WO2015133620A1 - Film barrière contre les gaz - Google Patents

Film barrière contre les gaz Download PDF

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Publication number
WO2015133620A1
WO2015133620A1 PCT/JP2015/056713 JP2015056713W WO2015133620A1 WO 2015133620 A1 WO2015133620 A1 WO 2015133620A1 JP 2015056713 W JP2015056713 W JP 2015056713W WO 2015133620 A1 WO2015133620 A1 WO 2015133620A1
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Prior art keywords
gas barrier
film
barrier film
barrier layer
layer
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PCT/JP2015/056713
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English (en)
Japanese (ja)
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圭一 須川
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コニカミノルタ株式会社
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Priority to JP2016506193A priority Critical patent/JPWO2015133620A1/ja
Publication of WO2015133620A1 publication Critical patent/WO2015133620A1/fr

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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates

Definitions

  • the present invention relates to a gas barrier film.
  • a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging articles in the fields of food, medicine, etc. It is used for.
  • a gas barrier film By using the gas barrier film, it is possible to prevent alteration of the article due to gas such as water vapor or oxygen.
  • PVD Physical Vapor Deposition: Physical vapor deposition method, physical vapor deposition method
  • Japanese Patent Application Laid-Open No. 2011-241421 discloses a gas barrier film including a silicon oxide thin film having an average particle diameter of 20 nm or less using a PVD method.
  • the PVD method tends to generate particles in the gas phase system.
  • it is common to perform columnar growth or island-like growth in the thin film growth process, so that grain boundaries are generated in the film and high barrier properties are exhibited. Have difficulty.
  • a CVD method Chemical Vapor Deposition: chemical vapor deposition method, chemical vapor deposition method
  • gas barrier performance and bending performance are improved by a silicon oxycarbide film formed by a plasma chemical vapor deposition method in which plasma is generated by discharging between a pair of film forming rolls. .
  • JP-A-2005-119155 and JP-A-2009-113355 disclose polyvinyl alcohol and alkoxy A sol-gel coating layer containing silane as a main component is laminated on a silicon oxide film formed by a vapor deposition method.
  • Japanese Patent Laid-Open No. 2008-536711 discloses perhydropolysilazane on a barrier layer formed by a vapor deposition method for the purpose of covering a defective portion of a metal oxide layer formed by a PVD method or a CVD method.
  • the silicon oxide layer is laminated by applying and curing the solution.
  • the present invention has been made in view of the above problems, and is to provide a gas barrier film that is excellent in bending resistance and suppresses a decrease in gas barrier performance even when the gas barrier film is bent.
  • the gas barrier film according to the present invention has a base material and a gas barrier layer formed on one surface of the base material by a chemical vapor deposition method, and a sample having a size of 100 mm ⁇ 100 mm is formed on the base material.
  • Gas barrier property wherein the gas barrier layer is placed on a flat surface so that the gas barrier layer is on the lower side, and the value of warpage calculated as an average value obtained by measuring the floating height from the four corner planes is 1 to 60 mm. It is a film.
  • the gas barrier film has a warp value as described above, it has excellent bending resistance and exhibits sufficient gas barrier performance even after bending.
  • the present inventor has the feature that the gas barrier layer is strong against the contraction stress but weak against the tensile stress. It is presumed that the permissible force against the tensile stress of the gas barrier layer is increased by keeping it in such a state (the film density is increased).
  • FIG. 1 It is a schematic diagram which shows an example of the manufacturing apparatus which can be utilized suitably in order to manufacture the gas barrier layer which concerns on this invention. It is an example of the organic electroluminescent panel which is an electronic device using the gas barrier film which concerns on this invention as a sealing film.
  • One embodiment of the present invention includes a base material and a gas barrier layer formed on one surface of the base material by a chemical vapor deposition method, and a sample having a size of 100 mm ⁇ 100 mm is formed on the base material with respect to the base material.
  • the gas barrier film is characterized in that a warp value calculated as an average value obtained by measuring the height of floating from the four corner planes is 1 to 60 mm. is there.
  • the gas barrier film according to the present invention has excellent bending resistance and exhibits sufficient gas barrier performance even after bending.
  • the gas barrier film according to the present invention preferably has a permeated water amount (WVTR) of less than 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) as measured by the method described in Examples below.
  • WVTR permeated water amount
  • X to Y indicating a range means “X or more and Y or less”.
  • measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
  • the gas barrier film first has a substrate.
  • a plastic film is usually used as a substrate.
