WO2016132901A1 - Film barrière au gaz et son procédé de fabrication - Google Patents

Film barrière au gaz et son procédé de fabrication Download PDF

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Publication number
WO2016132901A1
WO2016132901A1 PCT/JP2016/053164 JP2016053164W WO2016132901A1 WO 2016132901 A1 WO2016132901 A1 WO 2016132901A1 JP 2016053164 W JP2016053164 W JP 2016053164W WO 2016132901 A1 WO2016132901 A1 WO 2016132901A1
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Prior art keywords
gas barrier
gas
barrier layer
oxygen
film
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PCT/JP2016/053164
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English (en)
Japanese (ja)
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千明 門馬
大石　清
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コニカミノルタ株式会社
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Priority to JP2017500591A priority Critical patent/JPWO2016132901A1/ja
Publication of WO2016132901A1 publication Critical patent/WO2016132901A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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

Definitions

  • the present invention relates to a gas barrier film and a manufacturing method thereof. Specifically, the present invention provides a gas barrier film having a gas barrier layer having a specific oxygen distribution profile, high quality, and suppressed variation in performance, and a full length when continuously formed in a long length. -It is related with the manufacturing method of the gas barrier film which can obtain the stable performance over the whole width.
  • gas barrier films produced by laminating a plurality of gas barrier layers including thin films of metal oxides such as aluminum oxide, magnesium oxide and silicon oxide on the surface of plastic substrates and films are made of various gases such as water vapor and oxygen. It is widely used for packaging materials for preventing deterioration of packaging materials for articles that need to be blocked, such as foods, industrial products, and pharmaceuticals.
  • gas barrier films are required to be developed into flexible electronic devices such as solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, and other flexible electronic devices. Is being studied. However, in these flexible electronic devices, since a very high gas barrier property at the glass substrate level is required, a gas barrier film having sufficient performance has not been obtained yet.
  • a method for forming a gas barrier layer for example, an organic silicon compound typified by hexamethyldidioxane (hereinafter abbreviated as HMDSO) is used, and oxygen plasma is used under reduced pressure.
  • Chemical vapor deposition (CVD: Chemical Vapor Deposition), which forms a gas barrier layer on the substrate while being oxidized by oxygen, or vaporizes metal Si using a semiconductor laser and deposits it on the substrate in the presence of oxygen.
  • a vapor phase growth method such as a physical vapor deposition method (PVD method: Physical Vapor Deposition, for example, vacuum deposition method or sputtering method) for forming a gas barrier layer is known.
  • PVD method Physical Vapor Deposition, for example, vacuum deposition method or sputtering method
  • Patent Document 1 discloses a gas barrier laminate film containing silicon, oxygen and carbon using a plasma CVD apparatus.
  • the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the thickness direction of the gas barrier layer (the atomic ratio of silicon), the ratio of the amount of oxygen atoms
  • Gas barrier laminate film with improved gas barrier properties and flex resistance which is a method in which the relationship between (oxygen atomic ratio) and carbon atom quantity ratio (carbon atomic ratio) is specified under specific conditions Is supposed to be obtained.
  • Patent Document 2 in a gas barrier film having a gas barrier layer containing at least silicon and oxygen, the maximum value of the oxygen distribution curve closest to the surface of the gas barrier layer on the substrate side is the total value of the gas barrier layer.
  • a gas barrier film having a maximum value among the maximum values is disclosed.
  • the present invention has been made in view of the above problems and circumstances, and the solution to the problem is a gas barrier film having excellent gas barrier properties and bending resistance, and excellent uniformity in gas barrier properties, and performance stability during production. It is providing the manufacturing method of the gas barrier film excellent in the.
  • the present inventor is excellent in the gas barrier film that controls the distribution state of oxygen atoms in the layer thickness direction in the gas barrier layer to a specific state in the process of examining the cause of the above problems, etc. It has been found that the gas barrier property difference between the gas barrier film at the beginning and the tail of the gas barrier film can be reduced when continuously manufactured and has gas barrier properties and bending resistance.
  • a gas barrier film having a gas barrier layer containing a carbon atom, a silicon atom, and an oxygen atom on at least one surface of a base material, the composition of which changes continuously in the layer thickness direction,
  • the maximum maximum value of the oxygen distribution curve closest to the substrate surface side of the gas barrier layer is A (at%) and the minimum minimum value in the layer thickness direction of the gas barrier layer is B (at%)
  • the oxygen atom ratio difference (AB) between A (at%) and B (at%) is in the range of 20 to 50 (at%)
  • the maximum maximum value A of the oxygen distribution curve closest to the substrate surface side of the gas barrier layer is the maximum value among the maximum values of the oxygen distribution curve in the entire layer thickness direction of the gas barrier layer.
  • the position of the substrate surface side interface of the gas barrier layer is C (nm), and is the same as the oxygen atomic ratio at the position C through the maximum value A in the thickness direction.
  • the position where the oxygen atom ratio value of the quantity appears again is D (nm)
  • the distance (CD) between the position C (nm) and the position D (nm) is within the range of 25 to 55 (nm).
  • Item 4 The gas barrier film according to any one of Items 1 to 3, wherein the maximum maximum value A of the oxygen atomic ratio is in a range of 55 to 80 (at%).
  • a method for producing a gas barrier film which produces the gas barrier film according to any one of items 1 to 4,
  • a gas barrier layer is formed in at least one film forming chamber having a discharge plasma chemical vapor deposition apparatus having a discharge space between rollers to which a magnetic field is applied, using a source gas containing an organosilicon compound and an oxygen gas,
  • a gas barrier characterized by forming a mixed flow rate ratio of gas and oxygen gas (flow rate of oxygen gas (ml / min) / flow rate of source gas (ml / min)) within a range of 4.0 to 43.0
  • a method for producing a film
  • gas barrier layer deposition chambers equipped with a discharge plasma chemical vapor deposition apparatus having a discharge space between the rollers to which the magnetic field is applied, and in the first deposition chamber, the source gas and oxygen A part of the gas barrier layer is formed under the condition of a gas mixing flow rate ratio (oxygen gas flow rate (ml / min) / source gas flow rate (ml / min)) in the range of 4.0 to 43.0.
  • a gas mixing flow rate ratio oxygen gas flow rate (ml / min) / source gas flow rate (ml / min)
  • a gas barrier film having excellent gas barrier properties and bending resistance, and excellent uniformity of gas barrier properties, and a method for producing a gas barrier film having excellent performance stability during production Can be provided.
  • the gas barrier layer constituting the gas barrier film of the present invention is composed of at least carbon atoms, silicon atoms and oxygen atoms, and in the layer thickness direction of the gas barrier layer, its lower surface side, for example, an interface with a substrate or clear hard Designed to form the maximum value with the highest oxygen atomic ratio in the interface region with the coat layer, and the oxygen content difference between the maximum value and the minimum value to be a large value of 20 to 50 (at%) It is characterized by being.
  • the gas barrier layer is set so that the oxygen atom content is relatively maximized in the interface region with the substrate or the clear hard coat layer, that is, the SiO 2 content is increased in the interface region.
  • the SiO 2 content is increased in the interface region.
  • a region having a high SiO 2 content ratio is formed in the interface region with the base material or the clear hard coat layer, and after ensuring a desired gas barrier property, on the upper surface side thereof.
  • a region mainly composed of SiOC stress relaxation can be efficiently performed, and a gas barrier layer having excellent bending resistance can be obtained.
  • the formation of SiOC-based films suppresses steep composition fluctuations during film formation.
  • the gas barrier film of the present invention comprises a gas barrier layer containing carbon atoms, silicon atoms and oxygen atoms on at least one surface of a base material, and the film composition (each atomic composition) continuously changes in the layer thickness direction.
