WO2015190572A1 - Stratifié de film de barrière contre les gaz et composant électronique l'utilisant - Google Patents

Stratifié de film de barrière contre les gaz et composant électronique l'utilisant Download PDF

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Publication number
WO2015190572A1
WO2015190572A1 PCT/JP2015/066934 JP2015066934W WO2015190572A1 WO 2015190572 A1 WO2015190572 A1 WO 2015190572A1 JP 2015066934 W JP2015066934 W JP 2015066934W WO 2015190572 A1 WO2015190572 A1 WO 2015190572A1
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gas barrier
film
gas
layer
film laminate
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PCT/JP2015/066934
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English (en)
Japanese (ja)
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國信　隆史
正志 橋本
慧 七里
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Jnc株式会社
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Priority to JP2016527871A priority Critical patent/JPWO2015190572A1/ja
Publication of WO2015190572A1 publication Critical patent/WO2015190572A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • 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 gas barrier film laminate.
  • the present invention relates to a gas barrier film laminate in which water vapor permeation to electronic components can be effectively suppressed, and further, layer peeling is suppressed.
  • an organic electroluminescence element hereinafter also referred to as an OLED element
  • an organic solar cell element hereinafter also referred to as an OPV element
  • a liquid crystal element etc.
  • an inorganic filler is formed on a glass or plastic film having a high barrier property.
  • a gas barrier film laminate in which a mixed / dispersed resin composition film or metal oxide thin film is formed has been used.
  • a gas barrier film laminate composed of multiple layers, there is a problem of adhesion between a plastic film and a resin composition film or a metal oxide thin film.
  • Cited Document 1 discloses “an article including a base material and a barrier layer which is provided on the surface of the base material and has a moisture and oxygen permeation resistance” (paragraph 0007). Further, as an additional layer, It is disclosed to provide an adhesive layer (paragraph 0025, FIG. 1) that enhances the adhesion of the barrier layer to the substrate.
  • a chemical vapor deposition method for example, a plasma chemical vapor deposition method (CVD) is known.
  • CVD plasma chemical vapor deposition method
  • the plasma CVD method has a problem of abrupt compressive stress generated during film formation and curling due to this, and a thin film such as a metal oxide as a gas barrier layer needs to improve its adhesion. .
  • the present invention has been made in view of the above-described problems of the prior art, and improves the adhesion of the gas barrier layer in the formation of a gas barrier layer by a plasma CVD method using an organometallic compound as a raw material, and a sufficient gas barrier. It is an object of the present invention to provide a gas barrier film laminate having properties.
  • the present inventors have been able to form an adhesion layer by changing the composition of the film forming gas during film formation by the plasma CVD method. It has been found that the adhesion of the layer can be improved (hardly peeled off), and the present invention has been completed.
  • the gas barrier film laminate according to the first aspect of the present invention includes, for example, as shown in FIG. 1 (a), a resin film 11 as a base material; and a film formed on at least one side of the resin film 11.
  • “single-sided” refers to stacking on one side with or without contact. “Up” refers to laminating in contact.
  • the “compound containing ⁇ in the composition” may be a compound containing ⁇ in the composition. If comprised in this way, a gas barrier layer can be firmly adhere
  • the thickness of the adhesion layer 13 is 10 to 500 nm. If comprised in this way, a contact
  • the gas barrier film laminate according to the third aspect of the present invention is the gas barrier film laminate according to the first aspect or the second aspect of the present invention, wherein the adhesion layer 13 and the gas barrier layer 14 are continuously formed by a plasma CVD method.
  • the ratio of the reactive gas in the film forming gas when forming the adhesion layer 13 is larger than the ratio of the reactive gas in the film forming gas when forming the gas barrier layer 14.
  • the “film formation gas” refers to a gas used during film formation, such as a source gas, a reactive gas, a carrier gas, and a discharge gas.
  • the “source gas” is a gas that can form a thin film with a single source gas or a thin film with a combination of a source gas and an auxiliary gas.
  • the “reactive gas” is an auxiliary gas that cannot form a thin film such as a gas barrier layer or an adhesion layer by itself, for example, a gas for oxidizing or nitriding a raw material compound. If comprised in this way, the elemental composition of the interface vicinity of an adhesion layer and a gas barrier layer can be changed by changing the film-forming conditions of a plasma CVD method, and the adhesiveness of a gas barrier layer can be improved. Moreover, only the ratio of the reactive gas is changed, and the adhesion layer and the gas barrier layer can be formed efficiently, so that the productivity can be improved and the production cost can be reduced. Furthermore, since the adhesion layer and the gas barrier layer are formed by a plasma CVD method, a dense and flexible film can be formed. Therefore, defects and peeling are less likely to occur compared to other methods, and the gas barrier layer can have high gas barrier properties.
  • the gas barrier film laminate according to the fourth aspect of the present invention is the gas barrier film laminate according to the third aspect of the present invention, wherein the ratio of the reactive gas in the deposition gas during the formation of the adhesion layer 13 is The ratio of the reactive gas in the film-forming gas when forming the gas barrier layer 14 is 1.2 to 4.0 times. If comprised in this way, the contact
  • the gas barrier film laminate according to the fifth aspect of the present invention is the gas barrier film laminate according to any one of the first to fourth aspects of the present invention, wherein the resin film 11 is polyethylene terephthalate, It is a film mainly composed of a resin which is polyethylene naphthalate, cycloolefin polymer, polycarbonate, polyimide, or a mixture thereof.
  • the “main component” means containing 50% by weight or more of the compound. If constituted in this way, these resin films are preferred because of their excellent cost and availability. Moreover, resin according to a use, such as making it transparent, can be selected suitably.
