WO2018101084A1 - Film barrière aux gaz et dispositif électronique souple - Google Patents

Film barrière aux gaz et dispositif électronique souple Download PDF

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WO2018101084A1
WO2018101084A1 PCT/JP2017/041452 JP2017041452W WO2018101084A1 WO 2018101084 A1 WO2018101084 A1 WO 2018101084A1 JP 2017041452 W JP2017041452 W JP 2017041452W WO 2018101084 A1 WO2018101084 A1 WO 2018101084A1
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thin film
inorganic thin
layer
film layer
gas barrier
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PCT/JP2017/041452
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English (en)
Japanese (ja)
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伊藤　豊
山下　恭弘
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住友化学株式会社
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Priority to CN201780071065.7A priority Critical patent/CN109963711A/zh
Priority to KR1020197018723A priority patent/KR102446748B1/ko
Publication of WO2018101084A1 publication Critical patent/WO2018101084A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—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
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • 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
    • C23C16/503—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using dc or ac discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

Definitions

  • the present invention relates to a gas barrier film and a flexible electronic device having the gas barrier film.
  • Gas barrier films are widely used in packaging applications such as food, industrial products, and pharmaceuticals.
  • packaging applications such as food, industrial products, and pharmaceuticals.
  • a film having a gas barrier property that is further improved as compared with the food use and the like in flexible substrates of electronic devices such as solar cells and organic EL displays.
  • various studies have been made on the configuration of the gas barrier film, the production method thereof, and the like.
  • Patent Document 1 a base material having a specific thickness and a coating liquid containing a specific element are applied to at least one surface of the base material to obtain a coating layer, and then the coating layer is modified.
  • a gas barrier film having a first gas barrier layer formed by performing a quality treatment and a second gas barrier layer formed by a specific method adjacent to the first gas barrier layer is disclosed.
  • Patent Document 2 pays attention to the fact that a barrier layer may be cracked when an OLED substrate having a barrier layer and an aluminum-deposited PET layer on the surface side of the substrate is cut from the aluminum-deposited PET layer side.
  • an OLED substrate cutting device made is disclosed.
  • a gas barrier film is usually cut into a desired shape and used by being incorporated in an electronic device such as a display.
  • the gas barrier film is cut. Separation or cracking occurred due to the end face, and the gas barrier properties sometimes deteriorated over time.
  • an object of the present invention is to provide a gas barrier film in which the deterioration of the gas barrier property over time is suppressed particularly under high temperature and high humidity.
  • the present inventors have studied in detail the configuration of the gas barrier film, and have completed the present invention.
  • a gas barrier film having at least a base material layer containing a flexible base material and an inorganic thin film layer, and the adhesion between the base material layer and the inorganic thin film layer is measured according to ASTM D3359 2B or more, and the inorganic thin film layer has at least one cut end face and has at least one defect selected from the group consisting of peeling and cracking, or does not have the defect, In the case where the inorganic thin film layer has the defect, the existence region is in a range of 120 ⁇ m or less in the normal direction from the cut end face.
  • the base material layer further includes an organic layer A.
  • the present invention it is possible to suppress deterioration of the gas barrier property over time of the gas barrier film, particularly under high temperature and high humidity.
  • the gas barrier film of the present invention has at least a base material layer including a flexible base material and an inorganic thin film layer, and adhesion between the base material layer and the inorganic thin film layer according to ASTM D3359 is 2B or more and the inorganic thin film layer has at least one cut end face and has at least one defect selected from the group consisting of peeling and cracking, or does not have the defect, wherein When the inorganic thin film layer has the defect, the existence region is in a range of 120 ⁇ m or less in the normal direction from the cut end face.
  • the gas barrier film of the present invention even if the adhesion between the base material layer and the inorganic thin film layer is high and the inorganic thin film layer has a defect selected from the group consisting of peeling and cracking, the existence region of the defect Is within the predetermined range, it is possible to suppress deterioration of gas barrier properties with time, particularly under high temperature and high humidity.
  • defects such as cracks occur in the cut gas barrier film, if the adhesion between the base material layer and the inorganic thin film layer is low, for example, the defects propagate in the surface under high temperature and high humidity conditions, and the barrier property May be significantly reduced.
  • the gas barrier film since the gas barrier film has the base layer having the predetermined adhesion and the inorganic thin film layer, even if a defect occurs due to the stress applied to the gas barrier film at the time of cutting, it is suppressed to the minimum. In addition, it is possible to suppress a decrease in gas barrier properties over time.
  • the gas barrier film of the present invention has at least a base material layer including a flexible base material and an inorganic thin film layer.
  • the adhesion between the base material layer and the inorganic thin film layer by ASTM D3359 is 2B. That's it. If the adhesion between the base material layer and the inorganic thin film layer is lower than 2B, the inorganic thin film layer is liable to have defects such as cracks and peeling when the gas barrier film is cut, and desired gas barrier properties cannot be obtained. In addition, defects generated in the cut gas barrier film are likely to propagate over time, particularly under high temperature and high humidity, and the deterioration of gas barrier properties over time cannot be suppressed.
  • the adhesion between the base material layer and the inorganic thin film layer is preferably 3B or more, more preferably 4B or more, and further preferably 5B or more.
  • the adhesion between the base material layer and the inorganic thin film layer means the adhesion between the inorganic thin film layer and a layer included in the base material layer adjacent to the inorganic thin film layer.
  • the adhesion between the substrate layer and the inorganic thin film layer is, in other words, the flexible substrate.
  • the adhesion between the material and the inorganic thin film layer is shown in FIG. 1, for example, and in the gas barrier film 1, the flexible base material 20 included in the base material layer 2 is adjacent to and in close contact with the inorganic thin film layer 3.
  • a base material layer contains the flexible base material and the organic layer A mentioned later, and the organic layer A contained in a base material layer and an inorganic thin film layer adjoin, a base material
  • the adhesion between the layer and the inorganic thin film layer is the adhesion between the organic layer A and the inorganic thin film layer.
  • FIG. 2 In the gas barrier film 1, the base layer 2 has a flexible base layer 20 and an organic layer A 21, and the organic layer A 21 is adjacent to and closely adhered to the inorganic thin film layer 3. Yes.
  • the measurement of adhesion is performed in accordance with ASTM D3359.
  • the inorganic thin film layer has at least one cut end surface.
  • the barrier film of the present invention is obtained through at least one cutting step in at least the inorganic thin film layer, the inorganic thin film layer has at least one cut end face.
  • the inorganic thin film layer has at least one defect selected from the group consisting of peeling and cracking, or does not have the defect, wherein the inorganic thin film layer has the defect.
  • the existence region is within a range of 120 ⁇ m or less in the normal direction from the cut end face. Since the barrier film of the present invention has high adhesion between the base material layer and the inorganic thin film layer, for example, even if the gas barrier film is subjected to a cutting step, defects such as peeling and cracking are unlikely to occur in the inorganic thin film layer.
  • the inorganic thin film layer has a defect selected from the group consisting of exfoliation and cracking
  • the existence region is within the above range, the defect propagates over time particularly under high temperature and high humidity. It is possible to prevent the gas barrier property from being lowered. If there is a defect selected from the group consisting of exfoliation and cracking in a range exceeding 120 ⁇ m in the normal direction from the cut end face, sufficient gas barrier property cannot be obtained, and further, the gas barrier property deteriorates over time at high temperature and high humidity. Cannot be sufficiently suppressed.