  • a gas barrier film having a maximum value of an oxygen distribution curve closest to the substrate surface side of the gas barrier layer in an oxygen distribution curve in the depth direction by X-ray photoelectron spectroscopy of the gas barrier layer is A (at %)
  • the minimum extreme value (minimum value) in the thickness direction of the gas barrier layer is B (at%)
  • the oxygen atomic ratio difference between A (at%) and B (at%) ( AB) is in the range of 20 to 50 (at%)
  • the maximum value A of the oxygen distribution curve closest to the substrate surface side of the gas barrier layer is the oxygen distribution curve in the gas barrier layer. That it is the maximum of the maximum values.
  • butterflies This feature is a technical feature common to the inventions according to claims 1 to 7.
  • the peak having the maximum maximum value A in the oxygen distribution curve starts from the outermost surface of the gas barrier layer, and the gas barrier
  • the position of the substrate surface side interface of the layer is C (nm)
  • the position where the oxygen atom ratio value of the same amount as the oxygen atom ratio at the position C appears again through the maximum value A in the thickness direction is D.
  • the distance (C ⁇ D) between the position C (nm) and the position D (nm) is within the range specified above, that is, the base material of the gas barrier layer or the clear hard coat layer
  • CD layer thickness
  • the provision of a clear hard coat layer between the base material and the gas barrier layer prevents a decrease in bending resistance due to a difference in elastic modulus between the base material and the gas barrier layer due to the stress relaxation effect.
  • the adhesion between the material and the gas barrier layer can be improved, and the smoothness of the gas barrier layer due to foreign matters on the base material can be prevented from being lowered or the gas barrier property can be prevented from being lowered due to the occurrence of a short path.
  • the maximum value A of the oxygen atom ratio that appears first is in the range of 55 to 80 (at%), more excellent gas barrier properties, bending resistance, and film quality homogeneity can be obtained. It is preferable from the viewpoint.
  • a gas barrier layer is formed using at least one film forming chamber equipped with a discharge plasma chemical vapor deposition apparatus having a discharge space between rollers to which a magnetic field is applied, and organically.
  • a raw material gas containing silicon compound and oxygen gas are used, and a mixing flow rate ratio of the raw material gas and oxygen gas (flow rate of oxygen gas (ml / min) / flow rate of raw material gas (ml / min)) is 4.0 to 43. It is characterized by being formed within a condition range of 0.
  • the flow rate here can also be expressed as sccm, which is an abbreviation for Standard Cubic Centimeter per Minute (0 ° C, 1 atm standard), expressed as cc (ml) / min, and represents the flow rate per minute (ml). Show.
  • a gas barrier film having a desired oxygen atom distribution curve can be stably produced without variations in film quality during the manufacturing process (for example, the beginning and the end). can do.
  • the gas barrier layer is formed by a roll-to-roll method while conveying a long base material, or there are two or more gas barrier layer deposition chambers equipped with a discharge plasma chemical vapor deposition apparatus. Then, in the first film formation chamber, the mixing flow rate ratio of the source gas and oxygen gas (flow rate of oxygen gas (ml / min) / flow rate of source gas (ml / min)) is 4.0 to 43.0. It is preferable to form a part of the gas barrier layer under the conditions within the above range from the viewpoint of more stably producing a gas barrier film having a precisely controlled oxygen atom distribution curve.
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • the “gas barrier property” referred to in the present invention is a water vapor permeability (abbreviation: WVTR, temperature: 60 ⁇ 0.5 ° C., relative humidity (RH)) measured by a method according to JIS K 7129-1992. 90 ⁇ 2%) is 1 ⁇ 10 ⁇ 1 g / (m 2 ⁇ 24 h) or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 ⁇ 10 ⁇ 1 ml / (m 2 24h ⁇ atm) or less.
  • WVTR water vapor permeability
  • RH relative humidity
  • the gas barrier film of the present invention has a gas barrier layer containing carbon atoms, silicon atoms, and oxygen atoms on at least one surface of the base material, and the film composition continuously changes in the layer thickness direction. Furthermore, a more preferable aspect is a structure which has a clear hard-coat layer between a base material and a gas barrier layer.
  • FIG. 1A and FIG. 1B are schematic cross-sectional views showing an example of the basic configuration of the gas barrier film of the present invention.
  • the gas barrier film (1) shown in FIG. 1A contains carbon atoms, silicon atoms and oxygen atoms on a base material (2), for example, a transparent resin base material, and the film composition continuously changes in the layer thickness direction.
  • the gas barrier layer (3) according to the present invention is formed.
  • the gas barrier film (1) shown in FIG. 1B is composed of, for example, an ultraviolet curable resin between the base material (2) and the gas barrier layer (3), and the gas barrier layer has smoothness and adhesion. It is the structure which provided the clear hard-coat layer (4, hereafter may be abbreviated as CHC layer) for the purpose of improving.
  • CHC layer clear hard-coat layer
  • the maximum value of the oxygen distribution curve closest to the substrate surface side is A (at%)
  • the minimum extreme value (minimum value) in the layer thickness direction of the barrier layer is B (at%)
  • the oxygen atomic ratio difference (AB) between the A (at%) and B (at%) is as follows: It is characterized in that it has an oxygen distribution curve in the range of 20 to 50 (at%) and the maximum value A is the maximum value among the maximum values of the oxygen distribution curve in the gas barrier layer.
  • the element distribution curve referred to in the present invention is a graph in which the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer is indicated on the horizontal axis and the atomic ratio (at%) is indicated on the vertical axis.
  • the total amount of carbon atoms, silicon atoms and oxygen atoms is 100 (at%)
  • the ratio of the amount of oxygen atoms to the total amount is “oxygen atom ratio (at%)”
  • the ratio of the amount of silicon atoms Is referred to as “silicon atom ratio (at%)”
  • carbon atom ratio (at%) the ratio of the amount of carbon atoms
  • total amount of oxygen atoms, silicon atoms and carbon atoms means the total number of silicon atoms, oxygen atoms and carbon atoms, and “amount of silicon atoms”, “amount of oxygen atoms”, and “ “Amount of carbon atoms” means the number of silicon atoms, the number of oxygen atoms, and the number of carbon atoms, respectively.
  • the unit is displayed as “at% (atomic%)”.
  • the maximum maximum value of the oxygen atom ratio closest to the substrate surface side is A (at%)
  • the gas barrier layer When the minimum value of the oxygen atomic ratio in the layer thickness direction is B (at%), the oxygen atomic ratio difference (AB) between A (at%) and B (at%) is 20 to 50
  • the maximum value A of the oxygen atom ratio in the oxygen distribution curve closest to the substrate surface side of the gas barrier layer within the range of (at%) is the maximum among the maximum values of the oxygen atom ratio in the gas barrier layer. It is a value.
  • the maximum value of the oxygen atomic ratio as used in the present invention is a point where the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the gas barrier layer is changed.
  • the minimum value of is that the value of the oxygen atomic ratio changes from decreasing to increasing when the distance from the surface of the gas barrier layer is changed.
  • the oxygen distribution curve, carbon distribution curve, and silicon distribution curve in the thickness direction of the gas barrier layer according to the present invention are measured by X-ray photoelectron spectroscopy (XPS: Xray Photoelectron Spectroscopy) and rare gas ion sputtering such as argon. By using together, it can produce by what is called XPS depth profile measurement which performs a surface composition analysis, exposing the gas barrier layer surface which comprises a gas barrier film one by one.
  • XPS X-ray photoelectron spectroscopy
  • rare gas ion sputtering such as argon
  • a distribution curve obtained by such XPS depth profile measurement is created, for example, with the vertical axis representing the atomic ratio (unit: at%) of each element (O, C, Si) and the horizontal axis representing the etching time (sputtering time). can do.
  • the etching time generally correlates with the distance from the gas barrier layer surface in the layer thickness direction of the gas barrier layer in the layer thickness direction. “Distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer” is adopted as the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. can do.
  • etching rate is 0.05 nm / It is preferable to set to sec (SiO 2 thermal oxide film conversion value).
