WO2015029795A1 - Procédé de production de film barrière contre les gaz - Google Patents

Procédé de production de film barrière contre les gaz Download PDF

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Publication number
WO2015029795A1
WO2015029795A1 PCT/JP2014/071450 JP2014071450W WO2015029795A1 WO 2015029795 A1 WO2015029795 A1 WO 2015029795A1 JP 2014071450 W JP2014071450 W JP 2014071450W WO 2015029795 A1 WO2015029795 A1 WO 2015029795A1
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Prior art keywords
gas barrier
film
barrier layer
gas
layer
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PCT/JP2014/071450
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English (en)
Japanese (ja)
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近藤　麻衣子
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コニカミノルタ株式会社
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Priority to JP2015534138A priority Critical patent/JPWO2015029795A1/ja
Publication of WO2015029795A1 publication Critical patent/WO2015029795A1/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
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C16/50—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a method for producing 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, pharmaceuticals, 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.
  • a gas barrier layer is formed on a substrate such as a film by a plasma CVD method (Chemical Vapor Deposition). And a method of forming a gas barrier layer by applying a surface treatment (modification treatment) after applying a coating liquid containing polysilazane as a main component on a substrate.
  • Japanese Patent Application Laid-Open No. 2012-149278 discloses a method for manufacturing a gas barrier film in which a silicon nitride film or a silicon oxynitride film formed by a dry method is irradiated with light having a wavelength of 150 nm or less.
  • a silicon oxide film is formed by a dry method, a barrier film irradiated with light having a wavelength of 172 nm, a silicon film is formed by a wet method, and a barrier film subjected to plasma treatment is then formed.
  • a technique for improving the bending resistance by using the laminated film is disclosed.
  • the gas barrier film described in Japanese Patent Application Laid-Open No. 2012-106421 has a problem that dark spots are generated when an organic EL element is produced using a film after a bending test.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a means for obtaining a gas barrier film having excellent gas barrier properties and bending resistance, and having a smoothness that is not easily lowered.
  • the present inventor conducted intensive research to solve the above problems.
  • the present invention includes, after forming a gas barrier layer containing at least silicon atoms and carbon atoms on a base material by a vapor deposition method, irradiating the gas barrier layer with ultraviolet light having a wavelength of less than 250 nm. It is a manufacturing method of a gas barrier film.
  • FIG. 1 11 is a gas barrier film; 12 is a substrate; 13 is a production apparatus; 14 is a delivery roller; 15, 16, 17 and 18 are transport rollers; 19 and 20 are film forming rollers; 21 represents a gas supply pipe; 22 represents a power source for generating plasma; 23 and 24 represent magnetic field generators; 25 represents a take-up roller; and 26 represents a gas barrier layer.
  • FIG. 1 11 is a gas barrier film; 12 is a substrate; 13 is a production apparatus; 14 is a delivery roller; 15, 16, 17 and 18 are transport rollers; 19 and 20 are film forming rollers; 21 represents a gas supply pipe; 22 represents a power source for generating plasma; 23 and 24 represent magnetic field generators; 25 represents a take-up roller; and 26 represents a gas barrier layer.
  • FIG. 1 11 is a gas barrier film
  • 12 is a substrate
  • 13 is a production apparatus
  • 14 is a delivery roller
  • 15, 16, 17 and 18 are transport rollers
  • 19 and 20 are film forming rollers
  • F is a base material
  • 30 is a plasma discharge treatment apparatus
  • 31 is a plasma discharge treatment vessel
  • 32 is between counter electrodes (discharge space)
  • 35 is a roll rotating electrode (first electrode);
  • 40 is an electric field applying means having two power sources; 41 is a first power source; 42 is a second power source; 43 is a first filter;
  • 50 is a gas supply means;
  • 51 is a gas generator;
  • 53 is an exhaust port;
  • 60 is an electrode temperature adjusting means;
  • 61 is a pipe; 64, 67, 85 and 88 are guide rolls; 66 represents a nip roll; 68 and 69 represent partition plates, respectively.
  • the method for producing a gas barrier film according to this embodiment includes performing irradiation with ultraviolet light having a wavelength of less than 250 nm after forming a gas barrier layer containing at least silicon atoms and carbon atoms on a substrate by a vapor deposition method.
  • a method for producing a gas barrier film that is excellent in gas barrier properties and bending resistance, and that is less likely to deteriorate in smoothness.
  • an electronic device using the gas barrier film obtained by the production method of the present invention which is excellent in gas barrier properties and hardly generates dark spots is provided.
  • a film containing at least silicon atoms and carbon atoms formed by a vapor deposition method has flexibility because it contains carbon. Furthermore, the Si—C bond can be cleaved with lower energy than the Si—O bond or Si—N bond, and the bond is cleaved with energy of about 250 nm wavelength. For this reason, as in the manufacturing method of the present invention, a film containing silicon atoms and carbon atoms is irradiated with light having a wavelength of 250 nm or less, so that not only the film surface but also the film interior is homogeneous. It can be inferred that a film can be formed which can be modified to a smooth film and whose gas barrier property and smoothness are hardly deteriorated even when bent.
  • the above mechanism is based on speculation, and the present invention is not limited to the above mechanism.
  • the gas barrier film according to the present invention usually uses a plastic film 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 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, 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 base material is preferably made of a heat-resistant material. Specifically, a resin base material having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and Tg of 100 ° C. or more and 300 ° C. or less is used.
  • the base material satisfies the requirements for use as a laminated film for electronic parts and displays. That is, when the gas barrier film of the present invention is used for these applications, the gas barrier film may be exposed to a process at 150 ° C. or higher.
  • the substrate dimensions are not stable when the gas barrier film is passed through the temperature process as described above, and thermal expansion and contraction occur. Inconvenience that the shut-off performance is deteriorated or a problem that the thermal process cannot withstand is likely to occur. If it is less than 15 ppm / K, the film may break like glass and the flexibility may deteriorate.
  • 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. 2001-150584: 162 ° C.
  • polyimide for example, Neoprim (registered trademark): 260 ° C.
  • the gas barrier layer of the gas barrier film is directed to the inner side of the cell and arranged on the innermost side (adjacent to the element).
  • the retardation value of the gas barrier film is important.
  • the usage form of the gas barrier film in such an embodiment includes a gas barrier film using a base film having a retardation value of 10 nm or less and a circularly polarizing plate (1 ⁇ 4 wavelength plate + (1 ⁇ 2 wavelength plate) + straight line.
  • a polarizing plate is used in combination with a gas polarizing film using a base film having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate. preferable.
  • Examples of the substrate film having a retardation of 10 nm or less include, for example, cellulose triacetate (Fuji Film Co., Ltd .: Fujitac (registered trademark)), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace (registered trademark), Kaneka Corporation): Elmec (registered trademark)), cycloolefin polymer (manufactured by JSR Corporation: Arton (registered trademark), Nippon Zeon Corporation: ZEONOR (registered trademark)), cycloolefin copolymer (manufactured by Mitsui Chemicals, Inc .: APPEL (registered trademark)) (Pellets), manufactured by Polyplastics Co., Ltd .: Topas (registered trademark) (pellets)), polyarylate (manufactured by Unitika Co., Ltd .: U100 (pellets)), transparent polyimide (manufactured by Mitsubishi Gas Chemical Co., Ltd .
  • the quarter wavelength plate a film adjusted to a desired retardation value by appropriately stretching the above film can be used.
  • the plastic film of the present invention can be used as a device such as an organic EL element
  • 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 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.
  • 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 of the present invention is not particularly limited because it is appropriately selected depending on the use, but is typically 1 to 800 ⁇ m, preferably 10 to 200 ⁇ m.
  • These plastic films may have functional layers such as a transparent conductive layer, a smooth layer, and a clear hard coat layer.
  • As 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.
  • the substrate preferably has a high surface smoothness.
  • the surface smoothness those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the gas barrier layer is provided, may be polished to improve smoothness.
  • the base material using the above-described resins or the like may be an unstretched film or a stretched film.
  • the base material used in the present invention can be produced 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 2 to 10 times in each of 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 and methods 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 between the surface of the base material having the gas barrier layer, preferably between the base material and the base layer.
  • the smooth layer is provided to flatten the rough surface of the substrate on which protrusions and the like are present, or to fill the unevenness and pinholes generated in the gas barrier layer with the protrusions existing on the resin base material. .
  • the materials, methods, etc. disclosed in paragraphs “0233” to “0248” of JP2013-52561A are appropriately employed as the constituent material, forming method, surface roughness, film thickness, etc. of the smooth layer.
  • 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, forming method, film 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 method for producing a gas barrier film according to this embodiment includes forming a gas barrier layer containing at least silicon atoms and carbon atoms on a substrate by a vapor deposition method.
  • the thickness of the gas barrier layer (hereinafter also simply referred to as a gas barrier layer) formed by the vapor deposition method according to the present invention is not particularly limited, but in order to improve the gas barrier performance while making it difficult to cause defects, it is usually 20 to It is within the range of 1000 nm, preferably 50 to 300 nm.
  • the thickness of the vapor deposition gas barrier layer employs a film thickness measurement method by observation with a transmission microscope (TEM).
  • the vapor deposition gas barrier layer may have a laminated structure including a plurality of sublayers. In this case, the number of sublayers is preferably 2 to 30. Moreover, each sublayer may have the same composition or a different composition.
  • the gas barrier layer contains at least silicon atoms and carbon atoms.
  • silicon atoms and carbon atoms are present.
  • the presence of silicon atoms and oxygen atoms can further improve the gas barrier property, and the presence of carbon atoms can impart flexibility to the gas barrier layer.
  • the gas barrier property test was performed by depositing 70 nm-thick metal calcium on the gas barrier film and evaluating the time of 50% area as the degradation time, as described in the examples below. It was.
  • the gas barrier layer according to the present invention includes a condition (i) a distance (L) from the gas barrier layer surface in the film thickness direction of the gas barrier layer, and the amount of silicon atoms relative to the total amount of silicon atoms, oxygen atoms, and carbon atoms.
  • Silicon distribution curve showing the relationship with the ratio (atomic ratio of silicon), oxygen distribution showing the relationship between L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen) 90% or more of the film thickness of the gas barrier layer in the curve and the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of L and silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio) ( In the region of the upper limit: 100%, the following formula (A): formula (A) (carbon atomic ratio) ⁇ (silicon atomic ratio) ⁇ (oxygen atomic ratio) or the following formula (B): formula (B) (Atomic ratio of oxygen) ⁇ (atom of silicon ) ⁇ (Preferably has a size relationship of hierarchy represented by an atomic ratio of carbon).
  • 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 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. It is more preferable to satisfy
  • (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in order (atom The ratio is O> Si> C, the order of magnitude relationship represented by the formula (A)).
  • the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the layer is preferably 25 to 45 at%, and preferably 30 to 40 at%. More preferably.
  • 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 33 to 67 at%, more preferably 45 to 67 at%.
  • the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the layer is preferably 3 to 33 at%, and more preferably 3 to 25 at%.
  • the silicon distribution curve, oxygen distribution curve, and carbon distribution curve are sequentially obtained by using Xray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination to expose the inside of the sample. It can be created by so-called XPS depth profile measurement in which composition analysis is performed. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of each element and the horizontal axis as the etching time (sputtering time).
  • XPS Xray photoelectron spectroscopy
  • the silicon distribution curve, oxygen distribution curve, and carbon distribution curve were prepared under the following measurement conditions.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): SiO 2 equivalent film thickness of the gas barrier layer ⁇ 20 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 size: 800 ⁇ 400 ⁇ m oval.
