the surface side of the vapor deposition film is the maximum peak.
  • the region from Tp to the interface T 1 is referred to as a transition region.
  • the depth position of the maximum peak (Tp) with respect to X corresponding to the thickness of the thin-film deposition film exists at 55% or more and 95% or less from the surface side (opposite side to the base material side) of the thin-film deposition film. It is preferable to do so.
  • the ratio of the strength I P2 of the element bond Al 2 O 4 H to the strength I P 1 of the element bond Al 2 O 3 at the position Tp (IP2 / IP1 ) is preferably 0.10 or more and 4.00 or less.
  • the maximum peak derived from the elemental bond Al 2 O 4 H is 55% or more and 95% or less, that is, it is present on the base material side, so that the main region of Al 2 O 4 H is present on the base material side of the vapor deposition film.
  • the region near the surface of the vapor-deposited film there is mainly a region in the state of Al 2 O 3. That is, it has a configuration of Al 2 O 4 main region / Al 2 O 4 H main region / base material, and this configuration enables high barrier properties.
  • the ratio of the strength I 22 of the elemental bond Al 2 O 4 H to the strength I 21 of the elemental bond Al 2 O 3 in T 2 (I 22 / I 21 ), the depth position of the maximum peak (Tp), and the depth position of the maximum peak (Tp).
  • the ratio of the strength I P2 of the elemental bond Al 2 O 4 H to the strength I P1 of the elemental bond Al 2 O 3 at the position Tp (IP2 / IP1 ) is determined by the conditions of the pretreatment, especially the oxygen plasma treatment, and the time of vapor deposition. It can be adjusted by controlling the combination of the conditions of the plasma assist treatment and the oxygen concentration at the time of vapor deposition at the time of forming the aluminum oxide vapor deposition film.
  • the ratio of the absorption intensity of the absorption peak of 3350 cm -1 or more and 3550 cm -1 or less derived from the OH bond to the absorption intensity of the absorption peak of 940 cm -1 or more and 960 cm -1 or less derived from the Al—O bond is 0.20.
  • it is preferably 0.10 or less, and if it is within this range, the composition is close to that of a complete oxide film of aluminum oxide, and the barrier property is improved.
  • the FT-IR measurement conditions were measured under the conditions described in the examples.
  • FIG. 7B is a diagram showing an example of a laminated body 40b formed by using the barrier film according to the present embodiment.
  • the laminated body 40b includes the barrier film shown in FIG. 1 (b) and the sealant layer 7.
  • the laminated body 40b includes an adhesive layer 4, a second base material 5 composed of polyamide and the like, and an adhesive layer 6 on the vapor-deposited film of the barrier film shown in FIG. 1 (b).
  • the sealant layer 7 is provided in this order.
  • the laminate of the present invention is obtained by laminating at least one heat-sealable layer on a barrier film, and the heat-sealable thermoplastic resin is used as the innermost layer with or without an adhesive layer. It is laminated and has a sealing property such as a heat seal.
  • Example 1 A biaxially stretched polyethylene terephthalate film (PET film) having a thickness of 12 ⁇ m was used as the base material 1, and a plasma pretreatment step and a film forming step were performed using the film forming apparatus 10 shown in FIG.
  • PET film polyethylene terephthalate film
  • the vapor deposition film 2 containing aluminum oxide was deposited by the vacuum vapor deposition method using the evaporation mechanism 24 as shown in FIG. Specifically, after adjusting the degree of vacuum in the film forming chamber 12C to 1.5 Pa, the boat uses a resistance heating type evaporation mechanism 24 while supplying an aluminum metal wire as a vapor deposition material into the boat 24b. The vapor-deposited material in 24b was heated to evaporate the aluminum so as to reach the surface of the base material 1, and the vapor-deposited film 2 was formed on the surface of the base material 1 while supplying oxygen at 12500 sccm.
  • the plasma by opposing the anode, substrate It was pulled out between the surface of No. 1 and the evaporation mechanism 24 to perform plasma assist during vapor deposition.
  • a barrier film including the base material 1 shown in FIG. 1 and the vapor-deposited film 2 was produced at a transport speed of 600 m / min.
  • the thickness of the vapor-deposited film 2 of the produced barrier film was 8 nm.
  • Example 2 In Example 1, the barrier film of Example 2 was produced in the same manner as in Example 1 except that the transport speed was 480 m / min and the thickness of the vapor-deposited film 2 was 13 nm.