  • the average carbon atom ratio (at%) in each region is a value obtained by etching values in the depth direction by XPS depth profile measurement and averaging values measured at 5 nm intervals as the layer thickness.
  • the XPS depth profile measurement is performed on the formed gas barrier layer under the following conditions to obtain a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 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 ⁇ m ⁇ 400 ⁇ m ellipse
  • the gas barrier layer is formed in the film surface direction (gas direction) from the viewpoint of forming a gas barrier layer having a uniform composition throughout the film surface direction and having excellent gas barrier properties.
  • each elemental composition is substantially uniform.
  • the gas barrier layer in the film surface direction and the elemental composition are substantially uniform means that the carbon distribution curve and silicon distribution at any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement.
  • FIG. 2 shows an example of an oxygen atom distribution curve in the layer thickness direction according to the XPS depth profile in the gas barrier film (1) in which the gas barrier layer (3) is formed on the substrate (2) exemplified in FIG. 1A. Is.
  • a block (a) shown in FIG. 2 shows a part of the gas barrier layer (3) and the base material (2) in the same configuration as in FIG. 1A, and the block (b) shown in FIG. ) Shows an oxygen atom distribution curve corresponding to the thickness direction of the gas barrier layer (3).
  • oxygen atom distribution curve shown in the block (b) of FIG. 2 X-ray photoelectron spectroscopy measurement and rare gas ions such as argon are obtained from the surface of the gas barrier layer (3) (indicated as “S”, distance 0 nm). While performing sputtering and sequentially etching, for example, the oxygen atomic ratio is changed between the lowermost layer of the gas barrier layer (3) and the interface with the surface of the base material (2) (indicated as “I”, distance of about 138 nm). Measured and created oxygen atom distribution curve.
  • a (at%) is obtained as the maximum value of the oxygen distribution curve closest to the surface of the gas barrier layer (3) on the substrate (2) side, that is, the interface (I). Further, the minimum extreme value (minimum value) B (at%) in all the gas barrier layers (3) (layer thickness range of 0 to 138 nm) is obtained, and AB (at%) is calculated. In the present invention, this AB (at%) is in the range of 20 to 50 (at%), and the maximum value A is the maximum value among the maximum values in the oxygen atom distribution curve. To do.
  • FIG. 3 is a graph showing another example of the oxygen atom distribution curve in the gas barrier layer.
  • the block (a) in FIG. 3 is similar to that described in FIG. 1B, and the gas barrier layer (3) and In a configuration in which a clear hard coat layer (4) is provided between the substrates (2), the block (b) in FIG. 3 shows an oxygen atom distribution curve corresponding to the layer thickness direction of the gas barrier layer (3). It is. The details of the oxygen atom distribution curve are the same as those described in the block (b) of FIG.
  • the oxygen atomic ratio difference (AB) is 20 (at%) or more, the ratio is sufficient as SiO 2.
  • the oxygen atomic ratio difference (AB) is 50 (at%) or less, the difference in oxygen content with other regions does not become excessively large, so a rapid film quality change (for example, elastic modulus, etc.) Since it can be suppressed and film surface breakage due to stress concentration or the like can be prevented, both gas barrier properties and bending resistance can be achieved.
  • the maximum value A is preferably in the range of 55 to 80 (at%) as the number of oxygen atoms (at%). If the maximum value A is 55 (at%) or more, it is preferable from the viewpoint of expressing sufficient gas barrier properties in the vicinity of the base material, which is the target effect of the present invention. Since the difference in oxygen content from the region does not become excessively large, rapid film quality changes (for example, elastic modulus, etc.) can be suppressed, and film surface destruction due to stress concentration etc. can be prevented, achieving both gas barrier properties and bending resistance be able to.
  • the interface (I) is the position C (total thickness of the gas barrier layer: about 138 nm), the oxygen atom ratio at the position C is directed to the surface (S) direction of the oxygen atom distribution curve.
  • the layer thickness position when the value (at%) reappears exceeding the maximum maximum value A is defined as the position D (nm)
  • the distance between the position C (nm) and the position D (nm) (C In a preferred embodiment, -D) is in the range of 25 to 55 (nm).
  • the distance (CD) is 25 (nm) or more, the gas barrier property due to SiO 2 can be sufficiently imparted, and if it is 55 (nm) or less, the SiO 2 rich of relatively low flexibility. Without excessively thickening the region, it is possible to prevent film surface breakage and the like and maintain excellent gas barrier properties.
  • the oxygen atom distribution in the gas barrier layer according to the present invention is designed so that the maximum value of the oxygen content appears on the interface side (S) with the substrate. That is, by providing a region having a high SiO 2 content with a certain layer thickness on the substrate side, penetration of moisture and the like from the substrate surface side can be effectively prevented, and the surface (S From this point, by adopting a SiOC rich design, excellent bending resistance can be achieved due to the improvement in flexibility as a film and the stress relaxation effect. Details of specific achievement means will be described later.
  • the thickness of the gas barrier layer according to the present invention is preferably in the range of 5 to 800 nm, more preferably in the range of 10 to 600 nm, and still more preferably in the range of 50 to 400 nm. A range of 100 to 300 nm is particularly preferable.
  • the interface referred to in the present invention is a boundary surface generated between two layers (solid phase), and the interface (S) between the gas barrier layer (3) and the substrate (2) according to the present invention.
  • the interface between the gas barrier layer (3) and the clear hard coat layer (4) is a region where the distribution curve of the elements constituting each layer is obtained, and the composition ratio of the main components constituting each layer changes abruptly (Surface), a region (surface) where the density changes rapidly, or a region where the density of the image changes abruptly in the image of the cross section when the cross section is observed with an electron microscope An area where the image pattern or image quality changes.
  • the layer thickness of a gas barrier layer can be confirmed by calculating
  • a transmission electron microscope Transmission Electron Microscope: TEM
  • TEM Transmission Electron Microscope
  • ⁇ TEM image of cross section in layer thickness direction> As a cross-sectional TEM observation, the observation sample was subjected to TEM observation after a thin piece was prepared by the following focused ion beam (FIB) processing apparatus.
  • FIB focused ion beam
  • the gas barrier film of the present invention has a gas barrier layer containing a carbon atom, a silicon atom and an oxygen atom and having the oxygen atom distribution described above on at least one surface of a substrate.
  • the gas barrier layer forming method according to the present invention is not particularly limited as long as it is a thin film forming method capable of realizing the oxygen atom distribution profile defined in the present invention, but the gas barrier layer in which element distribution is precisely controlled. From the viewpoint that can be formed, a discharge plasma chemical vapor deposition apparatus having a discharge space between rollers to which a magnetic field is applied using a source gas containing an organosilicon compound and an oxygen gas is defined in the present invention.
  • the oxygen atomic ratio difference (AB) between the maximum maximum value A (at%) and the minimum maximum value B (at%) is set within a range of 20 to 50 (at%), and the position
  • the distance (C ⁇ D) between C (nm) and position D (nm) is set within the range of 25 to 55 (nm)
  • flexibility flexibility, bending resistance
  • mechanical strength mechanical strength
  • manufacturing uniformity it is possible to form the gas barrier layer to achieve both gas barrier performance.
  • the gas barrier layer according to the present invention uses an inter-roller discharge plasma processing apparatus to which a magnetic field is applied, wraps a resin substrate between a pair of film forming rollers, and supplies a film forming gas between the pair of film forming rollers.
  • it can be formed by a plasma chemical vapor deposition apparatus in which plasma discharge is performed to form a thin film on the resin substrate.
  • plasma chemical vapor deposition apparatus in which plasma discharge is performed to form a thin film on the resin substrate.
  • the gas barrier layer is preferably a layer formed by a continuous film forming process.
  • the gas barrier film of the present invention is formed by forming a gas barrier layer on the surface of a base material (a clear hard coat layer may be provided as necessary) using an inter-roller discharge plasma processing apparatus to which a magnetic field is applied. To manufacture.
