WO2017086170A1 - Film barrière aux gaz - Google Patents

Film barrière aux gaz Download PDF

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Publication number
WO2017086170A1
WO2017086170A1 PCT/JP2016/082653 JP2016082653W WO2017086170A1 WO 2017086170 A1 WO2017086170 A1 WO 2017086170A1 JP 2016082653 W JP2016082653 W JP 2016082653W WO 2017086170 A1 WO2017086170 A1 WO 2017086170A1
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WIPO (PCT)
Prior art keywords
gas barrier
ratio
film
layer
gas
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PCT/JP2016/082653
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English (en)
Japanese (ja)
Inventor
河村　朋紀
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コニカミノルタ株式会社
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Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to CN201680066364.7A priority Critical patent/CN108349210B/zh
Priority to JP2017551812A priority patent/JP6897567B2/ja
Publication of WO2017086170A1 publication Critical patent/WO2017086170A1/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
    • 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
    • C23C16/42—Silicides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

Definitions

  • the present invention relates to a gas barrier film. More specifically, the present invention provides a gas barrier that has good gas barrier properties, little deterioration in gas barrier properties due to contact between the front and back surfaces during winding of the roll, and the occurrence of cracks on the cut surface when cutting is suppressed. Related to 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 to wrap articles in the fields of food, medicine, etc. Used for applications.
  • a gas barrier film By using the gas barrier film, it is possible to prevent deterioration of the article due to gas such as water vapor or oxygen.
  • gas barrier films that prevent permeation of water vapor, oxygen, and the like have been demanded to be applied to electronic devices such as organic electroluminescence (EL) elements and liquid crystal display (LCD) elements. Is being studied. In these electronic devices, a high gas barrier property, for example, a gas barrier property comparable to a glass substrate is required.
  • a CVD method (Chemical Vapor Deposition) is used as a method for producing a gas barrier film that is more flexible than a glass substrate.
  • Patent Document 1 discloses that gas barrier properties, flexibility, and impact resistance are improved by a silicon oxide carbide (SiOC) film formed by a plasma chemical vapor deposition method.
  • SiOC silicon oxide carbide
  • the gas barrier film described in Patent Document 1 has a problem that the gas barrier property is not sufficient.
  • the gas barrier property is likely to be significantly lowered, and there is a problem that the effective area having the gas barrier performance is reduced due to generation of cracks.
  • Patent Document 2 also discloses a gas barrier that improves the durability against cracks while maintaining a dense structure by containing carbon atoms, silicon atoms, and oxygen atoms in a specific ratio range in the layer thickness direction. A film is described. However, since such a gas barrier film has a relatively uniform density and strength in the layer thickness direction, sufficient strength cannot be obtained with respect to stress applied from the surface and side surfaces during roll winding and cutting. There was a problem.
  • JP 2011-73430 A Japanese Patent Application Laid-Open No. 2014-00782
  • the present invention has been made in view of the above-described problems and situations, and the problem to be solved is that the gas barrier property is good, the gas barrier property is less deteriorated due to contact between the front and back surfaces when winding the roll, and cutting is performed. It is to provide a gas barrier film in which the occurrence of cracks on the cut surface is suppressed.
  • the present inventor in the gas barrier film having a gas barrier layer containing at least silicon atoms, oxygen atoms and carbon atoms on the substrate, By making the ratio of carbon atoms derived from C—C, C ⁇ C and C—H bonds in a predetermined region near the outermost surface of the gas barrier layer within a predetermined range, the gas barrier property is good,
  • the present inventors have found that a gas barrier film can be provided in which a decrease in gas barrier properties due to contact between the front and back surfaces during winding of a roll is small, and generation of cracks on a cut surface during cutting can be suppressed. That is, the said subject which concerns on this invention is solved by the following means.
  • the substrate On the substrate, it has a gas barrier layer containing at least silicon atoms (Si), oxygen atoms (O) and carbon atoms (C),
  • Si silicon atoms
  • O oxygen atoms
  • C carbon atoms
  • the composition ratio ratio converted from the ratio of peak intensity derived from silicon atoms (Si), oxygen atoms (O) and carbon atoms (C) in the layer thickness direction of the gas barrier layer
  • the composition ratio ratio X (converted from the ratio of peak intensities derived from C—C, C ⁇ C, and C—H bonds based on the C1s waveform analysis for carbon atoms %) Satisfy
  • the gas barrier film characterized by the above-mentioned.
  • the maximum value (%) of the ratio X in the -30% region is in the range of 5-41 (%).
  • the maximum value (%) of the ratio X in the layer thickness range of 5 to 30% is larger than the maximum value (%) of the ratio X in the layer thickness range of 30 to 95%. 4.
  • the average value (%) of the ratio X in the layer thickness range of 5 to 30% is larger than the average value (%) of the ratio X in the layer thickness range of 30 to 95%. 5.
  • the minimum value (%) of the ratio X in the layer thickness range of 5 to 30% is larger than the minimum value (%) of the ratio X in the layer thickness range of 30 to 95%.
  • the gas barrier film according to any one of items 5 to 5.
  • a gas barrier film having good gas barrier properties, less deterioration of gas barrier properties due to contact between the front and back surfaces during winding of the roll, and suppressing occurrence of cracks on the cut surface when cutting. Can be provided.
  • the expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.
  • the gas barrier film of the present invention carbon atoms derived from bonds of C—C, C ⁇ C, and C—H are present at a predetermined ratio in a region near the outermost surface of the gas barrier film layer.