  • Example 3 the barrier film of Example 3 was produced in the same manner as in Example 2 except that the plasma pretreatment was not performed.
  • Example 4 Using a film-forming apparatus different from those of Examples 1 to 3, the barrier film of Example 4 was produced in the same manner as in Example 3 except that the production conditions in Table 1 were changed.
  • Example 5 Using a film-forming apparatus different from those of Examples 1 to 3, the barrier film of Example 5 was subjected to plasma pretreatment in the same manner as in Example 1 except that the production conditions in Table 1 were changed.
  • Comparative Example 1 As shown in Table 1, in Example 1, EB (electron beam) type evaporation mechanism (not shown) was used instead of the resistance heating type evaporation mechanism 24 without performing plasma pretreatment, and plasma during vapor deposition was used.
  • the barrier film of Comparative Example 1 was produced in the same manner as in Example 1 except that the oxygen supply amount was 8500 sccm and the vacuum degree at the time of vaporization was 0.15 Pa without performing the assist treatment.
  • Comparative Example 2 As shown in Table 7, in Example 1, the degree of vacuum in the plasma pretreatment chamber 12B was 3.5 Pa, the plasma assist treatment during vapor deposition was not performed, the oxygen supply amount was 10000 sccm, and the degree of vacuum during vapor deposition was set. A barrier film of Comparative Example 2 was produced in the same manner as in Example 1 except that the value was 0.02 Pa.
  • Comparative Example 3 As shown in Table 7, the barrier film of Comparative Example 3 was produced in the same manner as in Comparative Example 2 except that the transport speed was 480 m / min and the thickness of the vapor-deposited film 2 was 13 nm in Comparative Example 2.
  • TOF-SIMS analysis For the barrier films of Examples 1 to 5 and Comparative Examples 1 and 2, a barrier using a time-of-flight secondary ion mass spectrometer (TOF.SIMS5 manufactured by ION TOF) under the same measurement conditions as in the first invention. From the surface side of the vapor-deposited film of the film, while repeating soft etching at a constant speed with a Cs (cesium) ion gun, C 6 (mass number 72.00) derived from the resin substrate and Al 2 O 3 derived from the aluminum oxide vapor-deposited film (mass number 101.94), aluminum oxide deposited film from the Al 2 O 4 H (mass number 118.93), was the mass spectrometry.
  • Cs cesium
  • FIGS. 21 to 27 Graph analysis diagrams of the measurement results are shown in FIGS. 21 to 27.
  • 21 is the measurement result of Example 1
  • FIG. 22 is the measurement result of Example 2
  • FIG. 23 is the measurement result of Example 3
  • FIG. 24 is the measurement result of Example 4.
  • FIG. 26 is the measurement result of Comparative Example 1
  • FIG. 27 is the measurement result of Comparative Example 2.
  • the unit on the vertical axis is the common logarithm of the intensity of ions
  • the unit on the horizontal axis (Ettimes (s)) is the number of seconds after etching.
  • the film base material and aluminum oxide vapor deposition The interface of the film was defined as the aluminum oxide vapor-deposited film from the surface of the vapor-deposited film (position before etching) to the interface, and the position of 1/3 from the surface of the vapor-deposited film in the total vapor-deposited film thickness was determined. Then, the ratio of the element-bonded Al 2 O 4 H strength to the element-bonded Al 2 O 3 strength (Al 2 O 4 H / Al 2 O 3 ) at a position 1/3 from the surface of the vapor-deposited film was determined.
  • the position representing the intensity peak of the measured elemental bond Al 2 O 4 H (mass number 118.93) is obtained by the number of etching seconds (peak position Y), and the depth position (peak) from the surface of the vapor-deposited film at that position is obtained.
  • the ratio (Al 2 O 4 H / Al 2 O 3 ) of the element bond Al 2 O 4 H strength to the element bond Al 2 O 3 strength at the position (position Y / X, unit%) was determined.
  • the layer of FIG. 7B is the same as that of the first invention, except that the adhesive layer 4 is formed by coating the vapor-deposited film 2 of the barrier film with a two-component curable polyurethane-based laminating adhesive. A laminated body having a structure was manufactured. Moreover, the value of the watering peel strength was measured by the same method as in the first invention. The results are shown in Table 10.
  • the ratio of the element-bonded Al 2 O 4 H strength to the element-bonded Al 2 O 3 strength at the position 1/3 from the surface of the vapor-deposited film by TOF-SIMS (Al 2 O 4 H / Al 2).