  • the defect existence region is preferably within a range of 100 ⁇ m or less in the normal direction from the cut end surface, more preferably within a range of 50 ⁇ m or less, and a range of 30 ⁇ m or less. Is more preferably within the range of 10 ⁇ m or less, and most preferably within the range of 5 ⁇ m or less.
  • the existence area of the defect selected from the group consisting of peeling and cracking is determined by using a microscope (for example, “DIGITAL MICROSCOPE KH7700” manufactured by Hilox Co., Ltd.) at an appropriate magnification (for example, 210). It is possible to evaluate by observing at (times). Specifically, with respect to peeling and cracks generated from the cut end face, the maximum length in the normal direction (perpendicular to the cross section) is measured from the cut end face, and the length is defined as the defect existence region. When the inorganic thin film layer has two or more cut end faces, the above observation is performed on all cut end faces.
  • FIG. 4 shows a schematic diagram of a gas barrier film having a base material layer 2 composed of a flexible base material 20 and an inorganic thin film layer 3 which is an embodiment of the laminated film of the present invention.
  • the inorganic thin film layer 3 in the gas barrier film shown in FIG. 4 has four cut end faces (four side portions). In this case, the size of the defect generated from the cut end face is observed using a microscope, and the distance a (5 in FIG. 4) of the maximum length is measured. In the gas barrier film of the present invention, the distance “a” in FIG. 4 is 120 ⁇ m or less.
  • the gas barrier film of the present invention has at least a base material layer including at least a flexible base material and an inorganic thin film layer.
  • the inorganic thin film layer should just be laminated
  • the inorganic thin film layer is not particularly limited as long as it is an inorganic material layer having gas barrier properties, and a known inorganic material layer having gas barrier properties can be appropriately used. Examples of inorganic materials include metal oxides, metal nitrides, metal oxynitrides, metal oxycarbides, and mixtures containing at least two of these.
  • the inorganic thin film layer may be a single layer film or a multilayer film in which two or more layers including at least the inorganic thin film layer are laminated.
  • the inorganic thin film layer has at least silicon atoms (Si) and oxygen atoms from the viewpoint of easily exhibiting higher gas barrier properties (especially water vapor permeation preventing properties) and bending resistance, ease of production and low production cost. It is preferable to contain (O) and a carbon atom (C).
  • the inorganic thin film layer may be a single layer or a plurality of layers. Further, the step of forming the inorganic thin film layer may be performed once or may be performed a plurality of times. When performed several times, it may be performed under the same conditions or may be performed under different conditions.
  • the inorganic thin film layer has a general formula of SiO ⁇ C ⁇ [wherein ⁇ and ⁇ independently represent a positive number less than 2. ]
  • the main component means that the content of the component is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more with respect to the mass of all components constituting the inorganic thin film layer. It means that.
  • Inorganic thin layer may contain one kind of compound represented by the general formula SiO ⁇ C ⁇ , may contain a general formula SiO alpha C beta in two or more compounds represented.
  • One or more of ⁇ and ⁇ in the general formula may be a constant value or may vary in the film thickness direction of the inorganic thin film layer.
  • the inorganic thin film layer contains an element other than silicon atom, oxygen atom and carbon atom such as hydrogen atom, nitrogen atom, boron atom, aluminum atom, phosphorus atom, sulfur atom, fluorine atom and chlorine atom. You may contain.
  • the inorganic thin film layer has a high density when the average atomic ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is expressed by C / Si, and defects such as fine voids and cracks
  • the range of C / Si preferably satisfies the formula (1). 0.02 ⁇ C / Si ⁇ 0.50
  • C / Si is more preferably in the range of 0.03 ⁇ C / Si ⁇ 0.45, further preferably in the range of 0.04 ⁇ C / Si ⁇ 0.40, and A range of 05 ⁇ C / Si ⁇ 0.35 is particularly preferable.
  • the inorganic thin film layer has a high density when the average atomic ratio of oxygen atoms (O) to silicon atoms (Si) in the inorganic thin film layer is expressed by O / Si, and fine voids, cracks, etc.
  • O oxygen atoms
  • Si silicon atoms
  • it is preferably in the range of 1.50 ⁇ O / Si ⁇ 1.98, more preferably in the range of 1.55 ⁇ O / Si ⁇ 1.97, and 1.60 ⁇ O. /Si ⁇ 1.96 is more preferable, and 1.65 ⁇ O / Si ⁇ 1.95 is particularly preferable.
  • the average atomic number ratios C / Si and O / Si are measured by XPS depth profile under the following conditions. From the obtained distribution curves of silicon atoms, oxygen atoms and carbon atoms, the averages in the thickness direction of the respective atoms. After obtaining the atomic concentration, the average atomic ratio C / Si and O / Si can be calculated.
  • the peak intensity ratio I 2 / I 1 calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si—CH 3 to Si—O—Si in the inorganic thin film layer.
  • An inorganic thin film layer that satisfies the relationship represented by the formula (2) has high density and is likely to reduce defects such as fine voids and cracks, and thus is considered to easily improve gas barrier properties and impact resistance.
  • the peak intensity ratio I 2 / I 1 is more preferably in the range of 0.02 ⁇ I 2 / I 1 ⁇ 0.04 from the viewpoint of easily maintaining high density of the inorganic thin film layer.
  • the gas barrier film of the present invention is appropriately slippery, and blocking is easily reduced. If the peak intensity ratio I 2 / I 1 is too large, it means that there is too much Si—C. In this case, the flexibility is poor and the slip tends to be difficult. On the other hand, if the peak intensity ratio I 2 / I 1 is too small, the flexibility tends to decrease due to too little Si—C.
  • Infrared spectroscopic measurement of the surface of the inorganic thin film layer is a Fourier transform infrared spectrophotometer (FT / IR-460Plus, JASCO Corporation) equipped with an ATR attachment (PIKEPMIRacle) using a germanium crystal as a prism. Can be measured by.
  • FT / IR-460Plus Fourier transform infrared spectrophotometer
  • PIKEPMIRacle ATR attachment
  • the peak intensity ratio I 3 / I 1 calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si—C, Si—O, etc. to Si—O—Si in the inorganic thin film layer. .
  • the inorganic thin film layer satisfying the relationship represented by the formula (3) is considered to be easily improved in flex resistance and easily improved in impact resistance since carbon is introduced while maintaining high density.
  • the peak intensity ratio I 3 / I 1 is preferably in the range of 0.25 ⁇ I 3 / I 1 ⁇ 0.50 from the viewpoint of maintaining a balance between the denseness and the bending resistance of the inorganic thin film layer, and 0.30 ⁇ I The range of 3 / I 1 ⁇ 0.45 is more preferable.
  • the thin film layer when subjected to infrared spectrometry the inorganic thin film layer surface (ATR method), a peak exists in the 770 ⁇ 830 cm -1 intensity (I 3), peaks at 870 ⁇ 910 cm -1 It is preferable that the intensity ratio with the intensity (I 4 ) satisfies the formula (4). 0.70 ⁇ I 4 / I 3 ⁇ 1.00 (4)
  • the peak intensity ratio I 4 / I 3 calculated from the infrared spectroscopic measurement (ATR method) is considered to represent the ratio between peaks related to Si—C in the inorganic thin film layer.