  • the plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold the barrier laminate, and can be appropriately selected depending on the purpose of use and the like.
  • Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide.
  • Resin cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring
  • thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.
  • the thickness of the substrate is not particularly limited because it is appropriately selected depending on the application, but is typically 1 ⁇ m or more, preferably 10 ⁇ m or more. On the other hand, it is typically 800 ⁇ m or less, preferably 200 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • These plastic films may have functional layers such as a transparent conductive layer and a smooth layer.
  • the functional layer in addition to those described above, those described in paragraph numbers 0036 to 0038 of JP-A-2006-289627 can be preferably employed.
  • various known treatments for improving adhesion, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, or lamination of a smooth layer may be combined as necessary. It can be carried out.
  • a gas barrier layer formed by a chemical vapor deposition method is disposed on one surface of the substrate.
  • This gas barrier layer is preferably a layer containing silicon, oxygen, and carbon. Further, the gas barrier layer preferably satisfies at least one of the following conditions (i) to (iii), more preferably satisfies at least two conditions, and satisfies the three conditions. It is even more preferable that everything is satisfied.
  • the resulting gas barrier film has better gas barrier properties and flexibility.
  • the relationship between the above (atomic ratio of oxygen), (atomic ratio of silicon) and (atomic ratio of carbon) is at least 90% or more (upper limit: 100%) of the film thickness of the gas barrier layer. ) And more preferably at least 93% or more (upper limit: 100%).
  • the term “at least 90% or more of the film thickness of the gas barrier layer” does not need to be continuous in the gas barrier layer.
  • the carbon distribution curve has at least two extreme values.
  • the carbon distribution curve preferably has at least three extreme values, more preferably at least four extreme values, but may have five or more.
  • the gas barrier property when the obtained gas barrier film is bent becomes better.
  • the upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 or less, more preferably 25 or less, for example. However, since the number of extreme values is also caused by the film thickness of the gas barrier layer, it cannot be specified unconditionally.
  • the distance (L from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer at one extreme value and the extreme value adjacent to the extreme value of the carbon distribution curve) ) Difference is preferably 200 nm or less, more preferably 100 nm or less, and particularly preferably 75 nm or less. If such a distance between extreme values is present, portions having a large carbon atom ratio (maximum value) are present in the gas barrier layer at an appropriate period, so that the gas barrier layer is imparted with an appropriate flexibility, Generation of cracks during bending can be more effectively suppressed / prevented.
  • the “extreme value” refers to the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer.
  • the “maximum value” is a point where the value of the atomic ratio of an element (oxygen, silicon or carbon) changes from increase to decrease when the distance from the surface of the gas barrier layer is changed.
  • the value of the atomic ratio of the element at the position where the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer from the point is further changed within the range of 4 to 20 nm than the value of the atomic ratio of the element at that point. It means a point that decreases by 3 at% or more.
  • the atomic ratio value of the element is reduced by 3 at% or more in any range when changing in the range of 4 to 20 nm.
  • the “minimum value” in this specification is a point in which the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from decrease to increase when the distance from the surface of the gas barrier layer is changed.
  • the atomic ratio value of the element at a position where the distance from the point in the thickness direction of the gas barrier layer from the point in the thickness direction of the gas barrier layer is further changed by 4 to 20 nm is 3 at%. This is the point that increases.
  • the atomic ratio value of the element when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range.
  • the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent.
  • the thickness is preferably 10 nm or more, and more preferably 30 nm or more.
  • C max ⁇ C min difference The absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve (hereinafter also simply referred to as “C max ⁇ C min difference”) is 3 at% or more.
  • the gas barrier property when the obtained gas barrier film is bent is further improved.
  • the C max -C min difference is preferably 5 at% or more, more preferably 7 at% or more, and particularly preferably 10 at% or more.
  • the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values.
  • the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values.
  • the upper limit of the C max -C min difference is not particularly limited, but it is preferably 50 at% or less in consideration of the effect of suppressing / preventing crack generation during bending of the gas barrier film, and is preferably 40 at% or less. It is more preferable that
  • the thickness of the gas barrier layer is preferably 50 to 500 nm. With such a thickness, even better bending resistance can be obtained while maintaining gas barrier properties.
  • the oxygen distribution curve of the gas barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and more preferably has at least three extreme values.
  • the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved.
  • the upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the film thickness of the gas barrier layer, and it cannot be defined unconditionally.