  • the plot position is defined by the number of counter rolls that pass (etching interval below).
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value) (data plot interval): SiO 2 equivalent film thickness of the barrier film ⁇ 10 ⁇ TR number (number of opposing rolls) (nm)
  • X-ray photoelectron spectrometer Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific Irradiation
  • X-ray Single crystal spectroscopy AlK ⁇
  • the carbon distribution curve preferably has at least one extreme value, preferably at least three extreme values, and more preferably at least five extreme values.
  • the carbon distribution curve has at least one extreme value, the carbon atom ratio continuously changes with a concentration gradient, and the gas barrier performance during bending is enhanced.
  • the “extreme value” in the carbon distribution curve refers to the distance (L) from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer and the maximum value or the minimum value of carbon atoms in the carbon distribution curve.
  • the maximum value in the carbon distribution curve means that the value of the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms changes from increasing to decreasing when the distance from the surface of the gas barrier layer is changed. That means.
  • the minimum value in the carbon distribution curve means that the value of the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms changes from decrease to increase when the distance from the surface of the gas barrier layer is changed. I mean.
  • the oxygen distribution curve of the gas barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, more preferably has at least three extreme values, and has at least five extreme values. It is particularly preferred.
  • 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 “extreme value” in the oxygen distribution curve means a distance (L) from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer and a maximum value or a minimum value of oxygen atoms in the oxygen distribution curve.
  • the maximum value in the oxygen distribution curve is the point where the value of the oxygen atomic ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms changes from increasing to decreasing when the distance from the surface of the gas barrier layer is changed.
  • the minimum value in the oxygen distribution curve means that when the distance from the surface of the gas barrier layer is changed, the value of the atomic ratio of oxygen with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms changes from decrease to increase. Say point.
  • the gas barrier layer preferably has an absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter, also simply referred to as “Cmax ⁇ Cmin difference”) of 5 at% or more.
  • Cmax ⁇ Cmin difference is 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 Cmax ⁇ Cmin difference is not particularly limited, but is preferably 50 at% or less, and preferably 40 at% or less in consideration of the effect of suppressing / preventing crack generation during bending of the gas barrier film. It is more preferable.
  • the total amount of carbon and oxygen atoms with respect to the thickness direction of the gas barrier layer is preferably substantially constant.
  • the distance (L) from the surface of the barrier layer in the thickness direction of the gas barrier layer and the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms Is preferably less than 5 at%, more preferably less than 4 at%, and even more preferably less than 3 at%.
  • the absolute value is less than 5 at%, the gas barrier property of the obtained gas barrier film is further improved.
  • the lower limit of the OCmax ⁇ OCmin difference is preferably 0 at% because the smaller the OCmax ⁇ OCmin difference is, but it is sufficient if it is 0.1 at% or more.
  • the gas barrier layer is preferably substantially uniform in the film surface direction (direction parallel to the surface of the gas barrier layer).
  • 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.
  • 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. Satisfying the condition expressed by the following formula (1) in the relationship between the distance from the surface in the film thickness direction (x, unit: nm) and the atomic ratio of carbon (C, unit: at%). Say.
  • the method for forming the gas barrier layer is not particularly limited, and can be applied in the same manner as in the conventional method or appropriately modified.
  • the gas barrier layer is preferably formed by a chemical vapor deposition (CVD) method, in particular, a plasma chemical vapor deposition method (plasma CVD, plasma-enhanced chemical vapor deposition (PECVD), hereinafter also simply referred to as “plasma CVD method”). It is preferred that
  • the plasma CVD method using the plasma CVD method of the atmospheric pressure or the atmospheric pressure described in the international publication 2006/033233, and the plasma CVD apparatus with a counter roll electrode is mentioned. .
  • the plasma CVD method may be a Penning discharge plasma type plasma CVD method.
  • a plasma CVD method using a plasma CVD apparatus having a counter roll electrode which is a preferable method for forming a gas barrier layer having the order of magnitude relationship represented by the above formula (A) or the above formula (B). explain.
  • plasma discharge is generated in a space between a plurality of film forming rollers.
  • a pair of film forming rollers is used, and a base material (here, the base material is treated with the base material or has an intermediate layer on the base material) is used. It is more preferable that a plasma is generated by disposing between the pair of film forming rollers.
  • 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 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 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.
  • each film-forming roller has a power source for generating plasma so that the pair of film-forming rollers (film-forming roller 19 and film-forming roller 20) can function as a pair of counter electrodes. 22 is connected. Therefore, in such a manufacturing apparatus 13, it is possible to discharge to the space between the film forming roller 19 and the film forming roller 20 by supplying electric power from the plasma generating power source 22, thereby Plasma can be generated in the space between the film roller 19 and the film formation roller 20.
  • the material and design may be changed as appropriate so that the film-forming roller 19 and the film-forming roller 20 can also be used as electrodes.
  • the pair of film forming rollers (film forming rollers 19 and 20) be arranged so that their central axes are substantially parallel on the same plane.
  • the film forming rate can be doubled as compared with a normal plasma CVD method that does not use a roller, and the structure is the same. Since the film can be formed, the extreme value in the carbon distribution curve can be at least doubled.
  • the base material 12 on the surface of the base material 12 (here, the base material includes a form in which the base material is processed or has an intermediate layer on the base material) by the CVD method.
  • the gas barrier layer 26 can be formed on the surface of the substrate 12 while depositing the gas barrier layer component on the surface of the substrate 12 on the film formation roller 19 and also on the surface of the substrate 12 on the film formation roller 20. Since layer components can be deposited, a gas barrier layer can be efficiently formed on the surface of the substrate 12.
  • magnetic field generators 23 and 24 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.
  • the magnetic field generators 23 and 24 provided on the film forming roller 19 and the film forming roller 20 respectively are a magnetic field generator 23 provided on one film forming roller 19 and a magnetic field generator provided on the other film forming roller 20. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between the magnetic field generators 24 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 roller 19 and the film forming roller 20 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generating device 23 and the other magnetic field generating device. It is preferable to arrange the magnetic poles so that the magnetic poles facing 24 have the same polarity.
  • the opposing 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 of each of the magnetic field generators 23 and 24 are opposed.
  • 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 12 is excellent in that the gas barrier layer 26 that is a vapor deposition film can be efficiently formed.
  • the film forming roller 19 and the film forming roller 20 known rollers can be appropriately used. 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.
  • the diameters of the film forming rollers 19 and 20 are 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 is not deteriorated, and it is possible to avoid applying the total amount of plasma discharge to the substrate 12 in a short time. It is preferable because damage to the material 12 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mm ⁇ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.
  • the base material 12 is disposed on a pair of film forming rollers (the film forming roller 19 and the film forming roller 20) so that the surfaces of the base material 12 face each other.
  • the base material 12 By disposing the base material 12 in this way, when the plasma is generated by performing discharge in the facing space between the film forming roller 19 and the film forming roller 20, the base existing between the pair of film forming rollers is present.
  • Each surface of the material 12 can be formed simultaneously. That is, according to such a manufacturing apparatus, the barrier layer component is deposited on the surface of the substrate 12 on the film forming roller 19 by the plasma CVD method, and the gas barrier layer component is further deposited on the film forming roller 20. Therefore, the gas barrier layer can be efficiently formed on the surface of the substrate 12.
  • the winding roller 25 is not particularly limited as long as the gas barrier film 11 having the gas barrier layer 26 formed on the substrate 12 can be wound, and a known roller may be used as appropriate. it can.
  • 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 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.
  • Such a plasma generation power source 22 can perform plasma CVD more efficiently, so that the polarity of the pair of film forming rollers can be alternately reversed (AC power source or the like). Is preferably used.
  • the plasma generating power source 22 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible to do this.
  • the magnetic field generators 23 and 24 known magnetic field generators can be used as appropriate.
  • the base material 12 in addition to the base material used in the present invention, a material in which the gas barrier layer 26 is formed in advance can be used. As described above, by using the substrate 12 in which the gas barrier layer 26 is previously formed, the thickness of the gas barrier layer 26 can be increased.
  • the gas barrier layer according to the present invention can be produced by appropriately adjusting the speed. That is, using the manufacturing apparatus 13 shown in FIG. 1, discharge is generated between a pair of film forming rollers (film forming rollers 19 and 20) while supplying a film forming gas (raw material gas or the like) into the vacuum chamber.
  • the film-forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer 26 is formed on the surface of the base material 12 on the film-forming roller 19 and the surface of the base material 12 on the film-forming roller 20 by plasma CVD. Formed by law. At this time, 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 axis of the film forming rollers 19 and 20, and the plasma is converged on the magnetic field. For this reason, when the base material 12 passes through the point A of the film forming roller 19 and the point B of the film forming roller 20 in FIG. 1, the maximum value of the carbon distribution curve is formed in the gas barrier layer.
  • the distance between the extreme values of the gas barrier layer (the difference between the distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (Absolute value) can be adjusted by the rotation speed of the film forming rollers 19 and 20 (conveyance speed of the substrate).
  • the substrate 12 is transported by the delivery roller 14 and the film formation roller 19, respectively, so that the surface of the substrate 12 is formed by a roll-to-roll continuous film formation process. Then, the gas barrier layer 26 is formed.
  • a raw material gas, a reactive gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more.
  • the source gas in the film forming gas used for forming the gas barrier layer 26 can be appropriately selected and used according to the material of the gas barrier layer 26 to be formed.
  • a source gas for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used.
  • organosilicon compounds examples include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane.
  • HMDSO hexamethyldisiloxane
  • HMDS hexamethyldisilane
  • 1,1,3,3-tetramethyldisiloxane vinyltrimethylsilane
  • methyltrimethylsilane hexamethyldisilane.
  • Methylsilane dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • phenyltrimethoxysilane methyltriethoxy
  • Examples include silane and octamethylcyclotetrasiloxane.
  • hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting gas barrier layer.
  • organosilicon compounds can be used alone or in combination of two or more.
  • organic compound gas containing carbon examples include methane, ethane, ethylene, and acetylene.
  • appropriate source gases are selected according to the type of the gas barrier layer 26.
  • a reactive gas may be used in addition to the raw material gas.
  • a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • a reactive gas for forming nitride nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.
  • a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber.
  • 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, for example, rare gases such as helium, argon, neon and xenon; hydrogen; nitrogen can be used.
  • the ratio of the raw material gas and the reactive gas is a reaction that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive as compared with the ratio of the amount of gas. By making the ratio of the reaction gas not excessive, the formed gas barrier layer 26 is excellent in that excellent gas barrier properties and bending resistance can be obtained. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than or equal to the theoretical oxygen amount required for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.
  • hexamethyldisiloxane organosilicon compound, HMDSO, (CH 3 ) 6 Si 2 O
  • oxygen (O 2 ) oxygen
  • the preferred ratio of the raw material gas to the reactive gas in the film forming gas will be described in more detail.
  • a film-forming gas containing hexamethyldisiloxane (HMDSO, (CH 3 ) 6 Si 2 O) as a source gas and oxygen (O 2 ) as a reaction gas is reacted by a plasma CVD method to form silicon-oxygen.
  • HMDSO, (CH 3 ) 6 Si 2 O hexamethyldisiloxane
  • O 2 oxygen
  • the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, a uniform silicon dioxide film is formed when oxygen is contained in the film forming gas in an amount of 12 moles or more per mole of hexamethyldisiloxane and a uniform silicon dioxide film is formed (a carbon distribution curve exists). Therefore, a gas barrier layer that satisfies the above conditions (i) and (ii) cannot be formed. Therefore, in the present invention, when the gas barrier layer is formed, the stoichiometric ratio of oxygen amount to 1 mol of hexamethyldisiloxane is set so that the reaction of the reaction formula (1) does not proceed completely.
