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WO2017090591A1 - Film doté de propriétés de barrière contre les gaz et dispositif électronique - Google Patents

Film doté de propriétés de barrière contre les gaz et dispositif électronique Download PDF

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Publication number
WO2017090591A1
WO2017090591A1 PCT/JP2016/084568 JP2016084568W WO2017090591A1 WO 2017090591 A1 WO2017090591 A1 WO 2017090591A1 JP 2016084568 W JP2016084568 W JP 2016084568W WO 2017090591 A1 WO2017090591 A1 WO 2017090591A1
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Prior art keywords
gas barrier
transition metal
region
layer
barrier layer
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English (en)
Japanese (ja)
Inventor
西尾　昌二
森　孝博
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Konica Minolta Inc
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Konica Minolta Inc
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    • 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
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots

Definitions

  • the present invention relates to a gas barrier film and an electronic device. Specifically, the present invention relates to a gas barrier film having high gas barrier performance even when thin and excellent in flex resistance, and an electronic device including the gas barrier film.
  • a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide or silicon oxide is formed on the surface of a plastic substrate or film has been altered by various gases such as water vapor and oxygen. In order to prevent this, it is used in applications for packaging articles that require shutoff of various gases.
  • organic EL elements In addition to the packaging applications described above, in order to prevent alteration due to various gases, it is used for sealing electronic devices such as solar cells, liquid crystal display elements, organic electroluminescence elements (hereinafter also referred to as organic EL elements). Has also been used.
  • a film having a gas barrier layer formed on a substrate such as a film by a plasma chemical vapor deposition method (hereinafter, also referred to as a plasma CVD method (CVD: Chemical Vapor Deposition)).
  • CVD plasma chemical vapor deposition
  • those having a gas barrier layer formed by applying a modification treatment after applying a coating liquid containing polysilazane as a main component on a substrate, or those using them in combination are known (for example, Patent Documents). See 1-3.)
  • JP 2009-255040 A Japanese Patent No. 3511325 JP 2012-106421 A
  • the present invention has been made in view of the above problems and circumstances, and the solution to the problem is that the present invention provides a gas barrier film excellent in gas barrier performance and flex resistance even if it is thin, and the gas barrier. It is providing the electronic device which comprises a conductive film.
  • the present inventor in the process of examining the cause of the above problems, the gas barrier film having a mixed region containing a transition metal and a non-transition metal in the gas barrier layer is very thin.
  • the present inventors have found that a high gas barrier property can be obtained and excellent in bending resistance, and have led to the present invention. That is, the said subject which concerns on this invention is solved by the following means.
  • a gas barrier film having a gas barrier layer on a substrate has a mixed region containing a non-transition metal M1 and a transition metal M2 at least in a thickness direction; In the mixed region, the ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is 0. The range of 02 to 49, and the region within the range is continuously 3 nm or more in thickness direction of the gas barrier layer, A gas barrier film, wherein the thickness of the gas barrier layer is in the range of 5 to 1000 nm.
  • the gas barrier layer includes, in the thickness direction, an A region containing the transition metal M2, a B region containing the non-transition metal M1, and the mixed region.
  • the atomic ratio of the transition metal M2 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is 5 atom% or more, 2.
  • the B region according to claim 1, wherein the atomic ratio of the non-transition metal M ⁇ b> 1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is 5 atom% or more.
  • An electronic device comprising the gas barrier film according to any one of items 1 to 8.
  • Item 10 The electronic device according to Item 9, which has a quantum dot-containing layer.
  • An electronic device comprising an organic electroluminescence element.
  • an oxygen-deficient composition film containing a non-transition metal (M1) compound for example, an oxide
  • M2 a transition metal
  • a sealing layer is formed using an oxygen-deficient composition film of a compound (for example, an oxide) alone, a tendency to improve the gas barrier property as the degree of oxygen deficiency increases is observed, but a remarkable gas barrier It did not lead to improvement of sex.
  • a single composition layer containing a compound (for example, oxide) whose main component is a non-transition metal (M1) and a compound (for example, oxide) whose main component is a transition metal (M2) A mixed region containing a composite oxide of a non-transition metal (M1) and a transition metal (M2) is formed, and the composite composition region has an oxygen deficiency composition. It has been found that the gas barrier property is remarkably improved as the size increases. As described above, this is because electronic bonds (interactions) between the non-transition metal (M1) and the transition metal (M2) rather than the bond between the non-transition metal (M1) and the bond between the transition metal (M2). It is estimated that the formation of oxygen vacancies in the mixed region forms a high-density structure in the mixed region and exhibits high gas barrier properties.
  • FIG. 2 shows the result of the composition analysis by the X-ray photoelectron spectroscopy (XPS) performed by the inventors on an example of the gas barrier layer having the mixed region according to the present invention.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 2 shows silicon (Si), niobium (Nb), oxygen (O), and nitrogen (in the gas barrier layer when silicon (Si) is used as the non-transition metal and niobium (Nb) is used as the transition metal.
  • the horizontal axis represents the depth in the thickness direction (sputter depth) from the surface of the gas barrier layer opposite to the substrate, and the vertical axis represents the atomic ratio (unit: atom%). .
  • the gas barrier layer according to the present invention has a mixed region (C in FIG. 2) containing a non-transition metal and a transition metal.
  • a non-transition metal and a transition metal bond are generated rather than a non-transition metal bond or a transition metal bond, and the density of each atom in the network is increased, and a dense structure is formed. It is assumed that high gas barrier properties were obtained. Further, as a result of the study by the present inventors, the mixed region can exhibit high gas barrier performance if it has a thickness of at least about 3 nm. Was also found to have high gas barrier performance. Thus, since the gas barrier film of the present invention can make the gas barrier layer very thin with high gas barrier performance, it is possible to obtain a gas barrier film having excellent bending resistance.
  • the atomic ratio of the non-transition metal and the transition metal gradually changes.
  • the stress in the gas barrier layer is not concentrated at one point at the time of bending or expansion / contraction, and the effect of stress relaxation can be obtained. Therefore, excellent bending resistance that cannot be obtained with conventional gas barrier films can be obtained. Inferred to have.
  • Sectional drawing which shows the structure of the gas barrier film of embodiment of this invention Graph showing the ratio of the number of atoms to the depth in the thickness direction of the gas barrier layer
  • Sectional drawing which shows an example of a structure of the organic EL element which is embodiment of the electronic device of this invention
  • Schematic sectional view showing an example of a vacuum ultraviolet ray irradiation apparatus applicable to formation of the B region constituting the gas barrier layer Top view of an evaluation device manufactured in the example
  • the gas barrier film of the present invention is a gas barrier film having a gas barrier layer on a substrate, and the gas barrier layer contains a non-transition metal M1 and a transition metal M2 at least in the thickness direction.
