WO2016194559A1 - Film étanche aux gaz - Google Patents

Film étanche aux gaz Download PDF

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Publication number
WO2016194559A1
WO2016194559A1 PCT/JP2016/063905 JP2016063905W WO2016194559A1 WO 2016194559 A1 WO2016194559 A1 WO 2016194559A1 JP 2016063905 W JP2016063905 W JP 2016063905W WO 2016194559 A1 WO2016194559 A1 WO 2016194559A1
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Prior art keywords
layer
silicon
gas barrier
film
barrier film
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PCT/JP2016/063905
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English (en)
Japanese (ja)
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礼子 小渕
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コニカミノルタ株式会社
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Publication of WO2016194559A1 publication Critical patent/WO2016194559A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides

Definitions

  • the present invention relates to a gas barrier film.
  • Gas barrier films are used as substrate films and sealing films in flexible electronic devices, particularly flexible organic EL devices. High barrier properties are required for gas barrier films used in these.
  • a gas barrier film is manufactured by forming an inorganic barrier layer on a base film by a vapor deposition method such as vapor deposition, sputtering, or CVD.
  • a manufacturing method for forming a gas barrier layer by applying energy to a precursor layer formed by applying a solution on a substrate has been studied.
  • studies using a polysilazane compound as a precursor have been widely conducted, and studies are being conducted as a technique for achieving both high productivity and barrier properties by coating.
  • the modification of the polysilazane layer using excimer light having a wavelength of 172 nm has attracted attention.
  • JP 2009-255040 A discloses a first step in which a polysilazane is coated on a resin substrate to form a polymer film having a thickness of 250 nm or less, and the formed polymer film is irradiated with vacuum ultraviolet light. And a third step of repeating the first step and the second step to form a film on the film formed in the second step, and a method for producing a flexible gas barrier film. It is disclosed.
  • an inorganic barrier layer or a gas barrier layer formed by excimer photo-modification of polysilazane by a vapor deposition method such as a sputtering method or a CVD method is used in a very severe environment of high temperature and high humidity such as 85 ° C. and 85% RH. Then, it turned out that gas-barrier property falls with time.
  • an object of the present invention is to provide a gas barrier film having excellent durability in a high temperature and high humidity environment.
  • the present invention relates to a gas barrier film having a resin base material and a silicon-containing layer, and the composition is SiMxNyOz in the atomic composition distribution profile obtained when the silicon-containing layer is subjected to XPS composition analysis in the thickness direction. It is a gas barrier film that has a region (A) that satisfies the following relational expression (1) when shown, and the region (A) is an ion implantation forming layer or an ion plating forming layer.
  • FIG. 1 is a schematic cross-sectional view showing a gas barrier film according to an embodiment of the present invention.
  • 10 is a gas barrier film
  • 11 is a resin substrate
  • 12 is a silicon-containing layer
  • 13 is a layer containing a transition metal compound.
  • 31 is a plasma CVD apparatus
  • 32 is a delivery roller
  • 33, 34, 35 and 36 are transport rollers
  • 39 and 40 are film forming rollers
  • 41 is a gas supply port
  • 42 is a power source for generating plasma
  • 43 and 44 Indicates a magnetic field generator
  • 45 indicates a winding roller.
  • FIG. 3 It is a conceptual diagram of a hollow cathode type ion plating apparatus.
  • 20 is an ion plating apparatus
  • 21 is a vacuum chamber
  • 22 is a hollow cathode (hollow cathode) electron gun
  • 23 is an anode
  • 24 is a permanent magnet disposed in the anode
  • 25 is a resin substrate and silicon.
  • 26 is a heater
  • 27 is an evaporation source
  • 28 is an RF power source
  • 29 is a vacuum exhaust system.
  • One embodiment of the present invention is a gas barrier film having a resin base material and a silicon-containing layer, wherein the silicon-containing layer is obtained by performing an XPS composition analysis in the thickness direction.
  • the composition is represented by SiMxNyOz
  • the gas barrier film has a region (A) satisfying the following relational expression (1), and the region (A) is an ion implantation forming layer or an ion plating forming layer.
  • Another embodiment of the present invention is a gas barrier film having a resin substrate and a silicon-containing layer, wherein the silicon-containing layer has an atomic composition distribution profile obtained when XPS composition analysis is performed in the thickness direction.
  • the gas barrier film has a region (A) satisfying the following relational expression (1) when the composition is represented by SiMxNyOz, and the region (A) is formed by an ion implantation method or an ion plating method.
  • Another embodiment of the present invention is a method for producing a gas barrier film having a resin base material and a silicon-containing layer, which is obtained when the silicon-containing layer is subjected to XPS composition analysis in the thickness direction.
  • the composition has a region (A) that satisfies the following relational expression (1) when the composition is represented by SiMxNyOz, and the region (A) is formed by an ion implantation method or an ion plating method. It is a manufacturing method of a gas barrier film.
  • an inorganic barrier layer or a gas barrier layer formed by excimer photo-modification of polysilazane by a vapor deposition method such as a sputtering method or a CVD method is very harsh at a high temperature and high humidity of 85 ° C. and 85% RH. Under such circumstances, the gas barrier property may deteriorate with time.
  • the gas barrier film of the present invention has a region (A) in the silicon-containing layer. Due to the presence of such a region (A), the durability under a high temperature and high humidity environment is remarkably improved.
  • the region (A) is likely to be oxidized prior to the silicon-containing layer.
  • the left side (4 + ⁇ ax) ⁇ (3y + 2z) of the above formula (1) (hereinafter also simply referred to as the left side of the formula (1)) is a sum of O and N with respect to the combined number of Si and M. This means that the number of couplings made is small. In other words, when the left side of Formula (1) is 0, it is the same as the theoretical number of bonds, whereas when it is greater than 0, the silicon and transition metal bonds are considered to be in a slightly surplus state. For this reason, the region (A) is a region where there is room for further oxidation.
  • FIG. 1 is a schematic cross-sectional view showing a gas barrier film according to an embodiment of the present invention.
  • a resin base material 11, a silicon-containing layer 12, and a layer (not including silicon) 13 containing a transition metal compound are arranged in this order.
  • the region (A) is formed in the silicon-containing layer near the interface between the silicon-containing layer 12 and the layer 13 containing the transition metal compound.
  • a resin substrate, a silicon-containing layer, and a layer containing a transition metal compound (not containing silicon) are arranged in this order, and the silicon-containing layer and the layer containing the transition metal compound are adjacent to each other. Be placed. Details of the layer containing the transition metal compound are the same as those described later.
  • other layers may be disposed between the substrate and the silicon-containing layer or on each layer.
  • the thickness of the silicon-containing layer (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 1000 nm, more preferably 50 to 600 nm, and more preferably 50 to More preferably, it is 300 nm. If it is this range, the balance of gas barrier property and durability becomes favorable and is preferable.
  • the silicon-containing layer may be a single layer or a laminated structure of two or more layers.