  • plasma CVD method in which a gas barrier layer is formed while supplying a film forming gas between rollers to which a magnetic field is applied according to the present invention
  • plasma is used. It is preferable to generate a plasma discharge in the formed discharge space while applying a magnetic field between the plurality of film forming rollers.
  • a pair of film forming rollers is used, and the pair of film forming rollers
  • a base material for example, a resin base material is wound around each of these, and plasma is generated by discharging in a state where a magnetic field is applied between the pair of film forming rollers.
  • the gas barrier film of the present invention preferably has a gas barrier layer formed on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity.
  • a film forming roller having at least a pair of magnetic field applying apparatuses and a plasma power source are provided. And it is the apparatus which becomes a structure which can be discharged between a pair of film-forming rollers.
  • a gas barrier film can be manufactured by a roll-to-roll method using a plasma enhanced chemical vapor deposition method using a discharge plasma chemical vapor deposition apparatus shown in FIG.
  • FIG. 4 is a schematic diagram showing an example of an inter-roller discharge plasma CVD apparatus to which a magnetic field that can be suitably used in the production of the gas barrier film of the present invention is applied, but is limited to the method exemplified here. It is not something.
  • the inter-roller discharge plasma CVD apparatus (S1, hereinafter also referred to as “plasma CVD apparatus”) to which the magnetic field shown in FIG. 4 is applied mainly includes a delivery roller (11A), a transport roller (22 and 23), Film forming rollers (31 and 32), film forming gas supply pipe (41), power source for plasma generation (51), and magnetic field generators (61 and 62) installed inside the film forming rollers (31 and 32) ) And a take-up roller (11B).
  • a delivery roller 11A
  • a transport roller 22 and 23
  • Film forming rollers 31 and 32
  • film forming gas supply pipe 41
  • power source for plasma generation 51
  • magnetic field generators 61 and 62
  • a plasma CVD apparatus S1
  • at least film forming rollers (31 and 32), a film forming gas supply pipe (41), a plasma generating power source (51), and a magnetic field generating apparatus (61 and 62) is disposed in a vacuum chamber (CH).
  • the chamber (CH) is connected to a vacuum pump (17), and the pressure in the chamber (CH) can be adjusted appropriately by this vacuum pump (17). It is possible.
  • each film-forming roller is configured so that a pair of film-forming rollers (film-forming roller 31 and film-forming roller 32) can function as a pair of counter electrodes. It is connected to a power source (51) for generating plasma.
  • a power source for generating plasma.
  • the film forming roller (31) and the film forming roller (32) are connected to each other. It is possible to discharge in the space, and thus plasma can be generated in a space (also referred to as a discharge space) between the film forming roller (31) and the film forming roller (32).
  • the film-forming roller (31) and the film-forming roller (32) are used as electrodes in this way, the materials and designs that can be used as electrodes may be changed as appropriate.
  • the pair of film forming rollers (film forming rollers 31 and 32) be arranged so that their central axes are substantially parallel on the same plane. In this way, the film forming rate can be doubled by arranging the pair of film forming rollers (film forming rollers 31 and 32).
  • a magnetic field generator (61 and 62) fixed so as not to rotate even when the film forming roller rotates is provided inside the film forming roller (31) and the film forming roller (32), respectively. It is a feature.
  • the film forming roller (31) and the film forming roller (32) known rollers can be appropriately used.
  • the film forming rollers (31 and 32) those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently.
  • the diameter of the film forming rollers (31 and 32) is preferably in the range of 100 to 1000 mm ⁇ , particularly in the range of 100 to 700 mm ⁇ from the viewpoint of discharge conditions, chamber (CH) space, and the like. If the diameter is 100 mm ⁇ or more, it is preferable that the plasma discharge space is not reduced, the productivity is not deteriorated, the total amount of heat of the plasma discharge can be prevented from being applied to the film in a short time, and the residual stress is hardly increased.
  • a diameter of 1000 mm ⁇ or less is preferable because practicality can be maintained in terms of device design including uniformity of the plasma discharge space.
  • the feed roller (11) and the transport rollers (22 and 23) used in such a plasma CVD apparatus (S1) known rollers can be appropriately selected and used.
  • the take-up roller (11B) is not particularly limited as long as it can take up the gas barrier film (1) on which the gas barrier layer is formed, and a known roller can be appropriately used. .
  • the film forming gas supply pipe (41) one capable of supplying or discharging the source gas and the oxygen gas at a predetermined speed and ratio can be used as appropriate.
  • the plasma generation power source (51) a conventionally known power source for a plasma generation apparatus can be used. Such a plasma generating power source (51) supplies power to the film forming roller (31) and the film forming roller (32) connected thereto, and uses them as a counter electrode for discharge. Make it possible.
  • the plasma CVD method can be carried out more efficiently, so that the polarity of the pair of film forming rollers can be alternately reversed (AC power source). Etc.) is preferably used.
  • the applied power can be in the range of 100 W to 10 kW, and the AC frequency can be set. Is more preferably in the range of 50 Hz to 500 kHz.
  • a magnetic field generator 61 and 62
  • a well-known magnetic field generator can be used suitably.
  • a gas barrier film having a gas barrier layer having an atomic profile defined in the present invention can be produced. That is, using the plasma CVD apparatus shown in FIG. 4, a magnetic field is applied between the pair of film forming rollers (film forming rollers 31 and 32) while supplying a film forming gas (raw material gas or the like) into the chamber (CH).
  • the film forming gas (raw material gas or the like) is decomposed by the plasma, and the surface of the substrate (2 or 2 + 4) on the film forming roller (31) and the film forming roller (32).
  • a gas barrier layer according to the present invention is formed on the surface of the upper substrate (2 or 2 + 4) by a plasma CVD method.
  • the base material (2 or 2 + 4) is conveyed by the delivery roller (11A), the film formation roller (31), etc., respectively, so that the roll-to-roll type continuous formation is performed.
  • the gas barrier layer (3) is formed on the surface of the substrate (2 or 2 + 4) by a film process.
  • a plasma CVD apparatus shown in FIG. 4 is used, and in a first step (in the present invention, abbreviated as 1S), a desired gas composition and transport conditions are used.
  • a gas barrier layer is formed in the vicinity of the substrate.
  • the gas barrier layer of the first area having a desired composition is formed in one pass.
  • a method can be used in which the conveyance direction is reversed under the same conditions, and processing is performed a plurality of times.
  • second S film formation conditions
  • third S third S
  • the film formation conditions for example, transfer speed, gas composition, number of passes, etc.
  • the method to do can be used suitably.
  • the gas barrier layer according to the present invention has a difference in oxygen atomic ratio (AB) between the maximum maximum value A (at%) defined in the present invention and the minimum minimum value B (at%) in the oxygen distribution curve.
  • AB oxygen atomic ratio
  • the maximum value A of the oxygen distribution curve closest to the substrate side of the gas barrier layer is the maximum value of the oxygen distribution curve in the gas barrier layer.
  • the distance (C ⁇ D) between the position C (nm) and the position D (nm) in the peak having the maximum maximum value A in the oxygen distribution curve is 25 to 55 (nm)
  • limiting in particular as a method to control in this range It is preferable to employ
  • the method for controlling the oxygen atomic ratio so as to obtain the desired distribution defined in the present invention in the gas barrier layer is not particularly limited, but a discharge plasma having a discharge space between rollers to which a magnetic field is applied. It is preferable to employ the following method using a chemical vapor deposition apparatus.