  • the gas barrier film laminate according to the sixth aspect of the present invention is the gas barrier film laminate according to any one of the first to fifth aspects of the present invention, wherein water vapor at 40 ° C. and 90% RH is used.
  • the transmittance is 0.005 g / m 2 / day or less. If comprised in this way, a gas barrier film laminated body can be used for electronic elements, such as an OLED element and OPV element by which high gas barrier property is calculated
  • the gas barrier film laminate according to the seventh aspect of the present invention is the gas barrier film laminate according to any one of the first to sixth aspects of the present invention, for example, as shown in FIG.
  • the organic film layer 12 sandwiched between the resin film 11 and the adhesion layer 13 is provided. If comprised in this way, the unevenness
  • the gas barrier film laminate according to the eighth aspect of the present invention is obtained by photopolymerizing the photocurable resin composition in the gas barrier film laminate according to the seventh aspect of the present invention. Layer. If comprised in this way, since the photocurable resin composition is used, manufacture of an organic film layer becomes easy and production efficiency can be raised.
  • the electronic component according to the ninth aspect of the present invention includes, for example, an electronic element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes, as shown in FIG.
  • the gas barrier film laminate 10 according to any one of the first to eighth aspects of the present invention to be protected is provided. “Protecting from water vapor” is typically performed by enclosing the electronic device, in addition to enclosing the entire electronic device, as well as enclosing the entire device together with other protective bodies. Is also included. When configured in this way, the gas barrier film laminate is excellent in gas barrier properties, so that it is possible to prevent water vapor and oxygen from penetrating into the inside of the electronic element to deteriorate components constituting the electronic element and suppress performance from being deteriorated. it can.
  • the electronic component according to a tenth aspect of the present invention is the electronic component according to the ninth aspect of the present invention, wherein the gas barrier film laminate is transparent, and the electronic element is an OLED element or an OPV element.
  • Transparent means a state in which the gas barrier film laminate transmits visible light and the opposite side of the gas barrier film laminate can be seen through. If comprised in this way, when it uses for an OLED element, since the light emission from an element is not prevented, luminous efficiency is not deteriorated. Moreover, when it uses for a photoelectric element like an OPV element, it can comprise so that sunlight reception may be performed from the gas barrier film laminated body side.
  • the present invention it is possible to improve the adhesion of a gas barrier layer formed by a plasma CVD method and provide a gas barrier film laminate having a sufficient gas barrier property. Furthermore, the gas barrier film laminate can be used to protect electronic elements such as OLED elements and OPV elements from intrusion of water vapor.
  • FIG. 1 is the schematic of the gas barrier film laminated body 10 which concerns on the 1st Embodiment of this invention.
  • FIG. 1B is a schematic view of a gas barrier film laminate 10 ′ according to the second embodiment of the present invention.
  • FIG. 2 is the schematic of the electronic component which has an OLED element by a solid sealing system.
  • FIG. 2B is a schematic view of an electronic component using the gas barrier film laminate 10 of the present invention as an alternative.
  • FIG. 3 is a schematic view of another electronic component using the gas barrier film laminate 10 of the present invention.
  • FIG. 4A is a schematic view of an electronic component having an OLED element with a conventional hollow structure.
  • FIG. 4B is a schematic view of an electronic component using the gas barrier film laminate 10 of the present invention as an alternative.
  • FIG. 5 is a schematic view of a roll-to-roll system.
  • FIG. 6 is an XPS depth profile of the first embodiment.
  • FIG. 7 is an XPS depth profile of the second embodiment.
  • FIG. 8 is an XPS depth profile of Comparative Example 1.
  • FIG. 9 is an XPS depth profile of Comparative Example 2.
  • the gas barrier film laminate 10 includes, as shown in FIG. 1A, for example, a resin film 11 serving as a base material and an adhesion formed on at least one side of the resin film.
  • a layer 13 and a gas barrier layer 14 formed on the adhesion layer 13 are provided.
  • the adhesion layer 13 and the gas barrier layer 14 are preferably continuously formed by a plasma CVD method. By changing the film formation conditions of the plasma CVD method, the composition of elements in the vicinity of the interface between the adhesion layer 13 and the gas barrier layer 14 can be changed, and the adhesion of the gas barrier layer can be improved (hard to peel off).
  • the resin film 11 serving as the base material of the gas barrier film laminate 10 is not particularly limited as long as it is formed of an organic material that can hold each layer laminated on the resin film 11.
  • polyethylene terephthalate PET
  • polybutylene terephthalate polyethylene naphthalate
  • PC polycarbonate
  • PVC polyvinyl chloride
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • nylon Ny
  • cycloolefin polymer aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, acrylic ester polymer, methacrylic ester polymer, polyimide, polyetherimide, etc.
  • Heat-resistant transparent film based on sesquioxane (product name: Sila-DEC, manufactured by JNC Co., Ltd.), resin film made by laminating two or more layers of the above plastic, The composite film of resin-impregnated glass cloth and the like.
  • a film mainly composed of polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polycarbonate, polyimide, or a mixture thereof can be preferably used.
  • the thickness of the resin film is not particularly limited, but is preferably 20 to 500 ⁇ m, more preferably 30 to 300 ⁇ m.
  • the thickness is 20 ⁇ m or more, the rigidity as a base material is not sufficient, and stability does not decrease during film formation on a roll-to-roll basis. Further, when the thickness is 500 ⁇ m or less, it is possible to avoid that the flexibility is lowered and the cost is increased.
  • the resin film is transparent, the gas barrier layer and the like laminated on the resin film are also transparent, so that a transparent gas barrier film laminate can be obtained.