  • the silicon-containing layer is preferably obtained by forming a silicon-containing precursor layer and then applying an ion implantation method or an ion plating method which is a means for forming the region (A).
  • the silicon-containing precursor layer means a layer containing silicon.
  • the silicon-containing precursor layer does not have region (A).
  • the silicon-containing precursor layer preferably contains any one selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, silicon oxynitride and silicon oxycarbide, and includes silicon oxide, silicon oxycarbide and More preferably, any one selected from the group consisting of silicon oxynitride is included.
  • the thickness of the silicon-containing precursor layer (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 1000 nm, more preferably 50 to 600 nm, and more preferably 50 to 300 nm. Is more preferable.
  • the silicon-containing precursor layer is preferably a vapor-deposited layer obtained by a vapor deposition method, or a polysilazane coating-forming layer obtained by applying and drying a coating liquid containing polysilazane, and a high-temperature and high-humidity environment.
  • the polysilazane coating layer is more preferred because the durability under the coating is particularly good.
  • “obtained by applying and drying a coating liquid containing polysilazane” means that the silicon-containing precursor layer and the silicon-containing layer obtained thereafter apply and dry the coating liquid containing polysilazane. Means having any of the manufacturing stages.
  • the silicon-containing precursor layer and the silicon-containing layer are preferably polysilazane coating formation layers (obtained by coating and drying a coating solution containing polysilazane). Further, the silicon-containing precursor layer and the silicon-containing layer are a polysilazane vacuum ultraviolet modified layer obtained by irradiating a coating film obtained by applying and drying a coating liquid containing polysilazane with vacuum ultraviolet rays. It is more preferable.
  • the silicon-containing precursor layer is a polysilazane coating-forming layer
  • the transition metal atom in the region (A) silicon This is considered to be because it is easy to form a direct bond with the atom. Since the bond distance between the silicon atom and the transition metal atom is shorter than the bond distance between the silicon atom and the oxygen atom, the direct bond between the transition metal atom and the silicon atom results in a high-density film, and under high temperature and high humidity conditions. It is considered that the barrier performance is improved.
  • the vapor deposition method for forming the silicon-containing precursor layer is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, and ion plating, plasma CVD (chemical), and the like. Examples thereof include a chemical vapor deposition method such as a vapor deposition method and ALD (Atomic Layer Deposition). Considering productivity and the like, it is preferable to use the sputtering method or the plasma CVD method among the vapor phase film forming methods.
  • bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering 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 either DC (direct current) sputtering or RF (high frequency) sputtering may be used.
  • RF high frequency
  • 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 By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable.
  • a silicon oxide thin film can be formed by using silicon as a target and introducing oxygen into the process gas.
  • RF high frequency
  • a silicon oxide target can be used.
  • the inert gas used for the process gas He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used.
  • a silicon compound thin film such as silicon oxide, nitride, nitride oxide or carbonate can be produced.
  • 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, film material, film thickness, and the like.
  • chemical vapor deposition supplies a raw material gas containing a target thin film component onto a substrate and deposits a film by a chemical reaction in the substrate surface or in the gas phase.
  • a method of generating plasma or the like for the purpose of activating the chemical reaction, there is a method of generating plasma or the like.
  • CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of the film formation speed and the processing area.
  • the plasma CVD method is not particularly limited, but the plasma CVD method at or near atmospheric pressure described in International Publication No. 2006/033233 (US Patent Application Publication No. 2008/085418), a counter roll electrode, The plasma CVD method using the plasma CVD apparatus which has is mentioned. Especially, since productivity is high, it is preferable to form a silicon-containing precursor layer by a plasma CVD method using a plasma CVD apparatus having a counter roll electrode.
  • the plasma CVD method may be a Penning discharge plasma type plasma CVD method.
  • a method for producing a silicon-containing layer by a plasma CVD method using a plasma CVD apparatus having such a counter roll electrode is known, and is described in, for example, Japanese Patent Application Laid-Open No. 2014-100806.
  • FIG. 2 is a schematic view showing an example of a plasma CVD apparatus having a counter roll electrode.
  • the feed roller 32, the transport rollers 33, 34, 35, and 36, a pair of film forming rollers 39 and 40, a gas supply port 41, A plasma generating power source 42, magnetic field generators 43 and 44 installed inside the film forming rollers 39 and 40, and a winding roller 45 are provided.
  • at least the film forming rollers 39, 40, the gas supply port 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43, 44 made of permanent magnets are not shown. Located in the chamber.
  • each film-forming roller is for plasma generation so that a pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes.
  • a power source 42 Connected to a power source 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge to the facing space (discharge region) between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. In this way, plasma can be generated in the facing space between the film forming roller 39 and the film forming roller 40.
  • the film forming rate can be doubled and a film having the same structure can be formed.
  • magnetic field generators 43 and 44 are provided, which are fixed so as not to rotate even if these film forming rollers rotate.
  • a film forming gas (a raw material gas or the like) used in a plasma CVD method using a plasma CVD apparatus having a counter roll electrode
  • a raw material gas, a reactive gas, a carrier gas, or a discharge gas is used alone or in combination.
  • the raw material gas in the film forming gas used for forming the silicon-containing precursor layer can be appropriately selected and used according to the material of the silicon-containing precursor layer to be formed.
  • a source gas for example, an organosilicon compound containing silicon can be used.
  • organosilicon compounds examples include hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, silane, methylsilane, and dimethylsilane. And trimethylsilane, tetramethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), and the like.
  • HMDSO hexamethyldisiloxane
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • organosilicon compounds hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting silicon-containing layer.
  • these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
  • appropriate source gases are selected according to the type of the silicon-containing precursor layer.
  • a reactive gas may be used as the film forming gas.
  • a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used.
  • reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • reactive gas for forming nitride nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more.
  • a carrier gas may be used as necessary to supply the source gas into the vacuum chamber.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • carrier gas and discharge gas known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon, etc .; hydrogen can be used.
  • the ratio of the raw material gas and the reactive gas is a reaction that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive as compared with the ratio of the amount of gas.
  • the polysilazane used in forming the polysilazane coating-forming layer “obtained by coating and drying a coating liquid containing polysilazane” is a polymer having a silicon-nitrogen bond, and includes Si—N, Si Ceramic precursor inorganic polymers such as SiO 2 , Si 3 N 4 , and both intermediate solid solutions SiO x N y having bonds such as —H and N—H.
  • the polysilazane preferably has the following structure.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R 1 , R 2 and R 3 may be the same or different.
  • n is an integer
  • the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. Is preferred.
  • one of preferred embodiments is perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms.
  • polysilazane has a structure represented by the following general formula (II).
  • R 1 ′ , R 2 ′ , R 3 ′ , R 4 ′ , R 5 ′ and R 6 ′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group.
  • R 1 ′ , R 2 ′ , R 3 ′ , R 4 ′ , R 5 ′ and R 6 ′ may be the same or different.
  • n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that Note that n ′ and p may be the same or different.