  • the barrier property is higher than that in Comparative Examples 1 to 3.
  • absorption peaks exist at 940 cm -1 or more and 960 cm -1 or less derived from Al—O bond by FT-IR, and 940 cm -1 or more and 960 cm derived from Al—O bond.
  • the ratio of the absorption intensity of the absorption peak derived from the OH bond to the absorption intensity of the absorption peak of -1 or less is within the range of the present invention of 3350 cm -1 or more and 3550 cm -1 or less. It has a higher barrier property than 1.
  • the present invention (third invention) provides the following.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • a laminate comprising the barrier film according to (1) or (2) and a sealant layer.
  • a packaged product having the laminate described in (4) and (3) having the laminate described in (4) and (3).
  • FIG. 1C is a cross-sectional view showing an example of a barrier film according to the present embodiment.
  • Barrier films produced by using the film deposition apparatus of this embodiment for example, as a barrier film A 3 shown in FIG. 1 (c), a substrate 1, a deposited film 2, and the primer layer 3b, To be equipped.
  • the vapor deposition film 2 is located on one surface of the base material 1.
  • the barrier film A is laminated in the order of the base material 1, the vapor-deposited film 2, and the primer layer 3b, and the primer layer 3b is located on the surface of the barrier film.
  • FIG. 30 is a barrier film A 3 shown in FIG. 1 (c), the etching is performed using linear time-of from the surface side of the primer layer 3b ion mass spectrometry (TOF-SIMS), the barrier film
  • TOF-SIMS ion mass spectrometry
  • This is an example of a graph analysis diagram showing the strength of elements and element bonds when the contained elements and element bonds are measured.
  • the unit (intensity) on the vertical axis of the graph is the common logarithm of the ion intensity.
  • the unit (Et times) on the horizontal axis of the graph is the etching time.
  • At least the strength derived from CNO, the strength derived from Al 2 O 3 , and the strength derived from Al 2 O 4 H are detected from the barrier film according to the present embodiment.
  • FIG. 30 an example in which the strength of these three types of elemental bonds is measured is shown.
  • the intensity derived from Al 2 O 3 has an upward convex peak, and the range in which this peak exists is the range of the aluminum oxide vapor-deposited film.
  • the position of Et time T 1 where the intensity peak derived from Al 2 O 3 is reduced on the base material side and the integrity is halved is defined as the interface between the plastic base material and aluminum oxide.
  • the position of Et time T 2 where the intensity peak derived from Al 2 O 3 decreases on the primer layer side and the integrity is halved is defined as the interface between the primer layer and aluminum oxide.
  • T 1 to T 2 are formed as an aluminum oxide vapor-deposited film (X in FIG. 30).
  • the strength derived from CNO exists in the aluminum oxide vapor deposition film, that is, in the range of X in FIG. 30.
  • the strength derived from CNO is the strength derived from the urethane resin of the primer layer because CNO is a urethane bond.
  • the intensity derived from CNO has a downwardly convex peak Tp.
  • the depth position of the peak (Tp) at X is 0% or more and 70% or less, preferably 70% or less, from the surface side (primer layer side) of the vapor-deposited film. It is present in 10% or more and 70% or less, more preferably 20% or more and 70% or less, further preferably 30% or more and 70% or less, and particularly preferably 40% or more and 70% or less.
  • Tp is present on the primer layer side of the vapor deposition film. That is, it is suggested that the component containing CNO, which is presumed to have a low molecular weight, is mainly migrated into the vapor-deposited film in the primer layer. In the present invention, since the degree of this migration is small, as a result, the influence on the aluminum oxide vapor-deposited film is small, and the barrier performance can be improved by maintaining a dense aluminum oxide-deposited film.
  • the presence of the downwardly convex peak Tp derived from CNO and the depth position of Tp are determined by the conditions of pretreatment, especially oxygen plasma treatment, plasma assist treatment during vapor deposition, and the formation of an aluminum oxide vapor deposition film. It can be adjusted by controlling the combination of the oxygen concentration at the time of vapor deposition in.
  • the primer layer 3b laminated on the surface of the aluminum oxide vapor-deposited film 2 improves the adhesion when laminating the aluminum oxide and other layers, and also improves the barrier performance.
  • the primer layer 3b will be described.