  • a transparent gas barrier film laminate can be used as a substrate such as an OLED element or an OPV element.
  • the adhesion layer 13 and the gas barrier layer 14 included in the gas barrier film laminate 10 illustrated in FIG. 1A are continuously formed by a plasma CVD method.
  • the adhesion layer 13 and the gas barrier layer 14 are films in which the composition ratio of the compound to be contained is changed.
  • the adhesion layer 13 and the gas barrier layer 14 may be films containing an organic component whose main component is a metal oxide. Further, it may be a single film or a composite film. Note that a film mainly containing a metal nitride or a mixture of a metal oxide and a metal nitride may be used instead of the metal oxide.
  • the adhesion layer 13 contains a compound containing SiO x in the composition satisfying 1.8 ⁇ x ⁇ 2.2, or containing a compound containing SiCy in the composition satisfying 0 ⁇ y ⁇ 0.15.
  • the compound containing SiO x on the composition to form a composition of SiO x repeatedly bound elemental Si and O, Similarly SiO x C y, SiO x N y, a composition such as SiO x N y C z Examples of the material to be formed (0 ⁇ y, 0 ⁇ z), a group of molecules such as SiO 2 , or a mixture thereof. The same applies to SiCy.
  • the adhesion layer 13 preferably contains, as a main component, a compound containing SiO x in the composition or a compound containing SiC y in the composition.
  • the gas barrier layer 14 contains a compound containing SiO x C y in the composition that satisfies 1.1 ⁇ x ⁇ 1.9 and 0 ⁇ y ⁇ 0.9.
  • the gas barrier layer 14 preferably contains a compound containing SiO x C y as a main component.
  • the thickness of the adhesion layer is preferably 10 to 500 nm, more preferably 30 to 400 nm, and still more preferably 50 to 250 nm in terms of the SiO 2 equivalent film thickness. When it is 10 nm or more, sufficient adhesion is expressed. When the thickness is 500 nm or less, the gas barrier film laminate can be prevented from becoming too thick.
  • the thickness of the gas barrier layer is preferably 0.2 to 2 ⁇ m in terms of SiO 2 thickness, more preferably 0.3 to 1.5 ⁇ m, and even more preferably 0.4 to 1.0 ⁇ m, resulting in good film thickness uniformity. Excellent gas barrier performance. When the thickness is 2 ⁇ m or less, generation of cracks due to bending can be suppressed.
  • a physical vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a thermochemical vapor deposition method
  • CVD chemical vapor deposition
  • the vacuum deposition method is widely used as a highly productive process, but the gas barrier performance is inferior.
  • a dense film can be formed by sputtering, the film formation rate is low and sufficient productivity cannot be obtained.
  • the film formed by the PVD method is inorganic and brittle, defects and peeling are likely to occur, and high barrier properties cannot be imparted.
  • the plasma CVD method has an advantage in terms of productivity as compared with the sputtering method, and can form a film having good gas barrier performance as compared with the vacuum evaporation method and the sputtering method.
  • the plasma CVD method can be preferably used as a method for forming the adhesion layer and the gas barrier layer. More preferably, a roll-to-roll type plasma CVD method can be used in terms of productivity and quality stability.
  • CVD Chemical Vapor Deposition
  • one or more source gases of a compound containing constituent elements of a thin film material to be manufactured are supplied onto a film formation target (for example, a substrate), and the vapor phase or the surface of the substrate is supplied.
  • a film formation target for example, a substrate
  • the plasma CVD method is a method in which a film forming gas is brought into a plasma state, active radicals and ions are generated, and a chemical reaction is performed in an active environment.
  • the roll-to-roll means that a film-forming target wound in a roll shape is sent out from a sending-out roll 31, and a target substance is formed and printed on the surface, and another roll (winding-up) is again made.
  • This is a production method in which the take-up roll 32) is wound up and collected.
  • the roller 33 is for conveying a film.
  • Japanese Patent Publication No. 2005-504880 includes a pair of film forming rolls that wind and convey a film to be formed, forms a magnetic field across the rolls, and the two film forming rolls are the same.
  • HMDSO hexamethyldisiloxane
  • Japanese Patent No. 2587507 discloses a pair of film forming rolls (metal drums) arranged facing each other in a vacuum chamber, an AC power source in which one and the other electrode are connected to one and the other film forming rolls, respectively.
  • a plasma CVD film forming apparatus having a discharge chamber disposed in an opposing space between film forming rolls and having a surface facing the film forming roll opened, and a monomer (raw material) gas supply means connected to the discharge chamber is described. Has been.
  • a pulse voltage accompanied by alternating current or polarity reversal is applied to the film forming rolls arranged to face each other under reduced pressure, and a facing space (film forming zone) between the film forming rolls arranged opposite to each other.
  • a device for generating a film by plasma CVD on a belt-like base material wound around facing a facing space of a film forming roll As an example, a plasma CVD apparatus (Roll coater W35) manufactured by Kobe Steel, Ltd. can be preferably used.
  • Examples of the metal oxide that is a main component of the adhesion layer and the gas barrier layer include silicon oxide, aluminum oxide, titanium oxide, and zinc oxide.
  • Examples of the metal nitride include silicon nitride, aluminum nitride, titanium nitride, and zinc nitride. In applications where transparency is required for the gas barrier film laminate, silicon oxide is more preferable.
  • the source gas used for forming the adhesion layer and the gas barrier layer is preferably an organometallic compound.
  • an organosilicon compound containing silicon, an organoaluminum compound containing aluminum, or the like can be used.
  • these source gases it is more preferable to use an organosilicon compound from the viewpoints of handling properties of the compound and imparting flexibility and high gas barrier properties to the obtained adhesion layer and gas barrier layer.