  • the abundance of atoms is increased compared to conventional gas barrier films.
  • the region near the outermost surface of the gas barrier layer of the present invention was made into a region having high density and appropriate flexibility, the gas barrier property was good and the front and back surface contact during roll winding It is thought that the damage caused by.
  • the area near the outermost surface of the gas barrier layer could be made into an area with few fine voids, when cutting from the vicinity of the outermost surface, the occurrence of cracks on the cut surface is suppressed, It is thought that cracks due to shear force are less likely to enter.
  • Sectional drawing which shows an example of the gas barrier film of this invention
  • the graph which shows an example of distribution of the silicon atom of the gas barrier layer which concerns on this invention, an oxygen atom, and a carbon atom
  • the schematic diagram which shows an example of the manufacturing apparatus used for formation of the gas barrier layer which concerns on this invention
  • the graph which shows an example of distribution of the silicon atom of the gas barrier layer which concerns on a comparative example, an oxygen atom, and a carbon atom
  • the gas barrier film of the present invention has a gas barrier layer containing at least silicon atoms (Si), oxygen atoms (O), and carbon atoms (C) on a substrate, and was obtained by X-ray photoelectron spectroscopy.
  • Si silicon atoms
  • O oxygen atoms
  • C carbon atoms
  • the ratio X (%) of the composition ratio converted from the ratio of the peak intensity derived from the bond of C—C, C ⁇ C, and C—H based on the C1s waveform analysis for the carbon atom is the following (1): It is characterized by satisfying.
  • This feature is a technical feature common to the claimed invention.
  • the maximum value (%) of the ratio X is in the range of 5 to 41 (%).
  • the average value (%) of the ratio X in the layer thickness range of 5 to 30% is in the range of 2 to 20%. It is preferable.
  • the minimum value (%) of the ratio X in the layer thickness range of 5 to 30% is in the range of 1 to 10%. It is preferable.
  • the maximum value (%) of the ratio X in the layer thickness range of 5 to 30% is the above-described value in the layer thickness range of 30 to 95%. It is preferable that the ratio X is larger than the maximum value (%).
  • the average value (%) of the ratio X in the layer thickness range of 5 to 30% is set to It is preferable that the ratio X is larger than the average value (%).
  • the minimum value (%) of the ratio X in the layer thickness range of 5 to 30% is set to the value in the layer thickness range of 30 to 95%. It is preferable that the ratio X is larger than the minimum value (%).
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • the gas barrier film 1 of the present invention is configured by laminating a gas barrier layer 3 on a substrate 2.
  • the gas barrier layer 3 contains silicon oxide carbide (SiOC), and its composition and bonding state change in the layer thickness direction.
  • the gas barrier layer according to the present invention contains at least a silicon atom (Si), an oxygen atom (O), and a carbon atom (C), and in the spectrum obtained by X-ray photoelectron spectroscopy, the thickness direction of the gas barrier layer Based on the C1s waveform analysis for carbon atoms, where the total amount of the composition ratio converted from the ratio of the peak intensity derived from silicon atoms (Si), oxygen atoms (O), and carbon atoms (C) is 100%. , C—C, C ⁇ C, and the ratio X (%) of the composition ratio converted from the ratio of the peak intensity derived from the bond of C—H satisfies the following (1).
  • the gas barrier layer has a high density, has an appropriate flexibility, and can reduce the number of fine voids, so that the gas barrier property is good, and the gas barrier property due to the contact between the front and back surfaces during winding of the roll is good. It is possible to obtain an effect that the decrease is small and the generation of cracks on the cut surface when cutting is suppressed.
  • the “interface with the substrate” as used in the present invention means “the gas barrier layer when the composition ratio of oxygen atoms (O), which is a part of the composition forming the gas barrier layer, is 30% or less. "The position of the depth from the outermost surface side in the layer thickness direction”.
  • the composition ratio of oxygen atoms (O) can be calculated by X-ray photoelectron spectroscopy described later.
  • the average value (%) of the ratio X is preferably in the range of 2 to 20% in the layer thickness range of 5 to 30%, and the minimum value of the ratio X ( %) Is preferably in the range of 1 to 10%. This improves the internal durability of the gas barrier layer due to the distribution of carbon bonds derived from C—C, C ⁇ C and C—H in the 5-30% region of the gas barrier layer. The effect of the present invention can be expressed more effectively.
  • the maximum value (%), the average value (%), and the minimum value (%) of the ratio X in the layer thickness range of 5 to 30% are the values in the layer thickness range of 30 to 95%.
  • the ratio X is preferably larger than the maximum value (%), the average value (%), and the minimum value (%).
  • the amount of carbon bonds to be distributed can be more distributed as an absolute amount, and the effects of the present invention can be expressed more effectively.
  • Carbon distribution curve (distance from the outermost surface of the gas barrier layer in the thickness direction of the gas barrier layer (L) and the ratio of the number of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon Curve representing the relationship with the atomic ratio), silicon distribution curve (distance L and the ratio of the number of silicon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (silicon atom ratio) X-rays) and oxygen distribution curve (curve showing the relationship between the distance L and the ratio of the number of oxygen atoms (oxygen atom ratio) to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%)).
  • the XPS depth profile can be measured, for example, under the following conditions to obtain a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve with respect to the distance from the surface of the thin film layer in the layer thickness direction.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 2 nm
  • X-ray photoelectron spectrometer Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific Irradiation X-ray: Single crystal spectroscopy AlK ⁇ X-ray spot and its size: 800 ⁇ m ⁇ 400 ⁇ m oval
  • the distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (at%) of each element and the horizontal axis as the etching time (sputtering time).
