Gas-barrier thin films and methods for manufacturing gas-barrier thin films

Abstract

A gas barrier film comprises, in sequence, a substrate film of a resin film with a glass transition temperature of 100°C or less, a first gas barrier layer, and a second gas barrier layer. The second gas barrier layer is a layer formed by a coating containing a silicon-containing polymer compound. In X-ray photoelectron spectroscopy, nitrogen atoms, oxygen atoms, and silicon atoms are present in the second gas barrier layer, and the ratio of oxygen atoms to nitrogen atoms, expressed as [average mole % of oxygen atoms] / [average mole % of nitrogen atoms], is 1.0 to 6.0. The substrate film is manufactured without heating to 110°C or higher.

Description

[Technical Field]

[0001] This invention relates to a gas barrier film and a method for manufacturing a gas barrier film. [Previous Technology]

[0002] In recent years, gas barrier films have been widely used as substrate materials or sealing materials. For gas barrier films, a high gas barrier property is required to suppress the permeation of water vapor or oxygen, etc. Furthermore, it is required, for example, to improve light transmittance without compromising the visual recognizability of the object to which the gas barrier film is attached, such as electronic devices, or without compromising the lightweight nature of the object. From the above perspective, it is known to coat a curable composition containing a curable compound onto a support, cure the curable compound contained in the resulting coating layer to form a thin resin layer, and form a gas barrier layer composed of an inorganic film, etc., directly or in between, on this resin layer.

[0003] For example, Patent Document 1 describes a substrate on which a UV-curable acrylate resin composition is formed on a polyethylene terephthalate (PET) film, and a gas barrier layer is formed on the substrate on which the curable film is formed to obtain a gas barrier film. Hereinafter, the property of inhibiting the permeation of water vapor or oxygen is referred to as "gas barrier property", and a film having gas barrier property is referred to as "gas barrier film".

[0004] Gas barrier films are often manufactured in industry as elongated shapes, then wound into rollers to form a wound body, which is then stored and transported as an intermediate product before being assembled into the final product such as the aforementioned electronic devices. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2019 / 078069 [Summary of the Invention]

[0006] [The problem the invention aims to solve]

[0007] As shown in Patent Document 1, the glass transition temperature (Tg) of the PET film is below 100°C. When a composition containing polysilazane is coated onto a substrate lacking heat resistance to obtain a gas barrier film, if the drying temperature of the polysilazane coating is high, the PET film may shrink or deform, leading to various undesirable conditions. To avoid these undesirable conditions, when the drying temperature is lowered, the inventors have discovered that fine scratches will occur in the final gas barrier layer. For example, organic devices such as organic EL are easily affected by moisture, therefore, the gas barrier film for sealing requires extremely high gas barrier performance. Therefore, the presence of such fine scratches, even if it does not affect the water vapor permeability at the time of manufacturing, still raises concerns about the reliability during use, potentially causing problems in applications such as sealing of the aforementioned organic devices.

[0008] The present invention addresses the above-mentioned problems by providing a gas barrier film that can be used with a substrate exhibiting low heat resistance and minimal scratch formation. [Means for solving the problems]

[0009] As a result of repeated and in-depth investigations in order to solve the above-mentioned problems, the inventors discovered that by forming two gas barrier layers on the substrate film and setting the ratio of a specific element of one of them to a specific range, the above-mentioned problems can be solved, and the present invention is completed. That is, the present invention provides the following [1] to [7].