  • the difference in distance from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer at one extreme value and the extreme value adjacent to the extreme value of the oxygen distribution curve is preferably 200 nm or less, and more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks during bending of the gas barrier film can be more effectively suppressed / prevented.
  • the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, but considering the improvement effect of crack generation suppression / prevention when the gas barrier film is bent, the thermal expansion property, etc.
  • the thickness is preferably 10 nm or more, and more preferably 30 nm or more.
  • the silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination.
  • XPS X-ray photoelectron spectroscopy
  • rare gas ion sputtering such as argon in combination.
  • XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample.
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).
  • the etching time is generally correlated with the distance (L) from the surface of the gas barrier layer in the film thickness direction of the barrier layer in the film thickness direction.
  • “Distance from the surface of the gas barrier layer in the film thickness direction of the barrier layer” is the distance from the surface of the barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. be able to.
  • the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve were prepared under the following measurement conditions.
  • Etching ion species Argon (Ar + ); Etching rate (converted to SiO 2 thermal oxide film): 0.05 nm / sec; Etching interval (SiO 2 equivalent value): 10 nm;
  • X-ray photoelectron spectrometer Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific; Irradiation X-ray: Single crystal spectroscopy AlK ⁇ X-ray spot and its size: 800 ⁇ 400 ⁇ m oval.
  • each gas barrier layer has the above thickness.
  • the thickness of the entire gas barrier layer in the case where the gas barrier layer is composed of two or more layers is not particularly limited, but the thickness (dry film thickness) of the entire gas barrier layer is preferably about 1000 to 2000 nm. With such a thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending.
  • the gas barrier layer is substantially uniform in the film surface direction (direction parallel to the surface of the barrier layer) from the viewpoint of forming a gas barrier layer having a uniform and excellent gas barrier property over the entire film surface. It is preferable.
  • the gas barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon are measured at any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement.
  • XPS depth profile measurement XPS depth profile measurement.
  • the carbon distribution curve is substantially continuous.
  • the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously.
  • the carbon distribution curve is calculated from the etching rate and the etching time. In the relationship between the distance (x, unit: nm) from the surface of the gas barrier layer in the film thickness direction of at least one of the gas barrier layers to be formed and the atomic ratio of carbon (C, unit: at%), Satisfying the condition represented by (1).
  • the silicon atomic ratio, the oxygen atomic ratio, and the carbon atomic ratio are in the region of 90% or more of the film thickness of the gas barrier layer (i).
  • the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer is preferably 20 to 45 at%, More preferably, it is 40 at%.
  • the atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer is preferably 45 to 75 at%, and more preferably 50 to 70 at%.
  • the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer is preferably 1 to 25 at%, and more preferably 2 to 20 at%.
  • the gas barrier layer is formed by a chemical vapor deposition method.
  • the chemical vapor deposition method is also called chemical vapor deposition method or CVD method.
  • the gas barrier layer is formed by plasma CVD (PECVD (plasma-enhanced chemical vapor deposition), hereinafter referred to as “plasma CV” It is preferably formed by the “D method”.
  • the substrate is formed by a plasma CVD method in which a substrate is disposed on a pair of film forming rollers, and plasma is generated by discharging between the pair of film forming rollers.
  • PECVD plasma-enhanced chemical vapor deposition
  • the plasma CVD method may be a Penning discharge plasma type plasma CVD method.
  • plasma discharge in a space between a plurality of film forming rollers it is preferable to generate plasma discharge in a space between a plurality of film forming rollers.
  • a pair of film forming rollers is used, and each of the pair of film forming rollers is used.
  • the substrate is disposed and discharged between a pair of film forming rollers to generate plasma.
  • one film forming roller it is possible not only to produce a thin film efficiently because it is possible to form a film on the surface part of the base material existing in the film while simultaneously forming a film on the surface part of the base material present on the other film forming roller.
  • the film formation rate can be doubled compared to the plasma CVD method without using any roller, and a film having substantially the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled. It is possible to form a layer that satisfies at least one of the above conditions (i) to (iii).
  • the film forming gas used in such a plasma CVD method preferably contains an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation.
  • the gas barrier layer is preferably a layer formed by a continuous film forming process.
  • an apparatus that can be used when producing a gas barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film formation rollers and a plasma power source, and the pair of film formations. It is preferable that the apparatus has a configuration capable of discharging between rollers. For example, when the manufacturing apparatus shown in FIG. 1 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible.
  • FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing a gas barrier layer according to the present invention.