  • the atomic ratio (at%) in each region is a value obtained by etching values in the depth direction by XPS depth profile measurement and averaging values measured at intervals of 2 nm, for example.
  • a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve can be obtained by performing a wide scan spectrum analysis for measuring the entire region of the gas barrier layer.
  • the bonding state of carbon is analyzed by a high resolution spectrum (narrow scan analysis) of C1s.
  • C carbon bond
  • the carbon bond (C) based on the waveform analysis of C1s, (1) C—C, C ⁇ C and C—H, (2) C—SiO, ( 3) C—O, (4) C ⁇ O, (5) O—C—O, divided into five bond groups, and derived from (1) to (5) from the intensity ratio of each peak. The ratio of carbon atoms to be calculated is calculated.
  • the percentage (%) is calculated.
  • the analysis of the peak intensity can be performed using, for example, data analysis software PeakFit (manufactured by SYSSTAT Software Inc.).
  • the analysis result about the gas barrier film of this invention is shown in FIG.
  • the horizontal axis represents the depth in the thickness direction of the gas barrier layer (the depth (%) when the outermost surface is 0% and the interface with the substrate is 100%)
  • the vertical axis Represents the ratio (%) of each atom when the total amount of the composition ratio converted from the ratio of the peak intensity derived from the silicon atom, oxygen atom and carbon atom determined by X-ray photoelectron spectroscopy is 100%.
  • Carbon atoms are divided into the above-mentioned five bond groups.
  • (1) to (5) in FIG. 2 are respectively (1) C—C, C ⁇ C and C—H, (2) C—SiO, (3) C—O, (4) C ⁇ O.
  • (5) corresponds to a carbon atom derived from O—C—O
  • (6) corresponds to an oxygen atom
  • (7) corresponds to a silicon atom.
  • the layer thickness of the gas barrier layer is determined by measuring the depth from the outermost surface to the interface with the substrate in the stacking direction of the gas barrier layer by observing a cross section with a transmission electron microscope (TEM). be able to.
  • TEM transmission electron microscope
  • the layer thickness is arbitrarily measured at 10 locations, and the average value is taken as the layer thickness of the gas barrier layer.
  • FIB focused ion beam
  • the layer thickness of the gas barrier layer according to the present invention is preferably in the range of 10 to 500 nm, and more preferably in the range of 20 to 300 nm, from the viewpoint of achieving both thinning and gas barrier properties.
  • the gas barrier layer preferably has gas barrier properties.
  • having a gas barrier property means that only a gas barrier layer is laminated on a substrate, and a water vapor permeability (38 ° C., relative humidity 90) measured using a MOCON water vapor permeability measuring apparatus Aquatran manufactured by MOCON. % RH) is less than 0.1 g / (m 2 ⁇ day), and preferably less than 0.01 g / (m 2 ⁇ day).
  • a plastic film is used as the base material of the gas barrier film of the present invention.
  • the plastic film used is not particularly limited in material, thickness and the like as long as it can hold the gas barrier layer, and can be appropriately selected according to the purpose of use.
  • 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, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modification
  • thermoplastic resins such as polycarbonate resin, fluorene ring-modified polyester resin, and acryloyl compound.
  • the substrate is preferably made of a material having heat resistance.
  • a material having heat resistance within the linear expansion coefficient of 15 ⁇ 10 -6 ⁇ 100 ⁇ 10 -6 (/ K), and the glass transition temperature Tg is used is a resin base material in the range of 100 ⁇ 300 ° C. .
  • the base material satisfies the requirements for use as a laminated film for electronic parts and displays. That is, when using a gas barrier film for these uses, the gas barrier film may be exposed to a process of 150 ° C. or higher.
  • the linear expansion coefficient of the base material in the gas barrier film is in the range of 15 ⁇ 10 ⁇ 6 to 100 ⁇ 10 ⁇ 6 (/ K)
  • the heat resistance is high and the flexibility is good.
  • the linear expansion coefficient and Tg of the base material can be adjusted by an additive or the like.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • alicyclic polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C, manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 190 ° C), cycloolefin Copolymer (COC: Compound described in JP-A No.
  • the plastic film is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the light transmittance is determined by measuring the total light transmittance and the amount of scattered light using the method described in JIS K 7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. Can be calculated.
  • an opaque material can be used as the plastic film.
  • the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.
  • the thickness of the plastic film used for the gas barrier film is not particularly limited because it is appropriately selected depending on the application, but is typically in the range of 1 to 800 ⁇ m, and preferably in the range of 10 to 200 ⁇ m.
  • These plastic films may have a functional layer such as a known transparent conductive layer or smooth layer used in conventional gas barrier films.
  • a functional layer in addition to those described above, those described in paragraphs 0036 to 0038 of JP-A-2006-289627 can be preferably employed.
  • the base material using the above-described resins or the like may be an unstretched film or a stretched film.
  • the base material can be manufactured by a conventionally known general method.
  • an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.
  • the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc.
  • a stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis).
  • the draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably in the range of 2 to 10 times in the vertical axis direction and the horizontal axis direction.
  • an anchor coat layer may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion).
  • the constituent material and formation method of the anchor coat layer the materials, methods and the like disclosed in paragraphs 0229 to 0232 of JP2013-52561A are appropriately employed.
  • the gas barrier film of the present invention may have a smooth layer on the surface of the substrate having the gas barrier layer.