  • the amount is preferably less than 12 moles.
  • the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas Even if the (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane (flow rate), the reaction cannot actually proceed completely, and the oxygen content is reduced.
  • the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is changed to the hexamethyldioxide raw material.
  • the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. .
  • the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.
  • the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.
  • 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 power to be applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 0.1 kW 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. It can suppress that the temperature of the substrate surface rises. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.
  • the conveyance speed (line speed) of the substrate 12 can be adjusted as appropriate 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. More preferably, it is in the range of 5 to 100 m / min.
  • the substrate is transported to a plasma CVD apparatus having a counter roll electrode at a transport speed of 5 m / min or more (more preferably 10 m / min or more) to form a gas barrier layer containing silicon, oxygen and carbon.
  • the upper limit of the line speed is not particularly limited, and is preferably faster from the viewpoint of productivity. However, if it is 100 m / min or less, it is excellent in that a sufficient thickness as a gas barrier layer can be secured.
  • the gas barrier layer is formed by a plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is what. 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. This is because it is possible to efficiently produce a barrier layer having both the barrier performance and the barrier performance.
  • 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.
  • an apparatus used in this method there is a jet type atmospheric pressure plasma discharge treatment apparatus described in FIG. 3 of International Publication No. 2006/033233.
  • the jet type atmospheric pressure plasma discharge treatment apparatus is an apparatus having a gas supply means and an electrode temperature adjusting means in addition to the plasma discharge treatment apparatus and the electric field applying means having two power sources. If a plurality of jet-type atmospheric pressure plasma discharge treatment apparatuses are arranged in series and arranged in series, and each apparatus jets a gas in a different plasma state, a laminated thin film having different layers can be formed.
  • an atmospheric pressure plasma discharge treatment apparatus for treating a substrate between the counter electrodes described in FIG. 4 of International Publication No. 2006/033233 can be used.
  • Other examples of the atmospheric pressure plasma discharge treatment apparatus include Japanese Patent Application Laid-Open Nos. 2004-68143, 2003-49272, and WO 02/48428.
  • FIG. 2 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus of a type that treats a substrate between counter electrodes that is useful when forming the gas barrier layer of the present invention.
  • a method of changing the gap between the electrodes by tilting the fixed electrode group with respect to the roll rotating electrode, or A gas barrier layer can be obtained by appropriately selecting the type and supply amount of the film forming raw material to be supplied or the output conditions at the time of plasma discharge.
  • FIG. 2 is an apparatus including at least a plasma discharge processing apparatus 30, an electric field applying means 40 having two power sources, a gas supply means 50, and an electrode temperature adjusting means 60. Then, a thin film is formed by subjecting the base material F to plasma discharge treatment between the counter electrodes (discharge space) 32 between the roll rotating electrode (first electrode) 35 and the square tube type fixed electrode (group) (second electrode) 36. To do.
  • a pair of rectangular tube type fixed electrode group (second electrode) 36 and roll rotating electrode (first electrode) 35 form one electric field. Is formed.
  • FIG. 2 shows an example of a configuration having a total of five units having such a configuration. In each unit, the type of raw material to be supplied, the output voltage, and the like are arbitrarily controlled independently.
  • a gas barrier layer can be formed continuously.
  • the roll rotating electrode (first electrode) 35 has a first power source. 41 to the first high-frequency electric field of frequency ⁇ 1, electric field intensity V1, and current I1, and the rectangular tube-shaped fixed electrode group (second electrode) 36 has a frequency ⁇ 2 and electric field intensity V2 from the corresponding second power source 42. A second high-frequency electric field of current I2 is applied.
  • a first filter 43 is installed between the roll rotation electrode (first electrode) 35 and the first power supply 41, and the first filter 43 easily passes a current from the first power supply 41 to the first electrode.
  • the current from the second power supply 42 is grounded so that the current from the second power supply 42 to the first power supply is difficult to pass.
  • a second filter 44 is provided between the square tube type fixed electrode group (second electrode) 36 and the second power source 42, and the second filter 44 is connected to the second electrode from the second power source 42. It is designed so that the current from the first power supply 41 is grounded and the current from the first power supply 41 to the second power supply is difficult to pass.
  • the roll rotating electrode 35 may be the second electrode, and the square tube type fixed electrode group 36 may be the first electrode.
  • the first power source is connected to the first electrode, and the second power source is connected to the second electrode.
  • the first power source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ⁇ 1 ⁇ 2.
  • the current is preferably I1 ⁇ I2.
  • the current I1 of the first high-frequency electric field is preferably 0.3 mA / cm 2 to 20 mA / cm 2 , more preferably 1.0 mA / cm 2 to 20 mA / cm 2 .
  • the current I2 of the second high-frequency electric field is preferably 10 mA / cm 2 to 100 mA / cm 2 , more preferably 20 mA / cm 2 to 100 mA / cm 2 .
  • the gas G generated by the gas generator 51 of the gas supply means 50 is introduced into the plasma discharge treatment vessel 31 from the air supply port while controlling the flow rate.
  • the base material F is unwound from the original winding (not shown) and is transported or is transported from the previous process, and the air and the like that is entrained by the base material by the nip roll 65 through the guide roll 64 is blocked. Then, while being wound while being in contact with the roll rotating electrode 35, it is transferred between the square tube fixed electrode group 36 and the roll rotating electrode (first electrode) 35 and the square tube fixed electrode group (second electrode) 36. An electric field is applied from both of them to generate discharge plasma between the counter electrodes (discharge space) 32.
  • the base material F (here, the base material includes a form in which the base material has been processed or has an intermediate layer on the base material) is in a plasma state while being wound while being in contact with the roll rotating electrode 35. To form a thin film.
  • the base material F passes through the nip roll 66 and the guide roll 67 and is wound up by a winder (not shown) or transferred to the next process.
  • Discharged treated exhaust gas G ′ is discharged from the exhaust port 53.
  • a medium whose temperature is adjusted by the electrode temperature adjusting means 60 is used as a liquid feed pump. P is sent to both electrodes through the pipe 61, and the temperature is adjusted from the inside of the electrode.
  • Reference numerals 68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.
  • source gas As the film forming gas (source gas etc.) supplied from the gas generator 51 to the counter electrode (discharge space) 32, source gas, reaction gas, carrier gas, discharge gas are used alone or in combination of two or more. Can be used.
  • the source gas, reaction gas, carrier gas, or discharge gas used at this time is the gas described in the column of (1) Method of forming a gas barrier layer by plasma CVD using a plasma CVD apparatus having a counter roll electrode. Can be used as appropriate.
  • the plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but may be made of metal as long as it can be insulated from the electrodes.
  • polyimide resin or the like may be pasted on the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation.
  • FIG. 2 it is preferable to cover both side surfaces (up to the vicinity of the base material surface) of both parallel electrodes with an object made of the above-described material.
  • Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500 A2 Shinko Electric Co., Ltd. 5kHz SPG5-4500 A3 Kasuga Electric 15kHz AGI-023 A4 Shinko Electric 50kHz SPG50-4500 A5 HEIDEN Laboratory 100kHz * PHF-6k A6 Pearl Industry 200kHz CF-2000-200k A7 Pearl Industry 400kHz CF-2000-400k A8 Applied electricity 80kHz And the like, and any of them can be used.
  • * indicates a HEIDEN Laboratory impulse high-frequency power source (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave. It is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.
  • the power applied between the electrodes facing each other supplies power (power density) of 1 W / cm 2 or more to the second electrode (second high-frequency electric field), excites the discharge gas to generate plasma, and the energy is thinned.
  • a thin film is formed by applying the forming gas.
  • the upper limit value of the power supplied to the second electrode is preferably 50 W / cm 2 , more preferably 20 W / cm 2 .
  • the lower limit is preferably 1.2 W / cm 2 .
  • discharge area (cm ⁇ 2 >) points out the area of the range which discharge occurs in an electrode.
  • the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved.
  • it is 5 W / cm 2 or more.
  • the upper limit value of the power supplied to the first electrode is preferably 50 W / cm 2 .
  • the waveform of the high-frequency electric field is not particularly limited.
  • a continuous sine wave continuous oscillation mode called a continuous mode
  • an intermittent oscillation mode called ON / OFF intermittently called a pulse mode
  • the second electrode side second
  • the high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.
  • controlling the film quality it can be achieved by controlling the electric power on the second power source side.
  • An electrode used for such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance.
  • Such an electrode is preferably a metal base material coated with a dielectric.
  • the gas barrier layer can also be formed by a vacuum plasma apparatus described in US Pat. No. 7,015,640.
  • the gas barrier film according to the present invention includes a step of forming a gas barrier layer on a base material by a vapor deposition method and further irradiating the gas barrier layer with ultraviolet light having a wavelength of 250 nm or less. Yes.
  • the use of ultraviolet light having a wavelength of 250 nm or less causes the chemical bond of the deposited film to vibrate and break, and it is estimated that the deposited film surface and the inside can be modified into a stable film with few defects. .
  • the shorter the irradiation wavelength the larger the energy, so that many bonds can be vibrated and broken, and the film can be reformed to a more homogeneous film. Therefore, it is preferably 180 nm or less, and more preferably 150 nm or less. Is particularly preferred.
  • any light source can be used as long as it generates ultraviolet light of 250 nm or less.
  • Specific examples include a KrF excimer laser (wavelength 248 nm), a KrCl excimer laser (wavelength 220 nm), an Xe excimer lamp (wavelength 172 nm), a Kr excimer lamp (wavelength 146 nm), an Ar excimer lamp (wavelength 126 nm), and the like. .
  • the irradiation intensity and the irradiation time are set within a range in which the substrate carrying the irradiated gas barrier layer is not damaged.
  • the substrate surface has a strength of 20 to 300 mW / cm 2 , preferably 50 to 200 mW / cm 2.
  • the distance between the ultraviolet light irradiation lamps can be set and irradiation can be performed for 0.1 seconds to 10 minutes.
  • the temperature of the substrate during the ultraviolet light irradiation treatment is 150 ° C. or higher, the properties of the substrate are impaired in the case of a plastic film or the like, such as deformation of the substrate or deterioration of its strength. become.
  • a film having high heat resistance such as polyimide
  • a modification treatment at a higher temperature is possible. Therefore, there is no general upper limit for the substrate temperature at the time of ultraviolet light irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate.
  • Ultraviolet light irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used.
  • a laminate having a gas barrier layer on the surface can be processed in an ultraviolet light firing furnace equipped with the ultraviolet light generation source as described above.
  • the ultraviolet light baking furnace itself is generally known.
  • an ultraviolet light baking furnace manufactured by I-Graphics Co., Ltd. can be used.
  • the laminated body which has a gas barrier layer on the surface is a long film form, by irradiating ultraviolet light continuously in the drying zone equipped with the above ultraviolet light generation sources, conveying this. It can be made into ceramics.
  • the time required for the ultraviolet light irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the base material and gas barrier layer used.
  • ⁇ Excimer lamps have high light generation efficiency and can be lit with low power. In addition, it does not emit light with a long wavelength that causes a temperature increase due to light, and irradiates energy in the ultraviolet light region, that is, with a short wavelength, and therefore has a feature that suppresses the increase in the surface temperature of the object to be fired. . For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.
  • the efficiency in the ultraviolet light irradiation process tends to decrease due to the absorption by oxygen. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of ultraviolet light irradiation is preferably 10 to 50000 volume ppm, more preferably 50 to 20000 volume ppm.