  • a method of changing the film formation gas concentration during film formation a method of supplying the ratio of the oxygen concentration in the film formation gas composition higher than the steady state in the initial stage of film formation on the substrate;
  • Method of supplying gas at a plurality of places Usually, the gas supply port (41) is provided at one place in the center of the pair of film forming rollers (31 and 32), but the pair of film forming rollers (31 or 32) Is further provided with another supply port (41B) in the vicinity of the substrate, and a method for controlling the supply concentration of the film forming gas, specifically, a mixing flow rate ratio of source gas and oxygen gas (flow rate of oxygen gas (ml / min) / A method of forming a film under conditions where the flow rate of the source gas (ml / min) is in the range of 4.0 to 43.0 (ml / min)
  • a method of controlling the gas flow by installing a baffle plate near the gas supply port A movable baffle plate is installed near the
  • a method for controlling the gas supply flow from the film to control the deposition gas supply concentration (Iv) Method of performing plasma CVD a plurality of times by changing the film forming gas concentration: For example, as shown in FIG. 5, a plurality of plasma CVD apparatuses (S1 to S3) are connected to form a plasma tandem plasma CVD apparatus.
  • the film gas concentration is increased on the first film formation apparatus (S1) side, which is the base material side, and then the film formation is performed while sequentially decreasing the gas concentration on the second film formation apparatus (S2) and third film formation apparatus (S3) side How to control, (V) Method of changing the position of the gas supply port: A method of controlling the deposition gas concentration while bringing the position of the gas supply port (41) close to one of the deposition rollers between the deposition rollers (31 or 32). In this method, the deposition gas concentration can be increased by bringing the gas supply port closer to the deposition roller.
  • a means for controlling the conveyance speed in the discharge plasma chemical vapor deposition apparatus for the substrate a means for controlling the voltage condition applied between the film forming rollers, a means for controlling the diameter of the pair of opposing rolls, etc. are appropriately selected.
  • a method of obtaining a desired oxygen atom distribution curve by applying the methods described in (i) to (v) above is preferable.
  • FIG. 5 is a schematic view showing an example of a method for producing a tandem type gas barrier film in which three chambers equipped with the plasma CVD apparatus described above are arranged.
  • FIG. 5 shows a configuration in which the first chamber (CH1) to the third chamber (CH3) each incorporating the plasma CVD apparatus (S1 to S3) are arranged in a tandem type.
  • the first chamber (CH1) sets the oxygen gas concentration with respect to the source gas as a film forming gas to a high value, and forms the maximum value A of the oxygen distribution curve in the nearest region on the substrate surface side.
  • the oxygen concentration is set relatively low.
  • FIG. 7 shows an example of an apparatus in which a first chamber (CH1) containing a plasma CVD apparatus (S1) and a second chamber (CH2) containing a plasma CVD apparatus (S2) are arranged in a tandem type. It is.
  • the atomic composition of the gas barrier layer (3) according to the present invention is constant from the beginning to the rear of the gas barrier film (1) because the stability of the gas barrier property is high.
  • the film quality homogeneity is lowered when the gas barrier layer is deposited. This is because, for example, when moisture or the like is released as a gas from the base material side, the atomic composition of the gas barrier layer (3) changes under the influence of the released gas, so that the gas barrier performance is improved at the head and tail. May be different.
  • the ratio of SiO 2 having a high gas barrier property is formed in the initial stage of film formation, that is, in the interface area with the substrate.
  • the influence of moisture and the like can be suppressed from the base material side, and a gas barrier layer having a uniform film quality can be stably formed from the beginning to the tail when continuous film formation is performed.
  • the source gas constituting the film forming gas used for forming the gas barrier layer according to the present invention uses an organosilicon compound containing at least silicon.
  • organosilicon compound applicable to the present invention examples include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, and trimethyl.
  • examples thereof include silane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane.
  • organosilicon compounds hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling in film formation and gas barrier properties of the obtained gas barrier layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
  • the film forming gas contains oxygen gas as a reaction gas in addition to the source gas.
  • the oxygen gas is a gas that reacts with the raw material gas to become an inorganic compound such as an oxide.
  • a carrier gas may be used as necessary in order to supply the source gas into the chamber (CH).
  • 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, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.
  • Such a film-forming gas contains a source gas containing an organosilicon compound containing silicon and an oxygen gas, it is preferable to appropriately adjust the ratio of the source gas to the oxygen gas.
  • 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-
  • HMDSO, (CH 3 ) 6 Si 2 O hexamethyldisiloxane
  • O 2 oxygen
  • a reaction represented by the following reaction formula (1) occurs by the film forming gas, and a thin film mainly composed of silicon dioxide SiO 2 is formed.
  • Reaction formula (1) (CH 3 ) 6 Si 2 O + 12O 2 ⁇ 6CO 2 + 9H 2 O + 2SiO 2
  • the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, in the initial stage of film formation, a silicon dioxide film having a high oxygen atom ratio and a uniform composition can be obtained by completely reacting by adding 12 mol or more of oxygen to 1 mol of hexamethyldisiloxane in the film forming gas.
  • the raw material gas flow rate ratio is controlled to a flow rate that is equal to or lower than the theoretical reaction raw material ratio, thereby causing the incomplete reaction to occur and increasing the ratio to SiOC.
  • 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. Even if the molar amount (flow rate) of oxygen is 12 times the molar amount (flow rate) of hexamethyldisiloxane as a raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when the oxygen content is supplied in a large excess compared to the stoichiometric ratio.
  • the molar amount (flow rate) of oxygen may be 20 times or more the molar amount (flow rate) of the raw material hexamethyldisiloxane. Therefore, 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. .
  • hexamethyldisiloxane and oxygen By including hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer, and the gas has a desired atomic profile.
  • a barrier layer can be formed, and the resulting gas barrier film can exhibit excellent barrier properties and bending resistance (also referred to as flexibility). If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas is too small, unoxidized carbon atoms and hydrogen atoms will be excessively taken into the gas barrier layer. become.
  • the pressure (degree of vacuum) in the chamber can be appropriately adjusted according to the type of source gas and the like, but is preferably set within the range of 0.5 Pa to 100 Pa.
  • an electrode drum connected to a plasma generating power source (51) for discharging between film forming rollers (31 and 32) (In FIGS. 4 to 7, it is installed on the film forming rollers (31 and 32).)
  • the power applied to the film forming rollers (31 and 32) can be adjusted as appropriate according to the type of source gas, the pressure in the chamber, and the like. Although it cannot be generally defined, it is preferably in the range of 0.1 to 10 kW. If the applied power is in such a range, no generation of particles (illegal particles) is observed, and the amount of heat generated during film formation is within the control range.
  • the conveyance speed (line speed) of the base material can be appropriately adjusted according to the type of source gas, the pressure in the chamber, etc. as one of means for obtaining the oxygen electron ratio defined in the present application. It is preferably in the range of 25 to 100 m / min, and more preferably in the range of 0.5 to 20 m / min. When the line speed is within the above range, wrinkles due to the heat of the resin base material hardly occur, and the thickness of the formed gas barrier layer can be sufficiently controlled.
  • ⁇ Base material ⁇ As the base material of the gas barrier film of the present invention, it is preferable to use a plastic film having flexibility.
  • the plastic film used is not particularly limited in material, thickness and the like as long as it can hold the gas barrier layer, and can be appropriately selected according to the purpose of use.
  • plastic film examples include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide resin.
  • Cellulose acylate resin Polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modification
  • thermoplastic resins such as polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.
  • the base material is composed of a material having heat resistance, and satisfies the necessary conditions as a film for electronic parts or a laminated film for display. Preferably it is.
  • a gas barrier film may be exposed to 150 degreeC or more in the manufacture process.
  • the linear expansion coefficient of the base material in the gas barrier film is in the range of 15 to 100 ppm / K, the heat resistance is strong and the flexibility is good.
  • a resin base material having a glass transition temperature Tg in the range of 100 to 300 ° C. is preferable. The linear expansion coefficient and Tg of the base material can be adjusted by additives as well as the selection of the resin material.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • COC cycloolefin copolymer
  • the plastic film is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the light transmittance is determined by measuring the total light transmittance and the amount of scattered light using the method described in JIS K 7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. Can be calculated.
  • the base material using the above-described resins or the like may be an unstretched film or a stretched film.