  • organosilicon compounds include HMDSO, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethoxysilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyl Examples include triethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, octamethylcyclotetrasiloxane, and hexamethyldisilazane.
  • organosilicon compounds HMDSO, 1,1,3,3-tetramethyldisiloxane, tetraethoxysilane, hexamethyldisilane are used from the viewpoint of characteristics such as handling of the compound and gas barrier properties of the obtained thin film layer. Silazane is particularly preferred. These raw materials such as organosilicon compounds can be used singly or in combination of two or more. Examples of the organoaluminum compound include trimethylaluminum.
  • a reactive gas can be used.
  • the reactive gases e.g., oxygen (O 2), ozone (O 3), nitrogen monoxide (NO), nitrous oxide (N 2 O), nitrogen dioxide (NO 2), hydrogen peroxide (H 2 Oxidizing gas such as O 2 ) and nitride forming gas such as nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), dimethyl hydrazine (N 2 H 2 (CH 3 ) 2 ) Can be used.
  • These reactive gases can be used alone or in combination of two or more.
  • a carrier gas may be used as necessary for supplying the source gas into the vacuum chamber as a film forming gas.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • carrier gas and discharge gas known ones can be used as appropriate, and for example, rare gases such as helium, argon, neon, xenon, and the like can be used.
  • the reactive gas may be used as a discharge gas. Reactive gas and noble gas can be used alone or in combination of two or more.
  • film formation gas gas used for film formation
  • source gas reactive gas
  • carrier gas carrier gas
  • discharge gas discharge gas
  • the adhesion layer is preferably formed with a reactive gas mixture ratio higher than the reactive gas mixture ratio in the film forming gas when forming the gas barrier layer.
  • the mixing ratio of the reactive gas in the film forming gas when forming the adhesion layer is 1.2 to the mixing ratio of the reactive gas in the film forming gas when forming the gas barrier layer. It is preferably 4.0 times. More preferably, it is 1.5 to 3.0 times, and particularly preferably 1.8 to 2.7 times. When the ratio is 1.2 to 4.0 times, an adhesion layer having an appropriate elemental composition for expressing adhesion can be formed.
  • the pressure (degree of vacuum) in the vacuum chamber of the plasma CVD apparatus can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.1 Pa to 50 Pa.
  • the electric power applied for discharging 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 0.2 to 10 kW.
  • the applied power is equal to or higher than the lower limit, the reaction of the source gas is not insufficient and the barrier property is not lowered. As a result, wrinkles are not generated on the film formation target, and irregularities are not generated on the film surface and the appearance is not impaired.
  • the conveyance speed of the film formation target 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 0.1 to 50 m / min, preferably 0.3 to 20 m. / Min is more preferable.
  • the line speed is equal to or higher than the lower limit, wrinkles due to heat tend not to occur in the resin film being conveyed.
  • the line speed is equal to or lower than the upper limit, the thickness of the formed thin film layer does not become too thin.
  • the adhesion layer and the gas barrier layer contain an organic component.
  • an organic component for example, when a thin film is formed by a plasma CVD method from a film forming gas (a mixed gas of HMDSO as a source gas and oxygen gas as an oxidizing gas (also functioning as a discharge gas)) and a gas barrier layer is formed, the following reaction formula is obtained.
  • the formed film contains Cy (a trace amount of carbon component) as an organic component. (CH 3 ) 3 Si—O—Si (CH 3 ) 3 + O 2 ⁇ SiO x C y (1)
  • the adhesion layer and the gas barrier layer are formed by plasma CVD using HMDSO as a source gas and oxygen gas as an oxidizing gas
  • the adhesion layer satisfies a composition satisfying 1.8 ⁇ x ⁇ 2.2. It is preferable to contain a compound containing SiO x or containing a compound containing SiCy in the composition satisfying 0 ⁇ y ⁇ 0.15. More preferably, 1.7 ⁇ x ⁇ 2.1 or 0.02 ⁇ y ⁇ 0.13. An adhesion layer satisfying such a composition ratio is preferable because it exhibits excellent adhesion.
  • Gas barrier layer satisfies 1.1 ⁇ x ⁇ 1.9,0 ⁇ y ⁇ 0.9, preferably contains a compound containing a SiO x C y in the composition. More preferably, 1.3 ⁇ x ⁇ 1.7 and 0 ⁇ y ⁇ 0.7.
  • a gas barrier layer satisfying such a composition ratio is preferable because it exhibits excellent gas barrier properties.
  • FIG. 6 shows an XPS depth profile in which etching is started from the surface of the gas barrier layer of the adhesion layer and the gas barrier layer formed by plasma CVD using HMDSO as the source gas and oxygen gas as the oxidizing gas.
  • the horizontal axis represents the etching time (minutes), and the vertical axis represents the atomic number concentration (%).
  • the adhesion layer contains a compound containing SiO x in which the composition ratio changes within a range of 1.8 ⁇ x ⁇ 2.2, or the composition ratio is 0 ⁇ y ⁇ 0.15. comprising a compound containing SiC y varying in the range.
  • the gas barrier layer contains a compound containing SiO x C y whose composition ratio changes in the range of 1.1 ⁇ x ⁇ 1.9 and 0 ⁇ y ⁇ 0.9.
  • a gas barrier film laminate 10 ′ according to the second embodiment of the present invention is formed on at least one side of a resin film 11 as a substrate and the resin film 11, for example, as shown in FIG.
  • An organic film layer 12 is provided between the contact layer 13 and the contact layer 13.