  • a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
  • the illuminance of the ultraviolet light on the gas barrier layer surface is preferably 1 mW / cm 2 to 10 W / cm 2 , more preferably 30 mW / cm 2 to 200 mW / cm 2 , and 50 mW / cm 2. More preferably, it is ⁇ 160 mW / cm 2 . If it is less than 1 mW / cm 2 , the reforming efficiency may be greatly reduced. If it exceeds 10 W / cm 2 , there is a concern that the gas barrier layer may be ablated or the base material may be damaged.
  • Irradiation energy amount of ultraviolet light is preferably 10 ⁇ 10000mJ / cm 2, more preferably from 50 ⁇ 6000mJ / cm 2, further preferably 100 ⁇ 3000mJ / cm 2. Is less than 10 mJ / cm 2, there is a fear that the reforming becomes insufficient, 10000 mJ / cm 2 than the cracking or due to excessive modification concerns the thermal deformation of the substrate emerges.
  • the gas barrier layer preferably contains a nitrogen element from the viewpoint of stress relaxation and absorbing ultraviolet light used in forming a gas barrier layer formed by a coating method described later.
  • a nitrogen element from the viewpoint of stress relaxation and absorbing ultraviolet light used in forming a gas barrier layer formed by a coating method described later.
  • the gas barrier property is improved by improving the adhesion between the gas barrier layer and a gas barrier layer formed by a coating method described later. Such effects as described above are obtained and preferable.
  • a coating film formed by applying and drying a coating liquid containing polysilazane on the gas barrier layer (deposited film) is subjected to a modification treatment, thereby forming a gas barrier layer (hereinafter referred to as a gas barrier layer). , Simply referred to as a coating barrier layer).
  • the method for forming the coating barrier layer is not particularly limited, but a coating liquid for forming a coating barrier layer containing an inorganic compound, preferably polysilazane, and, if necessary, a catalyst in an organic solvent is applied by a known wet coating method.
  • a method is preferred in which the solvent is removed by evaporation, and then the modification treatment is performed by irradiating with active energy rays such as ultraviolet rays, ultraviolet rays, electron beams, X rays, ⁇ rays, ⁇ rays, ⁇ rays and neutron rays.
  • Polysilazane is a polymer having a silicon-nitrogen bond, such as SiO 2 , Si 3 N 4 having a bond such as Si—N, Si—H, or N—H, and ceramics such as both intermediate solid solutions SiO x N y. It is a precursor inorganic polymer.
  • the polysilazane preferably has the following structure.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. .
  • R 1 , R 2 and R 3 may be the same or different.
  • examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms.
  • the aryl group include aryl groups having 6 to 30 carbon atoms.
  • non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc.
  • non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, nap
  • the (trialkoxysilyl) alkyl group includes an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specific examples include 3- (triethoxysilyl) propyl group and 3- (trimethoxysilyl) propyl group.
  • the substituent optionally present in R 1 to R 3 is not particularly limited, and examples thereof include an alkyl group, a halogen atom, a hydroxyl group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO 3 H), a carboxyl group (—COOH), a nitro group (—NO 2 ) and the like. Note that the optionally present substituent is not the same as R1-R3 to be substituted. For example, when R 1 to R 3 are alkyl groups, they are not further substituted with an alkyl group.
  • R 1 , R 2 and R 3 are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.
  • n is an integer
  • the polysilazane having the structure represented by the general formula (I) may be determined to have a number average molecular weight of 150 to 150,000 g / mol. preferable.
  • one of preferred embodiments is perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms.
  • polysilazane has a structure represented by the following general formula (II).
  • R 1 ′ , R 2 ′ , R 3 ′ , R 4 ′ , R 5 ′ and R 6 ′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group.
  • R 1 ′ , R 2 ′ , R 3 ′ , R 4 ′ , R 5 ′ and R 6 ′ may be the same or different.
  • the substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.
  • n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that Note that n ′ and p may be the same or different.
  • R 1 ′ , R 3 ′ and R 6 ′ each represent a hydrogen atom, and R 2 ′ , R 4 ′ and R 5 ′ each represent a methyl group;
  • R 1 ' , R 3' and R 6 ' each represents a hydrogen atom, R 2' , R 4 ' each represents a methyl group, and R 5' represents a vinyl group;
  • R 1 ' , R 3' , R 4 A compound in which ' and R 6' each represent a hydrogen atom and R 2 ' and R 5' each represents a methyl group is preferred.
  • polysilazane has a structure represented by the following general formula (III).
  • R 1 ′′ , R 2 ′′ , R 3 ′′ , R 4 ′′ , R 5 ′′ , R 6 ′′ , R 7 ′′ , R 8 ′′ and R 9 ′′ are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R 1 ′′ , R 2 ′′ , R 3 ′′ , R 4 ′′ , R 5 ′′ , R 6 ′′ , R 7 ′′ , R 8 ′′ and R 9 ′′ may be the same or different.
  • the substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.
  • n ′′, p ′′ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ′′, p ′′, and q may be the same or different.
  • R 1 ′′ , R 3 ′′ and R 6 ′′ each represent a hydrogen atom
  • R 2 ′′ , R 4 ′′ , R 5 ′′ and R 8 ′′ each represent a methyl group.
  • R 9 ′′ represents a (triethoxysilyl) propyl group
  • R 7 ′′ represents an alkyl group or a hydrogen atom.
  • the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard.
  • the ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, perhydropolysilazane and organopolysilazane may be selected as appropriate according to the application, and may be used in combination.
  • Perhydropolysilazane is presumed to have a structure in which a linear structure and a ring structure centered on 6- and 8-membered rings coexist.
  • the number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), and there are liquid or solid substances, and the state varies depending on the molecular weight.
  • Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a coating solution for forming a coating barrier layer.
  • Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. Is mentioned.
  • polysilazane examples include, but are not limited to, for example, a silicon alkoxide-added polysilazane obtained by reacting the polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-23827), and a glycidol reaction.
  • a silicon alkoxide-added polysilazane obtained by reacting the polysilazane with a silicon alkoxide
  • glycidol-added polysilazane Japanese Patent Laid-Open No. 6-122852
  • alcohol-added polysilazane obtained by reacting alcohol
  • metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal obtained by adding metal fine particles Fine particle added policy Zhang such (JP-A-7-196986), and a polysilazane ceramic at low temperatures.
  • the content of polysilazane in the coating barrier layer before the modification treatment can be 100% by weight when the total weight of the coating barrier layer is 100% by weight.
  • the content of polysilazane in the layer is preferably 10% by weight or more and 99% by weight or less, and 40% by weight or more and 95% by weight or less. Is more preferably 70 wt% or more and 95 wt% or less.
  • the coating solution used when forming the coating barrier layer can contain an additive compound as necessary.
  • an additive compound By adding the additive compound to the coating solution, there is an advantage that the modification of the barrier layer easily proceeds.
  • the additive compound examples include at least one selected from the group consisting of water, alcohol compounds, phenol compounds, metal alkoxide compounds, alkylamine compounds, alcohol-modified polysiloxanes, alkoxy-modified polysiloxanes, and alkylamino-modified polysiloxanes.
  • Compounds At least one compound selected from the group consisting of alcohol compounds, phenol compounds, metal alkoxide compounds, alkylamine compounds, alcohol-modified polysiloxanes, alkoxy-modified polysiloxanes, and alkylamino-modified polysiloxanes is more preferable.
  • the alcohol compound used as the additive compound include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol, isohexanol, cyclohexyl alcohol, octanol, and isooctanol.
  • the alcohol compound undergoes a dehydrogenative condensation reaction between the Si—H group that can be included in the polysilazane skeleton and the OH group in the alcohol compound during the reforming process to form a Si—O—R bond. Therefore, the storage stability under high temperature and high humidity is further improved.
  • these alcohol compounds methanol, ethanol, 1-propanol, or 2-propanol having a small number of carbon atoms and a boiling point of 100 ° C. or less is more preferable.
  • phenol compound used as the additive compound include, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol.
  • the phenol compound also undergoes a dehydrogenative condensation reaction between the Si—H group that can be included in the polysilazane skeleton and the OH group in the phenol compound during the modification treatment, and Si—O. Since the —R bond is formed, the storage stability under high temperature and high humidity is further improved.
  • metal alkoxide compound used as the additive compound examples include beryllium (Be), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), calcium (Ca), scandium (Sc), and titanium (Ti). , Vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge) , Strontium (Sr), Yttrium (Y), Zirconium (Zr), Niobium (Nb), Molybdenum (Mo), Technetium (Tc), Ruthenium (Ru), Rhodium (Rh), Palladium (Pd), Silver (Ag) , Cadmium (Cd), indium (In), tin (Sn), barium (Ba), lanthanum (La), selenium (Ce), praseodymium (Pr), neodymium (Nd), prom
  • metal alkoxide compounds include, for example, beryllium acetylacetonate, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert borate.
  • Silsesquioxane can also be used as the metal alkoxide compound.
  • Silsesquioxane is a siloxane-based compound whose main chain skeleton is composed of Si—O bonds, and is also called T-resin, whereas ordinary silica is represented by the general formula [SiO 2 ].
  • Silsesquioxane (also referred to as polysilsesquioxane) is a compound represented by the general formula [RSiO 1.5 ].
  • a (RSi (OR ') 3 ) compound in which one alkoxy group of tetraalkoxysilane (Si (OR') 4 ) represented by tetraethoxysilane is replaced with an alkyl group or an aryl group.
  • the polysiloxane to be synthesized, and the molecular arrangement is typically amorphous, ladder-like, or cage-like (fully condensed cage-like).
  • Silsesquioxane may be synthesized or commercially available. Specific examples of the latter include X-40-2308, X-40-9238, X-40-9225, X-40-9227, x-40-9246, KR-500, KR-510 (all of which are Shin-Etsu Chemical) SR2400, SR2402, SR2405, FOX14 (perhydrosilcelsesquioxane) (all manufactured by Toray Dow Corning), SST-H8H01 (perhydrosilcelsesquioxane) (manufactured by Gelest), etc. Is mentioned.
  • a compound having a branched alkoxy group is preferable from the viewpoint of reactivity and solubility, and a compound having a 2-propoxy group or a sec-butoxy group is more preferable.
  • metal alkoxide compounds having an acetylacetonate group are also preferred.
  • the acetylacetonate group is preferable because it has an interaction with the central element of the alkoxide compound due to the carbonyl structure, so that handling is easy.
  • a compound having a plurality of alkoxide groups or acetylacetonate groups is more preferable from the viewpoint of reactivity and film composition.
  • the central element of the metal alkoxide an element that easily forms a coordinate bond with a nitrogen atom in polysilazane is preferable, and Al, Fe, or B having high Lewis acidity is more preferable.
  • More preferable metal alkoxide compounds are, specifically, triisopropyl borate, aluminum trisec-butoxide, aluminum ethyl acetoacetate diisopropylate, magnesium ethoxide, calcium isopropoxide, titanium tetraisopropoxide, gallium isopropoxide.
  • metal alkoxide compound a commercially available product or a synthetic product may be used.
  • commercially available products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH-TR (aluminum tris).
  • Ethyl acetoacetate Ethyl acetoacetate
  • aluminum chelate M aluminum alkyl acetoacetate / diisopropylate
  • aluminum chelate D aluminum chelate
  • aluminum chelate A W
  • AL-M acetoalkoxy aluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.
  • Moth Chicks series manufactured by Matsumoto Fine Chemical Co., Ltd.