  • the mixed region has a ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer. Is within the range of 0.02 to 49, and the region within the range is continuously 3 nm or more in the thickness direction of the gas barrier layer, and the layer thickness of the gas barrier layer is 5 nm or more. It is characterized by being in the range of ⁇ 1000 nm. This feature is a technical feature common to the claimed invention.
  • the gas barrier layer comprises an A region containing the transition metal M2 in the thickness direction and the non-transition metal M1.
  • the region B contains and the mixed region, and the region A has an atomic ratio of the transition metal M2 measured by X-ray photoelectron spectroscopy of 5 atom% or more in the thickness direction of the gas barrier layer.
  • the atomic ratio of the non-transition metal M1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer is preferably 5 atom% or more.
  • the layer thickness of the region A is preferably in the range of 3 to 100 nm from the viewpoint of obtaining excellent gas barrier properties and excellent bending resistance.
  • the non-transition metal M1 is preferably silicon (Si) from the viewpoint of obtaining excellent gas barrier properties and excellent bending resistance.
  • the transition metal M2 is a Group 5 element of a long-period periodic table from the viewpoint of obtaining excellent gas barrier properties and excellent bending resistance.
  • the transition metal M2 is niobium (Nb) or tantalum (Ta) from the viewpoint of obtaining excellent gas barrier properties and excellent bending resistance.
  • the composition of the mixed region further contains oxygen.
  • the composition of the mixed region is represented by the chemical composition formula (1), at least a part of the mixed region is used. Preferably satisfies the relational expression (2).
  • the gas barrier film of the present invention can be suitably provided for an electronic device.
  • the electronic device preferably has a quantum dot-containing layer.
  • the electronic device preferably includes an organic electroluminescence element.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the gas barrier film of the present invention is a gas barrier film having a gas barrier layer on a substrate, and the gas barrier layer contains a non-transition metal M1 and a transition metal M2 at least in the thickness direction.
  • the mixed region has a value of the ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1 measured by X-ray photoelectron spectroscopy in the thickness direction of the gas barrier layer.
  • the layer thickness is 3 nm or more continuously in the thickness direction of the gas barrier layer, and the layer thickness of the gas barrier layer is within the range of 5 to 1000 nm. It is characterized by being.
  • the entire gas barrier layer may be a mixed region.
  • the oxygen permeability measured by a method according to JIS K 7126-1987 Water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)%, measured by a method according to JIS K 7129-1992, 1 ⁇ 10 ⁇ 3 ml / m 2 ⁇ 24 h ⁇ atm or less.
  • RH is preferably a high gas barrier property of 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ 24 h or less.
  • the gas barrier layer contains an A region containing a transition metal M2 and a non-transition metal M1 in the thickness direction. It is preferable to have a B region and a mixed region. Details of each region will be described later.
  • FIG. 1 shows a cross-sectional configuration of a gas barrier film 1 according to an embodiment of the present invention.
  • the gas barrier film 1 includes a gas barrier layer 3 on a substrate 2.
  • FIG. 1 shows an example in which the gas barrier layer 3 is provided only on one surface of the substrate 2, but the gas barrier layer 3 can be provided on both surfaces of the substrate 2 or on one surface.
  • a plurality of gas barrier layers 3 may be provided.
  • the “region” means that the gas barrier layer is constant or arbitrary on a plane perpendicular to the thickness direction (stacking direction) of the gas barrier layer (that is, a plane parallel to the outermost surface of the gas barrier layer).
  • the “layer thickness” means the thickness of the gas barrier layer in the thickness direction.
  • the “layer thickness” in the present invention represents the sputter depth in XPS analysis in terms of SiO 2 .
  • the “layer thickness” of the gas barrier layer is from the outermost surface side of the gas barrier layer to the interface with the base material, and the “interface with the base material” refers to the gas barrier layer in the composition analysis by XPS described later. It was set as the position which becomes the intersection of the distribution curve of the main component element and the distribution curve of the main component element of the base material.
  • Constuent means a compound constituting a specific region of the gas barrier layer and a simple substance of metal or nonmetal.
  • the “mixture” refers to a product in a state where the constituent components of the A region and the B region are mixed without being chemically bonded to each other.
  • the “composite oxide” refers to a compound (oxide) formed by chemically bonding the constituent components of the A region and the B region.
  • it refers to a compound having a chemical structure in which a niobium atom and a silicon atom form a chemical bond directly or via an oxygen atom.
  • a complex formed by physically combining the constituent components of the A region and the B region with each other by intermolecular interaction is also included in the “composite oxide” according to the present invention.
  • seat which consists of colorless and transparent resin
  • the resin used for such a substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclopolyolefin; polyamide Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin; Cellulose ester resin.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclopolyolefin
  • Polystyrene resin Polyvinyl alcohol resin
  • Polyacrylonitrile resin Acetal resin
  • resins selected from polyester resins, polyimide resins, cyclopolyolefin resins, and polycarbonate resins are particularly preferable.
  • these resin can be used individually by 1 type or in combination of 2 or more types.
  • the thickness of the base material can be appropriately set in consideration of stability when producing the gas barrier film of the present invention.
  • the thickness of the substrate is preferably in the range of 5 to 500 ⁇ m from the viewpoint that the film can be conveyed even in a vacuum.
  • the thickness of the substrate is in the range of 50 to 200 ⁇ m because the gas barrier layer is formed while discharging through the substrate. It is more preferable that the thickness is in the range of 50 to 100 ⁇ m.
  • the A region contains a transition metal (M2) or a compound containing a transition metal (M2) (for example, a transition metal oxide or the like), and the X-ray photoelectron spectroscopy described later in the thickness direction of the gas barrier layer.
  • M2 transition metal
  • M2 transition metal oxide
  • the thickness of the region A is preferably in the range of 3 to 100 nm in the thickness direction of the gas barrier layer from the viewpoint of achieving both gas barrier properties and optical characteristics, and in the range of 4 to 25 nm. It is more preferable that the thickness is in the range of 5 to 15 nm.
  • the transition metal (M2) is not particularly limited, and any transition metal can be used alone or in combination.
  • the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and the transition metal includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta , W, Re, Os, Ir, Pt, and Au.
  • transition metal (M2) from which a favorable gas barrier property is obtained.
  • Nb, Ta, and V which are Group 5 elements, are considered to be preferably used because they are likely to be bonded to the non-transition metal (M1) contained in the gas barrier layer. be able to.
  • the transition metal (M2) is a Group 5 element (especially Nb) and the non-transition metal (M1) described later is Si, a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur.
  • the transition metal (M2) is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.
  • the B region contains a non-transition metal (M1) or a compound containing a non-transition metal (M1) (for example, a non-transition metal oxide or the like).
