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WO2018168671A1 - Revêtement formant barrière aux gaz, film formant barrière aux gaz, procédé de production d'un revêtement formant barrière aux gaz et procédé de production d'un film formant barrière aux gaz - Google Patents

Revêtement formant barrière aux gaz, film formant barrière aux gaz, procédé de production d'un revêtement formant barrière aux gaz et procédé de production d'un film formant barrière aux gaz Download PDF

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Publication number
WO2018168671A1
WO2018168671A1 PCT/JP2018/009140 JP2018009140W WO2018168671A1 WO 2018168671 A1 WO2018168671 A1 WO 2018168671A1 JP 2018009140 W JP2018009140 W JP 2018009140W WO 2018168671 A1 WO2018168671 A1 WO 2018168671A1
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Prior art keywords
gas barrier
barrier film
film
composition
gas
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PCT/JP2018/009140
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English (en)
Japanese (ja)
Inventor
森　孝博
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コニカミノルタ株式会社
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Priority to JP2019505959A priority Critical patent/JPWO2018168671A1/ja
Priority to CN201880017865.5A priority patent/CN110418859A/zh
Publication of WO2018168671A1 publication Critical patent/WO2018168671A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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

  • a lightweight and highly flexible gas barrier film is used for sealing electronic devices such as organic EL (Electro Luminescence) elements, liquid crystal display elements, and solar cells.
  • a gas barrier film includes a gas barrier film on a resin base film, and the gas barrier film can prevent intrusion of gas such as water and oxygen in the atmosphere.
  • the present invention provides a gas barrier film, a gas barrier film, a gas barrier film manufacturing method, and a gas barrier film manufacturing method capable of realizing high gas barrier properties and high transparency.
  • a gas barrier film a gas barrier film, a method for producing a gas barrier film, and a method for producing a gas barrier film capable of realizing high gas barrier properties and high transparency.
  • the CVD film of SiOxCy composition using HMDSO as a raw material has a problem that, when the carbon ratio y increases, the absorption in the visible light region increases and becomes yellowish.
  • the conventional CVD film having the SiOxCy composition using HMDSO as a raw material it is difficult to achieve both good barrier properties and good optical characteristics.
  • an organic silicon compound having 1 O atom relative to 1 Si atom is used as a CVD raw material. Furthermore, it is preferable to use an organosilicon compound having C atoms of less than 2 with respect to Si atom 1, and more preferably an organosilicon compound having C atoms of 1 or less as a CVD raw material. Furthermore, it is preferable to use an organosilicon compound having a Si—H bond as a CVD raw material.
  • a CVD film having a SiOxCy composition using the above cyclic siloxane as a raw material is formed under specific conditions, so that the sum of the oxygen ratio x and the carbon ratio y is in the range of [x + y ⁇ 2].
  • This is not only the structure in which O is replaced by CH 2 from the structure of SiO 2 shown in FIG. 1, that is, not only the structure in which two Si atoms are bonded to C, but also three or four Si atoms are bonded to C. It is thought that it has a structure. Note that, from the characteristics of CVD film formation, it can be assumed that highly reactive Si—H does not remain.
  • a CVD film having a SiOxCy composition using cyclic siloxane as a raw material Si—C is present together with CH 2 between Si—O, and therefore CH 2 interposed between Si—O is reduced.
  • a CVD film having a SiOxCy composition using cyclic siloxane as a raw material has a denser structure than a CVD film having a SiOxCy composition using HMDSO as a raw material.
  • the SiOxCy composition of the gas barrier film shown in the graph of FIG. 11 does not have a composition that falls within the range of the five points of ABCDE described above. Specifically, the SiOxCy composition of the gas barrier film shown in the graph of FIG. 11 is in a range where the carbon ratio y (C / Si) exceeds 0.8 or in a range of [x + y> 2]. Yes. For this reason, since this gas barrier film has low gas barrier properties and low optical properties, a gas barrier film excellent in gas barrier properties and optical properties cannot be realized.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 3 nm or less
  • X-ray photoelectron spectrometer Model name “VG Theta Probe” manufactured by Thermo Fisher Scientific Irradiation
  • X-ray Single crystal spectroscopy AlK ⁇ X-ray spot and size: 800 ⁇ 400 ⁇ m oval
  • the number of minute protrusions of 10 nm or more in the gas barrier film is defined by a value detected and counted by the following method.
  • the acquired three-dimensional surface roughness data is subjected to a process of removing a roughness waviness component by applying a high-pass filter having a wavelength of 10 ⁇ m.
  • protrusions having a height of 10 nm or more are counted when the maximum peak position when the data is displayed as a histogram is set to zero.
  • the counted number of protrusions is calculated as the number per mm 2 . More specifically, under the conditions of a measurement resolution of about 250 nm, was measured and counted (0.114 mm 2 as the area) range 6 field of 159.2 ⁇ m ⁇ 119.3 ⁇ m, calculates the number per 1 mm 2.