  • R 1 ′ , R 3 ′ and R 6 ′ each represent a hydrogen atom, and R 2 ′ , R 4 ′ and R 5 ′ each represent a methyl group;
  • R 1 ' , R 3' and R 6 ' each represents a hydrogen atom, R 2' , R 4 ' each represents a methyl group, and R 5' represents a vinyl group;
  • R 1 ' , R 3' , R 4 A compound in which ' and R 6' each represent a hydrogen atom and R 2 ' and R 5' each represents a methyl group is preferred.
  • polysilazane has a structure represented by the following general formula (III).
  • R 1 ′′ , R 2 ′′ , R 3 ′′ , R 4 ′′ , R 5 ′′ , R 6 ′′ , R 7 ′′ , R 8 ′′ and R 9 ′′ are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R 1 ′′ , R 2 ′′ , R 3 ′′ , R 4 ′′ , R 5 ′′ , R 6 ′′ , R 7 ′′ , R 8 ′′ and R 9 ′′ may be the same or different.
  • n ′′, p ′′ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ′′, p ′′ and q may be the same or different.
  • R 1 ′′ , R 3 ′′ and R 6 ′′ each represent a hydrogen atom
  • R 2 ′′ , R 4 ′′ , R 5 ′′ and R 8 ′′ each represent a methyl group.
  • R 9 ′′ represents a (triethoxysilyl) propyl group
  • R 7 ′′ represents an alkyl group or a hydrogen atom.
  • the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard.
  • the ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, these perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.
  • Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings.
  • the number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), and there are liquid or solid substances, and the state varies depending on the molecular weight.
  • Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a coating liquid for forming a polysilazane coating-forming layer.
  • Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. Is mentioned. These polysilazane solutions can be used alone or in combination of two or more.
  • polysilazane examples include, but are not limited to, for example, a silicon alkoxide-added polysilazane obtained by reacting the polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-23827), and a glycidol reaction.
  • a silicon alkoxide-added polysilazane obtained by reacting the polysilazane with a silicon alkoxide
  • glycidol-added polysilazane Japanese Patent Laid-Open No. 6-122852
  • alcohol-added polysilazane obtained by reacting alcohol
  • metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal obtained by adding metal fine particles Fine particle added policy Zhang such (JP-A-7-196986), and a polysilazane ceramic at low temperatures.
  • the content of polysilazane in the polysilazane coating film before the conversion treatment can be 100% by mass when the total mass of the polysilazane coating film is 100% by mass.
  • the content of polysilazane in the film is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass. % Or less, more preferably 70% by mass or more and 95% by mass or less.
  • the solvent for preparing the coating liquid for forming the polysilazane coating forming layer is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups that easily react with polysilazane (for example, hydroxyl groups, or An organic solvent that does not contain an amine group and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable.
  • the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc.
  • aprotic solvent for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc.
  • Hydrogen solvents Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like.
  • the solvent is selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.
  • the concentration of polysilazane in the coating liquid for forming the polysilazane coating forming layer is not particularly limited, and varies depending on the layer thickness and the pot life of the coating liquid, but is preferably 1 to 80% by mass, more preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass.
  • the polysilazane coating forming layer forming coating solution preferably contains a catalyst in order to promote the modification.
  • a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds.
  • the concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on polysilazane.
  • concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on polysilazane.
  • the following additives can be used in the polysilazane coating forming layer forming coating solution as required.
  • cellulose ethers, cellulose esters for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc.
  • natural resins for example, rubber, rosin resin, etc., synthetic resins
  • Aminoplasts particularly urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyester resins or modified polyester resins, epoxy resins, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.
  • Method of applying a coating liquid for forming a polysilazane coating forming layer As a method for applying the polysilazane coating forming layer forming coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method and the like. It is done.
  • the coating thickness can be appropriately set according to the preferred thickness and purpose.
  • the coating film After applying the coating solution, the coating film is dried. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable silicon-containing precursor layer can be obtained. The remaining solvent can be removed later.
  • the drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C.
  • the drying temperature is preferably set to 150 ° C. or lower in consideration of deformation of the base material due to heat.
  • the temperature can be set by using a hot plate, oven, furnace or the like.
  • the drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes.
  • the drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.
  • the coating film obtained by applying the polysilazane coating-forming layer forming coating solution may include a step of removing moisture before or during the irradiation of vacuum ultraviolet rays.
  • a method for removing moisture a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature.
  • a preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is ⁇ 5 ° C.
  • the dew point temperature is ⁇ 5 ° C. or lower and the maintaining time is 1 minute or longer.
  • the lower limit of the dew point temperature is not particularly limited, but is usually ⁇ 50 ° C. or higher, and preferably ⁇ 40 ° C. or higher. This is a preferred form from the viewpoint of promoting the dehydration reaction of the silicon-containing layer converted to silanol by removing water before or during the modification treatment.
  • the coating film containing polysilazane formed as described above is used as a silicon-containing precursor layer as it is, silicon is obtained by irradiating the obtained coating film with vacuum ultraviolet rays and performing a conversion reaction to silicon oxynitride or the like. It is good also as a containing precursor layer.
  • the amount of light is low because the thickness of the region (A) is thick.
  • the amount of vacuum ultraviolet light is low or not irradiated with vacuum ultraviolet light, the outermost surface of the silicon-containing precursor layer exists in a metastable state. For example, a transition metal compound is added to the silicon-containing precursor layer as described below.
  • the amount of vacuum ultraviolet light is low or vacuum ultraviolet light is not irradiated is preferably a vacuum ultraviolet light irradiation energy amount (irradiation amount) of 0 to 5.0 J / cm 2 , and 0 to 3 J / cm 2. more preferably cm 2.
  • the coating film containing polysilazane formed as described above can be used as a silicon-containing precursor layer as it is, the obtained coating film is irradiated with vacuum ultraviolet rays to convert it into silicon oxynitride ( It is good also as a silicon-containing precursor layer by performing (modification).
  • Vacuum ultraviolet irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the resin substrate used.
  • it can be processed in an ultraviolet baking furnace equipped with an ultraviolet ray generation source.
  • the ultraviolet baking furnace itself is generally known.
  • an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used.
  • the object when it is a long film, it can be converted to ceramics by continuously irradiating ultraviolet rays in a drying zone equipped with the ultraviolet ray generation source as described above while being conveyed.
  • the time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate used and the silicon-containing precursor layer.
  • the modification by vacuum ultraviolet irradiation uses a light energy of 100 to 200 nm, preferably a light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in polysilazane, and bonds the atoms with only photons called photon processes.
  • a film containing silicon oxynitride is formed at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly.
  • the vacuum ultraviolet ray source in the present invention may be any source that generates light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator (for example, Xe excimer lamp) having a maximum emission at about 172 nm, and an emission line at about 185 nm.
  • Excimer radiator for example, Xe excimer lamp
  • the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.
  • the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds.
  • the coating film can be modified in a short time by the high energy of the active oxygen, ozone and ultraviolet radiation.
  • ⁇ Excimer lamps have high light generation efficiency and can be lit with low power.
  • light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed.