[0010] [1] A gas barrier thin film, comprising in sequence a substrate thin film, a first gas barrier layer, and a second gas barrier layer, wherein the aforementioned substrate thin film is a resin thin film with a glass transition temperature of 100°C or less, and the aforementioned second gas barrier layer is a layer formed by a coating containing a silicon-containing polymer compound, wherein nitrogen atoms, oxygen atoms, and silicon atoms are present in the aforementioned second gas barrier layer in X-ray photoelectron spectroscopy, and the ratio of oxygen atoms to nitrogen atoms, expressed as [average mole % of oxygen atoms] / [average mole % of nitrogen atoms], is 1.0 to 6.0, and the aforementioned substrate thin film is manufactured without heating to 110°C or higher. [2] A gas barrier film, comprising in sequence a substrate film, a first gas barrier layer, and a second gas barrier layer, wherein the substrate film has a polyethylene terephthalate film layer, and the second gas barrier layer is a layer formed by a coating containing a silicon-containing polymer compound, wherein nitrogen atoms, oxygen atoms, and silicon atoms are present in the second gas barrier layer in X-ray photoelectron spectroscopy, and the ratio of oxygen atoms to nitrogen atoms, expressed as [average mole % of oxygen atoms] / [average mole % of nitrogen atoms], is 1.0 to 6.0, and the substrate film is manufactured without heating to 110°C or higher. [3] The gas barrier film as described in [1] or [2] above, wherein the gas barrier film is in the shape of a roller, and the number of scratches with an aspect ratio of 2 or higher on the surface of the second gas barrier layer is 200 or less per 1 m2. [4] The gas barrier film of any one of [1] to [3] above, wherein the first gas barrier layer contains at least one of a metal, a metal oxide, a metal nitride, and a metal carbide. [5] The gas barrier film of any one of [1] to [4] above, wherein the substrate film has not undergone heat treatment. [6] The gas barrier film of any one of [1] to [5] above, wherein a hard coating is not provided on the surface of the substrate film opposite to the side on which the first gas barrier layer is provided. [7] A method for manufacturing a gas barrier thin film includes a coating step of coating a composition containing a silicon-containing polymer compound onto the first gas barrier layer of a laminate having a first gas barrier layer and a substrate thin film to form a coating film; a heating step of heating the aforementioned coating film; an ultraviolet irradiation step of irradiating the aforementioned coating film with ultraviolet light after the heating step begins; and a modification step of subjecting the aforementioned coating film to a modification treatment different from the treatment performed in the aforementioned ultraviolet irradiation step after the ultraviolet irradiation step to obtain a second gas barrier layer. [Effects of the Invention]

[0011] According to the present invention, a gas barrier film with low heat resistance and minimal damage can be provided.

Implementation Method

[0013] The following describes a gas barrier film of an embodiment of the present invention (hereinafter referred to as "this embodiment").

[0014] 1. Gas Barrier Thin Film An embodiment of the present invention comprises a first gas barrier thin film, a first gas barrier layer, and a second gas barrier layer, wherein the aforementioned substrate thin film is a resin film with a glass transition temperature (Tg) of 100°C or less, and the aforementioned second gas barrier layer is a layer formed by a coating containing a silicon-containing polymer compound. In X-ray photoelectron spectroscopy, the aforementioned second gas barrier layer contains nitrogen atoms, oxygen atoms, and silicon atoms, and the ratio of oxygen atoms, expressed as [average mole % of oxygen atoms] / [average mole % of nitrogen atoms], is 1.0 to 6.0. The aforementioned substrate thin film is manufactured without heating to 110°C or higher. The second gas barrier film of an embodiment of the present invention comprises, in sequence, a substrate film, a first gas barrier layer, and a second gas barrier layer. The aforementioned substrate film has a polyethylene terephthalate film layer. The aforementioned second gas barrier layer is a layer formed by a coating containing a silicon-containing polymer compound. In X-ray photoelectron spectroscopy, the aforementioned second gas barrier layer contains nitrogen atoms, oxygen atoms, and silicon atoms. The ratio of oxygen atoms, expressed as [average moles of oxygen atoms] / [average moles of nitrogen atoms], is 1.0 to 6.0. The aforementioned substrate film is manufactured without heating to 110°C or higher.

[0015] Through in-depth research, the inventors discovered that the cause of the scratches is that if the heating temperature of the coating used to form the gas barrier layer is low, the conversion reaction of silicon-containing polymers such as polysilazane is not fully carried out, resulting in a low surface elasticity of the coating. Consequently, the gas barrier layer is damaged during subsequent manufacturing steps. More specifically, when manufacturing elongated gas barrier films using methods such as roll-to-roll, scratches occur when the gas barrier film comes into contact with the guide roller, when the gas barrier film is wound, or when the wound gas barrier film is rolled out, causing the gas barrier films to come into contact with each other.

