Method for producing laminate, and gas barrier material

Abstract

The present invention is a method for producing a laminate including a base material, a resin layer, and a barrier layer, the method comprising: a resin layer formation step for forming the resin layer by coating an alternating laminate with a resin-containing solution on the base material or the barrier layer to form a resin coating, then drying or curing the resin coating; and a barrier layer formation step for forming the barrier layer containing a polysilazane-cured material by applying a solution containing a polysilazane compound onto the base material or the resin layer to form a polysilazane coating, then curing the polysilazane compound by irradiating the polysilazane coating with energy rays having a wavelength of 200 nm or less under a nitrogen atmosphere or an oxygen-containing nitrogen atmosphere. The energy rays in the barrier layer formation step have an irradiation intensity between 280 mW / cm2 and 450 mW / cm2, inclusive.

Description

Method for manufacturing laminate and gas barrier material

[0001] The present invention relates to a method for producing a laminate and a gas barrier material.

[0002] Gas barrier films are used in a wide range of fields, including various packaging and electronics. In particular, electronic products require high barrier performance against water vapor. The water vapor transmission rate (WVTR) is an index of barrier performance against water vapor. For example, in semiconductor devices such as organic EL elements and solar cells, a water vapor transmission rate of 10 －３ ~10 －６ g / m ２ In particular, for use as a barrier layer in a perovskite solar cell, a barrier performance of 10 －４ g / m ２ A high water vapor permeability of 1000 kJ / day or less is required.

[0003] Inorganic barrier films fabricated by vacuum processes such as atomic layer deposition (ALD) and chemical vapor deposition (CVD) have achieved extremely low water vapor permeability. To alleviate the stress in such inorganic barrier films, a barrier structure has been proposed in which a polymer is introduced as a stress relaxation layer, resulting in an inorganic / organic alternating laminate structure of the inorganic barrier film and the stress relaxation layer.

[0004] However, vacuum processes have problems such as low material utilization efficiency and the repeated processes with a pressure difference between atmospheric pressure and vacuum, which can lead to problems such as the adhesion of foreign matter. Furthermore, the film formation speed is slower than that of wet processes. Furthermore, in the layer-by-layer structure, the polymer that forms the stress relaxation layer is generally produced by a coating method, which requires alternating between vacuum and coating processes, resulting in high manufacturing costs.

[0005] On the other hand, gas barrier layers in which both a stress relief layer and an inorganic barrier film are fabricated by a coating process have also been reported. Such gas barrier structures fabricated entirely by solution processes can achieve high resource efficiency and high throughput, while keeping manufacturing costs low.

[0006] However, the water vapor permeability of membranes obtained by all-solution processes such as the general sol-gel method is 3 to 350 g / m ２ / day, and its density and barrier properties are lower than those of the vacuum process.

[0007] Since the formation of a barrier film by a vacuum process has the problem of low throughput, such as low film formation speed, a film formation method that combines a vacuum process and a wet process using perhydropolysilazane (PHPS) has been investigated.

[0008] Perhydropolysilazane (PHPS) is a reactive polymer with Si-N bonds as its main skeleton, and can be formed into a film by wet processes such as coating. When heated in the atmosphere, it reacts with oxygen to form SiO ２ However, SiO2 can also be converted into a film by irradiating it with vacuum ultraviolet (VUV) light in the atmosphere without heating. ２ The SiO obtained from perhydropolysilazane can be converted into a film. ２ The barrier property of the film is 10 －１ ~10 －２ g / m ２ / day, and depending on the manufacturing conditions, －３ g / m ２ The water vapor permeability can be reduced to about 1 / day.

[0009] However, SiO ２ The barrier properties of the film were not sufficient for application to electronic products that are sensitive to water vapor. Therefore, a perhydropolysilazane (PHPS) film was irradiated with vacuum ultraviolet (VUV) light in a nitrogen atmosphere to form a silicon nitride (SiN ｘ It has been proposed to convert the film into a silicon nitride (SiN) film (Patent Document 1). ｘ ) based films have high water vapor barrier properties.

[0010] Non-Patent Document 1 describes a gas barrier layer fabricated by an all-solution process, using polydimethylsiloxane (PDMS) with Si-O bonds as the main skeleton for the stress relaxation layer and perhydropolysilazane (PHPS) for the barrier layer. The perhydropolysilazane (PHPS) film is irradiated with vacuum ultraviolet light (VUV) in a nitrogen atmosphere to form silicon nitride (SiN ｘ )-based film, and the resulting silicon nitride (SiN ｘ The water vapor permeability of the film is 10 －３ g / m ２ It is stated that the date has reached / day.

[0011] JP 2024-43265 A

[0012] ACS Appl. Mater. Interfaces 11 (46), 43425-43432 (2019)

[0013] The low water vapor permeability of cured perhydropolysilazane (PHPS) films is achieved by densifying the film through irradiation with vacuum ultraviolet light (VUV). When a perhydropolysilazane (PHPS) film is irradiated with vacuum ultraviolet light (VUV), not only are Si-H and N-H bonds broken, but the Si-N bonds in the main chain are repeatedly broken and recombined, causing atomic rearrangement. This atomic rearrangement reduces the porosity of the film, thereby promoting densification of the film.

[0014] Conventionally, in order to impart high density to a cured polysilazane film, the environment in which vacuum ultraviolet light (VUV) is irradiated needs to be a 100% nitrogen atmosphere, but in actual industrial applications, it has been difficult to prepare an environment with a 100% nitrogen atmosphere.

[0015] The present invention has been made in view of the above, and aims to provide a method for manufacturing a laminate that can form a laminate including a dense silicon nitride oxide film even in the presence of oxygen when a film made of a polysilazane compound is irradiated with vacuum ultraviolet light (VUV), and a gas barrier material made of a laminate obtained by the manufacturing method.

[0016] The present inventors have conducted extensive research to achieve the above object, and have found that irradiating a coating containing a polysilazane compound with vacuum ultraviolet light (VUV) at an irradiation intensity within a specific range allows for the formation of a dense silicon nitride oxide film not only in a 100% nitrogen atmosphere but also in the presence of oxygen, and as a result, a laminate having gas barrier properties equivalent to those of conventional laminates can be obtained, thereby completing the present invention.

[0017] That is, the present invention includes the following aspects.