  • it is suitable for flexible film materials such as PET that are easily affected by heat.
  • Oxygen is required for the reaction at the time of vacuum ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease.
  • it is preferably performed in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). More preferably.
  • the water vapor concentration during the conversion process is preferably in the range of 1,000 to 4,000 volume ppm.
  • the gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
  • the illuminance of the vacuum ultraviolet ray on the coating surface received by the coating film is preferably 1 mW / cm 2 to 10 W / cm 2 , more preferably 30 mW / cm 2 to 200 mW / cm 2. and further preferably 50mW / cm 2 ⁇ 160mW / cm 2. If it is 1 mW / cm 2 or more, the reforming efficiency is improved, and if it is 10 W / cm 2 or less, ablation that can occur in the coating film and damage to the substrate can be reduced.
  • the amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the surface of the coating film in the case of modification is preferably 0.1 to 10 J / cm 2 , more preferably 0.1 to 7 J / cm 2. . If it is this range, generation
  • the vacuum ultraviolet ray used may be generated by plasma formed of a gas containing at least one of CO, CO 2 and CH 4 .
  • the gas containing at least one of CO, CO 2 and CH 4 hereinafter also referred to as carbon-containing gas
  • the carbon-containing gas may be used alone, but carbon containing rare gas or H 2 as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.
  • heat treatment for example, a method of heating a coating film by contacting a substrate with a heating element such as a heat block, a method of heating an atmosphere by an external heater such as a resistance wire, an infrared region such as an IR heater, etc.
  • a heating element such as a heat block
  • an external heater such as a resistance wire
  • an infrared region such as an IR heater
  • the heating temperature is preferably adjusted appropriately within the range of 50 ° C to 250 ° C.
  • the region (A) is a region that satisfies the formula (1).
  • a co-oxynitride layer of Si and M is formed, and this co-oxynitride layer of Si and M is considered to exhibit high wet heat resistance.
  • the region (A) is a region where there is room for further oxidation, and it is considered that the deterioration of the silicon-containing layer accompanying oxygen intrusion is suppressed, and the durability under high temperature and high humidity conditions is further improved.
  • the location of the region (A) in the silicon-containing layer is not particularly limited, but it is preferably present in the surface layer facing the substrate of the silicon-containing layer.
  • the presence of the region (A) at such a position further suppresses deterioration of the silicon-containing layer accompanying oxygen intrusion from the surface layer, and further improves durability under high temperature and high humidity conditions.
  • M is a transition metal
  • a is the stoichiometric valence of the transition metal M
  • x is the existing atomic ratio of the transition metal M to the silicon atom
  • y is the existing atomic ratio of nitrogen to silicon atoms
  • z is the existing atomic ratio of oxygen to silicon atoms.
  • x is 0 ⁇ x, and preferably 0 ⁇ x ⁇ 10.
  • y is 0 ⁇ y, and preferably 0 ⁇ y ⁇ 10.
  • z is 0 ⁇ z, and preferably 0 ⁇ z ⁇ 100.
  • the stoichiometric valence indicates the maximum valence.
  • ⁇ ax means the sum of products of the stoichiometric maximum valence of each transition metal and the atomic ratio of each transition metal to silicon atom 1, for example, niobium having a valence of 5 is an atom with respect to a silicon atom.
  • the left side of the formula (1) is (4 + ax) ⁇ (3y + 2z).
  • region (B) where (4 + ⁇ ax) ⁇ (3y + 2z)> 1 in the region (A). It is preferable to have such a region (B) because it is further excellent in durability under high temperature and high humidity conditions.
  • the region (A) preferably has a region where (4 + ⁇ ax) ⁇ (3y + 2z)> 2 and more preferably has a region where (4 + ⁇ ax) ⁇ (3y + 2z)> 3.
  • the maximum value of (4 + ⁇ ax) ⁇ (3y + 2z) in region (A) is preferably 7 or less from the viewpoint of film coloring.
  • Control of the value of (4 + ⁇ ax) ⁇ (3y + 2z) is, for example, when the layer containing the transition metal compound is formed by an ion plating method (the following method (1)) as an example.
  • the value of (4 + ⁇ ax) ⁇ (3y + 2z) can be controlled by controlling, controlling the bias voltage to the base material, controlling the pressure in the reaction chamber, or the like.
  • the value of (4 + ⁇ ax) ⁇ (3y + 2z) can be increased by increasing the heating temperature of the substrate, increasing the bias voltage to the substrate, or decreasing the pressure in the reaction chamber.
  • the transition metal M included in the region (A) refers to a Group 3 element to a Group 12 element, and examples of the transition metal include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and 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.
  • the transition metal M included in the region (A) is preferably a metal having a lower redox potential than silicon.
  • a transition metal having a lower oxidation-reduction potential than silicon good barrier properties can be obtained.
  • Specific examples of transition metals having a lower oxidation-reduction potential than silicon include, for example, niobium (Nb), tantalum (Ta), vanadium (V), zirconium (Zr), titanium (Ti), hafnium (Hf), yttrium ( Y), lanthanum (La), cerium (Ce) and the like. These metals may be used alone or in combination of two or more.
  • niobium, tantalum, and vanadium which are Group 5 elements, can be preferably used because they have a high effect of suppressing oxidation of the silicon-containing layer, and niobium can be more preferably used.
  • the transition metal M is particularly preferably niobium or tantalum from which a compound with good transparency can be obtained.
  • the thickness of the region (A) is preferably 2 nm or more from the viewpoint of suppressing oxygen intrusion into the silicon-containing layer, and preferably 20 nm or less from the viewpoint of thinning. More preferably, the thickness of the region (A) is 4 to 20 nm, more preferably 10 to 16 nm, and still more preferably 12 to 16 nm. Note that the thickness of the region (A) is an integral multiple of 2.0 nm because the depth profile is obtained every 2.0 nm in the depth direction in terms of SiO 2 in the XPS analysis shown below (region) The number of plots satisfying the condition (A) is measured. When the number of plots is two, the film thickness of the region (A) is 2 nm, and when the number is three, the number is 4 nm.
  • the thickness of the region (A) can be adjusted by controlling the substrate temperature at the time of film formation or controlling the applied power.
  • the composition distribution profile in the thickness direction is measured by XPS analysis, and the value of (4 + ⁇ ax) ⁇ (3y + 2z) is obtained to determine whether the region (A) has the region (A).
  • XPS analysis conditions are as follows.
  • ⁇ XPS analysis conditions >> ⁇ Equipment: ULVAC-PHI QUANTERASXM ⁇ X-ray source: Monochromatic Al-K ⁇ ⁇ Sputtering ion: Ar (2 keV) Depth profile: After sputtering equivalent to 2.0 nm in terms of SiO 2 , measurement is repeated to obtain a depth profile for every 2.0 nm in the depth direction of SiO 2 Quantification: The peak obtained by obtaining the background by the Shirley method The area is quantified using the relative sensitivity coefficient method. Data processing uses MultiPak manufactured by ULVAC-PHI.