[0016] This tendency is more pronounced when the gas barrier layer is the second gas barrier layer, that is, when a coating of a silicon-containing polymer compound such as polysilazane is applied as the second gas barrier layer after the first gas barrier layer is applied to the substrate film. The reason for this is that when the coating for forming the second gas barrier layer is applied, the intrusion of water vapor from the substrate film side is blocked by the presence of the first gas barrier layer. Therefore, the conversion reaction of the silicon-containing polymer compound such as polysilazane is less likely to occur in this coating. Consequently, it can be considered that the surface hardness of the coating is lower, making it more prone to scratches due to contact with the guide roller.

[0017] Based on this understanding, the inventors have discovered that after forming a coating containing a silicon-containing polymer compound such as polysilazane and further irradiating it with ultraviolet light, a modification treatment such as ion implantation can be performed to prevent the formation of scratches during the modification treatment step. Furthermore, in this specification, ultraviolet light refers to ultraviolet light with a wavelength exceeding 200 nm, which is different from vacuum ultraviolet light. Specifically, ultraviolet light has a maximum intensity in the region where the wavelength exceeds 200 nm. When the silicon-containing polymer compound is polysilazane, the ultraviolet light preferably has a maximum intensity near the absorption wavelengths of polysilazane, around 260 nm and 320 nm. Furthermore, the inventors discovered that during the ultraviolet irradiation step of the above-mentioned manufacturing method, a conversion reaction of silicon-containing polymers such as polysilazane occurs. Therefore, the ratio of specific elements in the modified layer after the coating film has been modified is different from the corresponding element ratio in the modified layer when the modification treatment is performed without ultraviolet irradiation.

[0018] Other examples of treatments used to induce a conversion reaction in silicon-containing polymers include steam treatment by spraying water vapor onto a coating containing a silicon-containing polymer, or long-term storage at approximately 30-60°C for more than 180 hours. From the viewpoint of ease of treatment or the ability to be carried out in a short time, it is preferable to carry out the conversion reaction by ultraviolet irradiation.

[0019] According to the first and second gas barrier films described above, by using a substrate film lacking heat resistance, a gas barrier film can be provided that prevents scratches even when the drying temperature of the coating used to form the gas barrier layer is lowered. Specifically, regarding the drying temperature of the coating, the first and second gas barrier films are manufactured without heating the substrate film to 110°C or higher. Thus, by manufacturing the substrate film without a step involving high-temperature heating, a gas barrier film with low thermal deformation can be obtained. The degree of thermal deformation of the film, as described in the embodiments below, has traditionally been evaluated using fluorescent lamps, but quantitative evaluation and quantification are not yet widespread. Furthermore, even if the thermal deformation characteristics of the gas barrier film itself were to be quantified, such external characteristics of thermal deformation would vary due to factors such as the material or thickness of the substrate film, the drying time of the coating, and the tension applied to the gas barrier film. Therefore, measuring the thermal deformation of the gas barrier film under a variety of conditions would require an impractical number of experiments, resulting in excessive operating time and economic expenditure. Thus, directly identifying the aforementioned first and second gas barrier films based on their structure or characteristics is practically impossible or unrealistic. Therefore, the invention of the aforementioned first and second gas barrier films is characterized by a manufacturing method that does not involve high-temperature heating. Hereinafter, the first and second gas barrier films will be collectively referred to as "gas barrier films of the embodiments of the present invention."

[0020] 1-1. Example of the structure of a gas barrier film One specific structure of the gas barrier film of the present invention is shown in FIG1. ​​The gas barrier film 100 shown in the schematic cross-sectional view of FIG1 has a substrate film 10, a first gas barrier layer 11, and a second gas barrier layer 12 in sequence.

[0021] The substrate film 10 and the first gas barrier layer 11 can be in direct contact, or other layers can exist between the substrate film 10 and the first gas barrier layer. For example, a primer layer can be provided on the substrate film 10, and the first gas barrier layer 11 can be formed on the substrate film 10 through the primer layer. If the substrate film 10 and the first gas barrier layer 11 are in direct contact, the gas barrier film 100 is easily thinned. If a primer layer is provided between the substrate film 10 and the first gas barrier layer 11, the adhesion between the substrate film 10 and the first gas barrier layer 11 is easily improved. Furthermore, there are cases where protrusions such as protrusions on the substrate film 10 are embedded in the primer layer, which can make the surface of the primer layer smoother than the surface of the substrate film 10.

[0022] The first gas barrier layer 11 and the second gas barrier layer 12 may be in direct contact, or there may be other layers such as a bonding layer between the first gas barrier layer 11 and the second gas barrier layer 12.