  • metal alkoxide compound when using a metal alkoxide compound, it is preferable to mix with the solution containing polysilazane in inert gas atmosphere. This is to prevent the metal alkoxide compound from reacting with moisture and oxygen in the atmosphere and causing intense oxidation.
  • alkylamine compound examples include primary amine compounds such as methylamine, ethylamine, propylamine, n-butylamine, sec-butylamine, tert-butylamine, 3-morpholinopropylamine; dimethylamine, diethylamine, Secondary amine compounds such as methylethylamine, dipropylamine, di (n-butyl) amine, di (sec-butyl) amine, di (tert-butyl) amine; trimethylamine, triethylamine, dimethylethylamine, methyldiethylamine, tripropyl Amines, tri (n-butyl) amine, tri (sec-butyl) amine, tri (tert-butyl) amine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine, etc.
  • tertiary amine compounds Such as tertiary amine compounds.
  • a diamine compound can be used as the alkylamine compound.
  • the diamine compound include tetramethylmethanediamine, tetramethylethanediamine, tetramethylpropanediamine (tetramethyldiaminopropane), tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, tetraethylmethanediamine, tetraethylethane.
  • Examples include diamine, tetraethylpropanediamine, tetraethylbutanediamine, tetraethylpentanediamine, tetraethylhexanediamine, N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH), and tetramethylguanidine.
  • TDAH N-tetramethyl-1,6-diaminohexane
  • modified polysiloxanes such as hydroxy-modified polysiloxanes having hydroxy groups, alkoxy-modified polysiloxanes having alkoxy groups, and alkylamino-modified polysiloxanes having alkylamino groups can be preferably used as additive compounds.
  • polysiloxanes represented by the following general formula (4) or general formula (5) can be preferably used.
  • R 4 to R 7 are each independently a hydrogen atom, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylamino group, or a substituent. Or an unsubstituted aryl group, wherein at least one of R 4 and R 5 and at least one of R 6 and R 7 is a hydroxy group, an alkoxy group, or an alkylamino group, p and q are each independently an integer of 1 or more.
  • the modified polysiloxane may be a commercially available product or a synthetic product.
  • commercially available products include, for example, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250 KR-401N, X-40-9227, X-40-9247, KR-510, KR9218, KR-213, X-40-2308, X-40-9238 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Can be mentioned.
  • the degree of modification of the hydroxy group, alkoxy group or alkylamino group in the modified polysiloxane is preferably 5 mol% to 50 mol%, more preferably 7 mol% to 20 mol%, based on the number of moles of silicon atoms. More preferred is mol% to 12 mol%.
  • the polystyrene-reduced weight average molecular weight of the modified polysiloxane is preferably about 1,000 to 100,000, more preferably 2,000 to 50,000.
  • the solvent for preparing the coating liquid for forming the coating barrier layer is not particularly limited as long as it can disperse or dissolve polysilazane and an additive compound added as necessary, but water that easily reacts with polysilazane.
  • an organic solvent that does not contain a reactive group (such as a hydroxyl group or an amine group) and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable.
  • the solvent includes an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben.
  • an aprotic solvent for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben.
  • Hydrogen solvents Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include mono- and polyalkylene glycol dialkyl ethers (diglymes).
  • the solvent is selected according to the purpose such as the solubility of the silicon compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.
  • the concentration of polysilazane in the coating solution for forming the coating barrier layer is not particularly limited, and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by weight, more preferably 2 to 50% by weight, Particularly preferred is 3 to 40% by weight.
  • the coating solution for forming the coating barrier layer preferably contains a catalyst in order to promote modification.
  • a catalyst examples include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′—.
  • Amine compounds such as tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, and Pd compounds such as propionic acid Pd Metal catalysts such as Rh compounds such as Rh acetylacetonate, N-heterocyclic compounds, pyridine compounds such as pyridine, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, piperidine, lutidine, pyrimidine, pyridazine, DBU (1 , 8-diazabicyclo [5.4.0] -7-undecene), DBN (1,5-diazabicyclo [4 3.0] -5-nonene), acetic, propionic, butyric, valeric, maleic, stearic acids, organic acids etc., hydrochloric, nitric acid, sulfur
  • the concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, based on polysilazane. By setting the addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects, and the like.
  • the following additives may be used as necessary.
  • cellulose ethers, cellulose esters for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc.
  • natural resins for example, rubber, rosin resin, etc., synthetic resins
  • Aminoplasts especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.
  • Method of applying coating liquid for forming coating barrier layer As a method for applying the coating liquid for forming the coating barrier layer, a conventionally known appropriate wet coating method can be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
  • the coating thickness can be appropriately set according to the purpose.
  • the coating thickness per coating barrier layer is preferably about 10 nm to 10 ⁇ m after drying, more preferably 15 nm to 1 ⁇ m, and even more preferably 20 to 500 nm. If the film thickness is 10 nm or more, sufficient gas barrier properties can be obtained, and if it is 10 ⁇ m or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized.
  • the coating film After applying the coating solution, it is preferable to dry the coating film.
  • the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable coating barrier layer can be obtained. The remaining solvent can be removed later.
  • the drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C. (Example: 80 ° C.).
  • the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat.
  • the temperature can be set by using a hot plate, oven, furnace or the like.
  • the drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes.
  • the drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.
  • the coating film obtained by applying the coating solution for forming the coating barrier layer may include a step of removing moisture before or during the modification treatment.
  • a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature.
  • a preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is ⁇ 5 ° C. (temperature 25 ° C./humidity 10%) or less, and the maintaining time is the film thickness of the coating barrier layer. It is preferable to set appropriately.
  • the dew point temperature is ⁇ 5 ° C. or less and the maintaining time is 1 minute or more.
  • the lower limit of the dew point temperature is not particularly limited, but is usually ⁇ 50 ° C. or higher, and preferably ⁇ 40 ° C. or higher. This is a preferred form from the viewpoint of promoting the dehydration reaction of the coating barrier layer converted to silanol by removing water before or during the modification treatment.
  • the modification treatment of the coating film formed by the coating method in the present invention refers to the conversion reaction of polysilazane to silicon oxide or silicon oxynitride, and specifically, the coating barrier layer can contribute to the development of gas barrier properties. This refers to the treatment of forming a level inorganic thin film.
  • the conversion reaction of polysilazane to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method.
  • a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet light irradiation treatment is preferable.
  • a known method can be used as the plasma treatment that can be used as the modification treatment, and an atmospheric pressure plasma treatment or the like can be preferably used.
  • the atmospheric pressure plasma CVD method which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum.
  • the film speed is high, and further, under a high pressure condition of atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free path is very short, so that a very homogeneous film can be obtained.
  • nitrogen gas or a group 18 atom of the long-period periodic table specifically helium, neon, argon, krypton, xenon, radon, or the like is used.
  • nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
  • UV light irradiation treatment any commonly used ultraviolet ray generator can be used.
  • the coating film containing the polysilazane compound from which moisture has been removed is modified by treatment with ultraviolet light irradiation.
  • Ozone and active oxygen atoms generated by ultraviolet light have high oxidation ability, and can form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperatures. It is.
  • This ultraviolet light irradiation excites and activates O 2 and H 2 O, UV absorbers, and polysilazane itself that contribute to ceramicization. And the ceramicization of the excited polysilazane is promoted, and the resulting ceramic film becomes dense. Irradiation with ultraviolet light is effective at any time after the formation of the coating film.
  • the ultraviolet light generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm.
  • ultraviolet light including an electromagnetic wave having a wavelength of 10 to 200 nm called vacuum ultraviolet light is used.
  • the irradiation intensity and the irradiation time are set within a range in which the substrate carrying the coating containing the polysilazane compound before the modification is not damaged.
  • a 2 kW (80 W / cm ⁇ 25 cm) lamp is used, and the strength of the base material surface is 20 to 300 mW / cm 2 , preferably 50 to 200 mW / cm.
  • the distance between the base material and the ultraviolet irradiation lamp is set so as to be 2, and irradiation can be performed for 0.1 seconds to 10 minutes.
  • the temperature of the substrate during the ultraviolet irradiation treatment is 150 ° C. or higher, the properties of the substrate are impaired in the case of a plastic film or the like, for example, the substrate is deformed or its strength is deteriorated. .
  • a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate.
  • ultraviolet ray generating means examples include, but are not particularly limited to, metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers.
  • the polysilazane layer before modification is irradiated with the generated ultraviolet light, the polysilazane before modification is reflected after reflecting the ultraviolet light from the generation source with a reflector from the viewpoint of improving efficiency and uniform irradiation. It is desirable to hit the layer.
  • UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used.
  • the substrate having a coating layer containing a polysilazane compound is in the form of a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in a drying zone equipped with an ultraviolet ray source as described above while being conveyed. can do.
  • the time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the coating layer containing the substrate and polysilazane compound used.
  • the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment).
  • dry inert gas is preferably used, and dry nitrogen gas is particularly preferable from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
  • the method for modifying the layer containing the polysilazane compound before modification in the present invention is treatment by irradiation with vacuum ultraviolet light.
  • the treatment by vacuum ultraviolet light irradiation uses light energy of 100 to 200 nm, preferably light energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and the bonding of atoms is a photon called photon process.
  • This is a method in which a silicon oxide film is formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by only the action.
  • a vacuum ultraviolet light source required for this a rare gas excimer lamp is preferably used.
  • rare gas atoms such as Xe, Kr, Ar, and Ne are called inert gases because they are chemically bonded and do not form molecules.
  • rare gas atoms excited atoms
  • the rare gas is xenon, e + Xe ⁇ e + Xe * Xe * + Xe + Xe ⁇ Xe 2 * + Xe
  • excimer light vacuum ultraviolet light
  • ⁇ Excimer lamps are characterized by high efficiency because radiation concentrates on one wavelength and almost no other light is emitted. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.
  • the illuminance of the vacuum ultraviolet ray on the coating surface received by the coating film containing the polysilazane compound is preferably 1 mW / cm 2 to 10 W / cm 2 , and 30 mW / cm 2 to 200 mW / cm. more preferably 2, further preferably at 50mW / cm 2 ⁇ 160mW / cm 2. If it is 1 mW / cm 2 or more, sufficient reforming efficiency can be obtained. Moreover, if it is 10 W / cm ⁇ 2 > or less, the ablation of a coating film will not arise easily and it will be hard to give a damage to a base material.
  • Irradiation energy amount of the VUV in coated surface containing the polysilazane compound is preferably 10 ⁇ 10000mJ / cm 2, more preferable to be 100 ⁇ 8000mJ / cm 2, further preferable to be 200 ⁇ 6000mJ / cm 2, 500 It is particularly preferred to be ⁇ 6000 mJ / cm 2 (Example: 3000 mJ / cm 2 ). If 10 mJ / cm 2 or more sufficient reforming efficiency is obtained, 10000 mJ / cm 2 or less value, if difficult to thermal deformation of the cracks or the substrate occurs.
  • the oxygen concentration upon irradiation with vacuum ultraviolet light (VUV) is preferably 300 to 10000 volume ppm (1 volume%), more preferably 500 to 5000 volume ppm (Example: 0.0. 1% by volume).
  • VUV vacuum ultraviolet light
  • Dielectric barrier discharge refers to lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. It is a similar very thin discharge called micro discharge.
  • electrodeless electric field discharge is also known as a method for efficiently obtaining excimer light emission.
  • the electrodeless field discharge is a discharge due to capacitive coupling, and is also called an RF discharge.
  • the lamp, the electrode, and the arrangement thereof may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz.