  • the primer layer is formed by applying a primer solution containing a urethane resin and solidifying it. Then, if necessary, a silane coupling agent or silica fine particles may be further contained.
  • the film thickness of the primer layer after drying is preferably 0.01 to 30 ⁇ m, more preferably 0.1 to 10 ⁇ m.
  • the primer layer contains urethane resin
  • the primer layer has appropriate elasticity or flexibility, the influence on the inorganic vapor deposition layer due to pressing during printing or laminating can be reduced, and deterioration of gas barrier properties can be suppressed.
  • the urethane resin either a conventionally known polyester urethane resin or a polyether urethane resin can be used.
  • a reaction product of a polyol such as a polyester polyol or a polyether polyol and a polyisocyanate can be used.
  • polyester polyol examples include a polyester polyol obtained by reacting a low molecular weight polyol with a polycarboxylic acid; and a polyester polyol obtained by ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolacton; Examples thereof include polyester polyols obtained by copolymerization. These polyester polyols can be used alone or in combination of two or more.
  • low molecular weight polyol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,3-butanediol having a molecular weight of about 50 to 300.
  • examples thereof include certain aliphatic polyols; polyols having an aliphatic cyclic structure such as cyclohexanedimethanol; polyols having an aromatic structure such as bisphenol A and bisphenol F.
  • polyester polyols examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecandicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid and the like. Aromatic polycarboxylic acids; examples thereof include anhydrides or esterified products thereof.
  • a polyester polyurethane polyol having a urethane bond in the molecular structure which is obtained by modifying the above polyester polyol with polyisocyanate, can also be used. These polyester polyols can be used alone or in combination of two or more.
  • Examples of the above-mentioned polyether polyol include those obtained by addition polymerization of an alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator.
  • Examples of the compound having two or more active hydrogen atoms include propylene glycol, trimethylolglycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, and di. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, water and hexanetriol.
  • alkylene oxide examples include propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.
  • polyether polyol a polyether polyurethane polyol having a urethane bond in the molecular structure, which is obtained by modifying the above-mentioned polyether polyol with a polyisocyanate, can also be used. These polyether polyols can be used alone or in combination of two or more.
  • polyisocyanate examples include polyisocyanates having an aliphatic cyclic structure such as cyclohexanediisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and carbodiimide-modified diphenylmethane diisocyanate.
  • Aromatic polyisocyanates such as crude diphenylmethane diisocyanate, phenylenediisocyanate, tolylene diisocyanate, naphthalenediocyanate; and aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate and tetramethylxylylene diisocyanate.
  • 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and crude diphenylmethane diisocyanate are preferable.
  • these polyisocyanates can be used alone or in combination of two or more.
  • silane coupling agent a conventionally known silane coupling agent can be used, and for example, the same one as that used for the above-mentioned gas barrier resin composition is preferably used.
  • silane coupling agent By containing a silane coupling agent in the primer layer, the adhesiveness with the vapor-deposited film can be improved.
  • silica can be used as the silica fine particles.
  • the primer layer containing silica fine particles makes it possible to suppress blocking during winding in the manufacturing process of the gas barrier vapor-deposited film.
  • Primer layer forming step examples of the means for forming the primer layer by coating include a roll coating such as a gravure roll coater, a spray coating, a spin coating, a dipping, a brush, a bar code, and an applicator.
  • the primer layer may be formed by one or more applications.
  • On the first coating film the above coating operation may be repeated to form a plurality of coating films composed of two or more layers.
  • the heat treatment is carried out at a temperature of 20 to 200 ° C. and lower than the melting point of the plastic substrate, preferably a temperature in the range of 50 to 180 ° C. for 0.2 seconds to 10 minutes.
  • the primer layer 3b can be formed on the aluminum oxide vapor deposition film.
  • FIG. 7C is a diagram showing an example of a laminated body 40c formed by using the barrier film according to the present embodiment.
  • the laminated body 40c includes the barrier film shown in FIG. 1 (c) and the sealant layer 7.
  • the laminated body 40c includes an adhesive layer 4, a second base material 5 composed of polyamide and the like, and an adhesive layer 6 on the primer layer of the barrier film shown in FIG. 1 (c).
  • the sealant layer 7 is provided in this order.
  • the laminate of the present invention is obtained by laminating at least one heat-sealable layer on a barrier film, and the heat-sealable thermoplastic resin is used as the innermost layer with or without an adhesive layer. It is laminated and has a sealing property such as a heat seal.