[0018] The present invention provides a method for producing a laminate including a substrate, a resin layer, and a barrier layer, the method comprising: a resin layer-forming step of applying a solution containing a resin onto the substrate or the barrier layer to form a resin-coated product, and drying or curing the resin-coated product to form a resin layer; and a barrier layer-forming step of applying a solution containing a polysilazane compound onto the substrate or the resin layer to form a polysilazane-coated product, and irradiating the polysilazane-coated product with energy rays having a wavelength of 200 nm or less under a nitrogen atmosphere or a nitrogen atmosphere containing oxygen to cure the polysilazane compound, thereby forming a barrier layer including a cured polysilazane product, wherein the irradiation intensity of the Xe excimer light in the barrier layer-forming step is 280 mW / cm or less. ２ More than 450mW / cm ２ The following is a method for producing the laminate.

[0019] The energy ray having a wavelength of 200 nm or less is preferably Xe excimer light.

[0020] The laminate preferably has the base layer, the resin layer, and the barrier layer laminated in this order.

[0021] The laminate preferably has the base layer, the barrier layer, and the resin layer laminated in this order.

[0022] It is preferable that the resin layer forming step and the barrier layer forming step be repeated alternately to form an alternating laminate in which the resin layers and the barrier layers are alternately laminated.

[0023] The polysilazane compound is preferably perhydropolysilazane.

[0024] The integrated light amount of the Xe excimer light in the barrier layer forming step is 1 J / cm ２ 10J / cm or more ２ It is preferable that:

[0025] The oxygen concentration is preferably more than 0.1% and not more than 5%.

[0026] The humidity during the irradiation of the energy rays in the barrier layer forming step is preferably 0% RH or more and 20% RH or less.

[0027] The resin is preferably at least one selected from the group consisting of ultraviolet-curable polysiloxane, acrylic resin, and epoxy resin.

[0028] The substrate is preferably an organic resin film.

[0029] The organic resin film is preferably a polyimide (PI) film or a polyethylene terephthalate (PET) film.

[0030] It is preferable that the organic resin film has a surface that has been modified by ozone cleaning using vacuum ultraviolet light or ultraviolet light, and that the resin coating material is formed on the surface that has been modified.

[0031] The present invention relates to a gas barrier material comprising a laminate obtained by the above-described method for producing a laminate.

[0032] According to the present invention, a stacked body including a dense silicon nitride oxide film can be formed not only in a 100% nitrogen atmosphere but also in a nitrogen atmosphere containing oxygen.

[0033] 1 shows the results of refractive index distribution by spectroscopic ellipsometry of the cured polysilazane layers of Reference Examples 1 to 3. 2 shows the results of refractive index distribution by spectroscopic ellipsometry of the cured polysilazane layers of Reference Examples 4 to 6. 3 is a graph showing the relationship between the refractive index of the TOP layer of the cured polysilazane layer and the lamp intensity (irradiation intensity).

[0034] [Method for manufacturing a laminate] The method for manufacturing a laminate of the present invention is a method for manufacturing a laminate including a substrate, a resin layer, and a barrier layer. Specifically, the method includes a resin layer forming step of forming a resin layer on the substrate or the barrier layer, and a barrier layer forming step of forming a barrier layer made of a cured polysilazane product on the substrate or the resin layer, and specifies the irradiance and atmosphere of energy rays with a wavelength of 200 nm or less in the barrier layer forming step. Each element will be described below.

[0035] <<Resin Layer Forming Step>> The resin layer forming step is a step of forming a resin layer by applying a solution containing a resin to a substrate or a barrier layer to form a resin-coated product, and drying or curing the resin-coated product. Note that the barrier layer may be a barrier layer formed by the barrier layer forming step described later.

[0036] In this step, a resin layer is formed above or below the barrier layer, or on both sides. By forming the resin layer above or below the barrier layer, or on both sides, stress in the barrier layer is alleviated, distortion is suppressed, and breakage of the barrier layer can be suppressed. The resin layer also functions as a planarizing layer that flattens the unevenness of the layer below on which the resin layer is formed, contributing to imparting high barrier performance to the resulting laminate.

[0037] In the resin layer forming step, the resin layer is formed on the substrate or the barrier layer. Also, in the barrier layer forming step described later, the barrier layer is formed on the substrate or the resin layer. That is, in the laminate manufacturing method of the present invention, either the resin layer or the barrier layer is formed on the surface of the substrate. The substrate will be described below.

[0038] <Substrate> The substrate used in the method for producing a laminate of the present invention is not particularly limited. The substrate may be an organic resin film. Since organic resin films generally have high moisture permeability, the laminate obtained by the present invention imparts high gas barrier properties.

[0039] The substrate used in the method for producing a laminate of the present invention is more preferably a polyimide (PI) film, a polyethylene naphthalate (PEN) film, a polyethylene terephthalate (PET) film, a polyethylene (PE) film, a polypropylene (PP) film, or a polycarbonate (PC) film, and even more preferably a polyimide (PI) film or a polyethylene terephthalate (PET) film.

[0040] The substrate used in the method for producing a laminate of the present invention may be a thin film glass having a thickness of about 10 μm to 150 μm depending on the application. The thin film glass may be a single film, or may be a thin film glass laminated or stacked with a metal foil such as aluminum foil or a resin. Furthermore, the substrate used in the method for producing a laminate of the present invention may be a metal foil such as stainless steel foil, aluminum foil, or copper foil.

[0041] The surface of the substrate may be degreased or washed before the step of forming the resin layer or the barrier layer is carried out. By degreasing or washing the surface of the substrate, the resin forming the resin layer or the polysilazane compound forming the barrier layer can be more easily attached to the substrate. Examples of methods for degreasing or washing the surface of the substrate include excimer treatment, UV ozone treatment, atmospheric pressure plasma treatment, plasma treatment, and corona discharge treatment.

[0042] <Resin> The resin used in the resin layer forming step is not particularly limited as long as it can relieve the stress of the barrier layer and flatten the unevenness of the underlying layer. The resin used in the resin layer forming step of the present invention may be, for example, a thermosetting resin that does not soften at high temperatures, or a photocurable resin that hardens with light such as ultraviolet light. In addition, not only one type of resin but also two or more types of resins may be used.

[0043] The resin used in the resin layer forming step is preferably at least one selected from the group consisting of ultraviolet-curable polysiloxane, acrylic resin, and epoxy resin.