  • the inorganic thin film layer satisfying the relationship represented by the formula (4) is considered to be easy to improve the flex resistance and the impact resistance because carbon is introduced while maintaining high density.
  • the range of the peak intensity ratio I 4 / I 3 the range of 0.70 ⁇ I 4 / I 3 ⁇ 1.00 is preferable from the viewpoint of maintaining the balance between the denseness and the bending resistance of the inorganic thin film layer, and 0.80
  • the range of ⁇ I 4 / I 3 ⁇ 0.95 is more preferable.
  • the thickness of the inorganic thin film layer is preferably 5 to 3000 nm from the viewpoint of making it difficult to break when the inorganic thin film layer is bent. Furthermore, as will be described later, when the inorganic thin film layer is formed by plasma CVD using glow discharge plasma, the inorganic thin film layer is formed while discharging through the base material, so that the thickness is 10 to 2000 nm. Is more preferably 100 to 1000 nm.
  • the inorganic thin film layer may have a high average density of preferably 1.8 g / cm 3 or more.
  • the “average density” of the inorganic thin film layer is the number of silicon atoms, the number of carbon atoms, the number of oxygen atoms, and the hydrogen forward scattering method (Hydrogen Forward Scattering) obtained by Rutherford Backscattering Spectrometry (RBS).
  • HSS hydrogen forward scattering method obtained by Rutherford Backscattering Spectrometry
  • the average density of the inorganic thin film layer is equal to or higher than the above lower limit because the denseness is high and a structure such as fine voids and cracks can be easily reduced.
  • the average density of the inorganic thin film layer is preferably less than 2.22 g / cm 3 .
  • the inorganic thin film layer contains at least silicon atoms (Si), oxygen atoms (O), and carbon atoms (C)
  • Si silicon atoms
  • O oxygen atoms
  • C carbon atoms
  • the surface of the inorganic thin film layer refers to a surface to be the surface of the gas barrier film of the present invention.
  • a curve indicating the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic ratio of oxygen atoms at each distance is referred to as an oxygen distribution curve.
  • a curve indicating the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic ratio of carbon atoms at each distance is referred to as a carbon distribution curve.
  • the atomic ratio of silicon atoms, the atomic ratio of oxygen atoms, and the atomic ratio of carbon atoms means the ratio of the number of atoms to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the inorganic thin film layer.
  • the ratio of the number of carbon atoms to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the inorganic thin film layer is continuous in the film thickness direction of the inorganic thin film layer. It is preferable to change it.
  • the atomic ratio of the carbon atoms continuously changes in the film thickness direction of the inorganic thin film layer means, for example, that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Represents.
  • the silicon distribution curve, oxygen distribution curve and carbon distribution curve of the inorganic thin film layer satisfy the following conditions (i) and (ii).
  • the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition expressed by the formula (5) in a region of 90% or more in the film thickness direction of the inorganic thin film layer.
  • the carbon distribution curve has at least one extreme value.
  • the carbon distribution curve of the inorganic thin film layer is preferably substantially continuous.
  • the carbon distribution curve being substantially continuous means that the carbon distribution curve does not include a portion where the carbon atomic ratio changes discontinuously. Specifically, when the distance from the surface of the thin film layer in the film thickness direction is x [nm] and the atomic ratio of carbon is C, it is preferable to satisfy the formula (6).
  • the carbon distribution curve of the inorganic thin film layer preferably has at least one extreme value.
  • the extreme value here is the maximum value or the minimum value of the atomic ratio of each element with respect to the distance from the surface of the inorganic thin film layer in the film thickness direction.
  • the extreme value is the atomic ratio at which the atomic ratio of the element changes from increasing to decreasing or when the atomic ratio of the element changes from decreasing to increasing when the distance from the inorganic thin film layer surface in the film thickness direction is changed. Is the value of The extreme value can be obtained based on the atomic ratio measured at a plurality of measurement positions in the film thickness direction, for example. For the measurement position of the atomic ratio, the interval in the film thickness direction is set to 20 nm or less, for example.
  • the measurement results at three or more different measurement positions are compared for a discrete data group including the measurement results at each measurement position. It can be obtained by determining the position that starts or decreases or decreases.
  • the position indicating the extreme value can also be obtained, for example, by differentiating the approximate curve obtained from the discrete data group.
  • the interval in which the atomic ratio monotonously increases or decreases from the position showing the extreme value is, for example, 20 nm or more
  • the absolute value of the difference is, for example, 0.03 or more.
  • the increase in the gas permeability after bending with respect to the gas permeability before bending satisfies the above condition. Less compared to the case without it. That is, by satisfying the above conditions, an effect of suppressing a decrease in gas barrier properties due to bending can be obtained.
  • the inorganic thin film layer is formed so that the number of extreme values of the carbon distribution curve is two or more, the amount of increase is reduced as compared with the case where the number of extreme values of the carbon distribution curve is one. .
  • the increase amount is larger than that in the case where the number of extreme values of the carbon distribution curve is two. Less.
  • the carbon distribution curve has two or more extreme values
  • the distance from the surface of the inorganic thin film layer in the film thickness direction at the position showing the first extreme value, and the second pole adjacent to the first extreme value is preferably in the range of 1 nm to 200 nm, and more preferably in the range of 1 nm to 100 nm. preferable.
  • the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve of the inorganic thin film layer is preferably larger than 0.01.
  • the amount of increase in the gas permeability after bending with respect to the gas permeability before bending is less than that in the case where the above conditions are not satisfied. That is, by satisfying the above conditions, an effect of suppressing a decrease in gas barrier properties due to bending can be obtained.
  • the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is 0.02 or more, the above effect is enhanced, and when it is 0.03 or more, the above effect is further enhanced.
  • the gas barrier property of the inorganic thin film layer tends to improve as the absolute value of the difference between the maximum value and the minimum value of the silicon atomic ratio in the silicon distribution curve decreases.
  • the absolute value is preferably less than 0.05 (less than 5 at%), more preferably less than 0.04 (less than 4 at%), and less than 0.03 (3 at%). Is particularly preferred.
  • the total atomic ratio is preferably less than 0.05, more preferably less than 0.04, and particularly preferably less than 0.03.
  • the gas barrier property of the inorganic thin film layer can be made uniform and improved.
  • the substantially uniform composition means that in the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve, the number of extreme values existing in each film thickness direction at any two points on the surface of the inorganic thin film layer. Are the same, and the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in each carbon distribution curve is the same or within 0.05.
  • the inorganic thin film layer formed so as to satisfy the above conditions can exhibit a gas barrier property required for a flexible electronic device using an organic EL element, for example.
  • the gas barrier film of the present invention As a processing method of the gas barrier film of the present invention, from the viewpoint of processing so as not to cause cracks in the hard inorganic thin film layer compared to the base material layer made of organic matter, Thomson type punching machine, super cutter, cross cutter, Cutting with a guillotine, shear cutter, rotary die cutter, press cutter, or ablation using various lasers is preferred. Further, the processed end face can be cut. As a method for cutting the processed end face, for example, as disclosed in Patent Document 3 (Japanese Patent Laid-Open No. 2001-54845), a method of cutting the outer peripheral end of a polarizing plate with a rotary blade, As disclosed in Patent Document 4 (Japanese Patent Laid-Open No.