  • the smooth layer is for flattening the rough surface of the substrate on which protrusions and the like exist, or for filling the unevenness and pinholes generated in the gas barrier layer with the protrusions existing on the resin base material.
  • the constituent material, forming method, surface roughness, layer thickness and the like of the smooth layer, materials, methods and the like disclosed in paragraphs 0233 to 0248 of JP2013-52561A are appropriately employed.
  • the gas barrier film of the present invention can further have a bleed-out preventing layer.
  • the bleed-out prevention layer is used for the purpose of suppressing a phenomenon that, when a film having a smooth layer is heated, unreacted oligomers migrate from the resin base material to the surface and contaminate the contact surface. It is provided on the opposite surface of the substrate.
  • the bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.
  • the constituent material, formation method, layer thickness, and the like of the bleed-out prevention layer the materials, methods, and the like disclosed in paragraphs 0249 to 0262 of JP2013-52561A are appropriately employed.
  • the gas barrier film of the present invention as described above has excellent gas barrier properties, transparency, and flexibility.
  • the gas barrier film of this invention is a gas barrier film used for electronic devices, such as packages, a photoelectric conversion element (solar cell element), an organic EL element, a liquid crystal display element, etc., and an electronic device using the same. It can be used for various purposes.
  • the gas barrier layer according to the present invention can be formed by a plasma chemical vapor deposition method (plasma CVD, plasma-enhanced chemical vapor deposition (PECVD), hereinafter also simply referred to as “plasma CVD method”).
  • plasma CVD plasma chemical vapor deposition method
  • PECVD plasma-enhanced chemical vapor deposition
  • the plasma CVD method using the plasma CVD method in the atmospheric pressure or the atmospheric pressure described in the international publication 2006/033233, and the plasma CVD apparatus with a counter roller electrode is mentioned. .
  • the plasma CVD method may be a Penning discharge plasma type plasma CVD method.
  • a source gas containing an organic silicon compound and an oxygen gas by a discharge plasma chemical vapor deposition method (a roll-to-roll method) having a discharge space between rollers to which a magnetic field is applied.
  • a discharge plasma chemical vapor deposition method a roll-to-roll method having a discharge space between rollers to which a magnetic field is applied.
  • the discharge plasma chemical vapor deposition method it is possible to easily produce a gas barrier layer having an extreme value and the carbon atom ratio in each region being controlled within a certain range, A gas barrier film having an appropriate stress balance in the layer can be produced.
  • the discharge plasma chemical vapor deposition method the gas barrier layer can be densified and the gas barrier property can be improved.
  • a plasma discharge in a space between a plurality of film forming rollers it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers.
  • a pair of film forming rollers is used, and a substrate is provided for each of the pair of film forming rollers.
  • the base material here includes a form in which the base material is treated.
  • the film forming gas used in such a plasma CVD method preferably contains an organic silicon compound and oxygen, and the oxygen content in the film forming gas is the total amount of the organic silicon compound in the film forming gas. It is preferable that the amount of oxygen be adjusted according to the theoretical oxygen amount required to completely oxidize.
  • FIG. 3 is a schematic view showing an example of a manufacturing apparatus that can be suitably used for manufacturing the gas barrier layer according to the present invention.
  • the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.
  • the 3 includes a feed roller 12, transport rollers 13 to 18, film forming rollers 19 and 20, a gas supply pipe 21, a plasma generating power source 22, and film forming rollers 19 and 20.
  • Magnetic field generators 23 and 24 and winding rollers 25 installed inside are provided.
  • 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 provided in the film forming (vacuum) chamber 28. Is arranged.
  • the film forming chamber 28 is connected to a vacuum pump (not shown), and the pressure in the film forming chamber 28 can be appropriately adjusted by such a vacuum pump.
  • the feed roller 12 and the transport roller 13 are disposed in the transport system chamber 27, and the winding roller 25 and the transport roller 18 are disposed in the transport system chamber 29.
  • the transfer system chambers 27 and 29 and the film forming chamber 28 are connected via connecting portions 30 and 31, respectively.
  • the film forming chamber 28 and the transfer system chambers 27 and 29 may be physically separated by providing a vacuum gate valve in the connecting portions 30 and 31.
  • the vacuum gate valve for example, only the film forming chamber 28 can be a vacuum system, and the transfer system chambers 27 and 29 can be in the atmosphere. Further, by physically separating the film forming chamber 28 and the transfer system chambers 27 and 29, it is possible to suppress the transfer system chambers 27 and 29 from being contaminated by particles generated in the film forming chamber 28. .
  • each film-forming roller 19 and 20 is a power source for plasma generation so that the pair of film-forming rollers (film-forming rollers 19 and 20) can function as a pair of counter electrodes. 22 is connected. Therefore, in such a manufacturing apparatus 10, it is possible to discharge to the space between the film forming roller 19 and the film forming roller 20 by supplying power from the plasma generating power source 22. Plasma can be generated in the space between the film roller 19 and the film formation roller 20.
  • the material and design may be appropriately changed so that the film-forming roller 19 and the film-forming roller 20 can also be used as electrodes.
  • the gas barrier layer 3 can be formed on the surface of the base material 2 (here, the base material includes a form in which the base material is treated) by a CVD method. It is possible to deposit a gas barrier layer component on the surface of the substrate 2 on the film forming roller 19 and further deposit a gas barrier layer component on the surface of the substrate 2 also on the film forming roller 20. Therefore, the gas barrier layer can be efficiently formed on the surface of the substrate 2.