[0023] A release liner or protective film may also be provided on at least one of the surfaces of the substrate film 10 opposite to the first gas barrier layer 11 and the second gas barrier layer 12 opposite to the first gas barrier layer 11. By providing a release liner or protective film, the gas barrier film 100 is protected when it is stored or transported in an intermediate product state before being used in the final product.

[0024] The thickness of the gas barrier film can be appropriately determined according to the intended use of the electronic device. From an operational point of view, the actual thickness of the gas barrier film in the embodiment of the present invention is preferably 1-200 μm, more preferably 5-100 μm, and even more preferably 15-60 μm. Furthermore, "actual thickness" refers to the thickness in the usage state. That is, when the gas barrier film has a release liner or protective film, the thickness of such release liner or protective film that is removed during use is not included in the "actual thickness".

[0025] From the viewpoint of ensuring high gas barrier properties, the water vapor permeability of the gas barrier membrane at 40°C and 90% relative humidity is preferably below 5.0 mg / m2 / day, more preferably below 3.0 mg / m2 / day, and even more preferably below 2.0 mg / m2 / day.

[0026] The gas barrier film of the embodiment of the present invention has a substrate film, a first gas barrier layer and a second gas barrier layer. By adjusting the formation method or element composition of each layer, it can be made into a film with excellent gas barrier properties, and the surface scratches of the second gas barrier layer are reduced and the thermal deformation is small.

[0027] 1-2. Substrate Film In the first gas barrier film of the embodiment of the present invention, a resin film with a glass transition temperature (Tg) of 100°C or lower can be used as the substrate film. Furthermore, in the second gas barrier film of the embodiment of the present invention, a film having a polyethylene terephthalate (PET) film layer can be used as the substrate film. Such substrate films are readily available, inexpensive, and have good light transmittance, but they have lower heat resistance, and therefore are prone to thermal deformation when heated at high temperatures during the formation of the gas barrier layer. As mentioned above, lowering the heating temperature can easily cause scratches on the gas barrier layer, but in the gas barrier film of this embodiment, the ratio of oxygen atoms to nitrogen atoms, expressed as [average moles of oxygen atoms] / [average moles of nitrogen atoms], is within a specific range, thus this problem is less likely to occur.

[0028] Tg is a resin film with a temperature below 100°C, such as PET film, polybutylene terephthalate (PBT) film, polylactic acid (PLA) film, etc. The substrate film is preferably treated with easy-bond treatment, such as setting an easy-bond layer, or corona treatment, flame treatment, etc.

[0029] The substrate film is preferably one that has not undergone heat-resistant treatment such as annealing. Performing heat-resistant treatment such as annealing on the substrate requires additional steps, reducing productivity. Furthermore, obtaining a heat-resistant substrate film results in a higher cost compared to an untreated substrate film. In the aforementioned first and second gas barrier films, since the substrate film is manufactured without being heated to 110°C or higher, even if the substrate film has not undergone heat-resistant treatment, a gas barrier film without thermal deformation can be obtained.

[0030] 1-3. The primer layer disposed on the substrate film may be composed of a curable product of an energy-curable resin. Here, an energy-curable resin refers to a curable resin composition that undergoes a curing reaction and transforms into a curable product by irradiation with active energy lines such as ultraviolet light or electron beams or by heating. Energy-curable resins are generally composed primarily of polymeric compounds. Here, "primary component" means a component in the energy-curable resin that accounts for 50% or more by mass in terms of solid content. The polymeric compound is a compound having an energy-polymerizable functional group. Examples of energy-polymerizable functional groups include vinyl unsaturated groups such as (meth)acrylonitrile, vinyl, allyl, and styrene. Among these, (meth)acrylonitrile is particularly preferred due to its high reactivity. Furthermore, in this specification, "(meth)acrylonitrile" means acrylonitrile or methacrylonitrile. The same applies to other similar terms such as "(meth)acrylic acid".

[0031] Polymerizable compounds having a (meth)acrylic group include, for example, polyfunctional acrylate compounds. Polyfunctional acrylate compounds refer to acrylate compounds or methacrylate compounds having two or more unsaturated bonds that participate in the polymerization reaction.