  • the region (A) is an ion implantation formation layer or an ion plating formation layer, and is formed by an ion implantation method or an ion plating method. Specifically, a method of forming a layer containing a transition metal compound by an ion plating method on the silicon-containing precursor layer (method (1)) or a transition metal ion by an ion implantation method on the silicon-containing precursor layer. This is a method of injection (method (2)). According to these methods, the thickness of the region (A) can be increased, and the durability under high temperature and high humidity conditions is remarkably improved.
  • a layer containing a transition metal compound (hereinafter also simply referred to as a transition metal compound layer) is formed on the silicon-containing layer (the form of FIG. 1).
  • a transition metal compound layer further improves the oxidation-inhibiting effect of the silicon-containing layer, and further improves the durability under high temperature and high humidity conditions.
  • the transition metal compound is not particularly limited, and examples thereof include transition metal oxides, nitrides, carbides, oxynitrides, and oxycarbides. Among these, from the viewpoint of more effectively suppressing the oxidation of the silicon-containing layer, the transition metal compound is preferably a transition metal oxide.
  • the transition metal compounds may be used alone or in combination of two or more.
  • a transition metal the thing similar to what was described in the transition metal M contained in a area
  • niobium, tantalum, and vanadium, which are Group 5 elements, can be preferably used because they have a high effect of suppressing oxidation of the silicon-containing layer, and niobium can be more preferably used.
  • the transition metal in the transition metal compound is particularly preferably niobium or tantalum from which a compound with good transparency can be obtained.
  • the transition metal M contained in the region (A) and the transition metal in the transition metal compound layer may be the same or different, but are preferably the same.
  • the content of the transition metal compound in the transition metal compound layer is not particularly limited as long as the effects of the present invention are exhibited, but it is preferably 50% by mass or more, more than 80% by mass with respect to the total mass of the transition metal compound layer. Is more preferably 95% by mass or more, particularly preferably 98% by mass or more, and 100% by mass (that is, the transition metal compound layer is made of a transition metal compound). Most preferred.
  • the transition metal compound layer may be a single layer or a laminated structure of two or more layers.
  • the transition metal compounds contained in the transition metal compound layer may be the same or different.
  • the transition metal compound layer adjacent to the silicon-containing layer preferably uses an ion plating method, but the other transition metal compound layer may be formed by other methods, for example, Chemical vapor deposition methods such as physical vapor deposition (PVD) methods such as sputtering, vapor deposition, and ion plating, plasma CVD (chemical vapor deposition), and ALD (Atomic Layer Deposition) can be used.
  • PVD physical vapor deposition
  • sputtering vapor deposition
  • vapor deposition vapor deposition
  • ion plating plasma CVD (chemical vapor deposition)
  • ALD Atomic Layer Deposition
  • a sputtering method using a transition metal oxide as a target is preferable because it has a higher film formation rate and higher productivity.
  • the thickness of the transition metal compound layer (the total thickness in the case of a laminated structure of two or more layers) is preferably 1 to 200 nm, preferably 2 to 100 nm, from the viewpoint of in-plane uniformity of the barrier property. Is more preferably 3 to 50 nm.
  • the ion plating method in method (1) is a method in which vaporized elements are ionized by an electron beam or arc discharge and accelerated by an electric field to form a film on a substrate as high energy particles of several ev to several tens ev.
  • the thickness of the region (A) can be increased, and durability under high temperature and high humidity conditions is improved, which is preferable.
  • Examples of the ion plating method include a multi-cathode method, a high-frequency method, a high-frequency heating method, an auxiliary electrode method, an activated reaction vapor deposition method, a hollow cathode method (HCD), an arc plasma method, and a cluster ion beam method.
  • the hollow cathode method is preferably used because of its high ionization rate and high film formation rate.
  • the hollow cathode method is a method in which a high current electron beam is generated by a hollow cathode (hollow cathode) electron gun, and the evaporation source and the ionization of the evaporated substance are simultaneously performed by the electron beam.
  • a hollow cathode (hollow cathode) electron gun the evaporation source and the ionization of the evaporated substance are simultaneously performed by the electron beam.
  • Fig. 3 shows a conceptual diagram of a hollow cathode ion plating apparatus.
  • the ion plating apparatus 20 of FIG. 3 includes a vacuum chamber 21, a hollow cathode (hollow cathode) electron gun 22, an anode 23, a permanent magnet 24 disposed in the anode, a heater 26, and a vacuum exhaust system 29.
  • the laminated body 25 in which the silicon-containing precursor layer is formed on the resin base material is installed at the time of film formation.
  • the region (A) can be formed by depositing a transition metal compound on the silicon-containing precursor layer formed on the resin substrate using the hollow cathode ion plating apparatus 20.
  • the evaporation source 27 is installed on the anode 23 to reduce the pressure in the vacuum chamber 21.
  • the inside of the vacuum chamber is preferably 1 ⁇ 10 ⁇ 4 Torr or less.
  • a plasma source gas such as argon gas (Ar) is introduced into the hollow cathode (hollow cathode) electron gun 22.
  • gas molecules inside the cathode are ionized by a high-frequency electric field, and an electron beam is generated by a hollow cathode (hollow cathode) electron gun 22.
  • the generated electron beam is drawn into the vacuum chamber 21 by a magnetic field formed by an auxiliary coil (not shown), converges on the evaporation source 27 by a magnetic field created by the permanent magnet 24 below the anode 23, and heats the evaporation source 27. To do.
  • the heated portion of the evaporation source 27 evaporates, and the evaporated molecules are ionized by the high-density plasma existing in the vicinity of the anode 23.
  • the ionized evaporation substance collides with the laminated body 25 to which a bias voltage is applied by an RF (radio frequency, high frequency) power source 28, and a region (A) and a transition metal compound layer are formed.
  • RF radio frequency, high frequency
  • raw materials evaporation sources
  • ions to be implanted examples include transition metal oxides such as niobium oxide, silicon oxide, and titanium oxide.
  • a reactive gas oxygen, nitrogen, etc.
  • a reactive gas oxygen, nitrogen, etc.
  • the heating method is not particularly limited, but oven heating by electric resistance heating, vacuum oven heating, heating using hot water, heating by infrared heater, heating by ultrasonic vibration, radiation heating by IR heater, film roll Examples include a method of heating a shaft or a jig in a running process by electrically heating the jig directly in contact with the film, heating by high frequency heating, or the like.
  • the substrate temperature at the time of heating is preferably 20 to 120 ° C, more preferably 80 to 120 ° C.
  • the pressure in the chamber during film formation is preferably 10 ⁇ 4 to 10 ⁇ 2 Torr.
  • ion implantation can be performed easily and efficiently uniformly.
  • the power applied to the laminate 25 at the time of film formation is preferably 200 to 2000 W, more preferably 500 to 1500 W because the region (A) can be easily formed.
  • the stoichiometric oxide for example, Nb 2 O 5 when the transition metal is Nb
  • the body layer preferably a polysilazane coating formation layer
  • the ion implantation method is a method in which an object is placed in plasma and a high voltage pulse is applied to suck and accelerate ions in the plasma into the object.