  • M1 non-transition metal
  • M1 for example, a non-transition metal oxide or the like
  • the thickness of the region B is preferably in the range of 10 to 1000 nm in the thickness direction of the gas barrier layer, and in the range of 20 to 500 nm, from the viewpoint of achieving both gas barrier properties and productivity. More preferably, it is more preferably in the range of 50 to 300 nm.
  • the non-transition metal (M1) is preferably a non-transition metal selected from Group 12 to Group 14 metals of the long-period periodic table.
  • the non-transition metal (M1) is not particularly limited, and any metal of Group 12 to Group 14 can be used alone or in combination. Examples thereof include Si, Al, Zn, In, and Sn. Can be mentioned. Especially, it is preferable that Si, Sn, or Zn is included as the non-transition metal (M1), Si is more preferable, and Si alone is particularly preferable.
  • the mixed region contains a non-transition metal (M1) and a transition metal (M2) or a compound containing them, and the non-transition metal measured by X-ray photoelectron spectroscopy described later in the thickness direction of the gas barrier layer.
  • the ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the transition metal M1 is in the range of 0.02 to 49, and the region within the range is continuously in the thickness direction of the gas barrier layer. This is a region having a layer thickness of 3 nm or more.
  • the mixed region may have a region at least a part of which overlaps with the A region or the B region.
  • the mixed region may be formed as a plurality of regions having different chemical compositions of the constituent components, or may be formed as a region in which the chemical compositions of the constituent components are continuously changed. .
  • the region other than the mixed region of the gas barrier layer may be a region such as a non-transition metal (M1) oxide, nitride, oxynitride, or oxycarbide, or a transition metal (M2) oxide. It may be a region of nitride, oxynitride, oxycarbide, or the like.
  • M1 non-transition metal
  • M2 transition metal
  • oxygen deficient composition In the present invention, it is preferable that oxygen is contained in the composition of the mixed region, and further, a non-stoichiometric composition (oxygen-deficient composition) in which a part of the composition contained in the mixed region is deficient in oxygen. It is preferable that In the present invention, the oxygen deficient composition is defined by the following relational expression (2) when at least a part of the composition of the mixed region is expressed by the following chemical composition formula (1). It is defined as satisfying the condition.
  • the oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region, the minimum value obtained by calculating (2y + 3z) / (a + bx) in the certain mixed region is used. Details will be described later.
  • Chemical composition formula (1) (M1) (M2) x O y N z Relational expression (2): (2y + 3z) / (a + bx) ⁇ 1.0
  • M1 represents a non-transition metal
  • M2 represents a transition metal
  • O represents oxygen
  • N represents nitrogen
  • x, y, and z represent stoichiometric coefficients, respectively.
  • a represents the maximum valence of M1
  • b represents the maximum valence of M2.
  • the composition represented by the chemical composition formula (1) is simply referred to as the composition of the composite region.
  • the composition of the composite region of the non-transition metal (M1) and the transition metal (M2) according to the present invention is represented by (M1) (M2) x O y N z which is the formula (1).
  • the composition of the composite region may partially include a nitride structure, and it is more preferable from the viewpoint of barrier properties to include a nitride structure.
  • the maximum valence of the non-transition metal (M1) is a
  • the maximum valence of the transition metal (M2) is b
  • the valence of O is 2
  • the valence of N is 3.
  • composition of the composite region (including a part of the nitride) is a stoichiometric composition
  • (2y + 3z) / (a + bx) 1.0.
  • This formula means that the total number of bonds of non-transition metal (M1) and transition metal (M2) is equal to the total number of bonds of O and N.
  • non-transition metal (M1) And the transition metal (M2) are bonded to either O or N.
  • the maximum valence of each element is set to The composite valence calculated by performing the weighted average according to the existence ratio is adopted as the values of a and b of each “maximum valence”.
  • the remaining bonds of the non-transition metal (M1) and the transition metal (M2) have the possibility of bonding to each other, and the metals of the non-transition metal (M1) and the transition metal (M2) When they are directly bonded, it is considered that a denser and higher-density structure is formed than when bonded between metals via O or N, and as a result, gas barrier properties are improved.
  • the mixed region is a region where the value of x satisfies 0.02 ⁇ x ⁇ 49 (0 ⁇ y, 0 ⁇ z). This is defined as a region where the value of the number ratio of transition metal (M2) / non-transition metal (M1) is in the range of 0.02 to 49 and the thickness is 3 nm or more. It is the same definition as that. In this region, since both the non-transition metal (M1) and the transition metal (M2) are involved in the direct bonding between the metals, a mixed region that satisfies this condition exists with a thickness of a predetermined value or more (3 nm). Therefore, it is thought that it contributes to the improvement of gas barrier properties.
  • the mixed region is a region satisfying 0.1 ⁇ x ⁇ 10. It is preferable to include a thickness of 3 nm or more, more preferably include a region satisfying 0.2 ⁇ x ⁇ 5 at a thickness of 3 nm or more, and a region satisfying 0.3 ⁇ x ⁇ 4 to a thickness of 3 nm or more. It is further preferable to contain.
  • the thickness of the mixed region where good gas barrier properties can be obtained is 3 nm or more as the sputtering thickness in terms of SiO 2 in the XPS analysis method described later, and this thickness is 5 nm or more. Is preferably 10 nm or more, more preferably 20 nm or more.
  • the thickness of the mixed region is not particularly limited from the viewpoint of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics. preferable.
  • a gas barrier layer having a mixed region having a specific configuration as described above exhibits a very high gas barrier property that can be used as a gas barrier layer for an electronic device such as an organic EL element.
  • composition analysis by XPS and measurement of thickness of each region The composition distribution in the A region, the B region, and the mixed region according to the present invention, the thickness of each region, and the like should be measured by X-ray photoelectron spectroscopy (abbreviation: XPS) described in detail below. It can ask for.
  • XPS X-ray photoelectron spectroscopy
  • the element concentration distribution curve (hereinafter referred to as “depth profile”) in the thickness direction of the gas barrier layer according to the present invention is the element concentration of the non-transition metal M1 (for example, silicon), the transition metal M2 (
  • the element concentration of niobium, oxygen (O), nitrogen (N), carbon (C) element concentration, etc. can be measured by combining X-ray photoelectron spectroscopy measurement with rare gas ion sputtering such as argon. It can be created by sequentially performing surface composition analysis while exposing the interior from the surface of the barrier layer.
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of each element (unit: atom%) and the horizontal axis as the etching time (sputtering time).
  • the etching time is generally correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the layer thickness direction, As the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement Can be adopted.
  • etching rate is 0.05 nm / It is preferable to set to sec (SiO 2 thermal oxide film conversion value).
  • ⁇ Analyzer QUANTERA SXM manufactured by ULVAC-PHI
  • X-ray source Monochromatic Al-K ⁇ ⁇ Sputtering ion: Ar (2 keV)
  • Depth profile Measurement is repeated at a predetermined thickness interval with a SiO 2 equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval is 1 nm (data every 1 nm is obtained in the depth direction).