  • the manufacturing apparatus 13 shown in FIG. 1 includes a delivery roller 14, transport rollers 15, 16, 17, 18, film formation rollers 19, 20, a gas supply pipe 21, a plasma generation power source 22, and a film formation roller 19. And 20 are provided with magnetic field generators 23 and 24 and winding rollers 25. Further, in such a manufacturing apparatus, at least the film forming rollers 19 and 20, the gas supply pipe 21, the plasma generating power source 22, and the magnetic field generating apparatuses 23 and 24 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 13, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.
  • the gas barrier layer according to the present invention is formed by plasma CVD using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is characterized by doing.
  • This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode.
  • Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.
  • the gas barrier film according to the present invention may have a hard coat layer. By disposing the hard coat layer, the long-term reliability of the device can be improved when the gas barrier film according to the present invention is used as a sealing film for an electronic device.
  • the hard coat layer may also have a function of preventing scratches on the surface of the electronic device.
  • the hard coat layer may be disposed between the substrate and the gas barrier layer (also referred to as “first hard coat layer”), or disposed on the surface of the substrate opposite to the gas barrier layer. It is also possible (also referred to as “second hard coat layer”). It is preferable that both the first hard coat layer and the second hard coat layer are arranged.
  • the first hard coat layer and the second hard coat layer have different thicknesses, and the first hard coat layer has a thickness larger than that of the second hard coat layer. More preferred.
  • the thickness of the hard coat layer (when a plurality of hard coat layers (for example, the first hard coat layer and the second hard coat layer are provided), the total thickness thereof) Is preferably 0.2 to 15 ⁇ m, more preferably 0.5 to 10 ⁇ m.
  • the thickness of the hard coat layer is within such a range, a gas barrier film having excellent flexibility can be achieved, and the warp (curl) value described later can be easily controlled within a suitable range. ,preferable.
  • the hard coat layer contains a curable resin.
  • the curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material with an active energy ray such as ultraviolet ray to be cured is heated.
  • the thermosetting resin etc. which are obtained by curing by the above method. These curable resins may be used alone or in combination of two or more.
  • Examples of the active energy ray-curable material used for forming the hard coat layer include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include compositions containing polyfunctional acrylate monomers such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate.
  • OPSTAR registered trademark
  • Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl.
  • the active energy ray-curable material is a (meth) acrylate compound, which is a trifunctional to octafunctional (meth) acrylate compound, and more preferably a trifunctional to octafunctional compound composed of only carbon, oxygen and hydrogen atoms. It is an octafunctional (meth) acrylate compound.
  • These (meth) acrylate compounds are preferably linear or branched.
  • the number of functional groups is particularly preferably 4 to 8 functions.
  • the active energy ray-curable material preferably contains phosphoric acid (meth) acrylate.
  • phosphoric acid (meth) acrylate By adding phosphoric acid (meth) acrylate, the adhesion to the substrate tends to be further improved.
  • Phosphoric acid (meth) acrylate is preferably added in a proportion of 1 to 15% by weight, preferably in a proportion of 2 to 10% by weight, based on the total amount of polymerizable compounds contained in the compound forming the hard coat layer. More preferably.
  • the hard coat layer according to the present invention is obtained by curing a polymerizable composition containing an active energy ray-curable material, and 85 wt% to 99 wt% of the polymerizable compound includes carbon atoms, oxygen atoms and hydrogen atoms. 4 to 8 functional (meth) acrylate consisting of 1 to 15% by weight of phosphoric acid (meth) acrylate, and the hard coat layer preferably has a pencil hardness of H or higher. . Thereby, it exists in the tendency which the effect of this invention improves more notably.
  • the composition containing the active energy ray-curable material contains a photopolymerization initiator.
  • a photopolymerization initiator Conventionally known materials can be used as the photopolymerization initiator.
  • thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nittobo Co., Ltd.
  • thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydrin Butter, and the like can be mentioned.
  • the method for forming the hard coat layer is not particularly limited, but a coating solution containing a curable material is applied to a spin coating method, a spray method, a blade coating method, a dipping method, a wet coating method such as a gravure printing method, or a vapor deposition method.
  • the coating film is irradiated with active energy rays such as visible rays, infrared rays, ultraviolet rays, X rays, ⁇ rays, ⁇ rays, ⁇ rays, and electron beams and / or heated.
  • active energy rays such as visible rays, infrared rays, ultraviolet rays, X rays, ⁇ rays, ⁇ rays, ⁇ rays, and electron beams and / or heated.