  • the plasma ion implantation method (A) a method of injecting ions present in plasma generated using an external electric field into a laminate in which a silicon-containing precursor layer is formed on a resin substrate, Or (B) without using an external electric field, ions existing in the plasma generated only by the electric field by the negative high voltage pulse applied to the laminate in which the silicon-containing precursor layer is formed on the resin substrate, A method of injecting into a laminate in which a silicon-containing precursor layer is formed on a resin substrate is preferable.
  • the pressure during ion implantation is preferably 1 Pa or less, and more preferably 0.01 to 1 Pa.
  • the pressure at the time of plasma ion implantation is in such a range, ion implantation can be performed easily and efficiently uniformly.
  • the method (B) does not require a high degree of vacuum, the processing operation is simple, and the processing time can be greatly shortened. Moreover, it can process uniformly over the whole coating-film layer, and the ion in plasma can be continuously inject
  • RF radio frequency
  • the pulse width when applying a negative high voltage pulse is preferably 1 to 15 ⁇ sec.
  • the pulse width is in such a range, a transparent and uniform ion implantation layer can be formed more easily and efficiently.
  • the applied voltage when generating plasma is preferably -1 kV to -50 kV, more preferably -1 kV to -30 kV, and particularly preferably -5 kV to -20 kV. If ion implantation is performed at an applied voltage greater than ⁇ 1 kV, the ion implantation amount (dose amount) becomes insufficient, and desired performance cannot be obtained.
  • the film is charged at the time of ion implantation, and defects such as coloring of the film are not preferable.
  • a plasma ion implanter is used to inject ions in the plasma into the coating layer.
  • the plasma ion implantation apparatus specifically, (a) a laminate in which a silicon-containing precursor layer is formed on a resin base material (hereinafter, also referred to as “layer to be ion-implanted”) has a negative high value.
  • a device that uniformly surrounds the periphery of an ion-implanted layer by superimposing high-frequency power on a feedthrough to which a voltage pulse is applied, and attracts, implants, collides, and deposits ions in the plasma Japanese Patent Laid-Open No.
  • Plasma is generated using an external electric field such as a high frequency power source such as a microwave, and a high voltage pulse is applied to attract and inject ions in the plasma
  • a plasma ion implantation apparatus that implants ions in plasma generated only by an electric field generated by applying a high voltage pulse without using an external electric field.
  • the plasma ion implantation apparatus (c) or (d) because the processing operation is simple, the processing time can be greatly shortened, and it is suitable for continuous use.
  • resin substrate Specific examples of the resin substrate according to the present embodiment include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, and polyamideimide.
  • Resin polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate
  • base materials containing thermoplastic resins such as resins, alicyclic modified polycarbonate resins, fluorene ring modified polyester resins, and acryloyl compounds. These resin substrates can be used alone or in combination of two or more.
  • the resin base material is preferably made of a heat-resistant material. Specifically, a resin base material having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 ° C. or more and 300 ° C. or less is used.
  • Tg glass transition temperature
  • the resin base material satisfies the necessary conditions as a laminated film for electronic parts and displays. That is, when the gas barrier film according to the present invention is used for these applications, the gas barrier film may be exposed to a process at 150 ° C. or higher.
  • the linear expansion coefficient of the resin base material in the gas barrier film is 100 ppm / K or less, the substrate dimensions are stabilized when the gas barrier film is passed through the temperature process as described above, and thermal expansion and contraction are prevented. It can be reduced, deterioration of the barrier performance can be suppressed, or it can withstand a thermal process. By setting it as 15 ppm / K or more, it can suppress that a film breaks like glass and flexibility deteriorates.
  • Polyolefin for example, ZEONOR (registered trademark) 1600: 160 ° C) manufactured by Nippon Zeon Co., Ltd., polyarylate (PAr: 210 ° C), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 190 ° C), cycloolefin Copolymer (COC: Compound described in JP-A No. 2001-150584: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C. manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: special Kai 2000-227603 Compound described in JP-A No.
  • the resin base material listed above may be an unstretched film or a stretched film.
  • the resin substrate can be produced by a conventionally known general method. The method for producing these base materials is described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 (paragraphs “0056” to “0060” of US Patent Application Publication No. 2014/106151). Can be adopted as appropriate.
  • the surface of the resin substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments may be combined as necessary. May go.
  • the resin base material may be subjected to an easy adhesion treatment.
  • the resin substrate may be a single layer or a laminated structure of two or more layers.
  • the resin base materials may be the same type or different types.
  • the thickness of the resin base material according to this embodiment (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 ⁇ m, and more preferably 20 to 150 ⁇ m.
  • An anchor coat layer may be formed on the surface of the resin substrate on the side on which the silicon-containing layer is formed for the purpose of improving the adhesion between the resin substrate and the silicon-containing layer.
  • polyester resins As anchor coating agents used for the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, 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 be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition.
  • a vapor phase 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 phase method, the gas generated from the substrate side is blocked to some extent.
  • an anchor coat layer can be formed for the purpose of 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 provided on the surface (one side or both sides) of the resin 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, that is, 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.
  • Specific examples of the active energy ray-curable resin include photosensitive materials for the smooth layer described below. You may use the commercially available resin base material in which the hard-coat layer is formed previously.
  • the thickness of the hard coat layer is preferably from 0.1 to 15 ⁇ m, more preferably from 0.1 to 5 ⁇ m, from the viewpoint of smoothness and bending resistance.
  • a smooth layer may be provided between the resin substrate and the silicon-containing layer.
  • the smooth layer used in the present embodiment is provided to flatten the rough surface of the resin base material on which the protrusions and the like exist, or to prevent the silicon-containing layer from having irregularities and pinholes due to the protrusions existing on the resin base material. It is done.
  • Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.
  • a resin composition containing an acrylate compound having a radical reactive unsaturated compound for example, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is 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 resistant epoxy resin), various silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd.
  • Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins.
  • an epoxy resin-based material having heat resistance is particularly preferable.
  • the method for forming the smooth 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.
  • 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.
  • additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive material as necessary.
  • an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.
  • the thickness of the smooth 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. Is preferred.
  • the smoothness of the smooth layer is a value expressed by the surface roughness defined by JIS B 0601: 2001, and the 10-point average roughness Rz is preferably 10 nm or more and 30 nm or less. Within this range, even when the silicon-containing precursor layer is formed by a coating method, for example, when the coating means is in contact with the smooth layer surface by a coating method such as a wire bar or a wireless bar. However, the applicability is hardly impaired, and the unevenness after application can be easily smoothed.
  • the gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, this invention provides the electronic device containing the gas barrier film of this invention, and an electronic device main body.
  • Examples of the electronic device body used in the electronic device of the present invention include, for example, 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. be able to. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.
  • organic EL element organic electroluminescence element
  • LCD liquid crystal display element
  • PV solar cell
  • Example 1 (1) Production of Resin Base Material
  • a polyethylene terephthalate film (Lumirror (registered trademark) (U48), manufactured by Toray Industries, Inc.) having a thickness of 100 ⁇ m and subjected to easy adhesion treatment on both surfaces was used.