  • Example 1 A biaxially stretched polyethylene terephthalate film (PET film) having a thickness of 12 ⁇ m was used as the base material 1, and a plasma pretreatment step and a film forming step were performed using the film forming apparatus 10 shown in FIG.
  • PET film polyethylene terephthalate film
  • the vapor deposition film 2 containing aluminum oxide was deposited by the vacuum vapor deposition method using the evaporation mechanism 24 as shown in FIG. Specifically, after adjusting the degree of vacuum in the film forming chamber 12C to 1.5 Pa, the boat uses a resistance heating type evaporation mechanism 24 while supplying an aluminum metal wire as a vapor deposition material into the boat 24b. The vapor-deposited material in 24b was heated to evaporate the aluminum so as to reach the surface of the base material 1, and the vapor-deposited film 2 was formed on the surface of the base material 1 while supplying oxygen at 12500 sccm.
  • the plasma by opposing the anode, substrate It was pulled out between the surface of No. 1 and the evaporation mechanism 24 to perform plasma assist during vapor deposition.
  • the vapor deposition film 2 was laminated on the base material 1 by the above method. At this time, the transport speed was 600 m / min, and the thickness of the vapor-deposited film 2 was 8 nm.
  • primer layer 3b was formed on the aluminum oxide vapor deposition film of the gas barrier vapor deposition film obtained above.
  • a liquid in which a polyester urethane resin (manufactured by Dainichi Seika Kogyo Co., Ltd.) (100 g), which is a cured product of polyester polyol and polyisocyanate, is dissolved is used as a main component, and an isocyanate compound (5 g), which is a curing agent, is mixed.
  • a primer solution was prepared.
  • the primer solution prepared above was coated on the aluminum oxide vapor deposition film of the gas barrier vapor deposition film formed above by the spin coating method.
  • a primer layer 3b having a thickness of about 200 nm is formed adjacently on the aluminum oxide vapor-deposited film, and the barrier of Example 1 having the primer layer 3b is formed.
  • the film was manufactured.
  • Example 2 Using a film-forming device different from that of Example 1, a barrier film of Example 2 was produced in the same manner as in Example 1 except that the production conditions in Table 11 were changed.
  • Example 3 Using a film-forming device different from that of Example 1, the barrier film of Example 3 was subjected to plasma pretreatment in the same manner as in Example 1 except that the production conditions in Table 11 were changed.
  • Comparative Example 1 In Example 1, the oxygen / argon ratio during plasma pretreatment was 2: 1, the degree of vacuum in the plasma pretreatment chamber 12B was 3.5 Pa, the plasma assist treatment during vapor deposition was not performed, and the oxygen supply amount was 9000 sccm.
  • the barrier film of Comparative Example 1 was produced in the same manner as in Example 1 except that the degree of vacuum at the time of vapor deposition was 0.02 Pa.
  • TOF-SIMS analysis For the barrier films of Example 1 and Comparative Example 1, a time-of-flight secondary ion mass spectrometer (TOF.SIMS5 manufactured by ION TOF) was used, and the vapor-deposited film of the barrier film was used under the same measurement conditions as in the first invention. From the surface side, while repeating soft etching at a constant speed with a Cs (cesium) ion gun, C 6 derived from a resin substrate (mass number 72.00) and Al 2 O 3 derived from an aluminum oxide vapor deposition film (mass number 101).
  • Cs cesium
  • FIGS. 30 to 32 Graph analysis diagrams of the measurement results are shown in FIGS. 30 to 32.
  • FIG. 30 is the measurement result of Example 1
  • FIG. 31 is the measurement result of Comparative Example 1.
  • FIG. 32 is a measurement result of Example 3.
  • the unit on the vertical axis (intensity) is the common logarithm of the intensity of ions
  • the unit on the horizontal axis is the number of seconds after etching.
  • the position representing the intensity peak of the measured elemental bond CNO (mass number 41.99) is determined by the number of etching seconds (peak position Y), and the depth position from the primer layer side surface of the vapor-deposited film at that position (FIG. The peak position Y / X at 8, unit%) was determined.
  • the layer of FIG. 7C is the same as that of the first invention, except that the primer layer 3b of the barrier film is coated with a two-component curable polyurethane-based laminating adhesive to form the adhesive layer 4.
  • a laminate of the composition was manufactured.
  • the value of the watering peel strength was measured by the same method as in the first invention. The results are shown in Table 13.