  • Quantification The background is obtained by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.
  • Data processing uses MultiPak manufactured by ULVAC-PHI.
  • the analyzed elements are non-transition metal M1 (for example, silicon (Si)), transition metal M2 (for example, niobium (Nb)), oxygen (O), nitrogen (N), and carbon (C).
  • the composition ratio is calculated, the non-transition metal (M1) and the transition metal (M2) coexist, and the ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1
  • the range where the value is 0.02 to 49 is obtained.
  • region in the said range is 3 nm or more of layer thickness continuously in the thickness direction of a gas barrier layer is defined as a "mixed area
  • the thickness of the mixed region represents the sputter depth in XPS analysis in terms of SiO 2 .
  • the thickness of the mixed region has no upper limit of the thickness in the mixed region from the viewpoint of gas barrier properties, but is preferably in the range of 3 to 100 nm, more preferably from the viewpoint of optical properties. Is in the range of 5 to 50 nm, more preferably in the range of 10 to 30 nm.
  • FIG. 2 is a graph showing the atomic ratio in the thickness direction of the gas barrier layer. Silicon in the gas barrier layer when silicon (Si) is used as the non-transition metal and niobium (Nb) is used as the transition metal. This is an example of analyzing the atomic composition of (Si), niobium (Nb), oxygen (O), nitrogen (N), and carbon (C).
  • the horizontal axis represents the depth in the thickness direction (sputter depth) from the surface of the gas barrier layer opposite to the substrate, and the vertical axis represents the atomic ratio (unit: atom%). . Carbon was omitted because almost no carbon was detected.
  • the arrow described on the graph has shown each position of A area
  • the A region of the present invention can be produced by forming a region containing a transition metal (M2) described below.
  • transition metal (M2) examples include Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, and the like from the viewpoint of obtaining good gas barrier properties as described above.
  • Nb, Ta, and V which are Group 5 elements, can be preferably used because they are likely to be bonded to the non-transition metal (M1) contained in the gas barrier layer.
  • the formation of the layer containing the transition metal (M2) oxide is not particularly limited.
  • a conventionally known vapor deposition method using an existing thin film deposition technique can be used to make the mixed region efficient. It is preferable from a viewpoint of forming.
  • the vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assist vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more.
  • the target application method is appropriately selected according to the target type, and any of DC (direct current) sputtering, DC pulse sputtering, AC (alternating current) sputtering, and RF (high frequency) sputtering may be used.
  • a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used.
  • a metal oxide film can be formed at a high film formation speed, which is preferable.
  • the inert gas used for the process gas He, Ne, Ar, Kr, Xe or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, thin films of non-transition metal (M1) and transition metal (M2) composite oxides, oxynitrides, oxycarbides, etc. are formed. can do. Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, the material of the film, the layer thickness, and the like.
  • the sputtering method may be a multi-source simultaneous sputtering method using a plurality of sputtering targets including a transition metal (M2) alone or its oxide.
  • M2 transition metal
  • a method for producing these sputtering targets and a method for producing a thin film made of a composite oxide using these sputtering targets for example, JP 2000-160331 A, JP 2004-068109 A, JP
  • JP The methods and conditions described in JP 2013-047361 A can be referred to as appropriate.
  • the film forming conditions for carrying out the co-evaporation method include the ratio of the transition metal (M2) and oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, and the gas concentration during the film forming. Examples include one or more conditions selected from the group consisting of supply amount, degree of vacuum during film formation, and power during film formation.
  • These film formation conditions preferably oxygen partial pressure
  • a mixed region made of a complex oxide having an oxygen deficient composition can be formed. That is, by forming the gas barrier layer using the co-evaporation method as described above, almost all regions in the thickness direction of the formed gas barrier layer can be mixed regions.
  • a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region.
  • what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area
  • the B region of the present invention can be produced by forming a region containing a non-transition metal (M1) described below.
  • the method for forming the B region containing the non-transition metal (M1) is not particularly limited, and for example, a vapor deposition method can be used by a known method.
  • the vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assisted vapor deposition, plasma CVD (chemical vapor deposition), and ALD.
  • PVD physical vapor deposition
  • Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • a non-transition metal is formed by a sputtering method. It can be used as a target.
  • a method of forming by a wet coating method using a polysilazane-containing coating solution containing Si as a non-transition metal is also a preferable method.
  • polysilazane applicable to the formation of the B region is a polymer having a silicon-nitrogen bond in the structure, and includes SiO 2 , Si 3 made of Si—N, Si—H, NH, or the like.
  • N is 4 and both of the intermediate solid solution SiO x N preceramic inorganic polymers, such as y.
  • the relatively Polysilazanes that can be modified to silicon oxide, silicon nitride, or silicon oxynitride at low temperatures are preferred.
  • Examples of such polysilazane include compounds having a structure represented by the following general formula (1).
  • R 1 , R 2 and R 3 each represent 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.
  • perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms is particularly preferred from the viewpoint of the denseness of the B region constituting the resulting gas barrier layer as a thin film.
  • the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to an adjacent substrate is improved and it may be hard.
  • the ceramic film made of polysilazane can be tough, and even when the layer thickness is increased, the generation of cracks is preferred.
  • perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.
  • Perhydropolysilazane is presumed to have a structure in which a linear structure and a ring structure centered on a 6- or 8-membered ring coexist.
  • the molecular weight of polysilazane is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight.
  • Mn number average molecular weight
  • These polysilazane compounds are commercially available in the form of a solution dissolved in an organic solvent, and commercially available products can be used as they are as coating solutions containing polysilazane compounds.
  • polysilazanes that are ceramicized at a low temperature include silicon alkoxide-added polysilazanes obtained by reacting the above polysilazanes with silicon alkoxides (Japanese Patent Laid-Open No. 5-238827), and glycidol-added polysilazanes obtained by reacting glycidol (specially No. 6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (Japanese Patent Laid-Open No. 6-240208), and a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (Japanese Patent Laid-Open No. 6-299118). No.
  • acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (JP-A-7- 1969 6 No.), and the like.
  • polysilazane examples include, for example, paragraphs (0024) to (0040) of JP2013-255910A, paragraphs (0037) to (0043) of JP2013-188942A, JP Paragraphs (0014) to (0021) of 2013-151123, Paragraphs (0033) to (0045) of JP2013-052569A, Paragraphs (0062) to (0075) of JP2013-129557A. ), And the contents described in paragraphs (0037) to (0064) of JP2013-226758A can be applied.
  • organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane.
  • Suitable organic solvents include, for example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers. it can.
  • organic solvents such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran.
  • organic solvents may be selected according to the purpose such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed.
  • the concentration of polysilazane in the coating liquid containing polysilazane varies depending on the thickness of the target gas barrier layer and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass.