[0044] (UV-curable polysiloxane) UV-curable polysiloxane is a silicone resin that is cured by UV irradiation. The UV-curable polysiloxane is not particularly limited as long as it is cured by UV irradiation. For example, it may be a compound having acrylic groups at both ends of the siloxane chain.

[0045] Among the ultraviolet-curable polysiloxanes, polydimethylsiloxane (PDMS) is particularly preferred, and modified PDMS may also be used.

[0046] UV-curable PDMS generally has a high viscosity, so it may be diluted with a low-molecular-weight siloxane before use. Examples of low-molecular-weight siloxanes include cyclic or linear siloxanes having 4 to 20 silicon atoms. Low-molecular-weight siloxanes with a high boiling point form silicone gels when coexisting with PDMS. The use of low-molecular-weight siloxanes in combination allows for adjustment of strength and softness.

[0047] Examples of low molecular weight siloxanes include cyclic octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), and linear siloxanes (L4 to L14) (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0048] (Acrylic Resin) The acrylic resin is a polymer of monomers including (meth)acrylic acid, (meth)acrylate, etc. Here, (meth)acrylic acid means at least one of acrylic acid and methacrylic acid, and (meth)acrylate means at least one of acrylate and methacrylate.

[0049] Examples of (meth)acrylates include those having a hydroxyl group, such as hydroxyethyl acrylate (HEA) and hydroxyethyl methacrylate (HEMA); those having a propylene glycol skeleton, such as tripropylene glycol diacrylate (TPGDA); those having a trimethylolpropane skeleton, such as trimethylolpropane triacrylate (TMPTA); those having a pentaerythritol skeleton, such as pentaerythritol dimethacrylate; those having a dipentaerythritol skeleton, such as dipentaerythritol hexaacrylate; urethane acrylates, and the like.

[0050] (Epoxy Resin) The epoxy resin is not particularly limited, and one or more types selected from the group consisting of alicyclic epoxy resins and aromatic epoxy resins can be used.

[0051] Examples of alicyclic epoxy resins include alicyclic glycidyl ether epoxy resins and alicyclic glycidyl ester epoxy resins. Furthermore, for example, 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexanecarboxylate (Celloxide 2021P, manufactured by Daicel Corporation) and its derivatives can be used. These are preferred because they are stable even at high temperatures, colorless and transparent, and have excellent adhesive strength.

[0052] Examples of aromatic epoxy resins include bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, fluorene-containing epoxy resins, and triglycidyl isocyanurate.

[0053] <Solvent> In the solution containing the resin for forming the resin layer, the solvent for dissolving the resin is not particularly limited, and can be appropriately selected from those that dissolve the selected resin. Note that, depending on the type of resin used, if the resin can be applied without a solvent, it is not necessary to use a solvent.

[0054] <Other Components> The resin-containing solution may contain other components in addition to the resin that forms the resin layer, as long as the effects of the present invention are not impaired. Examples of other components include additives such as fillers, leveling agents, antistatic agents, and ultraviolet absorbers, and surfactants.

[0055] <Coating Method> The method for coating a resin-containing solution onto an object is not particularly limited, and any known method can be used. Examples of the method for coating a resin-containing solution onto an object include spin coating, roll coating, flow coating, inkjet coating, spray coating, dip coating, casting, bar coating, die coating, gravure coating, gravure printing, and screen printing.

[0056] <Drying or Curing> The method for drying or curing the resin-coated material formed on the substrate or barrier layer is not particularly limited. The method for drying or curing the formed resin-coated material may be appropriately selected depending on the type of resin selected. When drying, for example, heat may be applied or natural drying may be performed in the atmosphere. When curing, for example, a method of applying light or heat required for curing may be used.

[0057] For example, when ultraviolet-curable polydimethylsiloxane (PDMS) is selected, it can be cured by a high-pressure mercury lamp or the like.

[0058] <Atmosphere> The atmosphere in which the resin layer forming step is carried out may be either a nitrogen atmosphere or air. It is more preferable that the resin layer forming step be carried out under air. The resin layer formed under air has very low wettability to water, so that, for example, when a coating is produced by carrying out a barrier layer forming step on the formed resin layer, it is easy to wet coat a solution containing a polysilazane compound. Furthermore, carrying out the step under air is also advantageous in terms of cost.

[0059] The resin layer obtained in the resin layer-forming step may be surface-modified by ozone cleaning using vacuum ultraviolet light or ultraviolet light. Active oxygen separated from ozone generated by vacuum ultraviolet light or ultraviolet light collides with the surface of the resin layer, decomposing and removing organic contaminants present on the surface of the resin layer. The resin layer surface-modified by ozone cleaning has improved wettability, and therefore, when a coating is produced by performing a barrier layer-forming step on the formed resin layer, a solution containing a polysilazane compound can be easily applied.

[0060] <Barrier Layer Forming Step> The barrier layer forming step is a step of applying a solution containing a polysilazane compound to a substrate or a resin layer to form a polysilazane coated material, and irradiating the polysilazane coated material with energy rays having a wavelength of 200 nm or less in a nitrogen atmosphere to cure the polysilazane compound, thereby forming a barrier layer containing a cured polysilazane material.

[0061] <Polysilazane Compound> The polysilazane compound used in the barrier layer forming step is not particularly limited, and can be arbitrarily selected as long as it does not impair the effects of the present invention.

[0062] The polysilazane compound used in the present invention may be an inorganic compound or an organic compound. The polysilazane compound may have a linear, branched, or partially cyclic structure, or may have these structures simultaneously. The polysilazane compound used in the method for producing a laminate of the present invention may be used alone or in combination of two or more types.

[0063] Examples of the polysilazane compound include organopolysilazanes such as hexamethyldisilazane (HMDS), as well as perhydropolysilazane (PHPS) and modified products thereof.

[0064] Among the polysilazane compounds used in the present invention, perhydropolysilazane (PHPS) or a modified product thereof is preferred. Perhydropolysilazane (PHPS) is a silicon-containing polymer that contains Si-N bonds as repeating units and is composed only of Si, N, and H. In perhydropolysilazane (PHPS), all elements bonded to Si and N, except for the Si-N bonds, are H, and other elements such as carbon and oxygen are substantially not contained. "Substantially not contained" means that the total content of other elements such as carbon and oxygen is 5% by mass or less.

[0065] The weight-average molecular weight of the polysilazane compound used in the present invention is, for example, from 100 to 50,000 in terms of solubility in a solvent and reactivity. The weight-average molecular weight referred to here is a weight-average molecular weight converted into polystyrene and can be measured by gel permeation chromatography.