  • Organic film layer 12 By providing an organic film layer on the gas barrier film laminate, the unevenness of the substrate surface is flattened, and curling of the gas barrier film laminate caused by residual stress generated during the film formation process of the adhesion layer and the gas barrier layer is suppressed. be able to. Therefore, the gas barrier film laminate can exhibit good processability. In addition, since cracks and film peeling due to curling are suppressed, good gas barrier properties can be maintained.
  • the thickness of the organic film layer is preferably 1 to 20 ⁇ m, more preferably 1.2 to 10 ⁇ m, still more preferably 2 to 8 ⁇ m.
  • the thickness is preferably 1 to 20 ⁇ m, more preferably 1.2 to 10 ⁇ m, still more preferably 2 to 8 ⁇ m.
  • the surface roughness of the organic film layer is preferably such that the arithmetic average roughness Sa is 5 nm or less, more preferably 3 nm or less, and even more preferably 2 nm or less.
  • the thickness is set to 5 nm or less, the adhesion layer and the gas barrier layer of the thin film laminated on the organic film layer can be uniformly treated, and the barrier property of the gas barrier film laminate is improved.
  • the organic film layer of the present invention is preferably a film obtained by photopolymerizing a photocurable resin composition.
  • the photocurable resin composition is preferably composed of a composition containing an acrylic resin.
  • the “photocurable resin composition” may be a composition that is photocured as a whole, and the photocurable resin does not necessarily have to be a main component.
  • Examples of the photocurable resin that is a precursor of the organic film layer include acrylic resins that can be cured by light such as ultraviolet irradiation.
  • examples thereof include resins having an unsaturated bond capable of radical polymerization, such as (meth) acrylate monomers, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, and urethane (meth) acrylate resins. .
  • These acrylic resins can be used alone or in admixture of two or more. Among them, polyester (meth) acrylate resin, urethane (meth) acrylate resin, (meth) acrylate monomer and the like alone or a mixture thereof are preferable.
  • an acrylic resin is used, an organic film layer excellent in transparency can be formed. Furthermore, an acrylic resin having photocurability is preferable because it has excellent curl prevention properties due to its hardness.
  • Examples of the (meth) acrylate monomer include compounds obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid.
  • the condensation product (unsaturated polyester) by esterification reaction of a polyhydric alcohol and unsaturated polybasic acid (and saturated polybasic acid as needed) was melt
  • the unsaturated polyester can be produced by polycondensation of an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol.
  • a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, and itaconic acid or its anhydride is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane
  • Polyhydric alcohols such as 1,4-dimethanol, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A are reacted as alcohol components, and phthalic acid, isophthalic acid, terephthalic acid, Such as tetrahydrophthalic acid, adipic acid, sebacic acid Polymerizable not have an unsaturated bond
  • polyester (meth) acrylate resin (1) a terminal carboxyl group polyester obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol contains an ⁇ , ⁇ -unsaturated carboxylic ester group.
  • saturated polybasic acid used as a raw material for polyester (meth) acrylate examples include polybasic compounds having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples thereof include acids or anhydrides thereof and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid and itaconic acid or anhydrides thereof. Further, the polyhydric alcohol component is the same as the unsaturated polyester.
  • the epoxy (meth) acrylate resin includes a polymerizable unsaturated bond formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid.
  • the vinyl ester is produced by a known method, and includes an epoxy (meth) acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid.
  • epoxy resins may be reacted with bisphenol (for example, A type) or dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Kasei Co., Ltd.) to impart flexibility.
  • bisphenol for example, A type
  • dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Kasei Co., Ltd.
  • examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether and its high molecular weight homologues, novolak glycidyl ethers, and the like.
  • urethane (meth) acrylate resin for example, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound are reacted. And a radical-polymerizable unsaturated group-containing oligomer that can be obtained.
  • polyisocyanates include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenyl.
  • Methane triisocyanate Bannock D-750, Crisbon NK (trade name; manufactured by DIC Corporation), Desmodur L (trade name; manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name; Nippon Polyurethane Industry Co., Ltd.) Manufactured), Takenate D102 (trade name; manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonate 143L (trade name; manufactured by Mitsubishi Chemical Corporation), and the like.
  • the polyhydroxy compound include polyester polyol and polyether polyol.
  • glycerin-ethylene oxide adduct examples include oxide adducts.
  • polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-butane.
  • the hydroxyl group-containing (meth) acrylic compound is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable, and specific examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl.
  • (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) An acrylate etc. are mentioned.
  • the photocurable resin composition contains a photopolymerization initiator.
  • a photoinitiator if it is a compound which generate
  • Photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, -Benzyl-2-dimethylamino-1- (4-
  • the amount of the polymerization initiator used in the above addition polymerization is preferably about 0.01 to 10 mol% based on the total number of moles of monomers. These photopolymerization initiators can be used alone or in combination of two or more.
  • a chain transfer agent may be used.
  • the molecular weight can be appropriately controlled by using the chain transfer agent.
  • chain transfer agents include thio- ⁇ -naphthol, thiophenol, butyl mercaptan, ethyl thioglycolate, mercaptoethanol, mercaptoacetic acid, isopropyl mercaptan, t-butyl mercaptan, dodecanethiol, thiomalic acid, pentaerythritol tetra (3 -Mercaptans such as mercaptopropionate) and pentaerythritol tetra (3-mercaptoacetate); disulfides such as diphenyl disulfide, diethyl dithioglycolate and diethyl disulfide; and the like, toluene, methyl isobutyrate, Carbon tetrachloride, isopropylbenzene, dieth
  • Solvents used when preparing a coating solution in which a photocurable resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, ⁇ - or ⁇ - Terpenes such as terpineol, etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glyco
  • a coating solution in which a photocurable resin is dissolved or dispersed in a solvent improves the surface fluidity and leveling properties of the coated coating solution and prevents pinholes and defects in the coating film due to poor wetting and repelling.