  • an amine or metal catalyst can be added to the coating liquid containing polysilazane in order to promote modification to silicon oxide, silicon nitride, or silicon oxynitride.
  • a polysilazane solution containing a catalyst such as NAX120-20, NN120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140 manufactured by AZ Electronic Materials Co., Ltd. as a commercial product is used. be able to.
  • these commercial items may be used independently and may be used in mixture of 2 or more types.
  • the addition amount of the catalyst is adjusted to 2% by mass or less with respect to polysilazane in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like. It is preferable.
  • the coating liquid containing polysilazane can contain an inorganic precursor compound in addition to polysilazane.
  • the inorganic precursor compound other than polysilazane is not particularly limited as long as a coating liquid can be prepared.
  • compounds other than polysilazane described in paragraphs “0110” to “0114” of JP2011-143577A can be appropriately employed.
  • An organometallic compound of a metal element other than Si can be added to the coating liquid containing polysilazane.
  • an organometallic compound of a metal element other than Si By adding an organometallic compound of a metal element other than Si, the replacement of N atom and O atom of polysilazane is promoted in the coating and drying process, and the coating composition can be changed to a stable composition close to SiO 2 after drying. it can.
  • metal elements other than Si include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), Magnesium (Mg), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), Examples include potassium (K), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), and the like.
  • Al, B, Ti and Zr are preferable, and among them, an organometallic compound containing Al is preferable.
  • Examples of the aluminum compound applicable to the present invention include aluminum isopoloxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, aluminum tri-n- Examples include butyrate, aluminum tri-sec-butylate, aluminum ethyl acetoacetate / diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. be able to.
  • Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate / diisopropylate), ALCH-TR (aluminum trisethyl acetoate).
  • the content of the additive metal element in the polysilazane-containing layer constituting the gas barrier film according to the present invention is preferably in the range of 0.05 to 10 mol% with respect to 100 mol% of silicon (Si). More preferably, it is in the range of 0.5 to 5 mol%.
  • the modification treatment is a treatment in which polysilazane is imparted with energy and part or all thereof is converted into silicon oxide or silicon oxynitride.
  • a known method based on the conversion reaction of polysilazane can be selected, and examples thereof include known plasma treatment, plasma ion implantation treatment, ultraviolet irradiation treatment, vacuum ultraviolet irradiation treatment and the like.
  • a conversion reaction using plasma, ozone, or ultraviolet light that can be converted at a low temperature is preferable.
  • Conventionally known methods can be used for plasma and ozone.
  • a gas barrier layer is formed by providing a coating film of a polysilazane-containing coating liquid of a coating method on a substrate and applying a vacuum ultraviolet irradiation treatment in which a vacuum ultraviolet ray (VUV) having a wavelength of 200 nm or less is irradiated to perform a modification treatment.
  • VUV vacuum ultraviolet ray
  • a rare gas excimer lamp is preferably used.
  • an excimer lamp (single wavelength of 172 nm, 222 nm, 308 nm, for example, manufactured by USHIO INC., Manufactured by M.D. Can be mentioned.
  • the treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in polysilazane, and the bonding of atoms is an action of only a photon called a photon process.
  • a silicon oxide film or a silicon oxynitride film is formed at a relatively low temperature (about 200 ° C. or lower) by proceeding an oxidation reaction with active oxygen or ozone while directly cutting.
  • the B region is formed by the above-described vapor deposition method
  • the ratio of the non-transition metal (M1) and oxygen in the deposition raw material, the ratio of the inert gas and the reactive gas during the deposition Mixing by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation Regions can be formed.
  • a film forming raw material type polysilazane type or the like
  • a mixed region can be formed by adjusting one or more conditions selected from the group consisting of time, reforming method, and reforming conditions.
  • a mixed region by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation can be formed.
  • the formation conditions of the method of forming the A region and the B region can be adjusted as appropriate.
  • a desired thickness can be obtained by controlling the deposition time.
  • a method of directly forming a mixed region of a non-transition metal and a transition metal is also preferable.
  • a co-sputtering method is preferable.
  • the co-sputtering method employed in the present invention is, for example, a composite target made of an alloy containing both a non-transition metal (M1) and a transition metal (M2), or a composite of a non-transition metal (M1) and a transition metal (M2).
  • M1 non-transition metal
  • M2 transition metal
  • M2 non-transition metal
  • M2 a composite of a non-transition metal
  • M2 transition metal
  • M2 a composite of a non-transition metal
  • M2 transition metal
  • the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single non-transition metal (M1) or its oxide and a single transition metal (M2) or its oxide. May be.
  • M1 non-transition metal
  • M2 single transition metal
  • the film forming conditions for carrying out the co-evaporation method include the ratio of the transition metal (M2) and oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, and the film forming process.
  • One or two or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation are exemplified, and these film formation conditions (preferably oxygen content)
  • these film formation conditions preferably oxygen content
  • a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region.
  • what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area
  • An anchor coat layer may be disposed on the surface of the base material on the side where the gas barrier layer according to the present invention is formed for the purpose of improving the adhesion between the base material and the gas barrier layer.
  • polyester resin isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, alkyl titanate, etc. are used alone Or in combination of two or more.
  • the above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to.
  • the application amount of the anchor coating agent is preferably about 0.1 to 5.0 g / m 2 (dry state).
  • the anchor coat layer can also be formed by a vapor deposition method such as physical vapor deposition or chemical vapor deposition.
  • a vapor deposition method such as physical vapor deposition or chemical vapor deposition.
  • an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.
  • an anchor coat layer as described in Japanese Patent Application Laid-Open No. 2004-314626, when an inorganic thin film is formed thereon by a vapor deposition method, a gas generated from the substrate side is reduced.
  • An anchor coat layer can also be formed for the purpose of blocking to some extent and controlling the composition of the inorganic thin film.
  • the thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 ⁇ m.
  • a hard coat layer may be disposed on the surface (one side or both sides) of the substrate.
  • the material contained in the hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold.
  • Such curable resins can be used singly or in combination of two or more.
  • the active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams.
  • active energy ray curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray.
  • a layer containing a cured product of the functional resin, ie, a hard coat layer is formed.
  • Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable. You may use the commercially available base material in which the hard-coat layer is formed previously.
  • the thickness of the hard coat layer is preferably in the range of 0.1 to 15 ⁇ m and more preferably in the range of 1 to 5 ⁇ m from the viewpoint of smoothness and bending resistance.
  • Examples of the active energy ray-curable resin applicable to the hard coat layer forming material include a resin composition containing an acrylate compound having a radical-reactive unsaturated compound, and a mercapto compound having an acrylate compound and a thiol group.
  • examples thereof include resin compositions, resin compositions in which polyfunctional acrylate monomers such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are dissolved.
  • a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.
  • thermosetting materials include Tutprom Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistance epoxy resin), various silicone resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd.