  • a method of continuously cutting the outer peripheral edge of a polarizing plate by a fly-cut method is a method for processing a gas barrier film of the present invention.
  • a protective film or a cover film with an adhesive such as OCA is applied from the viewpoint of processing so as not to cause cracks in the hard inorganic thin film layer compared to the base layer made of organic matter. May be combined.
  • a cover film with an adhesive such as a protective film or OCA a PET film is preferable from the viewpoint of the rigidity of the film.
  • the layer of the inorganic material containing such atoms is easy to increase the density and has defects such as fine voids and cracks.
  • CVD chemical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • An example of a raw material gas used in the chemical vapor deposition method is an organosilicon compound containing silicon atoms and carbon atoms.
  • organosilicon compounds are hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, 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 properties of the compound and gas barrier properties of the obtained inorganic thin film layer.
  • the source gas one of these organosilicon compounds may be used alone, or two or more thereof may be used in combination.
  • a reaction gas that can react with the source gas to form an inorganic compound such as an oxide or a nitride can be appropriately selected and mixed with the source gas.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • a reactive gas for forming nitride nitrogen and ammonia can be used, for example.
  • These reaction gases can be used singly or in combination of two or more.
  • the reaction gas for forming an oxide and the nitride are formed.
  • Can be used in combination with the reaction gas for The flow rate ratio between the source gas and the reaction gas can be adjusted as appropriate according to the atomic ratio of the inorganic material to be formed.
  • the value of C / Si can be controlled by adjusting the flow ratio of the source gas and the reaction gas.
  • HMDSO hexamethyldisiloxane
  • oxygen used as the reaction gas
  • the ratio of the oxygen flow rate to the HMDSO flow rate O 2 / HMDSO is in the range of 5 to 25, and the value of C / Si is It can be controlled within the above-mentioned range.
  • a carrier gas may be used as necessary.
  • a discharge gas may be used as necessary.
  • carrier gas and discharge gas known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon, etc .; hydrogen can be used.
  • the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 to 50 Pa.
  • FIG. 5 is a schematic view showing an example of a manufacturing apparatus used for manufacturing an inorganic thin film layer included in a gas barrier film, and is a schematic view of an apparatus for forming an inorganic thin film layer by a plasma chemical vapor deposition method.
  • the manufacturing apparatus shown in FIG. 5 includes a feed roll 6, a take-up roll 13, a transport roll 7, a gas supply pipe 10, a plasma generation power source 11, magnetic field forming apparatuses 11 installed inside the film forming rolls 8 and 9, and 12.
  • the film forming rolls 11 and 12 also serve as electrodes and are roll electrodes described later.
  • At least the film forming roll, the gas supply pipe, and the magnetic field forming apparatus are disposed in a vacuum chamber (not shown) when forming the inorganic thin film layer.
  • This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.
  • Plasma CVD film formation can be performed by a continuous film formation process using plasma.
  • the delivery roll is installed in a state where the film 14 before film formation is wound up, and the film is sent out while being unwound in the longitudinal direction. Further, a winding roll is provided on the end side of the film, and the film after film formation is wound while being pulled and accommodated in a roll shape.
  • the two film forming rolls extend in parallel and face each other. Both rolls are formed of a conductive material and convey the film while rotating respectively.
  • the two film forming rolls preferably have the same diameter, for example, preferably 5 cm or more and 100 cm or less.
  • the base material layer When forming the inorganic thin film layer, the base material layer is transported in close contact with the surface of the pair of roll electrodes, plasma is generated between the pair of electrodes, and the raw material is decomposed in the plasma to be flexible. It is preferable to form an inorganic thin film layer on a base material.
  • a magnet In the pair of electrodes, a magnet is preferably disposed inside the electrodes so that the magnetic flux density is high on the surfaces of the electrodes and the flexible substrate. As a result, the plasma tends to be constrained at a high density on the electrode and the flexible substrate when the plasma is generated.
  • the gas barrier film of the present invention has a base material layer including at least a flexible base material.
  • a flexible base material is a flexible base material which can hold
  • a resin film containing at least one resin as a resin component can be used as the flexible substrate.
  • the flexible substrate is preferably a transparent resin substrate.
  • resins that can be used for the resin film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin; polyamide resins; polycarbonate resins Polystyrene resin; polyvinyl alcohol resin; saponified ethylene-vinyl acetate copolymer; polyacrylonitrile resin; acetal resin; polyimide resin; polyether sulfide (PES).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin
  • polyamide resins polycarbonate resins
  • Polystyrene resin polyvinyl alcohol resin
  • saponified ethylene-vinyl acetate copolymer polyacrylonitrile resin
  • acetal resin polyimide resin
  • the flexible substrate may be an unstretched resin substrate, or the unstretched resin substrate may be uniaxially stretched, tenter-type sequential biaxial stretch, tenter-type simultaneous biaxial stretch, tubular-type simultaneous biaxial It may be a stretched resin base material stretched in a flow direction (MD direction) of the resin base material and / or a direction perpendicular to the flow direction of the resin base material (TD direction) by a known method such as stretching.
  • the flexible substrate may be a laminate in which two or more of the above-described resin layers are laminated.
  • the thickness of the flexible substrate may be appropriately set in consideration of the stability at the time of producing the gas barrier film, but from the viewpoint of facilitating the conveyance of the flexible substrate in a vacuum, 5 to The thickness is preferably 500 ⁇ m. Further, when the inorganic thin film layer is formed by the plasma CVD method, the thickness of the flexible substrate is more preferably 10 to 200 ⁇ m, and further preferably 15 to 100 ⁇ m. Here, the thickness of the flexible substrate is measured by a dial gauge or an interference thickness gauge.
  • the flexible substrate may be a retardation film having different in-plane two-component refractive indexes such as a ⁇ / 4 retardation film and a ⁇ / 2 retardation film.
  • cellulose resin, polycarbonate resin, polyarylate resin, polyester resin, acrylic resin, polysulfone resin, polyethersulfone resin, cyclic olefin resin, alignment solidification of liquid crystal compound A layer etc. can be illustrated.
  • polycarbonate resin films are preferably used because they are inexpensive and uniform.
  • a film forming method a solvent casting method or a precision extrusion method capable of reducing the residual stress of the film can be used, but the solvent casting method is preferably used in terms of uniformity.
  • the stretching method is not particularly limited, and roll-to-roll longitudinal uniaxial stretching, tenter transverse uniaxial stretching, and the like that can obtain uniform optical properties can be applied.
  • the in-plane retardation Re (550) at a wavelength of 550 nm can be 100 to 180 nm, preferably 110 to 170 nm, and more preferably. 120-160 nm.
  • the in-plane retardation Re (550) at a wavelength of 550 nm can be 220 to 320 nm, preferably 240 to 300 nm, and more preferably 250 to 280 nm.
  • the flexible substrate When the flexible substrate is a retardation film, it may exhibit reverse wavelength dispersion in which the retardation value increases according to the wavelength of the measurement light, and the retardation value decreases according to the wavelength of the measurement light.
  • a positive chromatic dispersion characteristic may be exhibited, or a flat chromatic dispersion characteristic in which the retardation value hardly changes depending on the wavelength of the measurement light may be exhibited.
  • the flexible substrate is a retardation film exhibiting reverse wavelength dispersion
  • the retardation at the wavelength ⁇ of the flexible substrate is expressed as Re ( ⁇ )
  • the flexible substrate is Re (450) / Re (550) ⁇ 1 and Re (650) / Re (550)> 1 can be satisfied.