  • magnetic field generators 23 and 24 fixed so as not to rotate even when the film forming rollers 19 and 20 rotate are provided, respectively.
  • the magnetic field generators 23 and 24 provided in the film forming rollers 19 and 20 are respectively a magnetic field generator 23 provided in one film forming roller 19 and a magnetic field generator 24 provided in the other film forming roller 20. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between each other and the magnetic field generators 23 and 24 form a substantially closed magnetic circuit.
  • the magnetic field generators 23 and 24 provided on the film forming rollers 19 and 20 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 23 and the other magnetic field generator 24 are It is preferable to arrange the magnetic poles so that the opposing magnetic poles have the same polarity.
  • each of the magnetic field generators 23 and 24 is opposed to the space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force oppose each other.
  • a racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained.
  • the material 2 is excellent in that the gas barrier layer 3 that is a vapor deposition film can be efficiently formed.
  • the tension on the substrate 2 in each of the film forming rollers 19 and 20 may all be the same, but only the tension in the film forming roller 19 or the film forming roller 20 may be increased.
  • the film forming rollers 19 and 20 known rollers can be used as appropriate. As such film forming rollers 19 and 20, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rollers 19 and 20 is preferably in the range of 300 to 1000 mm ⁇ , particularly in the range of 300 to 700 mm ⁇ , from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mm ⁇ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced.
  • each film-forming roller 19 and 20 may be provided with a nip roll, and by providing the nip roll, the adhesion of the base material 2 to the film-forming rollers 19 and 20 is improved. Thereby, heat exchange is efficiently performed between the base material 2 and the film forming rollers 19 and 20, and there is an advantage that film uniformity is improved and heat wrinkles are suppressed.
  • the base material 2 is arrange
  • a pair of film-forming rollers film-forming rollers 19
  • the gas barrier layer component is deposited on the surface of the substrate 2 on the film forming roller 19 by the plasma CVD method, and further the gas barrier layer is formed on the film forming roller 20.
  • a gas barrier layer can be efficiently formed on the surface of the substrate 2.
  • known rollers can be used as appropriate.
  • the take-up roller 25 is not particularly limited as long as it can take up the gas barrier film 1 in which the gas barrier layer 3 is formed on the substrate 2, and a known roller is appropriately used. Can do.
  • the feed roller 12 and the take-up roller 25 may be a turret type. The turret may be multiaxial with two or more axes, and may have a structure in which only some of the axes can be opened to the atmosphere.
  • gas supply pipe 21 and the vacuum pump those capable of supplying or discharging the raw material gas at a predetermined speed can be appropriately used.
  • the gas supply pipe 21 serving as a gas supply means is preferably provided in one of the facing spaces (discharge region, film formation zone) between the film formation roller 19 and the film formation roller 20, and is a vacuum serving as a vacuum exhaust means.
  • a pump (not shown) is preferably provided on the other side of the facing space. In this way, by providing the gas supply pipe 21 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 19 and the film formation roller 20. It is excellent in that the film formation efficiency can be improved.
  • the gas supply pipe 21 is provided on the center line between the film formation roller 19 and the film formation roller 20.
  • the present invention is not limited to this. You may shift
  • the gas supply pipe 21 is closer to one film formation roller and farther from the other film formation roller.
  • the film composition formed on the film forming roller 19 and the film composition formed on the film forming roller 20 become different, and the position of the gas supply pipe 21 may be appropriately shifted when it is desired to change the film quality.
  • the gas supply pipe 21 may be appropriately separated from or closer to the film forming roller on the center line (the arrangement position may be moved on the center line in the vertical direction).
  • the gas supply pipe 21 may be appropriately separated from or closer to the film forming roller on the center line (the arrangement position may be moved on the center line in the vertical direction).
  • particles can be prevented from adhering to the gas supply pipe 21 by moving the gas supply pipe 21 away from the center axis of the film forming roller and separating the gas supply pipe 21 from the discharge space.
  • the film forming rate can be improved by bringing the film closer to the discharge space on the central axis of the film forming roller.
  • FIG. 3 there is one gas supply pipe 21, but there may be a plurality of gas supply pipes 21, and different supply gases may be discharged from each nozzle.
  • the plasma generating power source 22 a known power source for a plasma generating apparatus can be used as appropriate.
  • a power source 22 for generating plasma supplies power to the film forming roller 19 and the film forming roller 20 connected thereto, and makes it possible to use them as a counter electrode for discharging.
  • a power source AC power source or the like
  • a plasma generating power source 22 is preferably capable of performing plasma CVD more efficiently, so that the applied power is preferably in the range of 100 W to 20 kW, and in the range of 100 W to 10 kW.
  • the AC frequency is preferably in the range of 50 Hz to 13.56 MHz, and more preferably in the range of 50 Hz to 500 kHz. Further, from the viewpoint of stabilizing the plasma process, a high frequency power source in which both the high frequency current wave and the voltage wave are sine waves may be used.
  • power is supplied to both the film forming rollers 19 and 20 by one plasma generating power source 22 (both film forming roller power supply), but is not limited to such a form.
  • the film roller may be supplied with power (one-side film formation roller power supply) and the other film formation roller may be grounded.
  • roller one-end power feeding from only one of the roller ends may be used, or roller both-end power feeding from both ends of the roller may be used. In the case of supplying a high frequency band, it is possible to supply both ends of the roller because uniform supply is possible.
  • two-frequency feeding may be performed in which different frequencies are applied, and one film-forming roller and the other film-forming roller may be applied even when two different frequencies are applied to one film-forming roller.
  • a different frequency may be applied.