[0066] <Cured Polysilazane> The cured polysilazane obtained by curing the polysilazane compound in the barrier layer forming step is a compound containing oxygen in addition to silicon, nitrogen, and hydrogen.

[0067] The barrier layer containing the cured polysilazane produced in the barrier layer forming step is a film formed on the substrate or the resin layer formed in the resin layer forming step.

[0068] The barrier layer containing the cured polysilazane produced in the barrier layer-forming step has a refractive index distribution in the thickness direction. In the absence of significant compositional changes, the refractive index is correlated with density, and serves as an index of densification. That is, the region close to the surface irradiated with energy rays having a wavelength of 200 nm or less has a high refractive index because polysilazane densification is likely to proceed, while the region close to the underlying substrate or the resin layer formed in the resin layer-forming step has a low refractive index because energy rays having a wavelength of 200 nm or less are unlikely to reach the region.

[0069] Specifically, the refractive index of the region close to the surface irradiated with energy rays having a wavelength of 200 nm or less is 1.6 or more and 2.0 or less, and the refractive index of the region close to the substrate or resin layer is 1.50 or more and 1.6 or less, preferably 1.50 or more and 1.54 or less.

[0070] The refractive index distribution in the thickness direction of the barrier layer containing the cured polysilazane can be determined by spectroscopic ellipsometry. ２ It is possible to create an analytical model with four layers.

[0071] <Solvent> The solvent for dissolving the polysilazane compound is not particularly limited. Examples include aromatic compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, and triethylbenzene; chain hydrocarbon compounds such as pentane, 2-methylbutane, hexane, 2-methylpentane, heptane, 2-methylhexane, octane, 2,2,4-trimethylpentane, nonane, decane, and 2-methylnonane; cyclic hydrocarbon compounds such as ethylcyclohexane, methylcyclohexane, cyclohexane, p-menthane, decahydronaphthalene, and dipentene; ethers such as dipropyl ether, dibutyl ether (DBE), and methyl t-butyl ether (MTBE); and ketones such as methyl isobutyl ketone (MIBK). These solvents may be used alone or in combination of two or more.

[0072] <Concentration> The concentration of the polysilazane compound in the solution containing the polysilazane compound may be 0.01% by mass or more and 50% by mass or less, preferably 0.1% by mass or more and 20% by mass or less, depending on the application method.

[0073] <Other Components> The solution containing the polysilazane compound may contain components other than the polysilazane compound within a range that does not impair the effects of the present invention. Examples of other components include additives such as fillers, leveling agents, antistatic agents, and ultraviolet absorbers, and surfactants. When a filler is added, the amount of the filler may be 0.05 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass or more and 3 parts by mass or less, per part by mass of the polysilazane compound.

[0074] <Coating Method> The method for coating a substrate or a resin layer with a solution containing a polysilazane compound is not particularly limited, and any known method can be used. Examples of the method for coating a substrate or a resin layer with a solution containing a polysilazane compound include spin coating, roll coating, flow coating, inkjet coating, spray coating, dip coating, casting, bar coating, die coating, gravure coating, gravure printing, and screen printing.

[0075] The solution containing the polysilazane compound is preferably applied to the substrate or the resin layer at room temperature in an inert atmosphere such as nitrogen or in the air. Applying the solution at room temperature in the air is more labor-saving and less expensive than applying the solution in an inert gas atmosphere, which requires a sealed system.

[0076] According to the method for producing a laminate of the present invention, a coating process can be used to obtain a laminate having high resource efficiency and high throughput, and which has high gas barrier properties in a short time even in a mild environment where oxygen is present.

[0077] <Energy Rays with a Wavelength of 200 nm or Less> The energy rays with a wavelength of 200 nm or less that are irradiated onto the polysilazane-coated product are vacuum ultraviolet (VUV) rays with a wavelength of 172 nm. The irradiation of vacuum ultraviolet (VUV) rays is usually carried out using a commercially available excimer lamp (wavelength 172 nm).

[0078] (Irradiation Intensity) In the barrier layer forming step, the irradiation intensity of the energy ray having a wavelength of 200 nm or less irradiated onto the polysilazane coating material is 280 mW / cm ２ More than 450mW / cm ２In the present invention, by using energy rays having an irradiation intensity within this range, it is possible to densify a film made of a polysilazane compound in a short time, not only in a 100% nitrogen atmosphere but also in a nitrogen atmosphere containing oxygen. Furthermore, it is possible to produce a laminate including a barrier layer with a sufficiently low water vapor permeability in a short time.

[0079] (Cumulative Light Amount) The cumulative light amount of energy rays with a wavelength of 200 nm or less irradiated onto the polysilazane coated material is 1 J / cm ２ 10J / cm or more ２ When the integrated light amount of the energy ray having a wavelength of 200 nm or less is in the above range, the refractive index of the top layer of the laminate can be increased. The integrated light amount of the energy ray having a wavelength of 200 nm or less is preferably 3 J / cm or less. ２ 10J / cm or more ２ More preferably, it is 3 J / cm or less. ２ 6J / cm or more ２ It is more preferable that the integrated light amount (mJ / cm ２ ) is the irradiation intensity (mW / cm) of energy rays with a wavelength of 200 nm or less. ２ ) × curing time (sec).

[0080] The cumulative light intensity is 10 J / cm ２ Although the integrated light amount may exceed this, in this case the effect obtained by the present invention becomes weaker.

[0081] The laminate manufacturing method of the present invention not only makes it possible to obtain a laminate including a barrier layer that exhibits a sufficiently low water vapor permeability in a short time, but also makes it possible to manufacture a laminate including a barrier layer that exhibits a higher level of gas barrier properties than conventional methods using an integrated light dose that is smaller than the integrated light dose that has conventionally been required. Thus, a laminate having gas barrier properties can be manufactured efficiently using a smaller amount of energy than conventional methods.

[0082] The laminate manufacturing method of the present invention can manufacture a laminate including a barrier layer with a higher level of gas barrier property than conventional methods, using an integrated light dose that is smaller than the integrated light dose conventionally required. Therefore, a laminate with gas barrier property can be manufactured efficiently using a smaller amount of energy than conventional methods. Furthermore, the laminate manufacturing method of the present invention can manufacture a laminate including a barrier layer with higher gas barrier property than conventional methods, using the same integrated light dose as conventional methods.