  • the flexible base material is preferably colorless and transparent from the viewpoint that light can be transmitted and absorbed. More specifically, the total light transmittance is preferably 80% or more, and more preferably 85% or more. Further, the haze is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less.
  • the flexible substrate can be used as a substrate of an organic device or an energy device
  • the flexible substrate is preferably insulative and preferably has an electric resistivity of 10 6 ⁇ cm or more.
  • the surface of the flexible substrate may be subjected to surface activation treatment for cleaning the surface from the viewpoint of adhesion to the inorganic thin film layer or the like.
  • surface activation treatment include corona treatment, plasma treatment, and flame treatment.
  • the base material layer includes other layers in addition to the flexible base material for the purpose of improving adhesion and / or flatness with the inorganic thin film layer. Also good.
  • the gas barrier film of the present invention may contain other layers in portions other than the base material layer. Examples of the other layers include organic layers such as a slippery layer, a planarization layer, and an anti-blocking layer.
  • the organic layer is also referred to as “organic layer A”.
  • the organic layer A may be laminated on the surface of the flexible base material included in the base material layer on the inorganic thin film layer side, or may be laminated on the surface opposite to the inorganic thin film layer side, You may laminate
  • the substrate layer preferably has an organic layer A laminated on the surface of the flexible substrate on the inorganic thin film layer side.
  • the organic layer A is preferably a planarization layer.
  • the organic layer A is formed by applying a resin composition containing a monomer and / or oligomer of a photocurable resin such as an ultraviolet ray or an electron beam curable resin on a flexible substrate, and drying the ultraviolet ray or an electron as necessary. It can be formed by curing by irradiation with a wire.
  • the resin composition may contain additives such as a solvent, a photopolymerization initiator, a thermal polymerization initiator, an antioxidant, an ultraviolet absorber, and a plasticizer as necessary.
  • Examples of methods by coating include various conventionally used coating methods such as spray coating, spin coating, bar coating, curtain coating, dipping method, air knife method, slide coating, hopper coating, reverse roll coating, gravure coating, Examples of the method include extrusion coating.
  • an acrylate resin can be used.
  • the acrylate resin is preferably a photocurable resin.
  • the photocurable resin is a resin that starts to be polymerized by ultraviolet rays, electron beams, or the like and cures.
  • a resin other than the acrylate resin may be included to the extent that the effect is not impaired.
  • Specific examples include polyester resins, isocyanate resins, ethylene vinyl alcohol resins, vinyl-modified resins, epoxy resins, phenol resins, urea melamine resins, styrene resins, and alkyl titanates, which contain one or more of these in combination. But you can.
  • the flatness of the surface can be improved by changing the drying conditions and curing conditions of the flattening layer, and it can also be used as an easy-sliding layer or an antiblocking layer.
  • the flattening layer when the temperature change of the elastic modulus of the flattening layer surface is evaluated by a rigid pendulum type physical property tester (for example, RPT-3000W manufactured by A & D Co., Ltd.), the flattening layer surface It is preferable that the temperature at which the elastic modulus is reduced by 50% or more is 150 ° C. or more.
  • a resin composition containing inorganic particles can be used.
  • the inorganic particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, and zirconium oxide.
  • a resin composition containing inorganic particles can be used.
  • the inorganic particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, and zirconium oxide.
  • the gas barrier film of the present invention may contain other layers in addition to the base material layer and the inorganic thin film layer.
  • the said organic layer A is mentioned, for example.
  • the organic layer A that can be contained in a portion other than the base material layer of the gas barrier film of the present invention is also referred to as “organic layer B” below.
  • an easy slipping layer, a flattening layer, an anti-blocking layer, a matting agent layer, a protective layer, an antistatic layer, a smoothing layer, an adhesion improving layer, a light shielding layer, an antireflection layer, a hard coat layer, stress relaxation Examples include a layer, an antifogging layer, an antifouling layer, a printing layer, and an easy adhesion layer.
  • the organic layer B may be laminated
  • the gas barrier film of the present invention preferably further has an organic layer B on the surface of the inorganic thin film layer opposite to the base material layer from the viewpoint of water vapor barrier properties.
  • Examples of the organic layer B include a layer composed of the resin described for the organic layer A in the above, a layer containing an additive for giving each function to the resin described for the organic layer A, and the like.
  • the film is appropriately selected depending on the use and usage of the conductive film.
  • Examples of the method for laminating the organic layer B include the methods described above for the organic layer A.
  • the organic layer B may be a layer formed using a composition containing an inorganic polymer such as polysilazane.
  • an inorganic polymer such as polysilazane.
  • the inorganic polymer layer can be adjusted to a desired film thickness by a single application, or can be adjusted to a desired film thickness by applying a plurality of times. In the case of applying a plurality of times, it is more effective to carry out the curing process for each application from the viewpoint of securing a diffusion path of gas generated by curing and correcting defects such as cracks.
  • the inorganic polymer layer can be formed by applying a coating liquid containing an inorganic polymer such as polysilazane on the inorganic thin film layer and drying it, followed by curing the formed coating film.
  • a coating liquid containing an inorganic polymer such as polysilazane
  • the coating solution a solution obtained by dissolving or dispersing an inorganic polymer in a solvent can be used.
  • concentration of the inorganic polymer in the coating solution may be appropriately adjusted according to the thickness of the inorganic polymer layer and the pot life requirement of the coating solution, but is usually 0.2 to 35% by mass.
  • examples of the polysilazane that is an inorganic polymer include perhydropolysilazane (PHPS) and organopolysilazane.
  • PHPS perhydropolysilazane
  • organopolysilazane organopolysilazane
  • the solvent a solvent that does not react with the inorganic polymer to be used, is suitable for dissolving or dispersing the inorganic polymer, and does not adversely affect the inorganic thin film layer can be appropriately selected and used.
  • the solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers.
  • examples of the solvent include hydrocarbons such as pentane, hexane, cyclohexane, toluene and xylene, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These solvents may be used as a mixture of two or more.
  • an amine catalyst When polysilazane is used as the inorganic polymer, an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, or an Rh compound such as Rh acetylacetonate is used in the coating solution to promote modification to silicon oxynitride.
  • a metal catalyst such as can also be added.
  • the amount of the catalyst added to the polysilazane is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and 0.5 to 2% by mass based on the total amount of the coating solution. More preferably. By setting the addition amount of the catalyst within the above range, it is possible to suppress excessive silanol formation, film density reduction, film defect increase, and the like due to rapid progress of the reaction.
  • Drying may be performed under conditions that can remove the solvent in the coating solution. Further, for example, the coating liquid may be applied and dried simultaneously on a heated hot plate.
  • Examples of the curing method for the formed coating film include curing the inorganic polymer in the coating film, such as plasma CVD, ion implantation, ultraviolet irradiation, vacuum ultraviolet irradiation, oxygen plasma irradiation, and heat treatment. Can be used. Among these, it is preferable to use a method of irradiating the coating film with vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less as a curing method. Moreover, the method of irradiating a coating film with vacuum ultraviolet light is more preferable when polysilazane is used as an inorganic polymer.
  • VUV light vacuum ultraviolet light
  • the coating film contains silanol groups, and there are cases where 2 ⁇ x ⁇ 2.5.