  • a UV curable resin manufactured by Aika Kogyo Co., Ltd., product number: Z731L was applied to a resin substrate so that the dry film thickness was 0.5 ⁇ m, dried at 80 ° C., and then high-pressure mercury in the air. Curing was performed using a lamp under the condition of an irradiation energy amount of 0.5 J / cm 2 .
  • a clear hard coat layer (smooth layer) having a thickness of 2 ⁇ m was formed on the surface of the resin substrate on the side on which the silicon-containing precursor layer is to be formed as follows.
  • a UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a resin substrate so as to have a dry film thickness of 2 ⁇ m, then dried at 80 ° C., and then using a high-pressure mercury lamp in the air. Then, curing was performed under the condition of an irradiation energy amount of 0.5 J / cm 2 . In this way, a resin base material with a hard coat layer was obtained.
  • this resin substrate with a hard coat layer is simply referred to as a resin substrate.
  • a magnetron sputtering apparatus is used on the resin substrate, a polycrystalline Si target is used as a target, and an oxygen flow rate is controlled by DC sputtering using Ar and O 2 as process gases.
  • a silicon oxide film having a thickness of 50 nm was formed by adjusting.
  • the silicon oxide film formed above was mounted in the chamber of a hollow cathode type ion plating apparatus so as to be a film formation surface.
  • the pressure in the chamber was reduced to an ultimate vacuum of 1 ⁇ 10 ⁇ 5 Torr by an oil rotary pump and an oil diffusion pump.
  • the film was heated at 60 ° C. in advance by an IR heater before film formation.
  • the degree of vacuum at this time was 1 ⁇ 10 ⁇ 4 Torr.
  • the pressure in the chamber was reduced to an ultimate vacuum of 1 ⁇ 10 ⁇ 5 Torr by an oil rotary pump and an oil diffusion pump.
  • Nb 2 O 5 was prepared as an evaporation source and mounted on the anode (Heath).
  • a hollow cathode type plasma gun introduced with nitrogen gas is used while maintaining the pressure in the chamber at the time of film formation at 1 ⁇ 10 ⁇ 3 Torr.
  • the evaporation source on the anode (Haas) is focused and irradiated to evaporate, and the evaporated molecules are ionized by the high-density plasma to form a thin film of niobium oxide (Nb 2 O 5 ) on the silicon oxide film ( A film thickness of 20 ⁇ m) was formed.
  • the applied power to the substrate during ion plating was 300 W.
  • a gas barrier film was obtained in which Nb 2 O 5 was formed on the silicon oxide film and a region (A) having a thickness of 4 nm was formed in the silicon-containing layer.
  • the gas barrier film had a structure of resin base material-silicon-containing layer-Nb 2 O 5 layer, and the region (A) was formed in the vicinity of the interface with the Nb 2 O 5 layer in the silicon-containing layer. .
  • Example 2 In Example 1, instead of forming a silicon oxide film (silicon-containing precursor layer), gas barrier properties were obtained in the same manner as in Example 1 except that the following silicon-containing precursor layer was formed on the resin substrate. A film was prepared.
  • the produced resin substrate is formed on the produced resin substrate by plasma CVD using the facing roll type roll-to-roll vacuum film forming apparatus of FIG. It was set in the plasma CVD film forming apparatus 31 and transported. Next, a magnetic field is applied between the film formation roller 39 and the film formation roller 40, and electric power is supplied to the film formation roller 39 and the film formation roller 40, respectively. During the discharge, plasma was generated.
  • a film-forming gas mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (also functioning as a discharge gas) as a reaction gas
  • HMDSO hexamethyldisiloxane
  • oxygen gas also functioning as a discharge gas
  • a gas barrier film was obtained in which Nb 2 O 5 was formed on the silicon-containing precursor layer and a region (A) having a thickness of 4 nm was formed on the silicon-containing layer.
  • the gas barrier film had a structure of resin base material-silicon-containing layer-Nb 2 O 5 layer, and the region (A) was formed in the vicinity of the interface with the Nb 2 O 5 layer in the silicon-containing layer. .
  • Example 3 In Example 1, instead of forming a silicon oxide film (silicon-containing precursor layer), a gas barrier film was obtained in the same manner as in Example 1 except that a polysilazane coating layer was formed on a resin substrate as described below. Was made.
  • the coating liquid 1 was applied on a resin substrate by a spin coating method so as to have a dry film thickness of 150 nm, and dried at 80 ° C. for 2 minutes.
  • a gas barrier film was obtained in which Nb 2 O 5 was formed on the polysilazane coating formation layer, and a region (A) having a thickness of 10 nm was formed in the silicon-containing layer.
  • the gas barrier film had a structure of resin base material-silicon-containing layer-Nb 2 O 5 layer, and the region (A) was formed in the vicinity of the interface with the Nb 2 O 5 layer in the silicon-containing layer. .
  • Example 4 In Example 3, a gas barrier film was obtained in the same manner as in Example 3 except that the applied power to the substrate during ion plating was 1500 W.
  • a gas barrier film was obtained in which Nb 2 O 5 was formed on the polysilazane coating-formed layer and a region (A) having a thickness of 14 nm was formed in the silicon-containing layer.
  • the gas barrier film had a structure of resin base material-silicon-containing layer-Nb 2 O 5 layer, and the region (A) was formed in the vicinity of the interface with the Nb 2 O 5 layer in the silicon-containing layer. .
  • Example 5 In Example 3, a gas barrier film was obtained in the same manner as in Example 3 except that the substrate temperature for preheating the resin substrate on which the polysilazane coating layer was formed was changed to 100 ° C.
  • a gas barrier film was obtained in which Nb 2 O 5 was formed on the polysilazane coating formation layer, and a region (A) having a thickness of 12 nm was formed in the silicon-containing layer.
  • the gas barrier film had a structure of resin base material-silicon-containing layer-Nb 2 O 5 layer, and the region (A) was formed in the vicinity of the interface with the Nb 2 O 5 layer in the silicon-containing layer. .
  • Example 6 In Example 4, a gas barrier film was obtained in the same manner as in Example 4 except that the substrate temperature for preheating the resin substrate on which the polysilazane coating layer was formed during ion plating was changed to 100 ° C. .
  • a gas barrier film was obtained in which Nb 2 O 5 was formed on the polysilazane coating formation layer, and a region (A) having a thickness of 16 nm was formed in the silicon-containing layer.
  • the gas barrier film had a structure of resin base material-silicon-containing layer-Nb 2 O 5 layer, and the region (A) was formed in the vicinity of the interface with the Nb 2 O 5 layer in the silicon-containing layer. .
  • Example 7 In Example 6, a DC sputtering using a magnetron sputtering apparatus on a niobium oxide (Nb 2 O 5 ) layer, an oxygen-deficient Nb 2 O 5 target as a target, and Ar and O 2 as process gases. Thus, Nb 2 O 5 was formed to a film thickness of 15 nm.