  • a method of forming by curing is preferred.
  • an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like is preferably used to irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm.
  • a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator can be used.
  • Solvents used when forming a hard coat layer using a coating solution in which a curable material is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol.
  • Aromatic hydrocarbons such as, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoe Glycol ethers such as chill ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolv
  • the hard coat layer can contain additives such as a thermoplastic resin, an antioxidant, an ultraviolet absorber, and a plasticizer, if necessary, in addition to the above-described materials.
  • an appropriate resin or additive may be used for improving the film formability and preventing the occurrence of pinholes in the film.
  • the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof and the like.
  • Examples include resins, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, and polycarbonate resins.
  • the pencil hardness of the hard coat layer according to the present invention is preferably HB or higher.
  • the pencil hardness is 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H in order from the softest. If the pencil hardness is equal to or higher than HB, scratch resistance on the surface of the electronic device can be sufficiently achieved.
  • the pencil hardness is preferably F or more, more preferably H or more.
  • the upper limit of the pencil hardness of the hard coat layer is not particularly limited, but is preferably 10H or less, and more preferably 8H or less.
  • the pencil hardness is JIS K5600-5-4: It can be measured by the method described in 1999. When measuring pencil hardness of 10H, 7B, 8B, 9B, 10B, use 10H, 7B, 8B, 9B, 10B pencils made by Mitsubishi Pencil Co., Ltd. Measure.
  • the gas barrier film of the present invention may have a primer layer (smooth layer) between the surface of the substrate having the gas barrier layer, preferably between the substrate and the gas barrier layer.
  • the primer layer is provided for flattening the rough surface of the substrate on which protrusions and the like exist.
  • Such a primer layer is basically formed by curing an active energy ray-curable material or a thermosetting material.
  • the primer layer may basically have the same configuration as the hard coat layer as long as it has the above function.
  • the examples of the active energy ray-curable material and the thermosetting material, and the method for forming the primer layer are the same as those described in the column of the hard coat layer, and thus the description thereof is omitted here.
  • the smoothness of the primer layer is a value expressed by the surface roughness defined by JIS B0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. Note that the lower limit of the maximum cross-sectional height Rt (p) is not particularly limited and is 0 nm, but it may normally be 0.5 nm or more.
  • the thickness of the primer layer is not particularly limited, but is preferably in the range of 0.1 to 10 ⁇ m.
  • the gas barrier film of the present invention can be further provided with functionalized layers such as another organic layer (anchor coat layer, bleed-out prevention layer, etc.), a protective layer, a moisture absorption layer, an antistatic layer, etc., if necessary.
  • functionalized layers such as another organic layer (anchor coat layer, bleed-out prevention layer, etc.), a protective layer, a moisture absorption layer, an antistatic layer, etc., if necessary.
  • the transparency of the gas barrier film is preferably high. That is, the total light transmittance is preferably 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.
  • One of the features of the gas barrier film according to the present invention is that when it is placed on a flat surface with the gas barrier layer below the substrate, it is warped (curled) to some extent upward. is there. More specifically, a 100 mm ⁇ 100 mm sample is placed on a plane with the gas barrier layer below the substrate, as measured in the Examples section described below, and floats from the four corner planes. A warp value is calculated as an average value of the measured height (distance from the plane).
  • the present invention is characterized in that the value of warpage measured in this way is 1 to 60 mm, preferably 20 to 55 mm, and more preferably 30 to 50 mm.
  • the gas barrier film has a warp value as described above, it has excellent bending resistance and exhibits sufficient gas barrier performance even after bending. .
  • the value of the warp is less than 1 mm or exceeds 60 mm, the bending resistance is not sufficient, and the gas barrier property after bending becomes insufficient.
  • the concept of “warp value is less than 1 mm” includes the case where the warp value is zero (the gas barrier film is flat), or the warp value is negative (the gas barrier film is warped in the opposite direction). (Curled) form).
  • the value of the warp is a value measured in the state of the gas barrier film.
  • the present inventor has the feature that the gas barrier layer is strong against the contraction stress but weak against the tensile stress. It is presumed that the permissible force against the tensile stress of the gas barrier layer is increased by keeping it in such a state (the film density is increased).
  • the film formation conditions of the plasma CVD method when forming the gas barrier layer (for example, applied power, raw material supply amount, etc.) ) May be controlled or the “warp value” may be controlled by adjusting the form (position, thickness, manufacturing method, etc.) when the hard coat layer is disposed. Furthermore, by changing the thickness of the base material, changing the type, or preparing a base material that has been wound in advance, the “warping value” is controlled by forming a gas barrier layer on the surface. May be.