  • the base material can be manufactured by a conventionally known general film forming method.
  • an unstretched substrate that is substantially amorphous and not oriented can be produced by heating and melting a resin as a material and then extruding it with an annular die or T-die using an extruder and quenching.
  • the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc.
  • a stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis).
  • the draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably in the range of 2 to 10 times in the vertical axis direction and the horizontal axis direction.
  • a curable resin such as a thermosetting resin or an active energy ray curable resin curable resin can be used.
  • active energy ray-curable resins are preferred because they are easy to mold.
  • thermosetting resin is not particularly limited, and examples thereof include various thermosetting resins such as epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, and vinylbenzyl resins. .
  • Any epoxy resin may be used as long as it has an average of two or more epoxy groups per molecule. Specifically, it is a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin, or a naphthol type epoxy.
  • naphthalene type epoxy resin bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (specifically, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, Diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy Fatty acid, epoxy resin having butadiene structure, phenol aralkyl type epoxy resin, epoxy resin having dicyclopentadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, glycidyl etherified product of phenol, diester of alcohol Examples thereof include glycidyl etherified products, alkyl-substituted products
  • the active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams.
  • Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin is particularly preferable.
  • Examples of the ultraviolet curable resin include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. Can do.
  • UV curable acrylic urethane resins generally have a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and the like obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having For example, a resin described in JP-A-59-151110 can be used.
  • UV curable polyester acrylate resins include resins that are easily formed when 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomers are generally reacted with polyester polyols.
  • a resin described in JP-A-59-151112 can be used.
  • ultraviolet curable epoxy acrylate resin examples include resins formed by reacting epoxy acrylate as an oligomer and adding a reactive diluent and a photoreaction initiator to the oligomer.
  • the resin described in Japanese Patent No. 105738 can be used.
  • UV curable polyol acrylate resins include polyfunctional acrylate resins.
  • the polyfunctional acrylate resin is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.
  • Examples of the monomer of the polyfunctional acrylate resin include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane.
  • UV curable resins examples include Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, ( ADEKA Co., Ltd.), Koei Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (from Guangei Chemical Co., Ltd.), Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, Dainichi KRM 7033, KRM 7039, KRM 7130, KRM 7131, UVECRY
  • the UV curable resin is preferably used together with a photopolymerization initiator in order to accelerate curing.
  • a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.
  • an onium salt it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator, and in particular, those described in JP-A Nos. 50-151996, 50-158680, etc.
  • Aromatic halonium salts Group VIA aromatic onium salts described in JP-A-50-151997, JP-A-52-30899, JP-A-59-55420, JP-A-55-125105, etc. 8428, 56-149402, 57-192429, etc., aromatic diazonium salts described in Japanese Patent Publication No. 49-17040, US Pat. No. 4,139,655, etc.
  • the thiopyrylium salts described are preferred.
  • an aluminum complex a photodegradable silicon compound type
  • the cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.
  • the amount of the photopolymerization initiator used is preferably in the range of 2 to 30% by mass with respect to the ultraviolet curable resin.
  • an ultraviolet curable organic / inorganic hybrid material organic modified fine particles combining an inorganic material and an organic component can be used.
  • organic modified fine particles it is particularly preferable to use silica fine particles whose surface is modified with an organic compound having a polymerizable unsaturated group.
  • Silica fine particles whose surface is modified with an organic compound having a polymerizable unsaturated group are, for example, usually on silanol groups on the surface of silica fine particles having an average particle size of about 0.5 to 500 nm, preferably an average particle size of 1 to 100 nm. It can be obtained by reacting a polymerizable unsaturated group-containing organic compound having a (meth) acryloyl group which is a functional group capable of reacting with the silanol group.
  • acrylic acid examples include acrylic acid, acrylic acid chloride, 2-isocyanatoethyl acrylate, glycidyl acrylate, 2,3-iminopropyl acrylate, 2-hydroxyethyl acrylate, and acryloyloxypropyltrimethoxysilane.
  • Etc. and methacrylic acid derivatives corresponding to these acrylic acid derivatives can be used.
  • These acrylic acid derivatives and methacrylic acid derivatives may be used alone or in combination of two or more.
  • organically modified fine particles examples include OPSTAR (registered trademark) Z7540, Z7521, Z7527 (pencil hardness: 4H), Z7541 (pencil hardness: 3H), KZ6445A (pencil hardness: 4H), and KZ6412 (pencil) manufactured by JSR. Hardness: 3H) or the like can be preferably used.
  • the hardness of each resin composition can be increased and adjusted to a desired hardness by making inorganic fine particles coexist with the above-described resin component.
  • inorganic fine particles include 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. O 5, CrO 2, MoO 2 , MoO 3, MnO 2, Mn 2 O 3, WO 3, LiMn 2 O 4, Cd 2 SnO4, CdIn 2 O 4, Zn 2 SnO 4, ZnSnO 3, Zn 2 In 2 O 5 , Cd 2 SnO 4 , CdIn 2 O 4 , Zn 2 SnO 4 , ZnSnO 3 , Zn 2 In 2 O 5 and the like.
  • the clear hard coat layer is irradiated with vacuum ultraviolet rays on the substrate surface or surface-treated by corona discharge, and then coated with a clear hard coat layer coating solution and cured. Can be formed.
  • a wet process such as a coating method using a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, a slide hopper coater, or the like, or an inkjet method can be used.
  • the clear hard coat layer coating solution is suitably applied within a range of 0.1 to 40.0 ⁇ m as a wet film thickness, and preferably within a range of 0.5 to 30.0 ⁇ m.
  • the layer thickness after drying is preferably in the range of 0.1 to 30.0 ⁇ m, more preferably in the range of 1 to 10 ⁇ m.
  • any light source that generates ultraviolet light can be used without limitation.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • Irradiation conditions vary depending on each lamp, but the irradiation amount of active energy rays is preferably in the range of 5 to 100 mJ / cm 2 , particularly preferably in the range of 20 to 80 mJ / cm 2 .
  • an overcoat layer can be appropriately formed on the outermost surface, and a bleed-out preventing layer can be appropriately formed on the back side of the substrate.
  • Gas barrier film of the present invention includes application to electronic devices and optical members.
  • the gas barrier film of the present invention can be preferably used for an electronic device that is easily affected by performance deterioration due to chemical components in the air (for example, oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.). .
  • Examples of the electronic device include an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL element or a solar cell, and particularly preferably applied to an organic EL element.
  • LCD liquid crystal display element
  • PV solar cell
  • Examples of organic EL elements using a gas barrier film are described in detail in Japanese Patent Application Laid-Open No. 2007-30387, etc.
  • Other application examples of the gas barrier film according to the present invention include, for example, Examples include a thin film transistor described in JP-A-512104, a touch panel described in JP-A-5-127822, JP-A-2002-48913, and electronic paper described in JP-A-2000-98326.
  • the gas barrier film according to the present invention can also be used as an optical member.
  • the optical member include a circularly polarizing plate.
  • a gas barrier film 1 as a comparative example was produced according to the following method.
  • resin base material As a resin substrate, a polyethylene terephthalate film having a length of 2000 m and a thickness of 100 ⁇ m, which is a thermoplastic resin support and is easily bonded on both surfaces (abbreviated as Toyobo Co., Ltd., Cosmo Shine A4300, PET).
  • the resin base material (2) was stored for 96 hours in an environment of a temperature of 25 ° C. and a relative humidity of 55% to adjust the humidity.
  • an OPSTAR Z7501 which is a UV curable organic / inorganic hybrid hard coat material manufactured by JSR Corporation, is applied under the condition that the film thickness after coating and drying is 4 ⁇ m. Apply using a rouge-type coater, dry at 80 ° C. for 3 minutes, and then cure under an air atmosphere using a high-pressure mercury lamp under a curing condition of 1.0 J / cm 2. Layer (4) was formed.