  • a spatially and temporally uniform discharge can be obtained in this way.
  • the Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the coating film containing the polysilazane compound can be modified in a short time.
  • the process time is shortened due to high throughput, the equipment area is reduced, and organic materials, plastic substrates, resin films, etc. that are easily damaged by heat are irradiated. It is possible.
  • heating the coating layer simultaneously with vacuum ultraviolet irradiation is also preferably used to promote the modification treatment.
  • the heating method is a method of heating the coating layer by heat conduction by bringing the substrate into contact with a heating element such as a heat block, a method of heating the atmosphere with an external heater such as a resistance wire, and an infrared region such as an IR heater.
  • a heating element such as a heat block
  • an external heater such as a resistance wire
  • an infrared region such as an IR heater.
  • the method using light etc. are mentioned, it does not restrict
  • a method capable of maintaining the smoothness of the coating layer may be appropriately selected.
  • the irradiation conditions of the vacuum ultraviolet rays vary depending on the substrate to be applied and can be appropriately determined by those skilled in the art.
  • the irradiation temperature (heating temperature) of vacuum ultraviolet rays is preferably 50 to 200 ° C., more preferably 80 to 150 ° C. It is preferable for the irradiation conditions to be within the above-mentioned range since deformation of the substrate and deterioration of strength are unlikely to occur, and the properties of the substrate are not impaired.
  • the film composition of the coating barrier layer can be measured by measuring the atomic composition ratio using an XPS surface analyzer.
  • the silicon-containing film can be cut and the cut surface can be measured by measuring the atomic composition ratio with an XPS surface analyzer.
  • the coating barrier layer may be a single layer or a laminated structure of two or more layers.
  • each coating barrier layer may have the same composition or a different composition.
  • the gas barrier film of the present invention may have an intermediate layer between the gas barrier layer and the coating barrier layer for the purpose of stress relaxation and the like.
  • a method of forming the intermediate layer a method of forming a polysiloxane modified layer can be applied.
  • a coating liquid containing polysiloxane is applied onto a gas barrier layer by a wet coating method and dried, and then the coating film obtained by drying is irradiated with vacuum ultraviolet light to form an intermediate layer. It is a method of forming.
  • the coating solution used for forming the intermediate layer preferably contains polysiloxane and an organic solvent.
  • the polysiloxane applicable to the formation of the intermediate layer is not particularly limited, but an organopolysiloxane represented by the following general formula (6) is particularly preferable.
  • organopolysiloxane represented by the following general formula (6) will be described as an example of polysiloxane.
  • R 8 to R 13 each independently represents an organic group having 1 to 8 carbon atoms. At this time, at least one of R 8 to R 13 is an alkoxy group or a hydroxyl group. M is an integer of 1 or more.
  • Examples of the organic group having 1 to 8 carbon atoms represented by R 8 to R 13 include halogenated alkyl groups such as ⁇ -chloropropyl group and 3,3,3-trifluoropropyl group, vinyl groups, and phenyl groups.
  • (Meth) acrylic acid ester groups such as ⁇ -methacryloxypropyl group, epoxy-containing alkyl groups such as ⁇ -glycidoxypropyl group, mercapto-containing alkyl groups such as ⁇ -mercaptopropyl group, ⁇ -aminopropyl group, etc.
  • Isocyanate-containing alkyl groups such as aminoalkyl groups and ⁇ -isocyanatopropyl groups, linear or branched alkyl groups such as methyl groups, ethyl groups, n-propyl groups and isopropyl groups, alicyclic groups such as cyclohexyl groups and cyclopentyl groups Linear or branched alkyl such as alkyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group Alkoxy group, an acetyl group, a propionyl group, a butyryl group, valeryl group, an acyl group such as caproyl group, and a hydroxyl group.
  • an organopolysiloxane having m of 1 or more and a polystyrene equivalent weight average molecular weight of 1,000 to 20,000 is particularly preferred. If the weight average molecular weight in terms of polystyrene of the organopolysiloxane is 1,000 or more, the protective layer to be formed is hardly cracked, and water vapor barrier properties can be maintained. The intermediate layer is sufficiently cured, so that a sufficient hardness can be obtained as a protective layer.
  • examples of the organic solvent applicable to the formation of the intermediate layer include alcohol solvents, ketone solvents, amide solvents, ester solvents, aprotic solvents, and the like.
  • examples of the alcohol solvent include n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec- Pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether and the like are preferable.
  • ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl.
  • ketone di-iso-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, acetylacetone, 2,4-hexanedione, 2 , 4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetrame Le-3,5-heptane dione, 1,1,1,5,5,5 beta-diketones such as hexafluoro-2,4-heptane dione and the like.
  • ketone solvents may be used alone or in combination of two or more.
  • amide solvents include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide solvents may be used alone or in combination of two or more.
  • ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, and iso -Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, methyl
  • Aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N -Methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl Examples include -2-imidazolidinone and 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone. These aprotic solvents may be used alone or in combination of two or more.
  • alcohol solvents are preferable among the above organic solvents.
  • Examples of the coating method for the coating liquid for forming the intermediate layer include spin coating, dipping, roller blade, and spraying.
  • the thickness of the intermediate layer formed by the coating liquid for forming the intermediate layer is preferably in the range of 100 nm to 10 ⁇ m. If the thickness of the intermediate layer is 100 nm or more, gas barrier properties under high temperature and high humidity can be ensured. Moreover, if the thickness of the intermediate layer is 10 ⁇ m or less, stable coating properties can be obtained when forming the intermediate layer, and high light transmittance can be realized.
  • the intermediate layer generally has a film density of 0.35 to 1.2 g / cm 3 , preferably 0.4 to 1.1 g / cm 3 , more preferably 0.5 to 1.0 g / cm 3. It is. If the film density is 0.35 g / cm 3 or more, sufficient mechanical strength of the coating film can be obtained.
  • the intermediate layer in the present invention is obtained by applying a coating solution containing polysiloxane onto a gas barrier layer by a wet coating method and drying it, and then irradiating the dried coating film (polysiloxane coating film) with vacuum ultraviolet light. Form.
  • vacuum ultraviolet light used for the formation of the intermediate layer vacuum ultraviolet light by the same vacuum ultraviolet light irradiation treatment as described in the formation of the barrier layer can be applied.
  • the integrated light quantity of ultraviolet light for forming the intermediate layer by reforming polysiloxane membrane 500 mJ / cm 2 or more, preferably 10,000 / cm 2 or less. If the accumulated amount of vacuum ultraviolet light is 500 mJ / cm 2 or more, sufficient gas barrier performance can be obtained, and if it is 10,000 mJ / cm 2 or less, an intermediate layer having high smoothness without deforming the substrate. Can be formed.
  • the intermediate layer in the present invention is preferably formed through a heating step in which the heating temperature is 50 ° C. or higher and 200 ° C. or lower. If the heating temperature is 50 ° C. or higher, sufficient barrier properties can be obtained, and if it is 200 ° C. or lower, an intermediate layer having high smoothness can be formed without deforming the substrate.
  • a heating method using a hot plate, an oven, a furnace, or the like can be applied to this heating step.
  • the heating atmosphere may be any condition such as air, nitrogen atmosphere, argon atmosphere, vacuum, or reduced pressure with controlled oxygen concentration.
  • a polysiloxane coating film is formed on the polysilazane coating film that has been subjected to the vacuum ultraviolet light irradiation treatment, and after the vacuum ultraviolet light irradiation treatment is applied to the polysiloxane coating film, a heat treatment of 100 ° C. or higher and 250 ° C. or lower is performed. And a gas barrier layer and an intermediate layer may be formed.
  • the gas barrier layer is caused by thermal stress due to the heat treatment. Generation of minute cracks in the gas barrier layer can be prevented, and the water vapor barrier performance of the gas barrier layer can be stabilized.
  • a protective layer containing an organic compound may be provided on the gas barrier layer or the coating barrier layer.
  • an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used.
  • These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary.
  • the “crosslinkable group” is a group that can crosslink the binder polymer by a chemical reaction that occurs during light irradiation treatment or heat treatment.
  • the chemical structure is not particularly limited as long as it is a group having such a function.
  • the functional group capable of addition polymerization include cyclic ether groups such as an ethylenically unsaturated group and an epoxy group / oxetanyl group.
  • the functional group which can become a radical by light irradiation may be sufficient,
  • a crosslinkable group a thiol group, a halogen atom, an onium salt structure etc. are mentioned, for example.
  • ethylenically unsaturated groups are preferable, and include functional groups described in paragraphs “0130” to “0139” of JP-A No. 2007-17948.
  • organic-inorganic composite resin for example, an organic-inorganic composite resin described as “ORMOCER (registered trademark)” in US Pat. No. 6,503,634 can be preferably used.
  • the elastic modulus of the protective layer can be adjusted to a desired value by appropriately adjusting the structure of the organic resin, the density of the polymerizable group, the density of the crosslinkable group, the ratio of the crosslinking agent, and the curing conditions.
  • the organic resin composition examples include a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, and urethane acrylate. And a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.
  • 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, n- Pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, di Cyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, Lysidyl acrylate, 2-
  • the composition of the photosensitive resin contains a photopolymerization initiator.
  • the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, ⁇ -amino acetophenone, 4,4-dichloro Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzyl
  • the protective layer can contain an inorganic material. Inclusion of an inorganic material generally leads to an increase in the elastic modulus of the protective layer.
  • the elastic modulus of the protective layer can be adjusted to a desired value by appropriately adjusting the content ratio of the inorganic material.
  • inorganic fine particles having a number average particle diameter of 1 to 200 nm are preferable, and inorganic fine particles having a number average particle diameter of 3 to 100 nm are more preferable.
  • inorganic fine particles metal oxides are preferable from the viewpoint of transparency.
  • metal oxide SiO 2, Al 2 O 3 , TiO 2, ZrO 2, ZnO, SnO 2, In 2 O 3, BaO, SrO, CaO, MgO, VO 2, V 2 O5, CrO 2, MoO 2, MoO 3, MnO 2, Mn 2 O 3, WO 3, LiMn 2 O 4, Cd 2 SnO 4, CdIn 2 O 4, Zn 2 SnO 4, ZnSnO 3, Zn 2 In 2 O 5, Cd 2 SnO 4 , and the like. These may be used alone or in combination of two or more.
  • the present invention provides a gas barrier film produced by the production method described above. According to the above production method, a gas barrier film having excellent gas barrier properties and bending resistance, and having a smoothness that is not easily lowered can be obtained.
  • the gas barrier film of the present invention as described above has excellent gas barrier properties, transparency, bending resistance, and the like. For this reason, the gas barrier film of this invention is used for electronic devices, such as packages, such as an electronic device, a photoelectric conversion element (solar cell element), an organic electroluminescent (EL) element, a liquid crystal display element. That is, the present invention provides an electronic device including an electronic device body and a gas barrier film produced by the production method of the present invention.
  • the electronic element main body is the main body of the electronic device, and is disposed on the gas barrier film side according to the present invention.
  • the electronic element body 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.
  • Organic EL device Examples of organic EL elements using a gas barrier film are described in detail in JP-A-2007-30387.
  • 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), an EC type, a B type.
  • TN type Transmission Nematic
  • STN type Super Twisted Nematic
  • HAN type Hybrid Aligned Nematic
  • VA Very Alignment
  • an EC type a B type.
  • OCB type Optically Compensated Bend
  • IPS type In-Plane Switching
  • CPA type Continuous Pinwheel 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 gas 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 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-2002-865554 can be suitably used. .