  • positioned at the gas barrier film mentioned above is also provided.
  • a protective film is arrange
  • the film which consists of a resin material at least is mentioned.
  • the protective film may be wound into a roll before being bonded to the gas barrier layer.
  • the protective film may be arrange
  • the resin material used for the protective film is not particularly limited, but is a polyolefin film such as polyethylene film or polypropylene film; a polyester film such as polyethylene terephthalate or polybutylene terephthalate; a polyamide film such as hexamethylene adipamide; Halogen-containing films such as chloride, polyvinylidene chloride, and polyfluoroethylene; plastic films such as polyvinyl acetate, polyvinyl acetate such as polyvinyl acetate, polyvinyl alcohol, and ethylene acetate pinyl copolymer, and their derivative films are different from paper in that they generate fine dust. It is preferable because it does not occur.
  • a polyethylene terephthalate film is preferably used from the viewpoints of heat resistance and availability.
  • the thickness of the protective film is not particularly limited, but, for example, a thickness of 10 ⁇ m to 300 ⁇ m is used. Preferably, the thickness is from 25 ⁇ m to 150 ⁇ m. If it is 10 ⁇ m or more, the film is sufficiently thick and easy to handle, and if it is 300 ⁇ m or less, it is sufficiently flexible and has excellent transportability and adhesion to a roll.
  • the type of the adhesive used for the adhesive layer is not particularly limited.
  • the gas barrier layer is formed by chemical vapor deposition on the other surface of the base material in a state where the protective film is disposed on the one surface of the base material. It has been found that a gas barrier film (with a protective film) that is even more excellent due to the gas barrier property can be obtained. That is, in the above-mentioned “gas barrier film with protective film”, the gas barrier layer is preferably formed on one surface of the substrate by a chemical vapor deposition method in the presence of the protective film. In addition, about the mechanism by which the effect as described above is expressed by forming a gas barrier layer in the presence of a protective film, the present inventor can set CVD conditions that place a load on the substrate even when the substrate is thin. This is presumed to be due to the expansion of the CVD condition setting range.
  • the gas barrier film of the present invention as described above has excellent gas barrier properties, transparency, and flexibility. Therefore, the gas barrier film of the present invention is a gas barrier film used for electronic devices such as packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various purposes such as an electronic device using the same.
  • packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various purposes such as an electronic device using the same.
  • the electronic element body is a body of an electronic device, and is disposed on the gas barrier layer side of the gas barrier film.
  • a known electronic device body to which sealing with a gas barrier film can be applied can be used.
  • an organic EL element, a solar cell (PV), a liquid crystal display element (LCD), electronic paper, a thin film transistor, a touch panel, and the like can be given.
  • the electronic element body is preferably an organic EL element or a solar battery.
  • the gas barrier film according to the present invention can also be used for device film sealing. That is, it is a method of providing the gas barrier film of the present invention on the surface of the device itself as a support.
  • the device may be covered with a protective layer before providing the gas barrier film.
  • the gas barrier film according to the present invention can also be used as a device substrate or a film for sealing by a solid sealing method.
  • the solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured.
  • an adhesive agent A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.
  • FIG. 2 is an example of an organic EL panel which is an electronic device using the gas barrier film according to the present invention as a sealing film.
  • a transparent electrode 4 is formed on a gas barrier film 10 as a substrate.
  • An organic EL element 5 is formed on the transparent electrode 4, and the organic EL element 5 is sealed with a counter film 7, and an adhesive layer 6 is provided in the gap between the transparent electrode 4 and the counter film 7. Is provided to complete the sealing.
  • the reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a ⁇ / 4 plate, and a polarizing film in order from the bottom.
  • the gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
  • the transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a ⁇ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a ⁇ / 4 plate, and a polarization It has a structure consisting of a film. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
  • the type of the liquid crystal cell is not particularly limited, but more preferably a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment E), EC type. Controlled birefringence), OCB type (Optically Compensated Bend), IPS type (In-Plane Switching), and CPA type (Continuous Pinheal Alignment) are preferable.
  • TN type Transmission Nematic
  • STN type Super Twisted Nematic
  • HAN type Hybrid Aligned Nematic
  • VA type Very Alignment E
  • EC type Controlled birefringence
  • OCB type Optically Compensated Bend
  • IPS type In-Plane Switching
  • CPA type Continuous Pinheal Alignment
  • the gas barrier film of the present invention can also be used as a sealing film for solar cell elements.