[0032] Multifunctional acrylate compounds include tricyclodecanediethanol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified di(meth)acrylate phosphate, di(acryloxyethyl)isocyanurate, allylated cyclohexyl di(meth)acrylate, and other difunctional acrylate compounds; Trifunctional acrylate compounds such as trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, and tris(2-acryloxyethyl)isocyanurate; quadrufunctional acrylate compounds such as diglycerol tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate; pentafunctional acrylate compounds such as propionic acid-modified dipentaerythritol penta(meth)acrylate; and hexafunctional acrylate compounds such as dipentaerythritol hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate. Among these, multifunctional acrylate compounds are preferred, especially 4- to 6-functional acrylate compounds, and more preferably 6-functional acrylate compounds. These multifunctional acrylate compounds can be used alone or in combination of two or more.

[0033] Energy-curing resins may also contain oligomers. Examples of such oligomers include polyester acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, and polyol acrylate oligomers.

[0034] The energy-curing resin may also contain polymerization initiators such as photopolymerization initiators or thermal polymerization initiators.

[0035] Photopolymerization initiators, including ketone-based photopolymerization initiators such as 2,2-dimethoxy-1,2-diphenylethane-1-one and 1-hydroxy-cyclohexyl-phenyl ketone; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)-phenylphosphite (phosphinate), bis(2,6-dimethoxybenzoyl)-2,4, Phosphorus-based photopolymerization initiators such as 4-trimethyl-pentylphosphine oxide; titanium-based photopolymerization initiators such as bis(η5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrolo-1-yl)-phenyl]titanium; oxime-based photopolymerization initiators; benzophenone-based photopolymerization initiators such as benzophenone, p-chlorobenzophenone, and 4,4'-diethylaminobenzophenone; thioxanthone-based photopolymerization initiators such as thioxanthone; and amine-based photopolymerization initiators such as triisopropanolamine. These can be used alone or in combination of two or more.

[0036] Examples of thermal polymerization initiators include hydrogen peroxide; persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; azo compounds such as 2,2'-azobis(2-methylammoniumpropane) dihydrochloride, 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobisisobutyronitrile, and 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile); and organic peroxides such as benzoyl peroxide, lauryl peroxide, peracetic acid, persuccinic acid, di-t-butyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide. These can be used alone or in combination of two or more.

[0037] When the energy line curing resin contains a polymerization initiator, its content is usually in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the polymerizable compound.

[0038] The energy-curing resin may also contain a crosslinking agent. Examples of crosslinking agents include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, imine-based crosslinking agents, aziridine-based crosslinking agents, and oxazoline-based crosslinking agents. Isocyanate-based crosslinking agents are not particularly limited, and compounds having two or more isocyanate groups in their molecules can be used. Examples include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isoflavone diisocyanate and hydrogenated diphenylmethane diisocyanate; and biuret bodies, isotricyanates, and further adducts of these compounds as reactants with low-molecular-weight compounds containing active hydrogen such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil. These crosslinking agents can be used alone or in combination of two or more.

[0039] When the energy line curing resin contains a crosslinking agent, the content of which yields better results than the present invention is usually 1 to 10 parts by mass, and preferably 2 to 8 parts by mass, relative to 100 parts by mass of the polymeric compound.

[0040] As an energy-curing resin, it is preferably a polymeric compound that is cured by ultraviolet radiation (UV-curing resin). By using a UV-curing resin, a hard coating can be formed efficiently.

[0041] Commercially available products can also be used as the energy line curing resin. Examples of commercially available products include "Opstar Z7530", "Opstar Z7524", "Opstar TU4086", and "Opstar Z7537" (all manufactured by JSR Corporation).

[0042] The energy line curing resin may further contain inorganic materials. By containing inorganic materials, the hardness of the base coating can be increased, or the curing shrinkage of the energy line curing resin can be suppressed.

[0043] Inorganic compounds that constitute inorganic materials may include metal oxides, alkyl silicates, metal fluorides, etc.

[0044] Furthermore, the energy-curing resin may also contain other components, to the extent that it does not impair the effects of the present invention. Other components may include antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, coloring pigments, etc. The content of these components may be appropriately determined according to the intended purpose.