  • Example 1 ⁇ Preparation of substrate 1> A 75 ⁇ m thick polyester film (Cosmo Shine (registered trademark) A4300, manufactured by Toyobo Co., Ltd.) with easy adhesion processing on both sides is used as a support, as shown below, a bleed-out prevention layer on one side, and a smooth surface on the opposite side What produced the layer was used as the base material 1.
  • a bleed-out prevention layer one side of the above support is coated with a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7535 manufactured by JSR Corporation, and a wire bar so that the film thickness after drying is 4 ⁇ m
  • OPSTAR registered trademark
  • Z7535 manufactured by JSR Corporation
  • a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 manufactured by JSR Corporation is applied to the opposite surface of the above support, and a wire is formed so that the film thickness after drying becomes 4 ⁇ m.
  • OPSTAR registered trademark
  • Z7501 manufactured by JSR Corporation
  • the obtained smooth layer had a surface roughness specified by JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) was 16 nm.
  • the base material on which such a bleed-out prevention layer and a smooth layer were formed was designated as “B0”.
  • the first to third vapor deposition layers 2 each contained a metal oxide (silicon oxide), and the thicknesses of the first to third vapor deposition layers 2 were a total of 160 nm of 100 nm, 30 nm, and 30 nm, respectively.
  • Discharge gas N 2 gas Reaction gas 1: 1% by volume of hydrogen gas with respect to the total gas Reaction gas 2: 0.5% by volume of TEOS (tetraethoxysilane) with respect to the total gas Film formation conditions; 1st electrode side Power supply type Frequency 80kHz Output density 8W / cm 2 Electrode temperature 115 ° C Second electrode side Power supply type Pearl Industrial 13.56MHz CF-5000-13M Frequency 13.56MHz Output density 10W / cm 2 Electrode temperature 95 ° C [Second deposition layer] Discharge gas: N 2 gas Reaction gas 1: 5% by volume of oxygen gas with respect to the total gas Reaction gas 2: 0.1% by volume of TEOS with respect to the total gas Film formation conditions; 1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k Frequency 100kHz Output density 10W / cm 2 Electrode temperature 120 ° C Second electrode side Power supply type Pearl Industrial 13.56MHz CF-5000-13
  • the high frequency power source used at this time was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm.
  • the source gas was introduced into the vacuum chamber with a silane gas flow rate of 7.5 sccm, an ammonia gas flow rate of 100 sccm, and a nitrous oxide gas flow rate of 50 sccm.
  • the film substrate temperature was 100 ° C. at the start of film formation, and the gas pressure during film formation. Was set to 100 Pa, and a silicon oxynitride thin film layer (SiON layer, gas barrier layer (2)) containing silicon oxynitride as a main component was formed to a thickness of 160 nm.
  • the gas barrier layer (2) is irradiated with ultraviolet light having a wavelength of 146 nm with an integrated light amount of 500 mJ / cm 2 (oxygen concentration: 1.0 vol%) to form the gas barrier layer (2a).
  • Gas barrier film 1-2 was obtained.
  • the high frequency power source used at this time was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm.
  • As source gases a silane gas flow rate of 7.5 sccm, an ammonia gas flow rate of 50 sccm, and a hydrogen gas flow rate of 200 sccm (sccm is cm 3 / min at 133.322 Pa) were introduced into the vacuum chamber.
  • the film substrate temperature was set to 100 ° C.
  • the gas pressure during film formation was set to 4 Pa
  • a silicon nitride thin film layer (SiN layer) mainly composed of silicon nitride was formed to a thickness of 100 nm.
  • the film substrate temperature was kept as it was, the gas pressure was set to 30 Pa, a second silicon nitride thin film layer (SiN layer) having a film thickness of 60 nm was continuously formed, and a gas barrier layer having a total film thickness of 160 nm was formed. .
  • the gas barrier layer (3) is irradiated with ultraviolet light having a wavelength of 146 nm at an integrated light quantity of 500 mJ / cm 2 (oxygen concentration: 1.0 vol%) to form the gas barrier layer (3a).
  • Gas barrier film 1-3 was obtained.
  • Discharge gas Nitrogen gas 94.9% by volume Thin film forming gas: Tetraethoxysilane 0.1% by volume Additive gas: Oxygen gas 5.0% by volume 1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k Frequency 100kHz Output density 10W / cm 2 Electrode temperature 120 ° C Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M Frequency 13.56MHz Output density 10W / cm 2 Electrode temperature 90 ° C [Second deposition layer] Discharge gas: Nitrogen gas 94.5% by volume Thin film forming gas: Tetraethoxysilane 0.5% by volume Additive gas: Oxygen gas 5.0% by volume 1st electrode side Power supply type Frequency 80kHz Output density 8W / cm 2 Electrode temperature 120 ° C Second electrode side Power supply type Pearl Industrial 13.56MHz CF-5000-13M Frequency 13.56MHz Output density 10W / cm 2 Electrode
  • the gas barrier layer (4) is irradiated with light having a wavelength of 248 nm by a KrF excimer laser, and the integrated light quantity is 500. Irradiation was performed at mJ / cm 2 (oxygen concentration: 1.0% by volume) to form a gas barrier layer (5a) to obtain a gas barrier film 1-5.
  • Example 1-6 Preparation of SiOC film
  • the gas barrier film 1--1 was prepared in the same manner as in Example 1-5, except that the wavelength of the irradiated light was changed from 248 nm to 220 nm (using a KrCl excimer laser) and the gas barrier layer (6a) was prepared. 6 was produced.
  • Example 1-7 Preparation of SiOC film ⁇ Preparation of substrate 2> A biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 ⁇ m, width: 350 mm, manufactured by Teijin DuPont Films Ltd., trade name “Teonex (registered trademark) Q65FA”) was used as the substrate 2.
  • PEN film thickness: 100 ⁇ m, width: 350 mm, manufactured by Teijin DuPont Films Ltd., trade name “Teonex (registered trademark) Q65FA”) was used as the substrate 2.
  • ⁇ Plasma CVD conditions Feed rate of source gas (hexamethyldisiloxane, 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 Transport speed of resin substrate: 2 m / min.
  • HMDSO hexamethyldisiloxane
  • O 2 oxygen gas
  • gas barrier layer (7) is irradiated with ultraviolet light of 220 nm using a KrCl excimer laser with an integrated light quantity of 500 mJ / cm 2 (oxygen concentration: 1.0 vol%) to form a gas barrier layer (7a), and gas barrier properties Film 1-7 was produced.
  • Example 1-8 Production of SiOC film A gas barrier film 1-8 was produced in the same manner as in Example 1-7, except that the wavelength of ultraviolet light to be irradiated was changed from 220 nm to 172 nm (using an Xe excimer lamp).
  • Example 1-9 Production of SiOC film A gas barrier film 1-9 was produced in the same manner as in Example 1-7, except that the wavelength of ultraviolet light to be irradiated was changed from 220 nm to 146 nm (using a Kr excimer lamp).
  • Example 1-10 Production of SiOC film A gas barrier film 1-10 was produced in the same manner as in Example 1-7 except that the wavelength of ultraviolet light to be irradiated was changed from 220 nm to 126 nm (using an Ar excimer lamp).
  • Example 2 ⁇ Comparative Example 2-1> (Formation of gas barrier layer by vapor deposition) A gas barrier layer 21 was formed in the same manner as the method for producing the gas barrier layer (1) described in Comparative Example 1-1.
  • a film having a thickness of 150 nm was formed on the substrate 1 with a spin coater and allowed to stand for 2 minutes, followed by additional heat treatment for 1 minute on a hot plate at 80 ° C. to form a polysilazane coating film.
  • vacuum ultraviolet light (MDI-COM excimer irradiation apparatus MODEL: MECL-M-1-200, wavelength 172 nm, stage temperature 100 ° C., integrated light quantity 3000 mJ / cm 2)
  • the gas barrier film was produced by irradiation with an oxygen concentration of 0.1% by volume.
  • Example 2-5 SiOC / PHPS (Formation of gas barrier layer by vapor deposition) A gas barrier layer was formed in the same manner as in Example 1-5 except that the wavelength of the ultraviolet light was changed from 248 nm to 172 nm (using an Xe excimer lamp).
  • Example 2-6 SiOC / PHPS (Formation of gas barrier layer by vapor deposition) A gas barrier layer was formed in the same manner as described in Example 1-7.
  • Example 2-7 A gas barrier film was produced in the same manner as in Example 2-6, except that the coating solution used in the production of the coating barrier layer was changed as follows.
  • Example 2-8> A gas barrier film was produced in the same manner as in Example 2-6, except that the coating solution used in the production of the coating barrier layer was changed as follows.
  • ALCH Korean Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate 0.46 g and dibutyl ether 19.2 g were added and mixed to prepare a coating solution.
  • Example 2-9 A gas barrier film was produced in the same manner as in Example 2-5 except that the wavelength of ultraviolet light was changed from 172 nm to 146 nm (using a Kr excimer lamp) in the formation of the gas barrier layer by the vapor deposition method.
  • Example 2-10> It was produced in the same manner as in Example 2-8 except that the wavelength of ultraviolet light was changed from 172 nm to 146 nm (using a Kr excimer lamp) in the formation of the gas barrier layer by the vapor deposition method.
  • the gas barrier layer formed by the above vapor deposition method is subjected to XPS depth profile measurement under the following conditions, and the silicon element distribution, oxygen element distribution, carbon element distribution and oxygen carbon distribution at the distance from the surface of the thin film layer in the layer thickness direction are measured. Obtained.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 10 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 ⁇ 400 ⁇ m oval.
  • the gas barrier layers formed by the vapor deposition methods of Comparative Example 1-4, Examples 1-5 to 1-10, Comparative Example 2-4, and Examples 2-5 to 2-10 were silicon atoms and carbon atoms. It was confirmed to contain.
  • the gas barrier layers formed by the vapor deposition methods of Examples 1-7 to 1-10 and Examples 2-6 to 2-10 have continuous change regions and extreme values in the film composition, and include silicon atoms, oxygen
  • the average atomic ratio of atoms and carbon atoms satisfies the relationship of (carbon atomic ratio) ⁇ (silicon atomic ratio) ⁇ (oxygen atomic ratio) in a region of 90% or more of the total thickness. confirmed.
  • the barrier property test was carried out by depositing 70 nm-thick metallic calcium on a gas barrier film and evaluating the time for 50% of the area as the degradation time.
  • Vapor Deposition Equipment Vacuum Deposition Equipment JEE-400 manufactured by JEOL Ltd. Constant temperature and humidity oven: Yamato Humidic Chamber IG47M (raw materials) Metal that reacts with water and corrodes: Calcium (granular) Water vapor impermeable metal: Aluminum ( ⁇ 3-5mm, granular) (Preparation of water vapor barrier property evaluation sample)
  • a vacuum vapor deposition apparatus vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
  • metallic calcium was vapor-deposited in a size of 12 mm ⁇ 12 mm through the mask on the surface of the gas barrier layer of the produced gas barrier film. At this time, the deposited film thickness was set to 70 nm.
  • the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet and temporarily sealed.
  • the vacuum state is released, and it is quickly transferred to a dry nitrogen gas atmosphere, and a quartz glass having a thickness of 0.2 mm is placed on the aluminum vapor deposition surface via a sealing ultraviolet light curing resin (manufactured by Nagase ChemteX Corporation).
  • a water vapor barrier property evaluation sample was prepared by pasting together and irradiating ultraviolet light to cure and adhere the resin to perform main sealing.
  • the obtained sample was stored under high temperature and high humidity of 85 ° C. and 85% RH, and the state in which metallic calcium was corroded with respect to the storage time was observed.