  • the gas barrier film of the present invention is preferably sealed so that the barrier layer is closer to the solar cell element.
  • the solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. For example, it is a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type.
  • Amorphous silicon-based solar cell elements III-V group compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI group compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I-III- such as copper / indium / selenium (so-called CIS), copper / indium / gallium / selenium (so-called CIGS), copper / indium / gallium / selenium / sulfur (so-called CIGS), etc.
  • Group VI compound semiconductor solar cell element dye-sensitized solar cell element, organic solar cell element, etc. And the like.
  • the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur.
  • CIS system copper / indium / selenium system
  • CIGS system copper / indium / gallium / selenium system
  • sulfur copper / indium / gallium / selenium / sulfur.
  • a group I-III-VI compound semiconductor solar cell element such as a system (so-called CIGSS system) is preferable.
  • the thin film transistor described in JP-T-10-512104 As other application examples, the thin film transistor described in JP-T-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., and described in JP-A-2000-98326 Electronic paper and the like.
  • the gas barrier film of the present invention can also be used as an optical member.
  • the optical member include a circularly polarizing plate.
  • a circularly polarizing plate can be produced by laminating a ⁇ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the ⁇ / 4 plate and the absorption axis of the polarizing plate is 45 °.
  • a polarizing plate one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used.
  • MD longitudinal direction
  • those described in JP-A-2002-86554 can be suitably used. .
  • Vapor deposition device JEOL Ltd., vacuum vapor deposition device JEE-400 Constant temperature and humidity oven: Yamato Humidic Chamber IG47M Metal that reacts with water and corrodes: Calcium (granular) Water vapor impermeable metal: Aluminum ( ⁇ 3-5mm, granular) (Preparation of water vapor barrier property evaluation cell)
  • a vacuum vapor deposition device vacuum vapor deposition device JEE-400, manufactured by JEOL Ltd.
  • the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet.
  • the vacuum state is released, and the aluminum sealing side is quickly passed through a UV-curable resin (manufactured by Nagase ChemteX Corporation) to 0.2 mm thick quartz glass in a dry nitrogen gas atmosphere.
  • an evaluation cell was produced by irradiating with ultraviolet rays.
  • the obtained sample with both sides sealed was stored at 60 ° C. and 90% RH under high temperature and high humidity, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water was calculated.
  • a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample was stored under the same high temperature and high humidity conditions of 60 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.
  • the permeated water amount (g / m 2 ⁇ day; “WVTR” in the table) of each gas barrier film measured as described above was evaluated by the Ca method.
  • gas barrier film sample 1 First, as a base material, a polyethylene terephthalate (PET) film having a thickness of 125 ⁇ m having both surfaces subjected to easy adhesion treatment was prepared.
  • PET polyethylene terephthalate
  • the substrate made of this PET film is mounted on a plasma CVD roll coater W35 series apparatus manufactured by Kobe Steel, Ltd., and using hexamethyldisiloxane (HMDSO), under the following film forming conditions (plasma CVD conditions), A gas barrier layer having a thickness of 300 nm was formed on the substrate. Thereby, a gas barrier film sample 1 was obtained. It was confirmed by XPS depth profile measurement (conditions described above) that the gas barrier layer formed above satisfies all the above conditions (i) to (iii) (hereinafter the same applies to all examples). Met).
  • ⁇ Film forming conditions Supply amount of raw material gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute) Supply amount of oxygen gas (O 2 ): 500 sccm Degree of vacuum in the vacuum chamber: 3Pa Applied power from the power source for plasma generation: 0.8 kW Frequency of power source for plasma generation: 70 kHz Film conveyance speed: 0.5 m / min.
  • HMDSO raw material gas
  • O 2 oxygen gas
  • gas barrier film sample 3 (Preparation of gas barrier film sample 3)
  • a hard coat layer (second HC layer; thickness 4 ⁇ m) is formed on the surface of the substrate opposite to the gas barrier layer by the same method as “Production of gas barrier film sample 2”. Formed. Thereby, the gas barrier film sample 3 was produced.
  • PET polyethylene terephthalate
  • a protective film with an adhesive layer (manufactured by Fujimori Kogyo Co., Ltd., product name MASTACK TFB series; PET base material (thickness 75 ⁇ m)) was prepared as a protective film to be disposed on the gas barrier film.