  • the plasma emission intensity in the discharge space is monitored from the outside. If the desired emission intensity is not obtained, the distance between the magnetic fields (distance between the opposing rollers), the magnetic field intensity, and the applied power of the power source.
  • a feedback circuit that adjusts the power supply frequency, the amount of supplied gas, and the like to obtain a desired plasma emission intensity may be provided. By having such a feedback circuit, film formation / production can be stabilized.
  • the magnetic field generators 23 and 24 known magnetic field generators can be used as appropriate.
  • the base material 2 in addition to the base material used in the present invention, a material in which the gas barrier layer 3 is previously formed can be used. As described above, the thickness of the gas barrier layer 3 can be increased by using the substrate 2 in which the gas barrier layer 3 is previously formed.
  • a gas barrier layer containing carbon atoms, silicon atoms, and oxygen atoms can be formed using the manufacturing apparatus 10 shown in FIG.
  • the method for controlling the atomic ratio of the carbon atom content of the gas barrier layer is not particularly limited, but the carbon atom content can be controlled by controlling the ratio of raw materials used, power, pressure, etc. The atomic ratio of can be controlled.
  • the pressure in the vacuum chamber (degree of vacuum) can be appropriately adjusted according to the type of the raw material gas, and is preferably about 0.5 to 50 Pa, and preferably within the range of 0.5 to 10 Pa. More preferred.
  • an electrode drum in this embodiment, the film forming roller 19 connected to the plasma generating power source 22 for discharging between the film forming roller 19 and the film forming roller 20.
  • the electric power to be applied can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, etc., and cannot be generally stated, but is 0.1 to 10 kW. It is preferable to be within the range. If the applied power is 0.1 kW (100 W) or more, the generation of particles can be sufficiently suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated during film formation can be suppressed, and the film formation can be suppressed. It can suppress that the temperature of the base-material surface at the time rises. Therefore, it is excellent in that wrinkles can be prevented from occurring during film formation without causing the substrate to lose heat.
  • the conveyance speed (line speed) of the substrate 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. A range of 0.5 to 100 m / min is more preferable.
  • the following methods (1) to (4) can be used to adjust the composition ratio of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer, and the ratio of the types of carbon bonds. Can be controlled within range.
  • Control by plasma CVD source gas It is possible to control by appropriately using plasma CVD source materials having different ratios of carbon, hydrogen, oxygen and silicon in the molecule.
  • an organosilicon compound having a low Si—C bond ratio in the molecule is preferably used as the raw material for plasma CVD.
  • the number of Si—C bonds in one molecule in these organosilicon compounds is preferably 2 or less, more preferably 1 or 0, per one Si atom in one molecule.
  • cyclic siloxanes such as octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane, and Si such as tetramethoxysilane and methyltrimethoxysilane
  • Si such as tetramethoxysilane and methyltrimethoxysilane
  • An alkoxysilane containing one per molecule is preferably used. These compounds can be used individually by 1 type or in combination of 2 or more types.
  • Control by supply amount of oxygen gas which is reaction gas It is possible to control by increasing / decreasing the supply amount of oxygen gas which is a reaction gas supplied during CVD film formation. Specifically, when forming the gas barrier film mainly composed of silicon atoms, oxygen atoms and carbon atoms by oxidizing the preferred raw material, the supply amount of oxygen gas is suppressed to such an extent that it is not completely oxidized, On the contrary, it is controlled by supplying a certain amount of oxygen gas to the raw material gas so that excessive carbon does not remain in the gas barrier layer.
  • Control of distance between electrodes in plasma discharge It can also be controlled by continuously changing the distance between electrodes for generating plasma discharge.
  • the plasma space generated on the surface of the base material in contact with the electrodes is continuously changed, so that the distance between the electrodes is continuously changed.
  • the composition in the gas barrier layer can be continuously changed by changing the film forming conditions.
  • a film forming gas for forming the gas barrier layer As the film forming gas, a reactive gas may be used in addition to the source gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide can be appropriately selected and used. Since the gas barrier layer 3 of the present embodiment contains oxygen, for example, oxygen and ozone can be used as the reactive gas, and oxygen is preferably used from the viewpoint of simplicity.
  • a reactive gas for forming a nitride may be used. For example, nitrogen or ammonia can be used. These reaction gases can be used alone or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for
  • a carrier gas may be used as necessary in order to supply the source gas into the film forming chamber 28.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • carrier gas and discharge gas known ones can be used as appropriate, and for example, rare gases such as helium, argon, neon, xenon, hydrogen, and nitrogen can be used.
  • the ratio of the source gas and the reactive gas is the theoretically necessary reactive gas for causing the raw material gas and the reactive gas to completely oxidize. It is preferable to adjust to 50% or more and 300% or more with respect to the ratio of the amount of 100%.
  • the ratio of the reaction gas within this range, the carbon atoms inside the formed gas barrier layer can be adjusted to a preferred composition distribution, and excellent gas barrier properties and bending resistance can be obtained.
  • the ratio is lower than the above ratio, the ratio of carbon atoms in the gas barrier layer becomes high and it is difficult to maintain a sufficient gas barrier property. It becomes difficult to form carbon-related bonds in the gas barrier layer.
  • discharge is generated between a pair of film forming rollers (film forming rollers 19 and 20) while supplying a film forming gas (such as a source gas) into the film forming chamber 28.
  • a film forming gas such as a source gas
  • the film-forming gas raw material gas or the like
  • the first film-forming layer is formed on the surface of the base material 2 on the film-forming roller 19 and on the surface of the base material 2 on the film-forming roller 20. Is formed by plasma CVD.