  • thermosetting urethane resin composed of a coat, an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin.
  • an epoxy resin-based material having heat resistance is particularly preferable.
  • the formation method of the hard coat layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method such as an evaporation method.
  • any hard coat layer may use an appropriate resin or additive for improving the film formability and preventing the generation of pinholes in the film.
  • the thickness of the hard coat layer is preferably in the range of 1 to 10 ⁇ m, more preferably in the range of 2 to 7 ⁇ m, from the viewpoint of improving the heat resistance of the film and facilitating the balance adjustment of the optical properties of the film. It is preferable.
  • the gas barrier film of the present invention can be preferably applied to an electronic device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air.
  • Examples of the electronic device body used in the electronic device provided with the gas barrier film of the present invention include, for example, a QD film having a quantum dot (QD) -containing resin layer, an organic electroluminescence element (organic EL element), and a liquid crystal display.
  • An element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like can be given.
  • the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.
  • the gas barrier film of the present invention can be applied to a QD film containing quantum dots (QD).
  • QD quantum dots
  • Quantum dots semiconductor nanoparticles exhibiting a quantum confinement effect with a nanometer-sized semiconductor material are also referred to as “quantum dots”.
  • quantum dots Such a quantum dot is a small lump within about 10 and several nanometers in which several hundred to several thousand semiconductor atoms are gathered, but when absorbing energy from an excitation source and reaching an energy excited state, the energy of the quantum dot Releases energy corresponding to the band gap.
  • quantum dots have unique optical characteristics due to the quantum size effect. Specifically, (1) By controlling the size of the particles, various wavelengths and colors can be emitted. (2) The absorption band is wide and fine particles of various sizes can be obtained with a single wavelength of excitation light. It has the characteristics that it can emit light, (3) it has a symmetrical fluorescence spectrum, and (4) it has excellent durability and fading resistance compared to organic dyes.
  • the quantum dots contained in the QD-containing resin layer may be known, and can be generated using any method known to those skilled in the art.
  • suitable QDs and methods for forming suitable QDs include US Pat. No. 6,225,198, US 2002/0066401, US Pat. No. 6,207,229, US Pat. No. 6,322,901. Description, US Pat. No. 6,949,206, US Pat. No. 7,572,393, US Pat. No. 7,267,865, US Pat. No. 7,374,807, US Patent Application No. 11/299299, and US Pat. No. 6,861,155 Can be mentioned.
  • the QD is generated from any suitable material, preferably an inorganic material and more preferably an inorganic conductor or semiconductor material.
  • suitable semiconductor materials include any type of semiconductor, including II-VI, III-V, IV-VI and IV semiconductors.
  • Suitable semiconductor materials include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb. , InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe , BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4 , Ge 3 N 4 , Al 2 O 3 , (Al,
  • the following core / shell type quantum dots for example, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, CdTe / ZnS, and the like can be preferably used.
  • Resin can be used for a QD containing resin layer as a binder holding a quantum dot.
  • a QD containing resin layer as a binder holding a quantum dot.
  • polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyester such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate Cellulose esters such as pionate and cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, norbornene, polymethylpentene, polyether ketone, polyether ketone imide And acrylic resins such as polyamide resins, fluororesins, nylon resins, and polymethyl methacrylate.
  • the QD-containing resin layer preferably has a thickness in the range of 50 to 200 ⁇ m.
  • the optimum amount of quantum dots in the QD-containing resin layer varies depending on the compound used, but is generally preferably in the range of 15 to 60% by volume.
  • An organic EL element which is a representative example of an electronic device to which the gas barrier film of the present invention is applied includes, for example, a pair of electrodes 20 and an organic functional layer 30 positioned between the pair of electrodes 20 on the transparent substrate 10. And a sealing material 40 that covers the organic functional layer 30.
  • the transparent substrate 10 includes the gas barrier film 1 of the present invention.
  • the organic functional layer 30 includes at least a light emitting layer, and includes a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and the like as necessary.
  • the light-emitting layer contains a light-emitting organic compound, and holes injected directly from one electrode 20 (anode) or injected from the anode through a hole transport layer and the like, and the other electrode 20 (cathode) ) Or electrons injected directly through the electron transport layer or the like are recombined to emit light.
  • the organic functional layer 30 and the electrode 20 are likely to be deteriorated by the intrusion of gases such as oxygen and water in the atmosphere.
  • the organic EL element G includes the above-described gas barrier film 1 as the transparent substrate 10 in order to suppress a decrease in light emission performance due to such deterioration of the organic functional layer 30 and the like, but a gas barrier as the sealing material 40.
  • the film 1 can also be provided.
  • Example 1 Production of gas barrier film >> Gas barrier films 1 to 19 were prepared according to the following method.
  • a UV curable resin manufactured by Aika Industry Co., Ltd., product number: Z731L
  • Z731L the dry layer thickness
  • the formed coating film is dried at 80 ° C., and then cured in air using a high-pressure mercury lamp under the condition of an irradiation energy amount of 0.5 J / cm 2 to clear the back side.
  • Hard coat layer 1 was formed.
  • UV curable resin “OPSTAR (registered trademark) Z7527” manufactured by JSR Corporation on the surface side of the PET film (surface on which the gas barrier layer is formed), wet coating so that the dry layer thickness is 2 ⁇ m. After coating by the method, it is dried at 80 ° C., and then cured under a condition of irradiation energy of 0.5 J / cm 2 using a high-pressure mercury lamp in the air, and a clear hard coat layer having a thickness of 2 ⁇ m on the surface side. 2 was formed.
  • ⁇ Formation of gas barrier layer 1> (Formation of region containing non-transition metal (M1))
  • a non-transition metal (M1) constituting a gas barrier layer is contained on the surface side of the substrate on which the clear hard coat layer 2 is formed by a vapor phase method / sputtering (magnetron sputtering apparatus manufactured by Canon Anelva, model EB1100). A region was formed.
  • the sputtering apparatus used is capable of two-way simultaneous sputtering.
  • a polycrystalline Si target was used as a target, and a mixed gas of Ar and O 2 was used as a process gas, so that the layer thickness was 900 nm by DC sputtering.
  • the sputtering power source power was 5.0 W / cm 2 and the film forming pressure was 0.4 Pa.
  • Film formation was performed by adjusting the oxygen partial pressure so that the composition was SiO 2 .
  • film formation using a glass substrate is performed in advance, and the condition of the composition is determined by adjusting the oxygen partial pressure. The condition where the composition near the depth of 10 nm from the surface layer becomes SiO 2 is found, and the condition is applied. did.
  • the data on the change in the layer thickness with respect to the film formation time is obtained in the range of 100 to 300 nm, the layer thickness formed per unit time is calculated, and then the film formation time is set to the set layer thickness.
  • the layer thickness was adjusted by setting.