[0083] (Irradiation Atmosphere) When a polysilazane coating is irradiated with energy rays having a wavelength of 200 nm or less, for example, vacuum ultraviolet light (VUV), the Si—N bonds in the main chain are repeatedly broken and recombined, causing atomic rearrangement, which reduces the porosity of the barrier layer, which is a cured polysilazane layer, and promotes densification of the film. Therefore, in order to facilitate the promotion of densification of the barrier layer, irradiation with energy rays having a wavelength of 200 nm or less is usually carried out in a nitrogen atmosphere.

[0084] Conventionally, in order to impart high density to a cured polysilazane film, the environment in which vacuum ultraviolet light (VUV) is irradiated has been a 100% nitrogen atmosphere, but in actual industrial applications, it has been difficult to prepare an environment in which the nitrogen atmosphere is 100%.

[0085] In contrast, the laminate manufacturing method of the present invention can form a sufficiently dense silicon nitride oxide film by irradiating with energy rays having a wavelength of 200 nm or less and an irradiation intensity within the above-mentioned specific range, even in a nitrogen atmosphere in which oxygen coexists. In particular, it is effective to apply the laminate manufacturing method of the present invention when irradiation is performed in a roll-to-roll system, in which it is difficult to create a 100% nitrogen atmosphere.

[0086] (Oxygen Concentration) That is, in the method for producing a laminate of the present invention, the energy ray having a wavelength of 200 nm or less to be irradiated in the barrier layer forming step may be irradiated in a nitrogen atmosphere containing oxygen in a specific range. The oxygen concentration in the nitrogen atmosphere containing oxygen is preferably more than 0.1% and not more than 5%, more preferably 0.1% to 4%, even more preferably 0.1% to 3%, still more preferably 0.1% to 2%, particularly preferably 0.1% to 1%, and most preferably 0%.

[0087] (Temperature) The temperature at which the barrier layer forming step is carried out is not particularly limited, and may be, for example, room temperature (generally 15° C. or higher and 40° C. or lower). The barrier layer forming step may also be carried out under heating, for example, at 100° C. or higher and 120° C. or lower. Even when the barrier layer forming step is carried out at room temperature, the same effect as that achieved under heating can be achieved.

[0088] (Humidity) The humidity during irradiation with energy rays having a wavelength of 200 nm or less in the barrier layer forming process was 309 mW / cm. ２ In this case, the relative humidity at 25°C is preferably 0% RH or more and 20% RH or less, more preferably 0% RH or more and 15% RH or less, even more preferably 0% RH or more and 10% RH or less, and particularly preferably 0% RH. However, it is not limited to 25°C.

[0089] <Configuration of Laminate> The laminate obtained by the laminate manufacturing method of the present invention may have a structure in which a resin layer is formed on a substrate layer, and a barrier layer is formed on the resin layer. That is, the laminate obtained by the laminate manufacturing method of the present invention may have a substrate, a resin layer, and a barrier layer laminated in this order.

[0090] Alternatively, the laminate obtained by the laminate manufacturing method of the present invention may have a structure in which a barrier layer is formed on a substrate layer and a resin layer is formed on the barrier layer. That is, the laminate obtained by the laminate manufacturing method of the present invention may have a substrate layer, a barrier layer, and a resin layer laminated in this order.

[0091] Furthermore, the method for producing a laminate of the present invention may be a method for forming an alternating laminate in which resin layers and barrier layers are alternately laminated by alternately repeating the resin layer forming step and the barrier layer forming step.

[0092] If two layers consisting of a resin layer and a barrier layer are considered to be one unit, the laminate obtained by the laminate manufacturing method of the present invention has a sufficient stress relaxation effect due to the resin layer even if it is a single unit, but it may have a structure in which about 5 units are stacked, and an alternating laminate of about 1 to 3 units is more preferred.

[0093] The thickness of the laminate obtained in the present invention is usually preferably 150 nm or more and 250 nm or less, and more preferably 200 nm or more and 250 nm or less.

[0094] <Gas barrier properties of laminate> The water vapor transmission rate (WVTR) of the laminate obtained in the present invention is 1×10 －６ g / m ２ / day or more 5 x 10 －４ g / m ２ / day or less. The water vapor transmission rate (WVTR) of the laminate according to the prior art is 3×10 －３ g / m ２ This is two orders of magnitude smaller than the previous water vapor transmission rate (WVTR) of approximately 1 / day, which is a significant improvement. ２ ) is the amount of water vapor (g) that permeates through the film.

[0095] <<Uses of Laminate>> The laminate obtained by the present invention has excellent gas barrier properties and can be used as various gas barrier materials.

[0096] Furthermore, the laminate containing the cured polysilazane barrier layer has excellent heat resistance and insulating properties in addition to gas barrier properties. Therefore, for example, the laminate having a resin film as the substrate can be used as an encapsulant for electronic devices such as organic EL elements and solar cells.

[0097] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0098] [Reference Example 1] First, it was examined how the refractive index of the top layer of the laminate changes depending on the irradiation intensity and integrated light amount of the lamp. <Preparation of Laminate> A solution containing perhydropolysilazane (PHPS) was applied to a silicon wafer (Si), and the resulting coating was irradiated with Xe excimer light (VUV light) at six different lamp intensities (irradiation intensities) to prepare a barrier layer, which was a cured polysilazane. Details are described below.

[0099] <Formation of Polysilazane Coating> A 20% perhydropolysilazane (PHPS) dibutyl ether (DBE) solution was diluted with anhydrous DBE solution under nitrogen to prepare a 10% PHPS DBE solution. The prepared 10% PHPS DBE solution was spin-coated onto a 30 x 30 mm silicon wafer (Si) in the atmosphere (25°C, 25% humidity) to produce a laminate "PHPS coated / Si." Spin coating was performed at a rotation speed of 2000 rpm for 30 seconds.

[0100] <Formation of Barrier Layer (Cured Polysilazane)> The PHPS-coated material of the obtained laminate "PHPS-coated material / Si" was irradiated with Xe excimer light (VUV light) to form a barrier layer made of a cured polysilazane material. The Xe excimer light (VUV light) irradiation was performed using an excimer irradiation device (wavelength = 172 nm) manufactured by M.D.COM.

[0101] (Irradiation Atmosphere) Irradiation with Xe excimer light (VUV light) was carried out in a nitrogen atmosphere (oxygen and water vapor concentration <0.01%).