  • y is basically 1 or less because nitriding is generally unlikely to proceed more than the oxidation of Si.
  • Si—H and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation with vacuum ultraviolet irradiation, etc. It is considered that it is recombined as -N (an Si dangling bond may be formed). That is, perhydropolysilazane is cured as a SiN y composition without being oxidized. In this case, cleavage of the polymer main chain does not occur. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. Cut H is released into the epidural as H 2.
  • Si—O—Si Bonds by Hydrolysis and Dehydration Condensation Si—N bonds in perhydropolysilazane are hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH.
  • Two Si—OH are dehydrated and condensed to form a Si—O—Si bond and harden. This is a reaction that occurs even in the atmosphere, but during vacuum ultraviolet irradiation in an inert atmosphere, it is considered that water vapor generated as outgas from the resin base material by the heat of irradiation becomes the main moisture source.
  • Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO 2.1 to SiO 2.3 is obtained.
  • composition of the silicon oxynitride of the layer obtained by subjecting the coating film containing polysilazane to vacuum ultraviolet irradiation is adjusted by appropriately combining the oxidation mechanisms (1) to (4) described above to control the oxidation state. It can be carried out.
  • intensity of the vacuum ultraviolet rays in the coated surface of the coating film containing polysilazane is subjected is preferably in the range of 1 ⁇ 100000mW / cm 2, it is within the range of 30 ⁇ 200mW / cm 2 It is more preferable. If the illuminance is 1 mW / cm 2 or more, there is no concern about the reduction of the reforming efficiency, and if it is 100000 mW / cm 2 or less, the coating film is not ablated and damages the flexible substrate. It is preferable because it is not.
  • the integrated light amount (integrated irradiation energy amount) of vacuum ultraviolet rays irradiated to the coating film containing polysilazane is 1.0 to 100 mJ / in the following formula normalized by the film thickness of the inorganic polymer layer. preferably cm 2 / nm is in the range of 1.5 to more preferably in the range of 30mJ / cm 2 / nm, still in the range of 2.0 ⁇ 20mJ / cm 2 / nm A range of 5.0 to 20 mJ / cm 2 / nm is particularly preferable.
  • the normalized integrated light quantity is 1.0 mJ / cm 2 / nm or more, the modification can be sufficiently performed.
  • the normalized integrated light quantity is 100 mJ / cm 2 / nm or less, the excessive reforming condition is not achieved, and cracks in the inorganic polymer layer can be prevented. Even when the inorganic polymer layer is cured a plurality of times in order to obtain a desired film thickness, it is preferable that the standardized integrated light amount is within the range for each layer.
  • a rare gas excimer lamp is preferably used as the vacuum ultraviolet light source.
  • Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules.
  • excited atoms of rare gases that have gained energy by discharge or the like can form molecules by combining with other atoms.
  • the rare gas is xenon, e + Xe ⁇ Xe * Xe * + 2Xe ⁇ Xe 2 * + Xe Xe 2 * ⁇ Xe + Xe + h ⁇ (172 nm)
  • excimer light having a wavelength of 172 nm is emitted.
  • ⁇ Excimer lamps are characterized by high efficiency because radiation concentrates on one wavelength and almost no other light is emitted. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.
  • Dielectric barrier discharge is a gas space that is generated in a gas space by applying a high frequency high voltage of several tens of kHz to the electrode by placing a gas space between both electrodes through a dielectric such as transparent quartz. This discharge is called a micro discharge (micro discharge). When the micro discharge streamer reaches the tube wall (derivative), the electric charge accumulates on the dielectric surface, and the micro discharge disappears.
  • Electrodeless electric field discharge by capacitive coupling, also called RF discharge.
  • the lamp, the electrodes, and their arrangement may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.
  • an electrode in which fine metal wires are meshed is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.
  • the outer diameter of the double-cylindrical lamp is about 25 mm, the difference in distance to the irradiation surface cannot be ignored directly below the lamp axis and on the side of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.
  • the biggest feature of the capillary excimer lamp is its simple structure.
  • the quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.
  • the outer diameter of the tube of the thin tube lamp is about 6-12mm. If it is too thick, a high voltage is required for starting.
  • either dielectric barrier discharge or electrodeless field discharge can be used.
  • the shape of the electrode the surface in contact with the lamp may be flat, but by setting the shape according to the curved surface of the lamp, the lamp can be firmly fixed and the discharge is more stable when the electrode is in close contact with the lamp. .
  • the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.
  • the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this excimer light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a small amount of oxygen.
  • the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy of the active oxygen and ozone and the ultraviolet radiation, the polysilazane layer can be modified in a short time.
  • ⁇ Excimer lamps have high light generation efficiency and can be lit with low power. In addition, it emits energy in the ultraviolet region, that is, in a short wavelength range because it does not emit light of a long wavelength that causes a temperature increase due to light irradiation, and has a feature that suppresses an increase in the surface temperature of an irradiation object. . For this reason, it is suitable for the modification
  • the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably in the range of 10 to 100,000 volume ppm, more preferably in the range of 50 to 50,000 volume ppm, and still more preferably in the range of 100 to 10,000 volume ppm. It is.
  • the gas that satisfies the irradiation environment at the time of irradiation with vacuum ultraviolet rays it is preferable to use a dry inert gas, and among these, dry nitrogen gas is preferably used from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation environment and changing the flow rate ratio.
  • the coefficient of static friction between one surface of the gas barrier film and the other surface is preferably 0.30 or more and 2.0 or less.
  • the coefficient of static friction is measured by dividing a gas barrier film having an upper surface and a lower surface into two sheets and bringing the upper surface of the first gas barrier film into contact with the lower surface of the second gas barrier film. Can do.
  • the coefficient of static friction can be measured in an environment of a temperature of 23 ° C. and a humidity of 50 RH% in accordance with the gradient method of JIS P8147.
  • the surface roughness on both sides of the gas barrier film may be adjusted.
  • the surface roughness of the exposed surface of the inorganic thin film layer and the surface roughness of the exposed surface of the base material layer may be adjusted.
  • the surface roughness of the exposed surface of one inorganic thin film layer and the surface roughness of the exposed surface of the other inorganic thin film layer may be adjusted.
  • the surface roughness of at least one surface of the gas barrier film is increased, the static friction coefficient between the front and back surfaces tends to decrease.
  • the surface roughness of the inorganic thin film layer can be changed, for example, according to conditions such as the pressure in the vacuum chamber (vacuum degree) and film thickness in the film formation conditions of the inorganic thin film layer, and the composition of the inorganic film formation layer.
  • the surface roughness of the inorganic thin film layer is adjusted by adjusting the surface roughness of the flexible base material serving as a base and the surface roughness of the intermediate layer disposed between the inorganic thin film layer and the flexible base material. Can also be adjusted.
  • a corona treatment or the like may be performed.
  • the arithmetic average roughness Ra of the surface of the inorganic thin film layer can be 3 nm or less.
  • the arithmetic average roughness Ra can be obtained by attaching the gas barrier film to an epoxy plate with an adhesive and then observing the surface with a white interference microscope.
  • the arithmetic average roughness Ra is an arithmetic average roughness according to JIS B 0601: 2001.
  • the average of the distances from the horizontal plane to the four corners is 2 mm or less.