[0045] 1-4. Second Gas Barrier Layer The gas barrier film of an embodiment of the present invention has a first gas barrier layer and a second gas barrier layer. The second gas barrier layer is a layer formed by a coating containing a silicon compound. Furthermore, in X-ray photoelectron spectroscopy, the second gas barrier layer contains nitrogen atoms, oxygen atoms, and silicon atoms, with the ratio of oxygen atoms to nitrogen atoms, expressed as [average mole % of oxygen atoms] / [average mole % of nitrogen atoms], being 1.0 to 6.0. When the ratio is less than 1.0, the conversion reaction of the silicon-containing polymer compound is not sufficiently carried out, and the second gas barrier layer cannot obtain sufficient hardness. When the ratio exceeds 6.0, the conversion reaction of the silicon-containing polymer compound is excessive, and sufficient modification effect is not obtained after modification treatment, resulting in reduced gas barrier performance.

[0046] The ratio of oxygen atoms to nitrogen atoms in the second gas barrier layer is preferably 1.0 to 5.5, more preferably 1.0 to 5.2, and even more preferably 1.0 to 4.9.

[0047] The second gas barrier layer is disposed on the side opposite to the substrate film of the first gas barrier layer, and is also the outermost layer of the gas barrier film. Therefore, it is exposed to the outside, as described above, and is in a state where it is easy to come into contact with guide rollers, etc. during the manufacturing process. However, in the gas barrier film of this embodiment, nitrogen atoms, oxygen atoms and silicon atoms are present in the second gas barrier layer in X-ray photoelectron spectroscopy, and the ratio of oxygen atoms to nitrogen atoms, expressed as [average mole % of oxygen atoms] / [average mole % of nitrogen atoms], is 1.0 to 6.0. Therefore, it has high hardness and elasticity and is not easily scratched.

[0048] Since a thin gas barrier layer with excellent gas barrier properties can be formed efficiently, the second gas barrier layer is preferably the second gas barrier layer obtained by performing the modification treatment described later on the coating containing a silicon-containing polymer compound.

[0049] The thickness of the second gas barrier layer is preferably 5~1,000 nm, more preferably 10~500 nm, even more preferably 15~300 nm, and even more preferably 20~200 nm from the point of view of preventing the formation of scratches and the gas barrier properties.

[0050] In the gas barrier layer obtained by modifying a layer containing a silicon-containing polymer compound (hereinafter referred to as "silicon-containing polymer layer"), the silicon-containing polymer compound used may be used alone or in combination of two or more.

[0051] Silicon-containing polymeric compounds, including polysilazane compounds (see Japanese Patent Publication No. 63-16325, Japanese Patent Application Publication No. 62-195024, Japanese Patent Application Publication No. 63-81122, Japanese Patent Application Publication No. 1-138108, Japanese Patent Application Publication No. 2-84437, Japanese Patent Application Publication No. 2-175726, Japanese Patent Application Publication No. 4-63833, Japanese Patent Application Publication No. 5-238827, Japanese Patent Application Publication No. 5- Japanese Patent Application Publication No. 345826, Japanese Patent Application Publication No. 2005-36089, Japanese Patent Application Publication No. 6-122852, Japanese Patent Application Publication No. 6-299118, Japanese Patent Application Publication No. 6-306329, Japanese Patent Application Publication No. 9-31333, Japanese Patent Application Publication No. 10-245436, Japanese Patent Publication No. 2003-514822, International Publication No. WO2011 / 107018, etc., and polycarbosilane compounds (refer to Journal). of Materials Science, 2569-2576, Vol.13, 1978; Organometallics, 1336-1344, Vol.10, 1991; Journal of Organometallic Chemistry, 1-10, Vol.521, 1996; Japanese Patent Application Publication No. 51-126300, Japanese Patent Application Publication No. 2001-328991, Japanese Patent Application Publication No. 2006-117917, Japanese Patent Application Publication No. 2009-286891, Japanese Patent Application Publication No. 2010-106100, etc.), polysilane compounds (see RDMiller, J. Michl; Chemical Review, Vol.89, p.1359 (1989); N. Matsumoto; Japanese Journal of Physics, Vol. 37, p. 5425 (1998), Japanese Patent Application Publication No. 2008-63586, Japanese Patent Application Publication No. 2009-235358, etc.