  • Surface conditioning agents leveling agents, wettability improvers, surfactants, etc.
  • the surface conditioner include polysiloxane, polyacrylate and wax.
  • an additive such as an antifoaming agent for preventing the generation of bubbles in the coating solution may be used.
  • antifoaming agents include mineral oil compounds and polysiloxane compounds.
  • the method for forming the organic film layer is not particularly limited, but it is preferable to use a wet coating method (coating method) in order to uniformly coat the photocurable resin composition.
  • a wet coating method coating method
  • excellent surface smoothness can be obtained.
  • the coating methods when a small amount is prepared, a spin coating method capable of simple and uniform film formation is preferable. In the case of roll-to-roll, where productivity is important, gravure coating method, die coating method, reverse coating method, roll coating method, slit coating method, dipping method, spray coating method, kiss coating method, reverse kiss coating method, air A knife coating method, a curtain coating method, a rod coating method and the like are preferable.
  • the coating method can be appropriately selected from these methods according to the required film thickness, viscosity, curing conditions, and the like.
  • the applied coating solution can be dried with hot air or the like in an environment of room temperature to about 200 ° C.
  • a photoactive energy beam or an electron beam is irradiated and cured by an active energy beam source.
  • an active energy beam source there is no particular limitation as a photoactive energy ray source, depending on the nature of the photopolymerization initiator used, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, a gas laser, a solid laser, An electron beam irradiation apparatus etc. are mentioned.
  • the drying furnace passage time for drying differs depending on the line speed, the type of coating liquid, the coating thickness, and the apparatus capacity (air volume, area, etc.). For example, 1 to 105 minutes can be mentioned. Similarly, the amount of irradiation for curing varies depending on the material and thickness. For example, when a high-pressure mercury lamp is used, about 200 to 700 mJ / cm 2 can be mentioned.
  • the surface (resin film surface, organic film layer surface, gas barrier layer surface) of the gas barrier film laminate of the present invention may be subjected to surface modification treatment such as corona treatment or plasma treatment for the purpose of improving adhesion.
  • the gas barrier film laminate of the present invention has, for example, an adhesion layer 13 and a gas barrier layer 14 on at least one surface of the resin film 11 (FIG. 1A). Or it has the organic film layer 12, the contact
  • the adhesion layer 13 and the gas barrier layer 14 are in contact with each other. More preferably, the resin film 11 and the organic film layer 12 are in contact with each other.
  • the order of the layers laminated on the resin film is resin film / adhesion layer / gas barrier layer or resin film / organic film layer / adhesion layer / gas barrier layer, and the adhesion layer is provided. It improves the adhesion of the gas barrier layer.
  • the gas barrier layer has a structure in which the gas barrier layer is laminated only on one side of the resin film. It is preferable because the weight can be reduced, the light transmittance can be improved, and the manufacturing process can be simplified.
  • the gas barrier film laminate of the present invention exhibits a high gas barrier property with a water vapor transmission rate (temperature: 40 ⁇ 0.5 ° C., relative humidity: 90 ⁇ 5% RH) of 0.005 g / m 2 / day or less. Unable to express less 0.001g / m 2 / day by optimizing the film forming conditions or the like, an organic film layer, the adhesion layer, by optimizing the thickness of the gas barrier layer, 0.0001 g / m 2 / Day or less is achieved.
  • the gas barrier film laminate of the present invention When used for a photoelectric element, an OLED element, an OPV element or the like, it is preferably composed only of a transparent material.
  • the total light transmittance measured according to the JIS 7105 method is preferably 80% or more, more preferably 85% or more, and particularly preferably 88% or more.
  • an opaque gas barrier film laminate may be produced.
  • the gas barrier film laminate of the present invention suppresses as much as possible the internal stress that tends to curl in the use environment, and exhibits good anti-curl properties. Thereby, after manufacturing the said gas barrier film laminated body, when passing through other processes, such as an assembly process to a device, favorable workability is exhibited. Further, there is no crack or film peeling due to curling, and good gas barrier properties can be maintained.
  • the gas barrier film laminate of the present invention formed by laminating on a PET film having a thickness of 125 ⁇ m is cut into 100 mm ⁇ 100 mm, placed on a surface plate, and fixed using a height measuring instrument such as a ruler.
  • the curl height is preferably 15 mm or less, more preferably 10 mm or less. Especially preferably, it is 5 mm or less.
  • the “curl height” is an average of the heights of the four corners of a square film.
  • the gas barrier film laminate of the present invention can be used for applications that require blocking of various gases such as water vapor and oxygen. Particularly preferably, it can be usefully used for blocking various gases of an electronic element such as an OLED element or an OPV element.
  • a gas barrier film laminated body is transparent, when it uses for a photoelectric element like an OPV element, it can comprise so that sunlight reception may be performed from the gas barrier film laminated body side. Further, when used in an OLED element, light emission from the element is not hindered, so that the light emission efficiency is not deteriorated.
  • FIG. 2A shows a schematic diagram of an electronic component having the OLED element 22 in a solid sealing system.
  • An OLED element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes is disposed on a glass substrate 21, and the OLED element 22 is entirely covered with a solid sealing agent 23.
  • the gas barrier film laminate 10 of the present application can be used in place of the glass substrate 21 as shown in FIG. Or as shown in FIG. 3, it is good also as a sandwich structure which pinched
  • FIG. 4A shows a schematic diagram of an electronic component having an OLED element with a conventional hollow structure.