  • This average value can be measured as follows. First, the gas barrier film is held for 48 hours under conditions of a temperature of 23 ° C. and a humidity of 50 RH%. Next, a 50 mm square part is cut out from the gas barrier film to obtain a sample. The sample is placed on the horizontal plane so that the center of the sample is in contact with the horizontal plane, and a total of four distances from the horizontal plane to the four corners are obtained. Finally, the average of these 4 points is obtained.
  • the stress of each inorganic thin film layer on the front and back surfaces or balance the stress between the inorganic thin film layer on one side and the coating layer below it. Or reducing the residual stress of the inorganic thin film layer itself, or combining these to balance the stress on both sides.
  • the stress can be adjusted by the film forming pressure and film thickness when forming the inorganic thin film layer, the degree of cure shrinkage when forming the coating layer, and the like.
  • the water vapor permeability of the gas barrier film of the present invention at 40 ° C. and 90% RH may be 0.1 g / m 2 / day or less, and may be 0.001 g / m 2 / day or less.
  • the water vapor permeability can be measured by a Ca corrosion test method in accordance with ISO / WD 15106-7 (Annex C).
  • the layer structure of the gas barrier film of the present invention is not particularly limited as long as it includes the base material layer and the inorganic thin film layer.
  • the gas barrier film of the present invention may have one organic layer A and / or one organic layer B, or two or more organic layers. You may have A and / or the organic layer B of 2 or more layers.
  • two or more organic layers A are included, two or more identical organic layers A may be included, or two or more organic layers A may be included. The same applies to the organic layer B.
  • the organic layer A and the organic layer B may be the same layer or different layers.
  • the layer configuration may be a two-layer configuration of flexible substrate / inorganic thin film layer (configuration shown in FIG.
  • inorganic thin film layer (configuration shown in FIG. 2), an inorganic thin film layer / flexible substrate / inorganic thin film layer, or a flexible substrate / organic layer A / inorganic thin film layer.
  • Organic layer B (configuration shown in FIG. 3), inorganic thin film layer / flexible substrate / organic layer A / inorganic thin film layer, etc.
  • the gas barrier film of the present invention can be produced by a method in which the base material layer and the inorganic thin film layer are separately produced and bonded, a method in which the inorganic thin film layer is formed on the base material layer, and the like.
  • the organic layer laminated on the surface of the flexible substrate or flexible substrate as described above It is preferable that the thin film layer is formed on A by using a known vacuum film forming method such as a CVD method using glow discharge plasma.
  • a further organic layer B may be formed on the laminated film thus obtained by a known method.
  • the inorganic thin film layer is preferably formed by a continuous film forming process.
  • the inorganic thin film layer may be formed while the flexible substrate is conveyed from the feed roll to the take-up roll. Then, you may form an inorganic thin film layer from the top by inverting a sending roll and a winding roll, and conveying a base material in the reverse direction.
  • the gas barrier film of the present invention is a film excellent in gas barrier property, in which the deterioration of the gas barrier property over time is suppressed particularly under high temperature and high humidity.
  • the gas barrier film of the present invention can be used as a packaging application for foods, industrial products, pharmaceuticals, etc. that require gas barrier properties.
  • the present invention also provides a flexible electronic device having the gas barrier film of the present invention.
  • the gas barrier film of the present invention can also be used as a flexible substrate for flexible electronic devices (for example, flexible displays) such as liquid crystal display elements, solar cells, and organic EL displays that require higher gas barrier properties.
  • the element may be formed directly on the gas barrier film of the present invention, or after the element is formed on another substrate, the present invention. These gas barrier films may be overlaid from above.
  • An inorganic thin film layer and an organic layer A are formed on a flexible substrate, and a step difference measurement between the non-deposited portion and the deposited portion is performed using a surf coder ET200 manufactured by Kosaka Laboratory Co., Ltd. (T) was determined.
  • X-ray photoelectron spectroscopy measurement on the surface of inorganic thin film layer The atomic ratio of the inorganic thin film layer surface of the gas barrier film was measured by X-ray photoelectron spectroscopy (manufactured by ULVAC-PHI, Inc., QuanteraSXM).
  • X-ray photoelectron spectroscopy manufactured by ULVAC-PHI, Inc., QuanteraSXM.
  • AlK ⁇ ray 1486.6 eV, X-ray spot 100 ⁇ m
  • a neutralization electron gun (1 eV) and a low-speed Ar ion gun (10 V) were used for charge correction at the time of measurement.
  • the analysis after the measurement was performed using a spectrum analysis using MultiPak V6.1A (ULVAC-PHI Co., Ltd.), and each of Si 2p, O 1s, N 1s and C 1s obtained from the measured wide scan spectrum. Using the peak corresponding to the binding energy, the surface atom number ratio of C to Si was calculated. As the surface atom number ratio, an average value of values measured five times was adopted.
  • Infrared spectroscopic measurement of inorganic thin film layer surface is a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, FT / IR) equipped with an ATR attachment (PIKE MIRacle) using a germanium crystal as a prism. -460Plus).
  • the total light transmittance of the gas barrier film was measured with a direct reading haze computer (model HGM-2DP) manufactured by Suga Test Instruments Co., Ltd. After measuring the background without a sample, the gas barrier film was set on a sample holder and the measurement was performed to determine the total light transmittance.
  • the gas barrier property was measured by a Ca corrosion test method in accordance with ISO / WD 15106-7 (Annex C) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, and the water vapor permeability of the gas barrier film was determined.
  • the inorganic thin film layer was laminated
  • ⁇ Film formation condition 1> Source gas supply: 50 sccm (Standard Cubic Centimeter per Minute) Supply amount of oxygen gas: 500sccm Degree of vacuum in the vacuum chamber: 1Pa Applied power from power source for plasma generation: 0.4kW Power supply frequency for plasma generation: 70kHz Film transport speed: 3.0m / min Number of passes: 28
  • Adhesion between base material layer and inorganic thin film layer Adhesion was measured according to ASTM D3359. Specifically, a gas barrier film is placed on a clean glass substrate so that the inorganic thin film layer is on the side opposite to the glass substrate, and the base material reaches the inorganic thin film layer using a cutter guide and a cutter knife. Make 6 x 6 cuts (25 squares). A tape (made by Nichiban Co., Ltd., Cellotape (registered trademark), CT-12M) is applied flatly to the lattice part (cross cut part) due to the cut so that air bubbles do not enter the lattice part +20 mm.
  • a tape made by Nichiban Co., Ltd., Cellotape (registered trademark), CT-12M
  • the attached tape is peeled off at an angle of 60 ° for 0.5 to 1 second, and the state of the lattice portion is observed with a microscope (for example, DIGITAL MICROSCOPE KH7700, manufactured by Hilox).
  • the degree was evaluated according to the following evaluation criteria.
  • Adhesion evaluation criteria 0B: Area ratio where peeling occurred in the crosscut portion 65% or more 1B: Area ratio where peeling occurred in the crosscut portion 35% to 65% 2B: Area ratio where peeling occurred in the crosscut portion 15% to 35% 3B: Area ratio where peeling occurred in the crosscut portion 5% to 15% 4B: Area ratio where peeling occurred in the crosscut portion 5% or less 5B: Area ratio where peeling occurred in the crosscut portion 0%
  • Example 1 Corona treatment on one side of a flexible base cycloolefin polymer film (COP film, thickness: 50 ⁇ m, width: 350 mm, manufactured by Nippon Zeon Co., Ltd., trade name “Zeonor (registered trademark) film, ZF-16”) After coating, the coating agent 1 (Toyochem Co., Ltd., Rioduras (registered trademark) TYAB500LC3NS, with particles) was applied by the gravure coating method, dried at 100 ° C. for 3 minutes, and then using a high-pressure mercury lamp.