  • a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the film forming rollers 19 and 20, and the plasma is converged on the magnetic field.
  • the maximum value of the carbon distribution curve when the substrate 2 passes through the point A of the film forming roller 19 and the point B of the film forming roller 20, the maximum value of the carbon distribution curve The minimum value of the oxygen distribution curve is formed.
  • the substrate 2 passes through the points C1 and C2 of the film forming roller 19 and the points C3 and C4 of the film forming roller 20 the minimum value of the carbon distribution curve and the maximum value of the oxygen distribution curve are obtained. It is formed.
  • the gas barrier layer according to the present invention is formed by the plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roller electrode shown in FIG. It is characterized by forming a film.
  • This is excellent in flexibility (flexibility), high gas barrier property under high temperature and high humidity, and mechanical strength when mass-produced using a plasma CVD apparatus (roll-to-roll system) having a counter roller electrode.
  • a gas barrier layer with few defects that reduce durability and gas barrier properties during conveyance from roll to roll can be efficiently produced.
  • Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce a gas barrier film that is required for durability against temperature changes used in solar cells, electronic parts, and the like.
  • a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 manufactured by JSR Corporation is used, and a wire bar is formed so that the layer thickness after drying becomes 3 ⁇ m. Then, the coating was dried at 80 ° C. for 3 minutes as a drying condition. Next, using a high-pressure mercury lamp in an air atmosphere, curing was performed under a curing condition of 1.0 J / cm 2 to form an anchor coat layer.
  • a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7535 manufactured by JSR Corporation is used, and a wire bar is formed so that the layer thickness after drying is 3 ⁇ m.
  • the coating was cured at 1.0 J / cm 2 using a high-pressure mercury lamp in an air atmosphere to form a bleed-out prevention layer.
  • this bleed-out prevention layer it was used as a resin substrate that was conditioned and stored for 96 hours in an environment of 35 ° C. under a reduced pressure of 5 Pa.
  • roller CVD method Formation of gas barrier layer: Roller CVD method
  • roller CVD method Using the inter-roller discharge plasma CVD apparatus to which the magnetic field shown in FIG. 3 is applied (hereinafter, this method is referred to as “roller CVD method”), the surface of the resin substrate on which the bleed-out prevention layer is formed contacts the film forming roller.
  • the resin base material is mounted on the apparatus, and among the following film formation conditions (plasma CVD conditions), the source gas, the oxygen gas, the degree of vacuum in the vacuum chamber, and the power applied from the power source for plasma generation are as follows:
  • plasma CVD conditions plasma CVD conditions
  • the source gas, the oxygen gas, the degree of vacuum in the vacuum chamber, and the power applied from the power source for plasma generation are as follows:
  • the gas barrier layer of the present invention is adjusted by increasing the supply amount of the raw material gas in the total supply gas or decreasing the supply amount of the oxygen gas to increase the carbon atom ratio, thereby adjusting the layer thickness. Therefore, the degree of vacuum in the vacuum chamber was increased or decreased. Further, the supply amounts of the raw material gas and the oxygen gas were adjusted and supplied so as to be the values shown in Table 1.
  • Table 1 TMCTS and MTMS are abbreviations for tetramethylcyclotetrasiloxane and methyltrimethoxysilane, respectively.
  • ⁇ Plasma CVD conditions Feed rate of source gas (described in Table 1): 50 or 100 sccm (Standard Cubic Centimeter per Minute) Supply amount of oxygen gas (O 2 ): 50 to 1000 sccm Degree of vacuum in the vacuum chamber: 1.0 to 3.5 Pa Applied power from the power source for plasma generation: 1.0 to 3.0 kW Frequency of power source for plasma generation: 70 kHz Resin substrate transport speed: 3 to 6 m / min Further, the gas barrier films 1 to 9 were formed once at a conveyance speed of 3 m / min. The gas barrier films 10 to 12 were formed twice at a conveyance speed of 6 m / min, and the oxygen gas supply amounts for the first time (lower layer side) and the second time (upper layer side) were as shown in Table 1. (Sccm).
  • the layer thickness of the gas barrier layer was measured by observing the depth from the outermost surface to the interface with the substrate in the stacking direction of the gas barrier layer by a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the layer thickness was arbitrarily measured at 10 locations, and the average value was taken as the layer thickness of the gas barrier layer.
  • FIB focused ion beam
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 2 nm
  • X-ray photoelectron spectrometer Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific Irradiation X-ray: Single crystal spectroscopy AlK ⁇ X-ray spot and its size: 800 ⁇ m ⁇ 400 ⁇ m oval
  • a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve were obtained by performing a wide scan spectrum analysis for measuring the entire layer region of the gas barrier layer.
  • the depth from the outermost surface side in the layer thickness direction of the gas barrier layer when the composition ratio of oxygen atoms (O) which is a part of the total composition forming the gas barrier layer is 30% or less is calculated.
  • the position of the interface is calculated.
  • the outermost surface of the gas barrier layer is 0%
  • the interface with the substrate is 100%
  • the silicon atoms, oxygen atoms, and carbon atoms of the gas barrier layer are as follows: Was analyzed.
  • composition was divided into five bond groups, and the ratio of carbon atoms derived from each group was calculated from the composition ratio converted from the ratio of the peak intensity of each spectrum.
  • the waveform analysis of C1s related to the carbon atoms is performed.