  • the observation was obtained by linearly interpolating the time when the area where metal calcium was corroded with respect to the metal calcium vapor deposition area of 12 mm ⁇ 12 mm to 50%, and the results are shown in Tables 1 and 2.
  • Deterioration resistance (water vapor transmission rate after bending test / water vapor transmission rate before bending test) ⁇ 100 (%) The deterioration resistance was classified into the following five grades and evaluated.
  • Deterioration resistance is 95% or more 5: Deterioration resistance is 90% or more and less than 95% 4: Deterioration resistance is 85% or more and less than 90% 3: Deterioration resistance is 80% or more and less than 85% 2: Deterioration resistance is 50% or more and less than 80% 1: Deterioration resistance is less than 50%.
  • the maximum cross-sectional height Rt (p) which is an index of surface roughness, is a cross-section of irregularities continuously measured with a detector having a stylus with a minimum tip radius using an AFM (Atomic Force Microscope; DI3100 manufactured by Digital Instruments). It was calculated from the curve, measured 30 times in a section with a measuring direction of 30 ⁇ m with a stylus with a very small tip radius, and obtained from the average roughness regarding the amplitude of fine irregularities.
  • the surface roughness (smoothness) was evaluated by classifying into the following five stages.
  • ⁇ Rt Maximum cross-sectional height (nm) Less than 6:10 5:10 or more but less than 15 4:15 or more, less than 20 3:20 or more, less than 30 2:30 or more, less than 50 1:50 or more.
  • Example 3 Production of electronic devices >> An organic EL (OLED) element, which is an organic thin film electronic device, was prepared by the following procedure using the gas barrier films described in Table 1 and Table 2 below as a substrate.
  • ITO indium tin oxide
  • first electrode layer On the gas barrier layer of the gas barrier film, ITO (indium tin oxide) having a thickness of 150 nm was formed by sputtering, and patterned by photolithography to form a first electrode layer.
  • the hole transport layer forming coating solution shown below was applied by an extrusion coater so that the thickness after drying was 50 nm, and then dried to form a hole transport layer. Formed.
  • the gas barrier film was subjected to cleaning surface modification using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm 2 and a distance of 10 mm.
  • the charge removal treatment was performed using a static eliminator with weak X-rays.
  • ⁇ Application conditions> The coating process was performed in an atmosphere of 25 ° C. and a relative humidity of 50% RH.
  • ⁇ Drying and heat treatment conditions> After applying the hole transport layer forming coating solution, the solvent was removed by applying hot air at a height of 100 mm toward the film formation surface, a discharge air speed of 1 m / s, a width of 5% of the wide air speed, and a temperature of 100 ° C. Subsequently, a back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using a heat treatment apparatus to form a hole transport layer.
  • ⁇ White luminescent layer forming coating solution 1.0 g of host material HA, 100 mg of dopant material DA, 0.2 mg of dopant material DB, and 0.2 mg of dopant material DC are dissolved in 100 g of toluene as a coating solution for forming a white light emitting layer. Got ready.
  • the chemical structures of the host material HA, the dopant material DA, the dopant material DB, and the dopant material DC are as shown in the following chemical formula.
  • the coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.
  • the coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.
  • an electron injection layer was formed on the electron transport layer formed above.
  • the substrate was put into a decompression chamber and decompressed to 5 ⁇ 10 ⁇ 4 Pa.
  • cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.
  • a mask pattern was formed by vapor deposition using aluminum as the second electrode forming material under a vacuum of 5 ⁇ 10 ⁇ 4 Pa and having a takeout electrode.
  • a second electrode having a thickness of 100 nm was stacked.
  • SiO 2 was laminated with a thickness of 200 nm by a CVD method, and a protective layer was formed on the second electrode layer.
  • a sealing member As a sealing member, a polyethylene terephthalate (PET) film (12 ⁇ m thickness) is used on a 30 ⁇ m thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.), and an adhesive for dry lamination (a two-component reaction type urethane adhesive) is used. What was dry-laminated (adhesive layer thickness 1.5 ⁇ m) was used, and sealing was performed using a sheet-like sealant TB1655 manufactured by ThreeBond Co., Ltd.
  • PET polyethylene terephthalate
  • the organic EL element which uses each gas barrier film was produced according to the above-mentioned process.
  • Example 4" photoelectric conversion element (solar cell)) Indium tin oxide (ITO) transparent conductive film deposited as a first electrode (anode) at a thickness of 150 nm on the gas barrier layer of the gas barrier film shown in Tables 1 and 2 below (sheet resistance 12 ⁇ / cm 2 ( ⁇ (square)) was patterned to a width of 10 mm using a normal photolithography method and wet etching to form a first electrode, and the patterned first electrode was formed using a surfactant and ultrapure water. After cleaning in the order of ultrasonic cleaning with and ultrasonic cleaning with ultrapure water, it was dried with nitrogen blow, and finally ultraviolet light ozone cleaning was performed.
  • ITO Indium tin oxide
  • PEDOT-PSS CLEVIOS (registered trademark) P VP AI 4083, Hereosu Co., conductivity: 1 ⁇ 10 -3 S / cm ) 2.0 quality
  • the substrate was coated and dried using a blade coater adjusted to 65 ° C. so that the dry film thickness was about 30 nm, and then heat-treated with warm air at 120 ° C. for 20 seconds. Then, a hole transport layer was formed on the first electrode, and after that, it was brought into a glove box and operated in a nitrogen atmosphere.
  • the element formed up to the hole transport layer was heated at 120 ° C. for 3 minutes in a nitrogen atmosphere.
  • This solution was applied and dried using a blade coater whose temperature was adjusted to 65 ° C. so that the dry film thickness was about 5 nm. Thereafter, heat treatment was performed for 2 minutes with warm air at 100 ° C. to form an electron transport layer on the photoelectric conversion layer.
  • the element on which the electron transport layer was formed was placed in a vacuum deposition apparatus. Then, the element was set so that the shadow mask with a width of 10 mm was orthogonal to the transparent electrode, the pressure inside the vacuum deposition apparatus was reduced to 10 ⁇ 3 Pa or less, and then 100 nm of silver was deposited at a deposition rate of 2 nm / second, A second electrode (cathode) was formed on the electron transport layer.
  • a sealing member As a sealing member, a polyethylene terephthalate (PET) film (12 ⁇ m thickness) is used on a 30 ⁇ m thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.), and an adhesive for dry lamination (two-component reaction type urethane adhesive) is used. Sealing was performed using a dry laminate (adhesive layer thickness 1.5 ⁇ m) using a sheet-like sealant TB1655 manufactured by ThreeBond Co., Ltd.
  • PET polyethylene terephthalate
  • the photoelectric conversion element (solar cell) using each gas barrier film was produced according to the above process.
  • the produced organic photoelectric conversion element is irradiated with light having an intensity of 100 mW / cm 2 using a solar simulator (AM1.5G filter), and a mask having an effective area of 1 cm 2 is overlaid on the light receiving portion to evaluate IV characteristics.
  • a solar simulator AM1.5G filter
  • a mask having an effective area of 1 cm 2 is overlaid on the light receiving portion to evaluate IV characteristics.
  • Tables 1 and 2 below show the composition and evaluation results of each gas barrier film. Note that “immediately” in Tables 1 and 2 indicates that a sample not subjected to accelerated deterioration treatment was evaluated.
  • the gas barrier film produced using the production method of the present invention was compared with the comparative example in the evaluation of the barrier property test, the bending resistance and the smoothness. Good results could be obtained.
  • the electronic device produced using the gas barrier film was able to obtain good results in the evaluation of dark spots (DS, black spots) and photoelectric conversion efficiency compared to the comparative example.
  • the gas barrier layer containing at least silicon atoms and carbon atoms formed by the vapor deposition method 1. Since it contains carbon atoms, the film is flexible, 2. Si—C bond can be cleaved with lower energy than Si—O bond or Si—N bond, and the bond is cleaved with energy of about 250 nm. This is considered to be due to the fact that the film can be modified not only to the surface of the gas barrier layer but also to the inside of the gas barrier layer so as to be a homogeneous film without distortion. Therefore, it is considered that a gas barrier layer in which gas barrier properties and smoothness are hardly lowered even when bent is formed.

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Abstract

L'invention a pour objet de fournir un procédé de production d'un film barrière contre les gaz. Pour ce faire, l'invention concerne un procédé de production d'un film barrière contre les gaz, qui comprend la formation d'une couche barrière contre les gaz contenant au moins un atome de silicium et un atome de carbone sur un matériau de base par une technique de dépôt en phase vapeur, puis l'irradiation de la couche barrière contre les gaz par une lumière ultraviolette ayant une longueur d'onde de moins de 250 nm.
PCT/JP2014/071450 2013-08-30 2014-08-14 Procédé de production de film barrière contre les gaz WO2015029795A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017099239A1 (fr) * 2015-12-11 2017-06-15 コニカミノルタ株式会社 Film de barrière vis-à-vis des gaz et procédé pour sa production
JP2017185789A (ja) * 2016-03-31 2017-10-12 住友化学株式会社 積層フィルム及びその製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012084307A (ja) * 2010-10-08 2012-04-26 Sumitomo Chemical Co Ltd 有機ｅｌ装置
JP2012106421A (ja) * 2010-11-18 2012-06-07 Konica Minolta Holdings Inc ガスバリアフィルムの製造方法、ガスバリアフィルム及び電子機器
JP2012140700A (ja) * 2010-12-15 2012-07-26 Tosoh Corp 炭素含有酸化ケイ素膜、封止膜及びその用途
WO2014142036A1 (fr) * 2013-03-11 2014-09-18 コニカミノルタ株式会社 Film de barrière contre les gaz, procédé de production d'un film de barrière contre les gaz, et élément électroluminescent organique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012084307A (ja) * 2010-10-08 2012-04-26 Sumitomo Chemical Co Ltd 有機ｅｌ装置
JP2012106421A (ja) * 2010-11-18 2012-06-07 Konica Minolta Holdings Inc ガスバリアフィルムの製造方法、ガスバリアフィルム及び電子機器
JP2012140700A (ja) * 2010-12-15 2012-07-26 Tosoh Corp 炭素含有酸化ケイ素膜、封止膜及びその用途
WO2014142036A1 (fr) * 2013-03-11 2014-09-18 コニカミノルタ株式会社 Film de barrière contre les gaz, procédé de production d'un film de barrière contre les gaz, et élément électroluminescent organique

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017099239A1 (fr) * 2015-12-11 2017-06-15 コニカミノルタ株式会社 Film de barrière vis-à-vis des gaz et procédé pour sa production
JPWO2017099239A1 (ja) * 2015-12-11 2018-10-04 コニカミノルタ株式会社 ガスバリア性フィルムおよびその製造方法
JP2017185789A (ja) * 2016-03-31 2017-10-12 住友化学株式会社 積層フィルム及びその製造方法
KR20170113350A (ko) * 2016-03-31 2017-10-12 스미또모 가가꾸 가부시키가이샤 적층 필름 및 그 제조 방법
JP2021151794A (ja) * 2016-03-31 2021-09-30 住友化学株式会社 積層フィルム及びその製造方法
KR102368460B1 (ko) 2016-03-31 2022-02-25 스미또모 가가꾸 가부시키가이샤 적층 필름 및 그 제조 방법
JP7133904B2 (ja) 2016-03-31 2022-09-09 住友化学株式会社 積層フィルム及びその製造方法
JP7261837B2 (ja) 2016-03-31 2023-04-20 住友化学株式会社 積層フィルム及びその製造方法

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