  • COP film cycloolefin polymer film, thickness: 50 ⁇ m, width: 350 mm
  • ZF-16 trade name “Zeonor (registered trademark) film, ZF-16”
  • the coating agent 1 Toyochem Co., Ltd., Rioduras (registered trademark) TYAB500LC3NS, with particles
  • the organic layer A1 (easy-sliding layer) having a thickness of 1.5 ⁇ m was laminated by irradiating with ultraviolet rays under conditions of an integrated light quantity of 500 mJ / cm 2 .
  • coating agent 2 (Aronix (registered trademark) UV3701 manufactured by Toa Gosei Co., Ltd.) was applied by the gravure coating method and dried at 100 ° C. for 3 minutes.
  • UV irradiation is performed under the condition of an integrated light quantity of 500 mJ / cm 2 , and an organic layer A 2 (planarization layer) having a thickness of 1.8 ⁇ m is laminated to form a laminated film as a base material layer. Obtained.
  • the inorganic thin film layer was laminated on the surface of the laminated film thus obtained on the organic layer A2 side according to the method for producing the inorganic thin film layer.
  • a protective film manufactured by Sanei Kaken Co., Ltd., NSA-35H, PET 50 ⁇ m
  • NSA-35H PET 50 ⁇ m
  • the gas barrier film 1 was obtained by punching into a size.
  • peeling / cracking of 200 ⁇ m or more was observed in the cross-sectional observation after 768 hours after storage.
  • the obtained gas barrier film is in the order of oxygen, silicon and carbon in the order of the atomic ratio in the region of 90% or more in the film thickness direction of the inorganic thin film layer, and the carbon distribution curve in the film thickness direction.
  • the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve was 5% or more.
  • the thickness of the inorganic thin film layer of the obtained gas barrier film was 0.7 ⁇ m. Further, the water vapor permeability of the obtained gas barrier film under conditions of a temperature of 40 ° C. and a humidity of 90% RH was 5.0 ⁇ 10 ⁇ 5 g / (m 2 ⁇ day).
  • Example 2 A film on which an inorganic thin film layer obtained in the same manner as in Example 1 was laminated was subjected to laser processing (produced by Em Rays, small excimer laser, output 6 mJ / cm 2 , frequency 500 Hz, processing speed 2 mm / sec), 50 mm ⁇ 50 mm. A gas barrier film 2 was obtained. As a result of measuring the wet heat durability time of the obtained test piece, peeling / cracking of 200 ⁇ m or more was observed in the cross-sectional observation after 768 hours after storage.
  • Example 3 In Example 1, the gas barrier film 3 was obtained in the same manner as in Example 1 except that the following ⁇ Film Formation Condition 2> and ⁇ Film Formation Condition 3> were continuously performed as the film formation conditions of the inorganic thin film layer. It was. As a result of measuring the wet heat durability time of the obtained test piece, peeling / cracking of 200 ⁇ m or more was observed in the cross-sectional observation for 1008 hours after storage.
  • ⁇ Film formation condition 2> Source gas supply: 50 sccm (Standard Cubic Centimeter per Minute) Supply amount of oxygen gas: 500sccm Degree of vacuum in vacuum chamber: 1Pa Applied power from power supply for plasma generation: 0.6kW Power supply frequency for plasma generation: 70kHz Film transport speed: 3.0m / min Number of passes: 4 times ⁇ Film formation condition 3>
  • Source gas supply: 50 sccm (Standard Cubic Centimeter per Minute) Supply amount of oxygen gas: 500sccm Degree of vacuum in the vacuum chamber: 1Pa Applied power from power source for plasma generation: 0.4kW Power supply frequency for plasma generation: 70kHz Film transport speed: 3.0m / min Number of passes: 24
  • the obtained gas barrier film is in the order of oxygen, silicon and carbon in the order of the atomic ratio in the region of 90% or more in the film thickness direction of the inorganic thin film layer, and the carbon distribution curve in the film thickness direction.
  • the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve was 5% or more.
  • the thickness of the inorganic thin film layer of the obtained gas barrier film was 0.7 ⁇ m. Further, the water vapor permeability of the obtained gas barrier film under conditions of a temperature of 40 ° C. and a humidity of 90% RH was 5.0 ⁇ 10 ⁇ 5 g / (m 2 ⁇ day).
  • Example 1 In Example 1, coating agent 2 (Aronix (registered trademark) UV3701 manufactured by Toa Gosei Co., Ltd.) was applied by gravure coating, and dried at 120 ° C. for 3 minutes in the same manner as in Example 1. A gas barrier film 4 was obtained. As a result of measuring the wet heat durability time of the obtained test piece, peeling / cracking of 200 ⁇ m or more was observed in the cross-sectional observation for 48 hours after storage.
  • coating agent 2 Aronix (registered trademark) UV3701 manufactured by Toa Gosei Co., Ltd.
  • the obtained gas barrier film is in the order of oxygen, silicon and carbon in the order of the atomic ratio in the region of 90% or more in the film thickness direction of the inorganic thin film layer, and the carbon distribution curve in the film thickness direction.
  • the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve was 5% or more.
  • the thickness of the inorganic thin film layer of the obtained gas barrier film was 0.7 ⁇ m. Further, the water vapor permeability of the obtained gas barrier film under conditions of a temperature of 40 ° C. and a humidity of 90% RH was 5.0 ⁇ 10 ⁇ 5 g / (m 2 ⁇ day).
  • a cutter knife manufactured by KOKUYO Co., Ltd., cutter knife (standard type), replaceable blade HA-100B
  • a film obtained by laminating an inorganic thin film layer obtained in the same manner as in Example 1 is 50 mm ⁇ 50 mm in size. Then, a gas barrier film 5 was obtained.
  • peeling / cracking of 200 ⁇ m or more was observed in a cross-sectional observation for 96 hours after storage.

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Abstract

L'objectif de la présente invention est de produire un film barrière aux gaz permettant de supprimer la réduction des propriétés de barrière aux gaz au fil du temps, en particulier à des températures élevées et en humidité élevée. La présente invention concerne un film barrière aux gaz comportant au moins une couche de film mince inorganique et une couche de matériau de base, comprenant au moins un matériau de base souple, l'adhésion entre la couche de matériau de base et la couche de film mince inorganique étant d'au moins 2B mesurée en fonction de ASTM D3359, la couche de film mince inorganique comportant au moins une face d'extrémité coupée, et comportant au moins un défaut choisi dans le groupe constitué par le pelage et le craquelage, ou ne comportant pas ledit défaut, la région dans laquelle le défaut est présent, si la couche de film mince inorganique comporte ledit défaut, étant située à 120 μm ou moins dans la direction normale de la face d'extrémité coupée.
PCT/JP2017/041452 2016-11-29 2017-11-17 Film barrière aux gaz et dispositif électronique souple WO2018101084A1 (fr)

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JP2018089959A (ja) 2018-06-14
TW201826584A (zh) 2018-07-16
JP6983039B2 (ja) 2021-12-17

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