  • the plasma CVD apparatus (S1) shown in FIG. 4 is used, and the base material (2 + 4) on which the above-prepared clear hard coat layer is formed in the chamber (CH) is fed with a feeding roller ( 11A).
  • the film forming roller (31) and the conveying roller (22) of the plasma CVD apparatus (S1) provided with the resin base (2 + 4) fed from the feeding roller (11A) in the chamber (CH) for forming the gas barrier layer.
  • the film was drawn in the order of the conveying roller (23) and the film forming roller (32), and the film was formed under the film forming conditions in the first step (first S) described below, and then wound around the winding roller (11B).
  • the conveyance direction was reversed, the base material (2 + 4) was conveyed from right to left on the paper surface, a film was formed under the same conditions, and the film was wound around the feeding roller (11A). Furthermore, the conveyance direction was reversed, the base material (2 + 4) was conveyed from the left to the right of the paper surface, a film was formed under the same conditions, and the film was wound around the take-up roller (11B).
  • the number of passes in the first step was 3, and an area 1 having a layer thickness of 61.0 nm as shown in FIG. 8 was formed.
  • a gas barrier film 1 having a gas barrier layer (3) having a layer thickness of 117.8 nm was prepared by forming an area 2 having a thickness of 56.8 nm.
  • the plasma CVD apparatus used for the production described above applies a magnetic field using a magnetic field generator (61 and 62) between a pair of film forming rollers (31 and 32) having a diameter of 180 mm, and each film forming roller.
  • (31 and 32) is supplied with power from a plasma generation power source (51), and plasma is generated between the film forming rollers to form a discharge space.
  • a plasma generation power source 51
  • plasma is generated between the film forming rollers to form a discharge space.
  • HMDSO hexamethyldisiloxane
  • oxygen gas as a reaction gas is supplied from a film forming gas supply pipe (41), and a thin film is formed by plasma CVD under the following film forming conditions (plasma CVD conditions).
  • the gas rear layer (3) was formed on one surface of the substrate (2 + 4).
  • ⁇ Second step> Raw material gas: Hexamethyldisiloxane (HMDSO) Supply amount: 150 sccm (Standard Cubic Centimeter per Minute, 0 ° C., 1 atm standard, mL / min) Reaction gas: Oxygen gas (O 2 ) Supply amount: 1280 sccm (0 ° C., 1 atm standard) Reaction gas (oxygen gas) / source gas (HMDSO) mixed flow rate ratio (B / C): 8.50 Degree of vacuum in chamber (CH): 1.5 Pa Applied power from the power source for plasma generation: 2.0 kW Frequency of power source for plasma generation: 84 kHz Transport speed of resin base unit: 10 m / min Number of passes: 3 times The thickness of the area 2 shown in FIG. 8 of the gas barrier layer (3) formed in the second step as described above was 56.8 nm.
  • gas barrier film 2 In the production of the gas barrier film 1, the gas barrier film 2 of the present invention was produced in the same manner except that the method for forming the gas barrier layer was changed to the following method.
  • a gas barrier having a layer thickness of 117.8 nm is formed on the clear hard coat layer of the produced resin base material by the first step to the third step using a chamber equipped with a plasma CVD apparatus for applying a magnetic field shown in FIG. The layer was formed and the gas barrier film 2 was produced.
  • the plasma CVD apparatus for applying the magnetic field shown in FIG. 4 is used, the transfer speed of the first step to the third step, the flow rate condition of the film forming gas, and the number of passes.
  • the gas barrier film 2 was produced while changing to the following conditions.
  • gas barrier films 3 to 10 In the production of the gas barrier film 2, the supply amounts of hexamethyldisiloxane (HMDSO) and oxygen gas (sccm, ml / min) in the first to third steps in the plasma CVD apparatus shown in FIG. Gas barrier films 3 to 10 were produced in the same manner except that the speed (m / min), applied power, degree of vacuum, number of passes, and formation layer thickness were changed to the conditions shown in Table 1.
  • HMDSO hexamethyldisiloxane
  • sccm, ml / min oxygen gas
  • an element distribution curve in the depth direction is prepared by X-ray photoelectron spectroscopy in accordance with the following method, and the maximum value A of the oxygen distribution curve closest to the substrate surface side of the gas barrier layer ( at%), the minimum extreme value (minimum value) B (at%) in the thickness direction of the gas barrier layer, the position C (nm) of the base surface side of the gas barrier layer, and the maximum value in the thickness direction.
  • a position D (nm) at which the oxygen atom ratio value of the same amount as the oxygen atom ratio at the position C appears again is obtained through A, and the oxygen atom ratio difference between A (at%) and B (at%) (A -B) and the distance (CD) between the position C (nm) and the position D (nm) were calculated, and the results obtained are shown in Table 2.
  • the formed gas barrier layer was subjected to XPS depth profile measurement under the following conditions to create a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 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 ⁇ m ⁇ 400 ⁇ m ellipse
  • FIG. 8 shows the element distribution curve of the gas barrier film 1 (comparative example)
  • FIG. 9 shows the gas barrier film 10. The element distribution curve of this invention is shown.
  • the element distribution curve of the gas barrier film 1 (comparative example) shown in FIG. 8 plots the thickness of the gas barrier layer correlated to the sputtering depth on the horizontal axis, and the atomic number composition (at%) on the vertical axis. It is an oxygen atom distribution curve (at%), and a broken line is a silicon atom distribution curve (at%).
  • Area 1 is a gas barrier layer formation region by the first chamber (CH1)
  • area 2 is a gas barrier layer formation region by the second chamber (CH2).
  • the gas barrier layer extends from the surface (S) of the gas barrier film to a depth of 117.8 (nm), and a clear hard coat layer (CHC layer) and a base material are disposed below the gas barrier layer.
  • the depth 117.8 (nm) is the interface (I) between the gas barrier layer and the CHC layer, and the maximum value of the oxygen distribution curve closest to the substrate surface side.
  • A is 55.2 (at%)
  • the minimum extreme value (minimum value) B in the entire gas barrier layer is 35.6 (at%)
  • AB is 19.6 (at%).
  • AB defined by the invention falls outside the range of 20 to 50 (at%).
  • the layer thickness position C of the oxygen atomic ratio (39.8 at%) at the interface (I) is 138.2 (nm)
  • the oxygen atom distribution curve is drawn in the surface direction, exceeds the maximum value A
  • CD is 20.5 (nm).
  • the maximum value A of the oxygen distribution curve closest to the interface is the maximum value, and AB is 29.5 (at%). It has a molecular ratio, CD is 34.4 (nm), and it can be seen that it has a region with a high SiO 2 ratio in the vicinity of the interface.
  • Area 1 is a gas barrier layer formation region by the first chamber (CH1)
  • area 2 is a gas barrier layer formation region by the second chamber (CH2)
  • area 3 is a gas by the third chamber (CH3). This is a barrier layer forming region.
  • a gas barrier film is cut out in an appropriate size from the center at 1000 m, and granular calcium is formed on the surface of the cut out gas barrier film using a vacuum deposition apparatus JEE-400 (manufactured by JEOL Ltd.).
  • a vacuum deposition apparatus JEE-400 manufactured by JEOL Ltd.
  • the size of the calcium layer was 12 mm ⁇ 12 mm using a mask.
  • the mask was removed in a vacuum state, and aluminum ( ⁇ 3 to 5 mm, granular) was deposited on the entire surface of the gas barrier film. Thereafter, the vacuum state was released, and it was quickly transferred to a dry nitrogen gas atmosphere.
  • An ultraviolet curable resin T470 / UR7134 (manufactured by Nagase ChemteX Corporation) was applied to the aluminum deposition surface, and a quartz glass having a thickness of 0.2 mm was disposed thereon.
  • An evaluation cell was produced by irradiating ultraviolet light through quartz glass to cure the ultraviolet curable resin.
