# US 2017/0288169 A1 · Laminated film and process for manufacturing the same, as well as method for analyzing laminated film > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2017/0288169 A1 - Document ID: US20170288169A1 - Status: Published application - Kind: A1 - Application number: 15/471,181 - Filed: 2017-03-28 - Published: 2017-10-05 - Earliest claimed: 2016-03-31 - Assignees: Sumitomo Chemical Company, Limited - Applicants: Sumitomo Chemical Company, Limited - Inventors: Yutaka ITO; Yukiko TAKENAKA - Web page: https://patentgrep.com/patent/US20170288169A1 ## CPC - C23C 16/401: {containing silicon} - C23C 16/509: using internal electrodes - G01N 23/18: Investigating the presence of flaws defects or foreign matter - H01J 37/244: Detectors; Associated components or circuits therefor - H01J 37/285: Emission microscopes, e.g. field-emission microscopes - H10K 50/844: Encapsulations - H10K 77/111: {Flexible substrates} - B05D 1/005: {Spin coating} - B05D 3/067: {Curing or cross-linking the coating} - C23C 16/402: {Silicon dioxide} - H10K 2102/00: Constructional details relating to the organic devices covered by this subclass - Y02E 10/549: Organic PV cells - Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product - 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 (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) - G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q) - H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H) - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES - B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02) - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract An object of the present invention is to provide a laminated film which can prevent permeation of the water vapor at the higher level, and the present invention provides a laminated film comprising at least a gas barrier layer and an inorganic polymer layer being laminated on a resin substrate, wherein a Y value calculated from a transmission electron microscope image of a cross section of the inorganic polymer layer by the following procedures (a) to (d) is 0.220 or less. (a) A standard deviation (σ) of the contrast of an electron beam-unirradiated part of the inorganic polymer layer is calculated. (b) An electron beam-irradiated part of the inorganic polymer layer is divided into twenty so that divided ones have a film thickness equal in a film thickness direction, and a standard deviation (σn: standard deviation of nth division, n=1˜20) of the contrast of each divided part is calculated. (c) Xn (n=1˜20) of each divided part is calculated from the expression (1). Xn=σn/σ(n=1˜20) (1) (d) A standard deviation of X3 to X18 is defined as Y. ## Claims ### Claim 1 A laminated film comprising at least a gas barrier layer and an inorganic polymer layer being laminated on a resin substrate, wherein a Y value which is calculated from a transmission electron microscope image of a cross section of the inorganic polymer layer by the following procedures (a) to (d) is 0.220 or less. (a) A standard deviation (σ) of the contrast of an electron beam-unirradiated part of the inorganic polymer layer is calculated. A standard deviation σ is obtained by performing division into twenty of the inorganic polymer layer of a transmission electron microscope image obtained by photographing so that a gradation average value of a carbon deposition layer in a cross-sectional sample of the laminated film of a width of 90 nm, which was prepared by microsampling using a focused ion beam machining observation device, becomes 80 to 90 with a standard deviation of 3 to 5, so that divided ones have an equal film thickness in a film thickness direction, obtaining a standard deviation from a histogram when each cross section of 3rd to 18th divisions is gray scale-displayed at 256 gradations, and calculating a standard deviation (σ) as an average value thereof. (b) An electron beam-irradiated part of the inorganic polymer layer is divided into twenty so that the divided ones have an equal film thickness in a film thickness direction, and a standard deviation of the contrast of each divided part (σn: standard deviation of nth division, n=1˜20) is calculated. A standard deviation an is obtained by irradiating a cross-sectional sample of the laminated film having a width of 90 nm, which was prepared by microsampling using a focused ion beam machining observation device, with an electron beam at 1.30×1016 ions/cm2, and calculating a standard deviation from a histogram when a transmission electron microscope image obtained by photographing a cross section of each divided part of the inorganic polymer layer after electron irradiation under the same condition as that of a gradation average value of a carbon deposition layer set at (a) is gray scale-displayed at 256 gradations. (c) Xn (n=1˜20) of each divided part is calculated from the expression (1). Xn=σn/σ(n=1˜20) (1) (d) A standard deviation of X3 to X18 is defined as Y. ### Claim 2 (depends on 1) The laminated film according to claim 1, wherein the Y value is 0.200 or less. ### Claim 3 (depends on 1) The laminated film according to claim 1, wherein the gas barrier layer is a silicon oxide-based layer which contains a silicon atom, an oxygen atom and a carbon atom, and satisfies all of the conditions (i) to (iii), in a silicon distribution curve, an oxygen distribution curve and a carbon distribution curve, each showing a relationship between a distance from a surface of the gas barrier layer in a film thickness direction of the gas barrier layer, and the ratio of an amount of a silicon atom (atomic ratio of silicon), the ratio of an amount of an oxygen atom (atomic ratio of oxygen) or the ratio of an amount of a carbon atom (atomic ratio of carbon), to a total amount of a silicon atom, an oxygen atom and a carbon atom. (i) The atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon satisfy the expression (2): (Atomic ratio of oxygen)>(atomic ratio of silicon)>(atomic ratio of carbon) (2) in a region of 90% or more of a film thickness of the gas barrier layer. (ii) The carbon distribution curve has at least one