[0102] (Irradiation intensity) Lamp intensity (irradiation intensity) is 103 mW / cm ２ The distance between the lamp and the laminate "PHPS-coated material / Si" was set to 2 mm. Here, the lamp intensity (irradiation intensity) represents the actual irradiation intensity on the PHPS-coated material. Specifically, using a power meter (C9536, sensor head: H9535-172) manufactured by Hamamatsu Photonics, the irradiation intensity of Xe excimer light (VUV light) was measured at a location where the distance between the sensor head and the lamp was 2 mm, similar to the distance between the lamp and the PHPS-coated material.

[0103] (Cumulative light amount) The cumulative light amount of Xe excimer light (VUV light) is 6 J / cm ２ , 12 J / cm ２ , 24 J / cm ２ , and 72 J / cm ２ It was decided.

[0104] Reference Examples 2 to 6 The same procedures as in Reference Example 1 were carried out except that the lamp intensity (irradiation intensity) was set as shown in Table 1.

[0105] [Measurement of refractive index distribution] The density of the obtained barrier layer (cured polysilazane product) was measured as a refractive index distribution in the film thickness direction using a spectroscopic ellipsometer (Model: WoollamVASE32, manufactured by J.A. Woollam Japan Co., Ltd.) In the absence of a significant change in composition, the refractive index is correlated with the density, and therefore the refractive index serves as an index representing the density (density).

[0106] The measurement wavelength of the spectroscopic ellipsometry was set to 250 nm or more and 1000 nm or less, and the incident angle was changed to seven angles: 45 degrees, 50 degrees, 55 degrees, 60 degrees, 65 degrees, 70 degrees, and 75 degrees. The obtained results were fitted as a four-layer structure of "barrier layer (cured polysilazane) / Si."

[0107] That is, it has been known from previous research that the optically densified polysilazane cured material layer has a refractive index distribution in the thickness direction (Adv. Mater. Interfaces, 2201517 (8 pp.) (2022)). Therefore, the outermost layer is made of SiO2 formed by natural oxidation of perhydropolysilazane (PHPS). ２ layer, and SiO ２ The SiN layer region between the SiN layer and the Si layer was divided into three layers (Top layer, Mid layer, and Bottom layer) in the thickness direction and fitted. In particular, the thickness of the Top layer was fixed at 30 nm to quantitatively evaluate the Top layer, which is most susceptible to photo-densification due to the strongest irradiation of Xe excimer light (VUV light).

[0108] The results are shown in Figures 1 and 2. In addition, the cumulative light amount at each irradiation intensity was 6 J / cm ２ , 12 J / cm ２ , 24 J / cm ２ , and 72 J / cm２ The refractive index of the TOP layer (30 nm) at this time is shown in Table 1 and FIG.

[0109]

[0110] [Discussion] It was found that for all lamp intensities (irradiation intensities), the refractive index of the TOP layer increased as the integrated amount of light increased.

[0111] Furthermore, it was confirmed that, for the same integrated light amount, the refractive index of the TOP layer increased as the lamp intensity (irradiation intensity) increased, indicating that the photo-induced densification reaction of polysilazane is highly dependent on the lamp intensity.

[0112] If the photo-densification reaction of polysilazane were a one-photon reaction, the refractive index would be determined by the integrated light amount, regardless of the lamp intensity (irradiation intensity). However, this experiment showed that the photo-densification reaction is highly dependent on the lamp intensity (irradiation intensity), indicating that the photo-densification reaction of polysilazane is a multi-photon reaction, not a one-photon reaction.

[0113] It was shown that, for the same cumulative light amount, the refractive index of the TOP layer increased as the lamp intensity (irradiation intensity) increased, but the increase in refractive index was smaller at a lamp intensity of 290 mW / cm ２ This indicates that a rapid acceleration effect occurs when the lamp intensity (irradiation intensity) is 290 mW / cm ２ The above demonstrates that polysilazane compounds can be effectively densified.

[0114] Example 1 Three units of [resin layer / barrier layer] were prepared on a film substrate, and the water vapor transmission rate (WVTR) was measured as a measure of the barrier performance.

[0115] <Surface Modification Step of Substrate> A highly flat polyimide film (PI film: manufactured by Xenomax Japan) having a size of 50 x 50 mm was prepared as a substrate. The surface of the PI film was subjected to UV ozone treatment.

[0116] <Formation of Resin Layer (PDMS)> Next, UV-curable polydimethylsiloxane (PDMS: manufactured by Shin-Etsu Chemical Co., Ltd.) was spin-coated on the surface of the PI film that had been subjected to the UV ozone treatment. Subsequently, UV curing (high-pressure mercury lamp: 20 mW / cm ２ , 2.4 J / cm ２ ) was performed to form a 130 nm PDMS layer on the surface of the PI film, producing a laminate "PDMS layer / PI." Furthermore, to improve the wettability of the PDMS surface of the laminate "PDMS layer / PI," the surface of the PDMS layer was irradiated with vacuum ultraviolet (VUV) light for surface modification.

[0117] <Formation of Barrier Layer (Cured Polysilazane)> A perhydropolysilazane (PHPS) coating was formed on the PDMS layer in the same manner as in Reference Example 1, and cured in the same manner as in Reference Example 1 to form a laminate [barrier layer (cured polysilazane) / PDMS layer / PI]. The irradiation atmosphere in the curing step was a nitrogen atmosphere (oxygen and water vapor concentrations <0.01%). The lamp intensity (irradiation intensity) was 103 mW / cm ２ and 309 mW / cm ２ It was carried out in two types.

[0118] <Preparation of Alternate Laminate of Multiple Units> A resin layer was formed on the prepared barrier layer (cured polysilazane) by the same procedure as above, and a barrier layer was further formed by the same procedure as above. The resin layer and the barrier layer were each laminated alternately three times. When [barrier layer / PDMS] was defined as one unit, an alternating laminate of three units was prepared.

[0119] The structure of the obtained alternate laminate was [barrier layer / PDMS / barrier layer / PDMS / barrier layer / PDMS / PI]. The lamp intensity (irradiation intensity) was 309 mW / cm ２ It was.