  • An OLED element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes is disposed on the glass substrate 21 and covered with a glass sealing material 28 that is present at a distance.
  • the glass substrate 21 and the glass sealing material 28 are bonded (sealed) with an adhesive 25 on both sides.
  • a getter 26 such as calcium oxide that adsorbs moisture is disposed inside the hollow, and is filled with N 2 gas 27.
  • the gas barrier film laminate 10 of the present application can be used as an alternative to the glass substrate 21 and the glass sealing material 28. 2 to 4, a gas barrier film laminate 10 ′ may be used in place of the gas barrier film laminate 10.
  • the gas barrier film laminate of the present application can be similarly used as an alternative to a glass substrate.
  • the gas barrier film laminate of the present invention when used as a transparent substrate for OLED elements, OPV elements, liquid crystal elements, etc., it is possible to meet the demands for weight reduction and size increase. Furthermore, roll-to-roll (feeding a substrate such as a resin film wound in a roll shape, processing the target substance on the surface of the substrate, etc., and then winding it up again to collect it In place of glass substrates that are heavy, easy to break, and difficult to increase in area. Can be satisfied.
  • film base materials such as transparent plastics have a problem that gas barrier properties are inferior to glass, but when the gas barrier film laminate of the present invention is used, for example, electronic components such as OLED elements and OPV elements When used as a material, the substrate having excellent gas barrier properties can prevent water (water vapor) or oxygen from permeating and degrading components constituting the device, thereby reducing performance.
  • the present invention mainly includes electronic elements such as organic electroluminescent elements (OLED elements) and display elements typified by liquid crystal elements, photoelectric elements typified by organic solar cell elements (OPV elements), or OLED elements.
  • OLED elements organic electroluminescent elements
  • It is a gas barrier film laminate that can be used for products such as lighting.
  • the gas barrier film laminate of the present invention is characterized by excellent gas barrier layer adhesion, good productivity, low curl, and good gas barrier properties.
  • the produced gas barrier film laminate was cut into a 10 cm square, attached to a stainless steel frame, stored at a temperature of 85 ° C. and a humidity of 85%, and the time until the gas barrier layer was peeled off (adhesion) was measured.
  • the method for measuring the water vapor transmission rate is not particularly limited, but metallic calcium is vapor-deposited on one side of the gas barrier film laminate, Ca is sealed with Al and wax, and the metallic Ca is corroded by moisture that has passed through the film. A method using the phenomenon was used. The water vapor transmission rate is calculated from the corrosion area and the time to reach the corrosion area. In the present invention, the evaluation was performed by the method described in Japanese Patent No. 3958235 and the following conditions.
  • Vapor deposition apparatus manufactured by Sanyu Electronics Co., Ltd., electron beam vacuum deposition apparatus SVC-700LEB Constant temperature and humidity chamber: Espec Co., Ltd., constant temperature and humidity chamber LHL-113 Metal that reacts with water and corrodes: Calcium (granular) Water vapor impermeable metal for Ca sealing: Aluminum ( ⁇ 3-5mm, granular) Sealing material: mixture of paraffin (melting point 60-62 ° C) / beeswax (melting point 61-65 ° C) in a weight ratio of 1: 1 Observation device: Calcium corrosion observation device MFB-1000 manufactured by Mitsuwa Frontec Co., Ltd.
  • XPS X-ray photoelectron spectroscopy
  • Example 1 ⁇ Base material As a base material, a polyethylene terephthalate (PET) film (trade name “Cosmo Shine A4300” manufactured by Toyobo Co., Ltd.) wound in a roll shape with a thickness of 125 ⁇ m and a width of 550 mm, which is easily bonded on both sides. Using.
  • PET polyethylene terephthalate
  • the coating solution is applied on the substrate so that the average film thickness after drying is 5 ⁇ m, and then the temperature is 85 ° C and the air volume is Drying was performed at 20 m / second and a residence time in the drying furnace of 50 seconds. Thereafter, photocuring was performed at a dose of 300 mJ / cm 2 using a high-pressure mercury lamp in a nitrogen atmosphere to form an organic film layer.
  • the adhesion layer was produced under the following conditions.
  • Source gas HMDSO (manufactured by AZMAX Co., Ltd., trade name “SIH6115.0”)
  • Supply amount 50sccm
  • Oxidizing gas Oxygen gas (manufactured by Suzuki Shokan Co., Ltd., high-purity oxygen, purity ⁇ 99.999%)
  • Supply amount 1000sccm
  • Pressure 3Pa Plasma power 1.3 kW
  • -Gas barrier layer deposition A gas barrier layer was deposited under the same plasma deposition apparatus and deposition conditions as those for the adhesion layer except that oxygen gas was changed to 500 SCCM under the deposition conditions in the plasma CVD method.
  • the laminated gas barrier layer has a SiO 2 equivalent film thickness of 560 nm.
  • the total SEM film thickness of the adhesion layer and the gas barrier layer is 861 nm.
  • PEN Polyethylene naphthalate
  • the laminated gas barrier layer has a SiO 2 equivalent film thickness of 590 nm.
  • the total SEM film thickness of the adhesion layer and the gas barrier layer is 946 nm.
  • the photocurable resin composition was prepared in the same manner as in the preparation of the coating solution, the organic film layer, and the gas barrier layer.
  • a base material a polyethylene terephthalate (PET) film (trade name “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) wound in a roll shape with a thickness of 125 ⁇ m and a width of 550 mm that is easily bonded on one side. Using.
  • PET polyethylene terephthalate
  • a gas barrier layer was formed under film conditions.
  • the laminated gas barrier layer has a SiO 2 equivalent film thickness of 690 nm.