  • the composition is a layer which is SiO 2 is a non-transition metal oxide was formed at a layer thickness of 900 nm.
  • a commercially available oxygen-deficient niobium oxide target (composition: Nb 12 O 29 ) was used, a mixed gas of Ar and O 2 was used as a process gas, a magnetron sputtering apparatus, DC sputtering, and a layer thickness of 100 nm.
  • the film was formed as follows.
  • the sputtering power source power was 5.0 W / cm 2 and the film forming pressure was 0.4 Pa. Further, the oxygen partial pressure was 12% under the film forming conditions. It should be noted that, by film formation using a glass substrate in advance, data on the layer thickness change with respect to the film formation time is obtained under the film formation conditions, and after calculating the layer thickness formed per unit time, the set layer thickness is obtained.
  • the film formation time was set as follows. Thus, a gas barrier layer having a layer thickness of 1000 nm was formed.
  • the layer thicknesses of the A region, the B region, and the mixed region were measured.
  • the composition distribution profile in the thickness direction was measured on the surface side of the gas barrier layer 1 by XPS analysis.
  • the XPS analysis conditions are as follows. The sample used for the analysis was a sample stored in an environment of 20 ° C. and 50% RH after sample preparation.
  • the region where the atomic ratio of Nb (transition metal M2) is 5 atom% or more is the A region, and (2) Si (non-transition metal M1).
  • the region where the atomic ratio is 5 atom% or more is the B region, and (3) the ratio of the atomic ratio of Si (non-transition metal M1) to the atomic ratio of Nb (transition metal M2) is 0.02 to 49
  • the region where the layer thickness within the range is 3 nm or more was defined as a mixed region, and the layer thickness of each region was measured.
  • the layer thickness represents the sputter depth in XPS analysis in terms of SiO 2 .
  • gas barrier film 11 In the production of the gas barrier film 1, a gas barrier film 11 was produced in the same manner except that the formation method of the region containing the transition metal (M2) was changed from the sputtering method to the following coating method.
  • the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment using an Xe excimer lamp with a wavelength of 172 nm under the conditions of an oxygen concentration of 0.1% by volume and an irradiation energy of 3.0 J / cm 2 to obtain a thickness of 25 nm.
  • the transition metal (M2) -containing layer was formed.
  • gas barrier films 12, 13 In the production of the gas barrier film 1, the formation of the region containing the non-transition metal (M1) and the formation of the region containing the transition metal (M2) are performed using a polycrystalline Si target and an Nb target as targets, Is the same except that a region containing a non-transition metal (M1) and a transition metal metal (M2) is formed using Ar and O 2 by performing a DC simultaneous sputtering dual sputtering. Thus, gas barrier films 12 and 13 were produced. The gas barrier layer was formed so that the gas barrier film 12 had a layer thickness of 100 nm and the gas barrier film 13 had a layer thickness of 20 nm.
  • gas barrier films 14 to 16 In the production of the gas barrier film 1, the method of forming the region (SiO 2 ) containing the non-transition metal (M1) is changed from a sputtering method to an excimer modification method using perhydropolysilazane (abbreviation: PHPS) described below. Gas barrier films 14 to 16 were produced in the same manner except that the film was formed by the following steps.
  • PHPS perhydropolysilazane
  • TDAH amine catalyst
  • NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.
  • the coating solution is applied by spin coating so that the dry layer thickness is 230 nm, dried at 80 ° C. for 10 minutes, and a coating film containing a non-transition metal (M1) Formed.
  • the dry layer thickness was formed to 230 nm in this way.
  • the gas barrier film 15 was formed to have a dry layer thickness of 60 nm, and the gas barrier film 16 was formed to have a dry layer thickness of 10 nm.
  • the sample on which the coating film containing the non-transition metal (M1) was formed was placed in the vacuum ultraviolet irradiation apparatus shown in FIG. 4 having the Xe excimer lamp with a wavelength of 172 nm, and the irradiation energy was 5.0 J / cm 2 . Vacuum ultraviolet irradiation treatment was performed. At this time, nitrogen and oxygen were supplied into the chamber, and the oxygen concentration in the irradiation atmosphere was adjusted to 0.1% by volume. The stage temperature for installing the sample was set to 80 ° C.
  • reference numeral 101 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) and exhausts the gas from a gas discharge port (not shown). It is possible to substantially remove water vapor from the water and maintain the oxygen concentration at a predetermined concentration.
  • Reference numeral 102 denotes an Xe excimer lamp (excimer lamp light intensity: 130 mW / cm 2 ) having a double tube structure that irradiates vacuum ultraviolet light of 172 nm
  • reference numeral 103 denotes an excimer lamp holder that also serves as an external electrode.
  • Reference numeral 104 denotes a sample stage.
  • the sample stage 104 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 101 by a moving means (not shown).
  • the sample stage 104 can be maintained at a predetermined temperature by a heating means (not shown).
  • Reference numeral 105 denotes a sample on which a polysilazane compound coating layer is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 3 mm.
  • Reference numeral 106 denotes a light-shielding plate, which prevents the application layer of the sample from being irradiated with vacuum ultraviolet rays during aging of the Xe excimer lamp 2.
  • the energy irradiated on the surface of the sample coating layer in the vacuum ultraviolet light irradiation step was measured using a 172 nm sensor head using a UV integrating photometer: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics.
  • the sensor head is installed in the center of the sample stage 104 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 101 is vacuum ultraviolet light. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the irradiation step, and measurement was performed by moving the sample stage 104 at a speed of 0.5 m / min.
  • an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.
  • the moving speed of the sample stage was adjusted to adjust the irradiation energy amount to 5.0 J / cm 2 .
  • the vacuum ultraviolet irradiation was performed after aging for 10 minutes.
  • the Ca method evaluation sample (type evaluated by permeation concentration) prepared as described below was stored in an environment of 85 ° C. and 85% RH, and the corrosion rate of Ca was observed at regular intervals. After 1 hour, 5 hours, 10 hours, 20 hours, and after that, observation and transmission density measurement (average of 4 points) every 20 hours, when the measured transmission density is less than 50% of the initial value of transmission density The observation time was obtained and used as an index of gas barrier properties. When the transmission density measured by storage for 500 hours was 50% or more of the initial value of transmission density, it was set to 500 hours or more.
  • thermosetting sheet-like adhesive epoxy resin
  • a sealing resin layer was bonded to the gas barrier layer surface with a thickness of 20 ⁇ m. This was punched out to a size of 50 mm ⁇ 50 mm, then placed in a glove box and dried for 24 hours.
  • One side of a 50 mm ⁇ 50 mm non-alkali glass plate was UV cleaned. Then, Ca was vapor-deposited by the size of 20 mm x 20 mm through the mask in the center of the glass plate using the vacuum vapor deposition apparatus made from an EILS technology. The thickness of Ca was 80 nm.