  • FIGS. 13 to 15 show images (159.2 ⁇ m ⁇ 119.3 ⁇ m) of the surface state of the gas barrier film in which the height of the three-dimensional surface roughness conversion data obtained by the above method is displayed in gray scale. .
  • the color is displayed whiter as the height increases from the reference position on the surface of the gas barrier film.
  • a gas-phase film-forming gas barrier film obtained by a vacuum plasma CVD method can produce a target compound by selecting conditions such as a film-forming gas as a raw material, a decomposition temperature, and input power.
  • 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-phase film-forming gas barrier film.
  • these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
  • FIG. 16 shows an example of a schematic diagram of a roll-to-roll (roll to roll) inter-roller discharge plasma CVD apparatus applied to the vacuum plasma CVD method.
  • FIG. 16 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 a gas-phase film-forming gas barrier film is applied.
  • a magnetic field generator 61 and a magnetic field generator 62 fixed so as not to rotate even when the film forming roller rotates are provided inside the film forming roller 53 and the film forming roller 56, respectively.
  • the amount of power to be supplied is in the range of 0.6 to 3.0 kW from the viewpoint of improving the gas barrier property. If it is 0.1 kW or more, the generation of foreign matters called particles can be suppressed. Moreover, if it is 10.0 kW or less, the emitted heat amount can be suppressed and the generation
  • the AC frequency is preferably in the range of 50 Hz to 500 kHz.
  • the magnetic field generators 61 and 62 known magnetic field generators can be used as appropriate.
  • an inter-roller discharge plasma processing apparatus to which a magnetic field is applied is used, the substrate is wound around a pair of film forming rollers, and the film is formed between the pair of film forming rollers. It is preferable to form the gas barrier film by a plasma chemical vapor deposition method in which plasma discharge is performed while supplying a film gas. Further, when discharging while applying a magnetic field between a pair of film forming rollers, it is preferable to reverse the polarity between the pair of film forming rollers alternately.
  • each of R 1 , R 2 , and R 3 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.
  • Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as a polysilazane-containing coating solution as it is.
  • Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials.
  • the illuminance of the VUV By setting the illuminance of the VUV to 30 mW / cm 2 or more, sufficient reforming efficiency can be obtained, and when it is 200 mW / cm 2 or less, the rate of damage to the coating film is extremely suppressed and damage to the substrate is also reduced. Can be made.
  • a rare gas excimer lamp is preferably used as the vacuum ultraviolet light source. Since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process is likely to decrease. Therefore, it is preferable to perform VUV irradiation in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration at the time of VUV irradiation is preferably in the range of 10 to 10,000 ppm, more preferably in the range of 50 to 5000 ppm, still more preferably in the range of 80 to 4500 ppm, and most preferably in the range of 100 to 1000 ppm.
  • R 4 to R 9 each represent the same or different organic group having 1 to 8 carbon atoms.
  • at least one group of R 4 to R 9 includes either an alkoxy group or a hydroxyl group.
  • m is an integer of 1 or more.
  • the organopolysiloxane represented by the general formula (2) it is particularly preferable that m is 1 or more and the weight average molecular weight in terms of polystyrene is 1000 to 20000. If the weight average molecular weight in terms of polystyrene of the organopolysiloxane is 1000 or more, the intermediate layer to be formed is hardly cracked and the gas barrier property can be maintained, and if it is 20000 or less, the formed intermediate layer is cured. And sufficient hardness as an intermediate layer can be obtained.
  • the gas barrier film 17 has a base material 11 and a gas barrier film 13 provided on the base material 11.
  • the gas barrier film 10 shown in FIG. In the gas barrier film 10, a plasma polymerization layer 12 is provided between the base material 11 and the gas barrier film 13.
  • the gas barrier film 10 should just have the base material 11 and the gas barrier film
  • the gas barrier film 13 has at least one chemical vapor deposition (CVD) film having a SiOxCy composition in the above-described predetermined composition range in the thickness direction in a range of 20 nm to 1000 nm. Yes.
  • the gas barrier film 13 may be provided in a plurality of layers on the substrate 11, and may be provided on both sides as well as one side of the substrate 11.
  • the thickness of the plasma polymerization layer 12 is preferably 10 nm to 10 ⁇ m, more preferably 100 nm to 5 ⁇ m, and further preferably 200 nm to 2 ⁇ m.
  • the thickness of the plasma polymerization layer 12 can be measured by cross-sectional SEM observation. When the interface of the plasma polymerization layer 12 is unclear, the composition analysis of the cross section is performed with an EDX (energy dispersive X-ray analysis) apparatus attached to the SEM apparatus, and the measured value is obtained after clarifying the interface. Can be sought.
  • EDX energy dispersive X-ray analysis