  • the SEM film thickness is 926 nm.
  • the adhesion layer was not present, and the film thickness of the gas barrier layer was 690 nm in terms of SiO 2 , and the SEM film thickness was 926 nm.
  • Preparation of the coating solution of the photocurable resin composition and film formation of the organic film layer were produced in the same manner as in Example 1.
  • FIG. 6 shows an XPS depth profile of the first embodiment.
  • the etching time of 0 to about 28 minutes indicates the atomic number concentration of the gas barrier layer, and about 28 minutes to about 35 minutes indicates the atomic number concentration of the adhesion layer. After about 35 minutes, the atomic number concentration of the organic film layer is obtained.
  • FIG. 7 shows an XPS depth profile of the second embodiment. When the etching time is from 0 to about 26 minutes, the atomic number concentration of the gas barrier layer is shown, and from about 26 minutes to about 32 minutes, the atomic number concentration of the adhesion layer is shown. After about 32 minutes, the concentration is the number of atoms in the organic film layer.
  • FIG. 8 shows an XPS depth profile of Comparative Example 1.
  • the etching time from 0 to about 35 minutes is the atomic concentration of the gas barrier layer, and after about 35 minutes is the atomic concentration of the organic film layer.
  • FIG. 9 shows an XPS depth profile of Comparative Example 2. The etching time from 0 to about 45 minutes is the atomic concentration of the gas barrier layer, and after about 45 minutes is the atomic concentration of the organic film layer.
  • the present invention mainly relates to a gas barrier film laminate used for an electronic component having an electronic element such as an OLED element, an OPV element, or a liquid crystal element, and an electronic component including the gas barrier film laminate.

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Abstract

　La présente invention vise à obtenir un stratifié de film de barrière contre les gaz comportant un film de barrière contre les gaz ayant des propriétés de barrière contre les gaz satisfaisantes, avec lequel la cohésion de la couche de barrière contre les gaz peut être améliorée pendant la formation de la couche de barrière contre les gaz par un processus de déposition en phase vapeur par procédé chimique sous plasma. À cet effet, l'invention porte sur un stratifié de film de barrière contre les gaz, lequel stratifié comporte : un film de résine (11) jouant le rôle de matériau de base ; une couche de cohésion (13) formée sur au moins un côté de surface du film de résine (11), la couche de cohésion (13) contenant un composé dont la composition comprend du SiOx, et qui satisfait à l'expression 1,8 < x < 2,2, ou une couche de cohésion (13) contenant un composé dont la composition comprend du SiCy, et qui satisfait à l'expression 0 < y < 0,15 ; et une couche de barrière contre les gaz (14) formée sur la couche de cohésion (13), la couche de barrière contre les gaz (14) contenant un composé dont la composition comprend du SiOxCy, et qui satisfait aux expressions 1,1 ≦ x ≦ 1,9 and 0 ≦ y ≦ 1,9.
PCT/JP2015/066934 2014-06-13 2015-06-11 Stratifié de film de barrière contre les gaz et composant électronique l'utilisant WO2015190572A1 (fr)

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WO2018138823A1 (fr) * 2017-01-26 2018-08-02 シャープ株式会社 Panneau à oled, procédé de fabrication d'un panneau à oled, et dispositif de fabrication de panneau à oled
CN109154081A (zh) * 2016-09-06 2019-01-04 株式会社丽光 透明高屏蔽膜、以及使用了它的高屏蔽层叠体
WO2023181489A1 (fr) * 2022-03-25 2023-09-28 富士フイルム株式会社 Stratifié et procédé de production de stratifié

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WO2010093041A1 (fr) * 2009-02-16 2010-08-19 三菱樹脂株式会社 Procédé de production d'une feuille multicouche formant barrière contre les gaz
JP2012193449A (ja) * 2011-03-01 2012-10-11 Toppan Printing Co Ltd ガスバリア性フィルムおよびその製造方法ならびにその製造装置
WO2013011872A1 (fr) * 2011-07-15 2013-01-24 コニカミノルタホールディングス株式会社 Film de barrière aux gaz et procédé de fabrication de celui-ci

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JP2005290560A (ja) * 2004-04-05 2005-10-20 Schott Ag 改善された耐薬品性を有する複合材料
WO2010093041A1 (fr) * 2009-02-16 2010-08-19 三菱樹脂株式会社 Procédé de production d'une feuille multicouche formant barrière contre les gaz
JP2012193449A (ja) * 2011-03-01 2012-10-11 Toppan Printing Co Ltd ガスバリア性フィルムおよびその製造方法ならびにその製造装置
WO2013011872A1 (fr) * 2011-07-15 2013-01-24 コニカミノルタホールディングス株式会社 Film de barrière aux gaz et procédé de fabrication de celui-ci

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Publication number Priority date Publication date Assignee Title
CN109154081A (zh) * 2016-09-06 2019-01-04 株式会社丽光 透明高屏蔽膜、以及使用了它的高屏蔽层叠体
CN109154081B (zh) * 2016-09-06 2020-12-08 株式会社丽光 透明高屏蔽膜、以及使用了它的高屏蔽层叠体
WO2018138823A1 (fr) * 2017-01-26 2018-08-02 シャープ株式会社 Panneau à oled, procédé de fabrication d'un panneau à oled, et dispositif de fabrication de panneau à oled
CN110226361A (zh) * 2017-01-26 2019-09-10 夏普株式会社 Oled面板、oled面板的制造方法、oled面板的制造装置
WO2023181489A1 (fr) * 2022-03-25 2023-09-28 富士フイルム株式会社 Stratifié et procédé de production de stratifié

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