[0120] [Comparative Example 1] Lamp intensity (irradiation intensity) was 103 mW / cm ２ A laminate was produced in the same manner as in Example 1, except that:

[0121] [Measurement of Water Vapor Transmission Rate (WVTR)] The water vapor transmission rate (WVTR) of the prepared alternate laminate was measured using a gas transmission rate measuring device (Super-Detect, manufactured by MORESCO Corporation). The measurement range for water vapor transmission rate was 40 mmφ, and the measurement conditions were 40°C / 90% RH. The measurement results for water vapor transmission rate are shown in Table 2.

[0122] Table 3 also shows the irradiation time of Xe excimer light (VUV light) required for one barrier layer (cured polysilazane product) under each irradiation condition in Example 1 and Comparative Example 1.

[0123]

[0124]

[0125] [Discussion] Lamp intensity (irradiation intensity) is 103 mW / cm ２ In Comparative Example 1, the cumulative light amount was 6 J / cm ２ When the water vapor transmission rate (WVTR) is 5.7 × 10 －５ g / m ２ / day, resulting in the highest barrier performance. ２ In order to obtain the value of 103 mW / cm in Comparative Example 1, ２ At a lamp intensity (irradiation intensity) of 10 ...

[0126] Lamp intensity (irradiation intensity) 309 mW / cm ２ In Example 1, the cumulative light amount was 6 J / cm ２ When the water vapor transmission rate (WVTR) is 1.6 × 10 －５ g / m ２ / day, resulting in the highest barrier performance. The irradiation time required in this case was 20 seconds, indicating that a significant time reduction was achieved. Since 20 seconds is the time per barrier layer (cured polysilazane product), when three units are produced as in this example, the time reduction effect is three times.

[0127] Furthermore, the highest barrier performance is achieved with an integrated light intensity of 6 J / cm ２ When comparing the results, it can be seen that Example 1 has a barrier performance three times or more that of Comparative Example 1.

[0128] In Example 1, the cumulative light amount was 3 J / cm ２ In this case, the cumulative light amount in Comparative Example 1, which has the highest barrier performance, is 6 J / cm ２ The water vapor transmission rate (WVTR) was equivalent to the value at the time of

[0129] The cumulative light intensity in Comparative Example 1 was 6 J / cm ２ The irradiation time is 58 seconds as described above, but the integrated light amount in Example 1 that gives an equivalent water vapor transmission rate (WVTR) is 3 J / cm ２ Therefore, the irradiation time, which conventionally required 58 seconds, can be reduced to 10 seconds, achieving a reduction of 1 / 6.

[0130] In both Comparative Example 1 and Example 1, the integrated light amount was 12 J / cm ２ So, 10 －４ Although a water vapor transmission rate (WVTR) on the order of 100% was achieved, the water vapor transmission rate (WVTR) increased and the barrier performance tended to decrease. This is presumably due to the progress of optical densification of the barrier layer (cured polysilazane) that constitutes the laminate, resulting in volumetric shrinkage.

[0131] [Examples 2 to 5] A solution containing perhydropolysilazane (PHPS) was applied onto a silicon wafer (Si), and the resulting coating was irradiated with Xe excimer light (VUV light) at two different lamp intensities (irradiation intensities) in a nitrogen atmosphere with different oxygen concentrations to form a barrier layer (cured polysilazane). Details are described below.

[0132] <Formation of Polysilazane Coating> As in Reference Example 1, a 20% PHPS (perhydropolysilazane) dibutyl ether (DBE) solution was diluted with anhydrous DBE solution under nitrogen to prepare a 10% PHPS DBE solution. A 30 x 30 mm silicon wafer (Si) was spin-coated with the 10% PHPS DBE solution in the atmosphere (25°C, 30% humidity) to produce a laminate "PHPS coated film / Si." Spin coating was performed at a rotation speed of 2000 rpm for 30 seconds.

[0133] <Formation of Barrier Layer (Cured Polysilazane)> The PHPS-coated material of the obtained laminate "PHPS-coated material / Si" was irradiated with Xe excimer light (VUV light) to form a barrier layer made of a cured polysilazane material. The Xe excimer light (VUV light) irradiation was performed using an excimer irradiation device (wavelength = 172 nm) manufactured by M.D.COM.

[0134] (Irradiation atmosphere) Irradiation with Xe excimer light (VUV light) was carried out by mixing nitrogen and dry air (dew point -60°C or less, oxygen concentration 20%) and controlling the oxygen concentration during irradiation to 0%, 1%, 2%, and 5%.

[0135] (Irradiation Intensity) The lamp intensity (irradiation intensity) was 309 mW / cm ２ The distance between the lamp and the laminate "PHPS coated film / Si" was set to 2 mm. Here, the lamp intensity (irradiation intensity) represents the actual irradiation intensity to the PHPS coated film. Specifically, using a power meter (C9536, sensor head: H9535-172) manufactured by Hamamatsu Photonics, the irradiation intensity of Xe excimer light (VUV light) was measured at a location where the distance between the sensor head and the lamp was 2 mm, similar to the distance between the lamp and the PHPS coated film.

[0136] (Cumulative light amount) The cumulative light amount of Xe excimer light (VUV light) is 6 J / cm ２ It was decided.

[0137] [Reference Examples 7 to 10] Lamp intensity (irradiation intensity) 103 mW / cm ２ A laminate was produced in the same manner as in Examples 2 to 5, except that:

[0138] [Measurement of refractive index distribution] As in Reference Example 1, the density of the obtained barrier layer (cured polysilazane layer) was measured as the refractive index distribution in the film thickness direction using a spectroscopic ellipsometer (model: WoollamVASE32, manufactured by J.A. Woollam Japan Co., Ltd.).

[0139] As in Reference Example 1, the outermost layer is SiO 2 formed by natural oxidation of PHPS. ２The SiN layer region was fitted as three layers (Top layer, Mid layer, and Bottom layer) in the thickness direction. In particular, the Top layer was fixed at 30 nm in thickness to quantitatively evaluate the Top layer, which is most susceptible to photo-densification due to the strongest irradiation of Xe excimer light (VUV light). The results are shown in Table 4.

[0140]

[0141] [Discussion] As shown in Table 4, a high refractive index of 1.60 or more was obtained at an oxygen concentration of 5% or less. This indicates that at an oxygen concentration of 5% or less, a dense cured coating was formed even when oxygen was mixed in.