  • the prepared evaluation cell was stored at a high temperature and high humidity of 60 ° C. and a relative humidity of 90% RH for 100 hours. Based on the calcium corrosion method described in Japanese Patent Application Laid-Open No. 2005-283561, the corrosion area of the calcium layer was changed to water vapor. The permeability (g / m 2 ⁇ 24h) was calculated, and the gas barrier properties were evaluated according to the following criteria.
  • a comparative evaluation cell using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film is the same as the above evaluation cell. It was made.
  • This comparative evaluation cell was similarly stored under high temperature and high humidity of 60 ° C. and 90% RH, and it was confirmed that there was no corrosion of calcium even after 1000 hours.
  • water vapor permeability 0.01g / m 2 ⁇ day less than a is 4: water vapor permeability, 0.01g / m 2 ⁇ day or more and less than 0.05g / m 2 ⁇ day 3: water vapor permeability
  • the degree is 0.05 g / m 2 ⁇ day or more and less than 0.10 g / m 2 ⁇ day 2:
  • the water vapor permeability is 0.10 g / m 2 ⁇ day or more and less than 0.20 g / m 2 ⁇ day 1:
  • the water vapor permeability is 0.20 g / m 2 ⁇ day or more.
  • Water vapor permeability fluctuation ratio is 1.0 or more and less than 2.0 4: Water vapor permeability fluctuation ratio is 2.0 or more and less than 3.0 3: Water vapor permeability fluctuation ratio is 3 0.0 or more and less than 4.0 2: Water vapor permeability fluctuation ratio is 4.0 or more and less than 5.0 1: Water vapor permeability fluctuation ratio is 5.0 or more [Evaluation of bending resistance ]
  • Each gas barrier film (1000 m position) produced above is cut into a size of 3 cm ⁇ 10 cm, and wound around a metal rod with a curvature of 6 mm ⁇ with the gas barrier layer surface side outside in a room temperature and humidity environment. After repeating 100 times, the number of occurrences of cracks was measured for 10 fields of view on the surface of the gas barrier film at a magnification of 50 times, an average value thereof was determined, and bending resistance was evaluated according to the following criteria.
  • the gas barrier film having the gas barrier layer having the configuration defined in the present invention is superior in gas barrier properties and bending resistance immediately after production to the comparative example, and is continuously produced. It can be seen that the characteristic fluctuation (water vapor permeability fluctuation) at the beginning and tail is small and the production stability is excellent.
  • the gas barrier film which has the outstanding gas barrier property and bending resistance, and was excellent in the uniformity of gas barrier property
  • the said gas barrier film is a chemical component in air ( For example, oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.), which are easily affected by performance degradation, such as organic EL elements, liquid crystal display elements (LCD), thin film transistors, touch panels, electronic paper, It can be applied to an electronic device such as a solar cell (PV).

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Abstract

L'objectif de la présente invention est de fournir un film barrière au gaz possédant d'exceptionnelles propriétés de barrière au gaz et une excellente résistance au pliage, ainsi que des propriétés de barrière au gaz exceptionnellement homogènes, et un procédé de fabrication d'un film barrière au gaz, possédant une excellente stabilité fonctionnelle pendant la production. Ce film barrière au gaz est caractérisé en qu'il comporte, sur un matériau de base, une couche de barrière au gaz qui contient des atomes de carbone, des atomes de silicium et des atomes d'oxygène, la composition de film variant de façon continue dans la direction d'épaisseur de couche, la différence de pourcentage d'atome d'oxygène (A – B), où A (% at.) désigne la plus grande valeur maximale de la courbe de distribution d'oxygène la plus proche du côté de surface de matériau de base de la couche de barrière au gaz parmi les courbes de distribution d'oxygène dans la direction en profondeur mesurées par spectroscopie de photo-émission de rayons X de la couche de barrière au gaz, et B (% at.) désigne la plus petite valeur minimale dans la direction d'épaisseur de couche de la couche de barrière au gaz, se trouve dans une plage de 20 à 50 (% at.), et la valeur maximale A de la courbe de distribution d'oxygène la plus proche du côté de surface de matériau de base de la couche de barrière au gaz est la quantité la plus importante parmi les valeurs maximales des courbes de distribution d'oxygène au sein de la couche de barrière au gaz.
PCT/JP2016/053164 2015-02-19 2016-02-03 Film barrière au gaz et son procédé de fabrication WO2016132901A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018079670A (ja) * 2016-11-18 2018-05-24 コニカミノルタ株式会社 ポリアリレートフィルム積層体
EP3871876A4 (fr) * 2018-10-23 2022-08-03 Sumitomo Chemical Company Limited Corps stratifié, dispositif électronique flexible et procédé de fabrication de corps stratifié

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010117046A1 (fr) * 2009-04-09 2010-10-14 住友化学株式会社 Pellicule multicouche barrière aux gaz
WO2012046738A1 (fr) * 2010-10-08 2012-04-12 住友化学株式会社 Dispositif électroluminescent organique
JP2012081632A (ja) * 2010-10-08 2012-04-26 Sumitomo Chemical Co Ltd 積層フィルム
WO2013146964A1 (fr) * 2012-03-27 2013-10-03 住友化学株式会社 Feuille stratifiée, dispositif à diodes électroluminescentes organiques, convertisseur photoélectrique et écran à cristaux liquides
JP2014083691A (ja) * 2012-10-19 2014-05-12 Konica Minolta Inc ガスバリアーフィルム及びガスバリアーフィルムの製造方法
WO2014123201A1 (fr) * 2013-02-08 2014-08-14 コニカミノルタ株式会社 Film barrière au gaz et son procédé de fabrication
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
JP2015024536A (ja) * 2013-07-25 2015-02-05 コニカミノルタ株式会社 ガスバリアー性フィルムの製造方法
WO2015083706A1 (fr) * 2013-12-02 2015-06-11 コニカミノルタ株式会社 Film de barrière contre les gaz et procédé pour sa production

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9540526B2 (en) * 2012-10-19 2017-01-10 Konica Minolta, Inc. Gas barrier film and method for manufacturing gas barrier film
WO2014125953A1 (fr) * 2013-02-15 2014-08-21 コニカミノルタ株式会社 Procédé de fabrication de film barrière aux gaz et dispositif électronique comprenant un film barrière aux gaz
US20140242367A1 (en) * 2013-02-25 2014-08-28 Au Optronics Corporation Barrier film and methods of making same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010117046A1 (fr) * 2009-04-09 2010-10-14 住友化学株式会社 Pellicule multicouche barrière aux gaz
WO2012046738A1 (fr) * 2010-10-08 2012-04-12 住友化学株式会社 Dispositif électroluminescent organique
JP2012081632A (ja) * 2010-10-08 2012-04-26 Sumitomo Chemical Co Ltd 積層フィルム
WO2013146964A1 (fr) * 2012-03-27 2013-10-03 住友化学株式会社 Feuille stratifiée, dispositif à diodes électroluminescentes organiques, convertisseur photoélectrique et écran à cristaux liquides
JP2014083691A (ja) * 2012-10-19 2014-05-12 Konica Minolta Inc ガスバリアーフィルム及びガスバリアーフィルムの製造方法
WO2014123201A1 (fr) * 2013-02-08 2014-08-14 コニカミノルタ株式会社 Film barrière au gaz et son procédé de fabrication
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
JP2015024536A (ja) * 2013-07-25 2015-02-05 コニカミノルタ株式会社 ガスバリアー性フィルムの製造方法
WO2015083706A1 (fr) * 2013-12-02 2015-06-11 コニカミノルタ株式会社 Film de barrière contre les gaz et procédé pour sa production

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018079670A (ja) * 2016-11-18 2018-05-24 コニカミノルタ株式会社 ポリアリレートフィルム積層体
EP3871876A4 (fr) * 2018-10-23 2022-08-03 Sumitomo Chemical Company Limited Corps stratifié, dispositif électronique flexible et procédé de fabrication de corps stratifié

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