  • the intensity derived from the elemental bond CNO has a downwardly convex peak, and the downwardly convex peak exists at a depth position of 0% or more and 70% or less from the surface side of the primer layer in the vapor deposition film.
  • the barrier property is higher than that in Comparative Example 1 in which a downward convex peak does not exist.
  • the strength derived from CNO is present throughout the vapor-deposited film, and the component having the CNO bond of the primer layer is migrated and migrated into the vapor-deposited film.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne : un film barrière ayant des propriétés de barrière élevées ; et un stratifié l'utilisant.　Le film barrière selon l'invention comprend un substrat, un film de dépôt d'oxyde d'aluminium et une couche de revêtement organique qui sont stratifiés dans cet ordre. Selon l'invention : lorsque le film de dépôt d'oxyde d'aluminium est gravé à partir du côté surface de la couche de revêtement organique du film barrière par spectrométrie de masse à ions secondaires à temps de vol (TOF-SIMS), une intensité dérivée d'une liaison élémentaire OH est détectée ; l'intensité dérivée de la liaison élémentaire OH présente un pic convexe vers le bas ; et le pic convexe vers le bas est présent dans le film de dépôt d'oxyde d'aluminium à une position de profondeur de 10-60 % à partir du côté surface de la couche de revêtement organique.
PCT/JP2020/033327 2019-09-06 2020-09-02 Film barrière, stratifié utilisant ledit film barrière, produit d'emballage utilisant ledit stratifié WO2021045127A1 (fr)

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JP2019162843 2019-09-06
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US20220162740A1 (en) * 2019-06-12 2022-05-26 Dai Nippon Printing Co., Ltd. Barrier film, laminate, and packaging product

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JP2008114444A (ja) * 2006-11-02 2008-05-22 Toppan Printing Co Ltd 透明複層フィルムの製造方法及びその方法で製造したガスバリア性透明複層フィルム並びに封止フィルム
JP2012196918A (ja) * 2011-03-23 2012-10-18 Toppan Printing Co Ltd 加圧加熱殺菌用包装材料
WO2013100073A1 (fr) * 2011-12-28 2013-07-04 大日本印刷株式会社 Dispositif de dépôt en phase vapeur possédant un dispositif de prétraitement au plasma
JP2017177343A (ja) * 2016-03-28 2017-10-05 東レフィルム加工株式会社 積層フィルムおよびその製造方法
WO2019087960A1 (fr) * 2017-10-30 2019-05-09 大日本印刷株式会社 Film stratifié, film stratifié barrière et matériau d'emballage barrière aux gaz et corps emballé barrière aux gaz utilisant chacun ledit film stratifié barrière
JP2019123925A (ja) * 2018-01-19 2019-07-25 大日本印刷株式会社 蒸着膜成膜装置及び蒸着膜成膜方法
JP2020029095A (ja) * 2018-08-20 2020-02-27 大日本印刷株式会社 バリアフィルムおよび包装材料

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JP2008114444A (ja) * 2006-11-02 2008-05-22 Toppan Printing Co Ltd 透明複層フィルムの製造方法及びその方法で製造したガスバリア性透明複層フィルム並びに封止フィルム
JP2012196918A (ja) * 2011-03-23 2012-10-18 Toppan Printing Co Ltd 加圧加熱殺菌用包装材料
WO2013100073A1 (fr) * 2011-12-28 2013-07-04 大日本印刷株式会社 Dispositif de dépôt en phase vapeur possédant un dispositif de prétraitement au plasma
JP2017177343A (ja) * 2016-03-28 2017-10-05 東レフィルム加工株式会社 積層フィルムおよびその製造方法
WO2019087960A1 (fr) * 2017-10-30 2019-05-09 大日本印刷株式会社 Film stratifié, film stratifié barrière et matériau d'emballage barrière aux gaz et corps emballé barrière aux gaz utilisant chacun ledit film stratifié barrière
JP2019123925A (ja) * 2018-01-19 2019-07-25 大日本印刷株式会社 蒸着膜成膜装置及び蒸着膜成膜方法
JP2020029095A (ja) * 2018-08-20 2020-02-27 大日本印刷株式会社 バリアフィルムおよび包装材料

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Publication number Priority date Publication date Assignee Title
US20220162740A1 (en) * 2019-06-12 2022-05-26 Dai Nippon Printing Co., Ltd. Barrier film, laminate, and packaging product

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