[0142] When irradiated with Xe excimer light (VUV light) in the presence of oxygen, PHPS (perhydropolysilazane) is oxidized to form SiOx, resulting in a decrease in the refractive index of the film and a decrease in the water vapor barrier performance. This is due to the lamp intensity (irradiation intensity) of 309 mW / cm ２ , and 103 mW / cm ２ In both cases, the refractive index of the barrier layer (cured polysilazane layer) decreases as the oxygen concentration increases.

[0143] However, if the lamp intensity (irradiation intensity) is within the range of the lamp intensity (irradiation intensity) used in the manufacturing method of the laminate of the present invention, the oxidation reaction due to oxygen diffusion and the optical densification reaction compete with each other, and it is thought that a high refractive index can be maintained even in the presence of oxygen up to an oxygen concentration of 5%.

[0144] [Examples 6 and 7] <Preparation of Alternate Laminate> As in Example 1 and Comparative Example 1, an alternating laminate was prepared in which resin layers and barrier layers were alternately laminated to form multiple units, assuming that one unit is a resin layer (PDMS) / barrier layer (cured polysilazane layer). In this case, the oxygen concentration in the nitrogen atmosphere during the formation of the barrier layer (cured polysilazane) was varied as shown in Table 5.

[0145] In Example 6, a three-unit alternating laminate was produced, and in Example 3, a two-unit alternating laminate was produced. That is, the structure of the alternating laminate in Example 2 was [barrier layer / PDMS / barrier layer / PDMS / barrier layer / PDMS / PI] (3 units). The structure of the alternating laminate in Example 3 was [barrier layer / PDMS / barrier layer / PDMS / PI] (2 units).

[0146] In both Examples 6 and 7, the lamp intensity (irradiation intensity) for forming the barrier layer (cured polysilazane product) was 309 mW / cm ２ , the cumulative light intensity is 6 J / cm ２ It was decided.

[0147] [Measurement of Water Vapor Transmission Rate (WVTR)] The water vapor transmission rate (WVTR) was measured for the alternate laminates produced in Examples 6 and 7. Table 5 shows the measurement results.

[0148]

[0149] [Discussion] In Example 6, where the oxygen concentration was 1%, very high barrier performance was obtained. ２ Water vapor transmission rate (WVTR) (1.6 x 10 －５ g / m ２ / day) and the results are equivalent.

[0150] In Example 7, where the oxygen concentration was 2%, the barrier performance was inferior to that of Example 6, but －４ g / m ２ It was shown that the barrier performance of the order of 1 / day is very high and that the film can be used as a barrier film for various purposes.

[0151] Example 7 showed that the irradiation time per layer was 20 seconds, and that even an oxygen concentration of 2% was sufficient for use as a gas barrier material, and therefore a laminate having sufficient gas barrier properties could be produced in a short time even in an atmosphere containing oxygen.

[0152] Furthermore, since the alternate laminate of Example 7 is a laminate of two units, by making it a three-unit structure as in Example 6, the barrier performance can be improved.

[0153] [Examples 8 to 11, Comparative Examples 2 and 3] Three-unit alternating laminates were produced in the same manner as in Example 6, except that the humidity during the formation of the resin layer (PDMS) was 20% RH, the humidity during the irradiation of Xe excimer light (VUV light) was 0% RH, and the oxygen concentration was as shown in Table 6.

[0154] [Measurement of Water Vapor Transmission Rate (WVTR)] The water vapor transmission rate (WVTR) of the prepared alternate laminate was measured. The measurement results are shown in Table 6.

[0155]

[0156] [Discussion] As shown in Table 6, even when the oxygen concentration was 5% or less, the water vapor permeability was 10 －４ g / m ２ On the other hand, in Comparative Examples 2 and 3 where the oxygen concentration was 10% and 20%, the barrier performance was 10%. －３ g / m ２ The water vapor permeability was on the order of 1 / day, resulting in poor barrier performance.

Claims

1. A method for producing a laminate including a substrate, a resin layer, and a barrier layer, comprising: a resin layer forming step of applying a solution containing a resin onto the substrate or the barrier layer to form a resin coating, and drying or curing the resin coating to form a resin layer; and a barrier layer forming step of applying a solution containing a polysilazane compound onto the substrate or the resin layer to form a polysilazane coating, and irradiating the polysilazane coating with energy rays having a wavelength of 200 nm or less under a nitrogen atmosphere or a nitrogen atmosphere containing oxygen to cure the polysilazane compound, thereby forming a barrier layer including a cured polysilazane product, wherein the irradiation intensity of the energy rays in the barrier layer forming step is 280 mW / cm or less. ２ 450mW / cm or more ２ A method for producing a laminate comprising the following steps:

2. The method for producing a laminate according to claim 1, wherein the energy ray having a wavelength of 200 nm or less is Xe excimer light.

3. The method for producing a laminate according to claim 1, wherein the laminate comprises the substrate layer, the resin layer, and the barrier layer stacked in this order.

4. The method for manufacturing a laminate according to claim 1, wherein the laminate comprises the substrate layer, the barrier layer, and the resin layer stacked in this order.

5. The method for producing a laminate according to claim 1, wherein the resin layer forming step and the barrier layer forming step are repeated alternately to form an alternating laminate in which the resin layers and the barrier layers are alternately stacked.

6. The method for producing a laminate according to claim 1, wherein the polysilazane compound is perhydropolysilazane.

7. The integrated light amount of the energy beam in the barrier layer forming step is 1 J / cm ２ More than 10J / cm ２ The method for producing a laminate according to claim 1, wherein the following is true:

8. The method for producing a laminate according to claim 1, wherein the oxygen concentration is more than 0.1% and not more than 5%.

9. The method for producing a laminate according to claim 1, wherein the humidity during the irradiation of the energy rays in the barrier layer forming step is 0% RH or more and 20% RH or less.

10. The method for producing a laminate according to claim 1, wherein the resin is at least one selected from the group consisting of ultraviolet-curable polysiloxane, acrylic resin, and epoxy resin.

11. The method for producing a laminate according to claim 1, wherein the substrate is an organic resin film.

12. The method for producing a laminate according to claim 11, wherein the organic resin film is a polyimide (PI) film or a polyethylene terephthalate (PET) film.

13. The method for producing a laminate according to claim 11, wherein the organic resin film has been surface-modified by ozone cleaning using vacuum ultraviolet light or ultraviolet light, and the resin coating is formed on the surface-modified surface.

14. A gas barrier material comprising a laminate obtained by the method for producing a laminate according to any one of claims 1 to 14.

Images