extreme value. (iii) An absolute value of a difference between a maximum value and a minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at % or more. ### Claim 4 (depends on 1) The laminated film according to claim 1, wherein the gas barrier layer contains a silicon atom, an oxygen atom and a nitrogen atom, and the gas barrier layer is a silicon oxide-based layer satisfying all of the following conditions (iv) and (v). (iv) The gas barrier layer has a second thin film layer, a first thin film layer and a third thin film layer which have different oxygen content ratios, from a resin substrate 101 side, and an average composition of a silicon atom, an oxygen atom and a nitrogen atom of the first thin film layer is in the range of 10 at %≦Si≦40 at %, 5 at %≦O≦30 at %, 50 at %≦N≦80 at %. (v) The elemental ratio of a nitrogen atom and a silicon atom of the second and third thin film layers is in the range of the expression (3). N/Si≦0.2 (3). ### Claim 5 (depends on 1) The laminated film according to claim 1, wherein the inorganic polymer layer is a layer consisting of a curing product of a composition comprising polysilazane. ### Claim 6 An analysis method for analyzing the cured state of an inorganic polymer layer in a laminated film comprising at least a gas barrier layer and an inorganic polymer layer being laminated on a resin substrate, comprising: a step of calculating a Y value from a transmission electron microscope image of a cross section of the inorganic polymer layer by the following procedures (a) to (d). (a) A standard deviation (σ) of the contrast of an electron beam-unirradiated part of the inorganic polymer layer is calculated. A standard deviation σ is obtained by performing division into twenty of the inorganic polymer layer of a transmission electron microscope image obtained by photographing so that a gradation average value of a carbon deposition layer in a cross-sectional sample of the laminated film of a width of 90 nm, which was prepared by microsampling using a focused ion beam machining observation device, becomes 80 to 90 with a standard deviation of 3 to 5, so that divided ones have an equal film thickness in a film thickness direction, obtaining a standard deviation from a histogram when each cross section of 3rd to 18th divisions is gray scale-displayed at 256 gradations, and calculating a standard deviation (σ) as an average value thereof. (b) An electron beam-irradiated part of the inorganic polymer layer is divided into twenty so that the divided ones have an equal film thickness in a film thickness direction, and a standard deviation of the contrast of each divided part (σm: standard deviation of nth division, n=1˜20) is calculated. A standard deviation σn is obtained by irradiating a cross-sectional sample of the laminated film having a width of 90 nm, which was prepared by microsampling using a focused ion beam machining observation device, with an electron beam at 1.30×1016 ions/cm2, and calculating a standard deviation from a histogram when a transmission electron microscope image obtained by photographing a cross section of each divided part of the inorganic polymer layer after electron irradiation under the same condition as that of a gradation average value of a carbon deposition layer set at (a) is gray scale-displayed at 256 gradations. (c) Xn (n=1˜20) of each divided part is calculated from the expression (1). Xn=σn/σ(n=1˜20) (1) (d) A standard deviation of X3 to X18 is defined as Y. ### Claim 7 A process for manufacturing a laminated film comprising at least a gas barrier layer and an inorganic polymer layer being laminated on a resin substrate, comprising: a step of forming the gas barrier layer by chemical vapor deposition, wherein a Y value calculated from a transmission electron microscope image of a cross section of the inorganic polymer layer by the following procedures (a) to (d) is 0.220 or less. (a) A standard deviation (σ) of the contrast of an electron beam-unirradiated part of the inorganic polymer layer is calculated. A standard deviation σ is obtained by performing division into twenty of the inorganic polymer layer of a transmission electron microscope image obtained by photographing so that a gradation average value of a carbon deposition layer in a cross-sectional sample of the laminated film of a width of 90 nm, which was prepared by microsampling using a focused ion beam machining observation device, becomes 80 to 90 with a standard deviation of 3 to 5, so that divided ones have an equal film thickness in a film thickness direction, obtaining a standard deviation from a histogram when each cross section of 3rd to 18th divisions is gray scale-displayed at 256 gradations, and calculating a standard deviation (σ) as an average value thereof. (b) An electron beam-irradiated part of the inorganic polymer layer is divided into twenty so that the divided ones have an equal film thickness in a film thickness direction, and a standard deviation of the contrast of each divided part (σn: standard deviation of nth division, n=1˜20) is calculated. A standard deviation σn is obtained by irradiating a cross-sectional sample of the laminated film having a width of 90 nm, which was prepared by microsampling using a focused ion beam machining observation device, with an electron beam at 1.30×1016 ions/cm2, and calculating a standard deviation from a histogram when a transmission electron microscope image obtained by photographing a cross section of each divided part of the inorganic polymer layer after electron irradiation under the same condition as that of a gradation average value of a carbon deposition layer set at (a) is gray scale-displayed at 256 gradations. (c) Xn (n=1˜20) of each divided part is calculated from the expression (1). Xn=σn/σ(n=1˜20) (1) (d) A standard deviation of X3 to X18 is defined as Y. ### Claim 8 (depends on 7) The process for manufacturing a laminated film according to claim 7, comprising a step of forming the inorganic polymer layer by curing a composition comprising an inorganic polymer by irradiation of vacuum ultraviolet light having the wavelength of 200 nm or less.