  • the gas barrier film has a structure of resin base material-silicon-containing layer-Nb 2 O 5 layer-Nb 2 O 5 layer, and the region (A) is Nb 2 adjacent to the silicon-containing layer in the silicon-containing layer. It was formed near the interface with the O 5 layer.
  • Example 8 In Example 3, a gas barrier film was obtained in the same manner as in Example 3 except that the polysilazane coating layer was formed as follows. In this way, Nb 2 O 5 was formed on the polysilazane coating formation layer to obtain a gas barrier film in which a region (A) having a thickness of 12 nm was formed on the silicon-containing layer. At this time, the gas barrier film had a structure of resin base material-silicon-containing layer-Nb 2 O 5 layer, and the region (A) was formed in the vicinity of the interface with the Nb 2 O 5 layer in the silicon-containing layer. .
  • the coating liquid 1 was applied on a resin substrate by a spin coating method so as to have a dry film thickness of 150 nm, and dried at 80 ° C. for 2 minutes.
  • the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment of 500 mJ / cm 2 using a vacuum ultraviolet ray irradiation apparatus having an Xe excimer lamp having a wavelength of 172 nm, thereby forming a polysilazane coating formation layer.
  • the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume.
  • the stage temperature for installing the sample was set to 80 ° C.
  • the coating liquid 1 was applied on a resin substrate by a spin coating method so as to have a dry film thickness of 150 nm, and dried at 80 ° C. for 2 minutes.
  • the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment of 3 J / cm 2 using a vacuum ultraviolet ray irradiation apparatus having an Xe excimer lamp having a wavelength of 172 nm to form a polysilazane coating formation layer.
  • the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume.
  • the stage temperature for installing the sample was set to 80 ° C.
  • Comparative Example 5 In Comparative Example 1, a silicon oxide film (SiO 2 ) was formed on the resin base material by further doubling the oxygen flow rate during film formation. Next, the following film formation was performed.
  • SiO 2 silicon oxide film
  • a magnetron sputtering apparatus is used, an oxygen-deficient Nb 2 O 5 target is used as a target, and Nb 2 O with a film thickness of 15 nm is formed on the silicon oxide film (SiO 2 ) by DC sputtering using Ar and O 2 as process gases. 5 was deposited. At this time, the oxygen partial pressure in the process gas was adjusted to form Nb 2 O 5 .
  • a niobium oxide layer was formed by sputtering on the silicon oxide film.
  • Comparative Example 6 In Comparative Example 2, a silicon-containing precursor layer was formed on the resin substrate in the same manner as in Comparative Example 2, except that the oxygen flow rate during CVD film formation was doubled. Next, as in Comparative Example 5, a niobium oxide layer was formed by sputtering on the silicon oxide film.
  • thermosetting sheet-like adhesive epoxy resin
  • One side of a 50 mm ⁇ 50 mm non-alkali glass plate was UV cleaned.
  • 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.
  • the glass plate on which Ca was vapor-deposited was taken out into the glove box, and was placed so that the sealing resin layer surface of the gas barrier film to which the sealing resin layer was bonded and the Ca vapor-deposited surface of the glass plate were in contact with each other, and were adhered by vacuum lamination. 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 prepare an evaluation sample.
  • the water vapor permeability of each gas barrier film was evaluated according to the following measurement method.
  • the evaluation sample prepared as described above was stored in an 85 ° C. and 85% RH environment.
  • the corrosion area ratio was measured after 24 hours and 100 hours in an 85 ° C. and 85% RH environment and evaluated based on the following evaluation criteria.
  • Corrosion area ratio after 100 hours is less than 10%
  • Corrosion area ratio after 100 hours is 10% or more and less than 20%
  • Corrosion area ratio after 20 hours or more and less than 30% Corrosion area ratio after 24 hours is 10% or more and less than 20%
  • corrosion area ratio after 100 hours is 30% or more
  • After 24 hours Corrosion area ratio is 30% or more Manufacturing conditions of gas barrier films of each example and comparative example, maximum value of left side of formula (1), and region (A), region (A) film thickness, region The maximum value and minimum value of the left side of the formula (1) in (A) and the evaluation results are shown in Table 2 below.
  • the gas barrier films of Examples 1 to 8 had high durability under high temperature and high humidity conditions for a long period of time.

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  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
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Abstract

[Problème] Fournir un film étanche aux gaz possédant une excellente durabilité dans un environnement à haute température et humidité élevée. [Solution] Ce film étanche aux gaz comprend un substrat de résine et une couche contenant du silicium, et il est caractérisé en ce que la couche contenant du silicium présente une région (A) dans laquelle le profil de répartition de la composition atomique obtenu à partir d'une analyse de composition XPS effectuée dans le sens de l'épaisseur satisfait à l'équation (1) lorsque la composition est représentée par SiMxNyOz, et en ce que la région (A) est une couche formée par implantation d'ions ou dépôt ionique.
PCT/JP2016/063905 2015-06-01 2016-05-10 Film étanche aux gaz WO2016194559A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021042402A (ja) * 2019-09-06 2021-03-18 神港精機株式会社 反応性イオンプレーティング装置および方法
WO2024047806A1 (fr) * 2022-08-31 2024-03-07 株式会社レニアス Procédé de production d'un produit multicouche transparent

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022196636A1 (fr) * 2021-03-19 2022-09-22 リンテック株式会社 Film formant barrière aux gaz et procédé de fabrication pour un film formant barrière aux gaz

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Publication number Priority date Publication date Assignee Title
JP2008100368A (ja) * 2006-10-17 2008-05-01 Asahi Kasei Chemicals Corp 酸化亜鉛系透明導電積層体およびおその製造方法
JP2010284845A (ja) * 2009-06-10 2010-12-24 Lintec Corp ガスバリア性フィルムおよびその製造方法
JP2011238567A (ja) * 2010-05-13 2011-11-24 Lintec Corp 透明導電性フィルムおよびその製造方法並びに透明導電性フィルムを用いた電子デバイス
JP2013000977A (ja) * 2011-06-16 2013-01-07 Dainippon Printing Co Ltd ガスバリア性フィルム及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008100368A (ja) * 2006-10-17 2008-05-01 Asahi Kasei Chemicals Corp 酸化亜鉛系透明導電積層体およびおその製造方法
JP2010284845A (ja) * 2009-06-10 2010-12-24 Lintec Corp ガスバリア性フィルムおよびその製造方法
JP2011238567A (ja) * 2010-05-13 2011-11-24 Lintec Corp 透明導電性フィルムおよびその製造方法並びに透明導電性フィルムを用いた電子デバイス
JP2013000977A (ja) * 2011-06-16 2013-01-07 Dainippon Printing Co Ltd ガスバリア性フィルム及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021042402A (ja) * 2019-09-06 2021-03-18 神港精機株式会社 反応性イオンプレーティング装置および方法
WO2024047806A1 (fr) * 2022-08-31 2024-03-07 株式会社レニアス Procédé de production d'un produit multicouche transparent

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