  • the film formation conditions of the plasma polymerization layer 12 are, for example, a gas pressure of 0.1 to 100 Pa, preferably 1 to 50 Pa, a substrate temperature of ⁇ 20 to 200 ° C., preferably 0 to 100 ° C., and the monomer component on the substrate. And a method of performing glow discharge (usually using high-frequency power) while supplying to the substrate.
  • TCTS tetramethylcyclotetrasiloxane
  • Hepta-MCTS heptamethylcyclotetrasiloxane
  • pentamethylcyclopentasiloxane shown in the above [Chemical Formula 1] are used as the film forming gas used for producing the plasma polymerization layer 12
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • COP polycycloolefin
  • the base material 11 has little light absorption and small haze. For this reason, the base material 11 can be appropriately selected from resin films that are generally applied to optical films.
  • the substrate 11 is not limited to a single wafer shape and a roll shape, but a roll shape applicable to a roll-to-roll production method is preferable from the viewpoint of productivity.
  • the thickness of the substrate 11 is not particularly limited, but is preferably about 5 to 500 ⁇ m.
  • the hard coat layer has fine particles of inorganic compounds such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, or polymethyl methacrylate to adjust the scratch resistance, slipperiness and refractive index.
  • the hard coat layer can be applied by a known wet coating method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method using the above coating solution.
  • the coating thickness of the coating solution is, for example, 0.1 to 30 ⁇ m.
  • surface treatment such as vacuum ultraviolet irradiation on the base material 11 in advance.
  • the source gas type, the gas supply amount, the degree of vacuum, and the applied voltage are set so that the film forming conditions in the first film forming unit and the second film forming unit are the film forming conditions 1 to 11 shown in Table 1 below
  • the power frequency, the film forming roll temperature, and the substrate roll conveying speed were set.
  • a gas barrier film or a plasma polymerization layer was prepared by applying any one of the film forming conditions 1 to 11 in each film forming unit. Further, as conditions common to the film forming conditions 1 to 11, the effective film forming width was about 300 mm, the power frequency was 80 kHz, and the temperature of the film forming roll was 10 ° C.
  • a gas barrier film having a thickness of 81 nm was formed on the substrate 1 using the film formation condition 1, and a gas barrier film of Sample 101 was prepared.
  • a gas barrier film of Sample 116 was produced in the same manner as Sample 105 described above, except that Substrate 5 was used instead of Substrate 1.
  • the XPS analysis was measured at 2.8 nm intervals in the thickness direction. Further, in the determination of the SiOxCy composition constituting the gas barrier film, the measurement points on the surface layer of the gas barrier film were excluded because of the influence of the surface adsorbate. Further, in the gas barrier film, the thickness within the range of the above-mentioned ABCDE or the above-mentioned A 1 B 1 CDE 1 is the second composition from the surface layer and the composition immediately below the surface layer because the film is continuously formed. It was judged that the composition of the measurement points was close, and the thickness was measured on the assumption that the composition of the second measurement point from the surface layer was continuously formed up to the surface position.
  • the number of protrusions of the obtained gas barrier film was evaluated according to the following criteria (rank). Less than 5:10 pieces / mm 2 4:10 pieces / mm 2 or more, 50 / mm 2 less than 3:50 pieces / mm 2 or more, 100 / mm 2 less than 2: 100 pieces / mm 2 or more, 200 / Less than mm 2 1: 200 / mm 2 or more
  • Samples 109 to 115 have a plasma polymerization layer as a base layer of the gas barrier film.
  • the sample 109 and the sample 110 have a lower water vapor transmission rate than the sample 105 in which the gas barrier film is directly formed on the substrate 1 under the same film formation condition 5. From this result, it is possible to realize a higher gas barrier property by producing a plasma polymerization layer as an underlayer of the gas barrier film. Furthermore, higher gas barrier properties can be realized by forming an overcoat layer on the gas barrier film as in samples 111 to 115.
  • the sample 101 and the sample 102 have a small supply amount of oxygen as a reaction gas in forming the gas barrier film.
  • the supply amount of oxygen as a reaction gas is excessive in the formation of the gas barrier film. Therefore, the samples 101 to 104 do not have a region having a composition within the range of the above-described ABCDE or the above-described A 1 B 1 CDE 1 .
  • the sample 101 and the sample 102 with a small supply amount of oxygen have a large carbon ratio y (C / Si) in the gas barrier film, and have a high light absorption rate of 450 nm. For this reason, the optical characteristics of the gas barrier film are not sufficient.
  • the sample 103 and the sample 104 in which the supply amount of oxygen is excessive have a deteriorated water vapor transmission rate because the oxygen ratio x (O / Si) in the gas barrier film increases. This is presumably because the presence of Si—OH in the gas barrier film increased due to the increase in the oxygen ratio x (O / Si) in the gas barrier film, and a water vapor path was formed by hydrophilic groups.
  • the sample 116 has a thickness within the range of A 1 B 1 CDE 1 described above of 20 nm or more, but the arithmetic average roughness (Ra) of the surface of the gas barrier film exceeds 2.0 nm.
  • Ra arithmetic average roughness