  • a glass plate on which Ca has been deposited is mounted in a glove box, and the sealing resin layer surface of the gas barrier film to which the sealing resin layer is bonded is placed in contact with the Ca deposition surface of the glass plate, and bonded by vacuum lamination. did. At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down, and cured for 30 minutes to produce an evaluation cell.
  • (T2 / T1) is 0.95 or more 4: (T2 / T1) is 0.90 or more and less than 0.95 3: (T2 / T1) is 0.85 or more and less than 0.90 2: ( T2 / T1) is 0.80 or more and less than 0.85 1: (T2 / T1) is less than 0.80
  • the gas barrier film of the present invention has high gas barrier performance and excellent bending resistance even when it is thin.
  • the gas barrier film of the comparative example was inferior in any item.
  • the ratio of the atomic ratio of the transition metal M2 to the atomic ratio of the non-transition metal M1 is 0.02 to The region within the range of 49 could not be formed so as to have a layer thickness of 3 nm or more continuously in the thickness direction of the gas barrier layer, and a mixed region could not be formed.
  • Example 2 [Production of Evaluation Devices 1 to 16] Evaluation devices 1 to 16 were prepared using the gas barrier films 1 to 16 of the present invention, and it was evaluated whether the gas barrier film of the present invention could be used for the evaluation device.
  • FIG. 5 shows the configuration of the evaluation device.
  • the evaluation device can be obtained by forming a Ca vapor deposition layer 202, an electrode 203, an organic polymer layer 204, and a gas barrier layer 205 in this order on a substrate 201 as shown in FIG.
  • the substrate 201 As the substrate 201, a non-alkali glass plate having a thickness of 0.7 mm and a size of 50 mm ⁇ 50 mm was used.
  • the Ca vapor deposition layer 202 was UV-cleaned on one side of the substrate 201 and then vapor-deposited Ca in the center of the substrate 201 with a size of 14 mm ⁇ 20 mm using a mask.
  • a vacuum vapor deposition apparatus manufactured by ALS Technology was used, and the thickness of the Ca vapor deposition layer 202 was set to 80 nm.
  • the mask used for the Ca deposition was replaced with a mask having a pattern for forming the electrode 203, and aluminum was deposited to form an electrode 203 having a thickness of 200 nm.
  • covered with the electrode 203 was 10 mm x 20 mm.
  • the organic polymer layer 204 was formed by flash evaporation using a mixture of the following raw materials.
  • the pressure at the time of flash vapor deposition was 3 Pa, and the conditions for the UV curing treatment were 2 J / cm 2 .
  • 1,9-nonanediol diacrylate 75 parts by weight Trimethylolpropane triacrylate 14 parts by weight Phenoxyethyl acrylate 6 parts by weight 2,4,6-trimethylbenzophenone 5 parts by weight
  • the organic polymer layer 204 was formed by using a mask so as to have a size of 26 mm ⁇ 26 mm in the center of the substrate 201. In the range of 22 mm ⁇ 22 mm in the central portion covering the Ca vapor deposition layer 202, the thickness is 1 ⁇ m, and outside the range of the central portion 22 mm ⁇ 22 mm, the thickness gradually decreases. The thickness of the organic polymer layer 204 was adjusted.
  • Gas barrier layer 205 having a size of 36 mm ⁇ 36 mm was formed in the center of the gas barrier layer substrate 201 as a gas barrier layer having the same composition as that of the gas barrier layer of the present invention produced in Example 1.
  • each of the evaluation devices 1 to 16 were connected to an electrical resistance measuring device, and the initial resistance value (unit) between the electrodes was measured. While being connected to the measuring apparatus, each of the evaluation devices 1 to 16 was stored in an environment of a temperature of 85 ° C. and a relative humidity of 85% RH, and a change in resistance value with time was measured. The time (h) when the resistance value was doubled from the initial resistance value was determined. The longer the time, the higher the gas barrier property.
  • the evaluation devices 1 to 16 using the gas barrier film of the present invention have high gas barrier properties and can be used for the evaluation device.
  • the gas barrier film of the present invention is excellent in gas barrier performance and excellent in flex resistance even if it is thin, and is suitable for use in sealing various electronic devices for the purpose of preventing deterioration due to various gases.
  • the electronic device include a QD film having a quantum dot (QD) -containing resin layer, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like.
  • QD quantum dot
  • organic EL element organic electroluminescence element
  • LCD liquid crystal display element
  • PV solar cell

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Abstract

L'invention concerne un film doté de propriétés de barrière contre les gaz, lequel présente d'excellentes propriétés de barrière contre les gaz même s'il est mince, et lequel possède une résistance supérieure à la flexion. L'invention concerne également un dispositif électronique mettant en oeuvre ce film doté de propriétés de barrière contre les gaz. Ce film (1) doté de propriétés de barrière contre les gaz possède une couche (3) barrière contre les gaz située sur un substrat (2). Ce film (1) doté de propriétés de barrière contre les gaz se caractérise en ce que la couche (3) barrière contre les gaz possède, du moins dans le sens de l'épaisseur, une région mixte contenant un métal de non-transition (M1) et un métal de transition (M2). Dans la région mixte, la valeur d'un rapport entre le nombre d'atomes de métal de transition (M2) et le nombre d'atomes de métal de non-transition (M1) telle que mesurée par spectroscopie photoélectronique à rayons X au moins dans le sens de l'épaisseur de la couche (3) barrière contre les gaz, est comprise dans la plage 0,02 à 49. En outre, la région dans la plage susmentionnée, a une épaisseur dans la direction de l'épaisseur de la couche (3) barrière contre les gaz, égale ou supérieure à 3nm, et l'épaisseur de la couche (3) barrière contre les gaz est comprise entre 5 et 1000nm.
PCT/JP2016/084568 2015-11-24 2016-11-22 Film doté de propriétés de barrière contre les gaz et dispositif électronique Ceased WO2017090591A1 (fr)

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JP2015-228383 2015-11-24
JP2015228383A JP2019010731A (ja) 2015-11-24 2015-11-24 ガスバリアー性フィルム及び電子デバイス

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003013202A (ja) * 2001-06-29 2003-01-15 Nippon Zeon Co Ltd 蒸着方法
JP2004322382A (ja) * 2003-04-23 2004-11-18 Oike Kaihatsu Kenkyusho:Kk 透明ガスバリアフィルム
JP2016203431A (ja) * 2015-04-17 2016-12-08 凸版印刷株式会社 積層体及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003013202A (ja) * 2001-06-29 2003-01-15 Nippon Zeon Co Ltd 蒸着方法
JP2004322382A (ja) * 2003-04-23 2004-11-18 Oike Kaihatsu Kenkyusho:Kk 透明ガスバリアフィルム
JP2016203431A (ja) * 2015-04-17 2016-12-08 凸版印刷株式会社 積層体及びその製造方法

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