  • the ratio of the composition ratio converted from the ratio of the peak intensity derived from the bond of C—C, C ⁇ C and C—H ((1) above) was defined as the ratio X (%).
  • Table 1 shows that when the outermost surface of the gas barrier layer is 0% and the interface with the substrate is 100% with respect to the thickness direction of the gas barrier layer, the layer thickness is 30% and the layer thickness is 30%. The maximum value (%), the average value (%), and the minimum value (%) of the ratio X in the ⁇ 95% region are shown.
  • the graph of the analysis result of the silicon atom in the gas barrier film 5 of this invention, an oxygen atom, and a carbon atom is shown in FIG.
  • the graph of the analysis result of the silicon atom in the gas barrier film 1 of a comparative example, an oxygen atom, and a carbon atom as a reference example is shown in FIG. 2 and 4, the horizontal axis represents the depth in the layer thickness direction of the gas barrier layer (the depth (%) when the outermost surface is 0% and the interface with the substrate is 100%).
  • the vertical axis is the ratio of each atom when the total amount of the composition ratio converted from the ratio of the peak intensity derived from the silicon atom, oxygen atom and carbon atom determined by X-ray photoelectron spectroscopy is 100% (%).
  • the carbon atoms are divided into the above-described five bond groups. 2 and 4, (1) to (5) are respectively (1) C—C, C ⁇ C and C—H, (2) C—SiO, (3) C—O, ( 4) C ⁇ O, (5) Corresponds to a carbon atom derived from O—C—O, (6) corresponds to an oxygen atom, and (7) corresponds to a silicon atom.
  • Water vapor transmission rate is less than 0.005 g / (m 2 ⁇ day)
  • Water vapor transmission rate is 0.005 g / (m 2 ⁇ day) or more and less than 0.010 g / (m 2 ⁇ day).
  • the 3 water vapor permeability, 0.010g / (m 2 ⁇ day ) or more 0.100g / (m 2 ⁇ day) under a is 2: water vapor permeability, 0.100g / (m 2 ⁇ day ) or more Less than 0.500 g / (m 2 ⁇ day)
  • Water vapor permeability is 0.500 g / (m 2 ⁇ day) or more
  • a vacuum deposition device manufactured by JEOL Ltd., vacuum deposition device JEE-400
  • Metallic calcium was deposited.
  • the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the calcium deposition surface.
  • the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere
  • the cell for evaluation was produced by irradiating with ultraviolet rays.
  • 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 point having a diameter exceeding 100 ⁇ m was generated even after 1000 hours.
  • the gas barrier film of the present invention has good gas barrier properties, there is little reduction in gas barrier properties due to front and back contact during roll winding, and the occurrence of cracks on the cut surface when cutting is suppressed. Gas barrier film.
  • the gas barrier film of the comparative example was inferior in any item.
  • the gas barrier film of the present invention has good gas barrier properties, is less likely to deteriorate in gas barrier properties due to contact between the front and back surfaces during roll winding, and suppresses the generation of cracks during cutting.
  • a gas barrier film can be suitably used for electronic devices that require high gas barrier properties, such as organic electroluminescence elements and liquid crystal display elements.

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Abstract

La présente invention aborde le problème de la réalisation d'un film barrière aux gaz qui possède d'excellentes propriétés de barrière aux gaz, peu de détérioration des propriétés de barrière aux gaz provoquées par contact des surfaces avant et arrière pendant un enroulement en rouleau, et une faible incidence de craquelage pendant la coupe. Le film barrière aux gaz est caractérisé en ce que, lorsqu'une valeur de 100 % est utilisée comme quantité totale des rapports de composition convertis à partir des rapports d'intensité de crête dérivés des atomes de silicium, des atomes d'oxygène et des atomes de carbone dans le sens de l'épaisseur d'une couche de barrière aux gaz dans des spectres obtenus en utilisant la spectroscopie photoélectronique à rayons X, la valeur maximale (%) de la proportion X dans la région où l'épaisseur de couche est de 5 à 30 % étant de 5 à 41 (%), X désignant la proportion du rapport de composition converti à partir du rapport d'intensité de crête dérivé de C−C, C=C et C−liaisons H basée sur l'analyse de la forme d'onde de C1s pour les atomes de carbone, 0 % étant l'épaisseur de la couche au niveau de la surface la plus à l'extérieure de la couche barrière aux gaz, et 100 % étant l'épaisseur de la couche au niveau de la jonction avec le substrat.
PCT/JP2016/082653 2015-11-18 2016-11-02 Film barrière aux gaz WO2017086170A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089859A (ja) * 2003-08-08 2005-04-07 Toyo Seikan Kaisha Ltd プラズマｃｖｄ法による蒸着膜
JP2009154449A (ja) * 2007-12-27 2009-07-16 Toppan Printing Co Ltd バリア性フィルム
JP2012096531A (ja) * 2010-10-08 2012-05-24 Sumitomo Chemical Co Ltd 積層フィルム

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Publication number Priority date Publication date Assignee Title
JP4380197B2 (ja) * 2003-03-28 2009-12-09 東洋製罐株式会社 プラズマｃｖｄ法による化学蒸着膜の形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089859A (ja) * 2003-08-08 2005-04-07 Toyo Seikan Kaisha Ltd プラズマｃｖｄ法による蒸着膜
JP2009154449A (ja) * 2007-12-27 2009-07-16 Toppan Printing Co Ltd バリア性フィルム
JP2012096531A (ja) * 2010-10-08 2012-05-24 Sumitomo Chemical Co Ltd 積層フィルム

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