  • a hard coat layer having a thickness of 2 ⁇ m was formed on one surface of the base material prepared above by the same method as “Preparation of gas barrier film sample 2”. Subsequently, the protective film prepared above was affixed on the exposed surface of this hard-coat layer through the adhesion layer.
  • a gas barrier layer having a thickness of 300 nm was formed on the exposed surface of the base material (the surface on which the hard coat layer was not formed) by the same method as “Preparation of gas barrier film sample 2”. Thereafter, a hard coat layer having a thickness of 4 ⁇ m was formed on the exposed surface of the gas barrier layer by the same method as “Preparation of Gas Barrier Film Sample 2”. Thereby, the gas barrier film sample 11 was produced.
  • gas barrier film samples 1 to 24 The specifications of gas barrier film samples 1 to 24 and various evaluation results are shown in Table 1 below.
  • COP is a cycloolefin polymer film (manufactured by ZEON Corporation, product name ZEONOR ZF-14-50)
  • PC is a polycarbonate film (manufactured by Teijin Limited, Pure ace (registered trademark) WRS5)
  • TAC is a triacetyl cellulose film (manufactured by Konica Minolta, product name Konica Minolta Tack KC6UY).
  • the result of “warp” of the sample 24 is “impossible to measure” means that the gas barrier film was rounded after the protective film was peeled off, and the value of the warp could not be measured.
  • the gas barrier film according to the present invention exhibits excellent flexibility because the value of warpage is a value within a predetermined range, and after the bending test, As can be seen from FIG.

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Abstract

La présente invention concerne un film barrière contre les gaz qui présente une excellente résistance à la flexion et grâce auquel une diminution de performance de barrière contre les gaz peut être supprimée même si le film barrière contre les gaz est courbé. Le film barrière contre les gaz selon l'invention comprend un substrat et une couche barrière contre les gaz formée selon un procédé de dépôt chimique en phase vapeur sur une surface du substrat et est caractérisé en ce qu'un échantillon d'une taille de 100 mm x 100 mm est placé sur une surface plate de sorte que la couche barrière contre les gaz soit sous le substrat, et la valeur de gauchissement qui est calculée comme la valeur moyenne obtenue par la mesure de la hauteur à laquelle les quatre coins flottent depuis la surface plate est de 1 à 60 mm.
PCT/JP2015/056713 2014-03-06 2015-03-06 Film barrière contre les gaz WO2015133620A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135216A1 (fr) * 2017-01-18 2018-07-26 コニカミノルタ株式会社 Stratifié de film fonctionnel et procédé de fabrication de dispositif électronique
JP2018144283A (ja) * 2017-03-02 2018-09-20 コニカミノルタ株式会社 機能性フィルム積層体の製造方法

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JP2005289041A (ja) * 2004-03-09 2005-10-20 Dainippon Printing Co Ltd 湾曲を防止したガスバリアフィルム
JP2005313560A (ja) * 2004-04-30 2005-11-10 Dainippon Printing Co Ltd ガスバリア性フィルム
JP2012081632A (ja) * 2010-10-08 2012-04-26 Sumitomo Chemical Co Ltd 積層フィルム
JP2012121149A (ja) * 2010-12-06 2012-06-28 Konica Minolta Holdings Inc ガスバリア性フィルム、ガスバリア性フィルムの製造方法、及びガスバリア性フィルムを有する有機電子デバイス

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JP2005289041A (ja) * 2004-03-09 2005-10-20 Dainippon Printing Co Ltd 湾曲を防止したガスバリアフィルム
JP2005313560A (ja) * 2004-04-30 2005-11-10 Dainippon Printing Co Ltd ガスバリア性フィルム
JP2012081632A (ja) * 2010-10-08 2012-04-26 Sumitomo Chemical Co Ltd 積層フィルム
JP2012121149A (ja) * 2010-12-06 2012-06-28 Konica Minolta Holdings Inc ガスバリア性フィルム、ガスバリア性フィルムの製造方法、及びガスバリア性フィルムを有する有機電子デバイス

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135216A1 (fr) * 2017-01-18 2018-07-26 コニカミノルタ株式会社 Stratifié de film fonctionnel et procédé de fabrication de dispositif électronique
CN110225823A (zh) * 2017-01-18 2019-09-10 柯尼卡美能达株式会社 功能性膜层叠体及电子器件的制造方法
JP2018144283A (ja) * 2017-03-02 2018-09-20 コニカミノルタ株式会社 機能性フィルム積層体の製造方法

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