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Abstract

Un revêtement formant barrière aux gaz présentant d'excellentes propriétés de barrière aux gaz et une remarquable transparence est préparé, le revêtement formant barrière aux gaz présentant une rugosité moyenne arithmétique (Ra) égale ou inférieure à 2,0 nm et possédant, dans une plage allant de 20 nm à 1 000 nm dans le sens de l'épaisseur, une composition qui, lorsqu'elle est exprimée de la façon suivante : SiOxCy, se situe à l'intérieur d'une zone enfermée par les cinq points A (x = 0,8, y = 0,8), B (x = 1,2, y = 0,8), C (x = 1,9, y = 0,1), D (x = 1,9, y = 0,0) et E (x = 0,8, y = 0,55) dans un système de coordonnées orthogonales où x correspond à l'axe horizontal et y à l'axe vertical.
PCT/JP2018/009140 2017-03-17 2018-03-09 Revêtement formant barrière aux gaz, film formant barrière aux gaz, procédé de production d'un revêtement formant barrière aux gaz et procédé de production d'un film formant barrière aux gaz WO2018168671A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2019505959A JPWO2018168671A1 (ja) 2017-03-17 2018-03-09 ガスバリア膜、ガスバリア性フィルム、ガスバリア膜の製造方法、及び、ガスバリア性フィルムの製造方法
CN201880017865.5A CN110418859A (zh) 2017-03-17 2018-03-09 气体阻隔膜、气体阻隔性膜、气体阻隔膜的制造方法、及气体阻隔性膜的制造方法

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Application Number Priority Date Filing Date Title
JP2017052964 2017-03-17
JP2017-052964 2017-03-17

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WO2018168671A1 true WO2018168671A1 (fr) 2018-09-20

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WO2020085248A1 (fr) * 2018-10-23 2020-04-30 住友化学株式会社 Corps stratifié, dispositif électronique flexible et procédé de fabrication de corps stratifié
JP2022128500A (ja) * 2019-09-30 2022-09-01 大日本印刷株式会社 バリア性積層体、該バリア性積層体を備えるヒートシール性積層体および該ヒートシール性積層体を備える包装容器
WO2023153307A1 (fr) * 2022-02-10 2023-08-17 日東電工株式会社 Film barrière aux gaz, son procédé de production, plaque de polarisation avec couche barrière aux gaz et dispositif d'affichage d'image
WO2023153010A1 (fr) * 2022-02-10 2023-08-17 日東電工株式会社 Film barrière aux gaz, procédé associé de production, plaque de polarisation à couche barrière aux gaz et dispositif d'affichage d'images
WO2024176674A1 (fr) * 2023-02-22 2024-08-29 日東電工株式会社 Stratifié, procédé de production de stratifié et polariseur avec couche barrière contre les gaz

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CN115431616B (zh) * 2022-08-31 2024-04-09 河南华福包装科技有限公司 复合纸质氧化硅高阻隔膜包装材料及其制备方法、应用

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WO2020085248A1 (fr) * 2018-10-23 2020-04-30 住友化学株式会社 Corps stratifié, dispositif électronique flexible et procédé de fabrication de corps stratifié
CN112912241A (zh) * 2018-10-23 2021-06-04 住友化学株式会社 层叠体、柔性电子器件及层叠体的制造方法
JP2022128500A (ja) * 2019-09-30 2022-09-01 大日本印刷株式会社 バリア性積層体、該バリア性積層体を備えるヒートシール性積層体および該ヒートシール性積層体を備える包装容器
JP7482401B2 (ja) 2019-09-30 2024-05-14 大日本印刷株式会社 バリア性積層体、該バリア性積層体を備えるヒートシール性積層体および該ヒートシール性積層体を備える包装容器
WO2023153307A1 (fr) * 2022-02-10 2023-08-17 日東電工株式会社 Film barrière aux gaz, son procédé de production, plaque de polarisation avec couche barrière aux gaz et dispositif d'affichage d'image
WO2023153010A1 (fr) * 2022-02-10 2023-08-17 日東電工株式会社 Film barrière aux gaz, procédé associé de production, plaque de polarisation à couche barrière aux gaz et dispositif d'affichage d'images
WO2024176674A1 (fr) * 2023-02-22 2024-08-29 日東電工株式会社 Stratifié, procédé de production de stratifié et polariseur avec couche barrière contre les gaz

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