[0052] Among these, it is possible to form a gas barrier layer with excellent gas barrier properties, and polysilazane compounds are particularly preferred. Examples of polysilazane compounds include inorganic polysilazanes and organic polysilazanes. Examples of inorganic polysilazanes include perhydropolysilazanes, and examples of organic polysilazanes include compounds in which some or all of the hydrogen atoms of perhydropolysilazanes are replaced by organic groups such as alkyl groups. Among these, inorganic polysilazanes are particularly preferred because they offer ease of use and the ability to form a gas barrier layer with excellent gas barrier properties. Furthermore, polysilazane compounds can also be commercially available as glass coating agents, etc. Polysilazane compounds can be used alone or in combination of two or more.

[0053] The silicon-containing polymer layer may contain other components besides the aforementioned silicon-containing polymer compounds, without hindering the purpose of the present invention. Other components may include hardeners, other polymers, anti-aging agents, light stabilizers, flame retardants, etc.

[0054] The content of silicon-containing polymer compounds in the silicon-containing polymer layer is preferably 50% by mass or more, and more preferably 70% by mass or more, to form a second gas barrier layer with excellent gas barrier properties.

[0055] A method for forming a silicon-containing polymer layer may include, for example, coating a layer-forming solution containing at least one silicon-containing polymer compound, other desired components, and solvents onto a substrate film or a base layer that is desired to be formed on the substrate film by a known method, and then drying the resulting coating film appropriately.

[0056] When forming the second gas barrier layer, for example, when using a polysilazane compound as described above, the polysilazane undergoes a conversion reaction by heating after coating, resulting in a coating film with gas barrier properties.

[0057] The thickness of the silicon-containing polymer layer is preferably 5~1,000 nm, more preferably 10~500 nm, even more preferably 15~300 nm, and still more preferably 20~200 nm. Even if the thickness of the silicon-containing polymer layer is at the nanometer level, a gas barrier film with sufficient gas barrier properties can be obtained by performing ultraviolet irradiation treatment and subsequent modification treatment.

[0058] As described above, the ultraviolet irradiation treatment uses ultraviolet light with a wavelength exceeding 200 nm, which differs from vacuum ultraviolet light. The aforementioned ultraviolet light can be irradiated using a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, etc. The wavelength of the ultraviolet light is preferably 200-400 nm, more preferably 220-380 nm. That is, the maximum intensity of the ultraviolet light is preferably located in the wavelength range of 200-400 nm, more preferably in the wavelength range of 220-380 nm. The irradiation dose is typically 50-1,000 mW / cm², and the light intensity is typically 50-5,000 mJ / cm², preferably 100-1,000 mJ / cm². The irradiation time is typically 0.1-1,000 seconds, more preferably 1-500 seconds, and even more preferably 1-100 seconds. Considering the heat load of the light irradiation step, irradiation can be repeated multiple times to meet the aforementioned light intensity.

[0059] The modification treatment is different from the ultraviolet irradiation described later. Examples include ion implantation and vacuum ultraviolet irradiation (irradiation by excimer laser, etc.). Among these, ion implantation is preferred as it yields high gas barrier performance. In ion implantation, the amount of ions implanted into the polymer layer is appropriately determined in accordance with the intended use of the gas barrier composite (necessary gas barrier performance, transparency, etc.).

[0060] The injected ions may include rare gas ions such as argon, helium, neon, krypton, and xenon; ions of fluorine, carbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; alkane gas ions such as methane, ethane, propane, butane, pentane, and hexane; alkene gas ions such as ethylene, propylene, butene, and pentene; diene gas ions such as pentadiene and butadiene; alkyne gas ions such as acetylene and methylacetylene; aromatic hydrocarbon gas ions such as benzene, toluene, xylene, indene, naphthalene, and phenanthrene; cycloalkane gas ions such as cyclopropane and cyclohexane; cycloalkene gas ions such as cyclopentene and cyclohexene; conductive metal ions such as gold, silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum; and ions of silane (SiH4) or organosilicon compounds.

[0061] Organosilicon compounds, including tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, tetran-butoxysilane, and tetrat-butoxysilane; unsubstituted or substituted alkylalkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and (3,3,3-trifluoropropyl)trimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane; and disiloxanes such as hexamethyldisiloxane (HMDSO). Amino silanes such as bis(dimethylamino)dimethylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylamino)dimethylsilane, diethylaminotrimethylsilane, dimethylaminodimethylsilane, tetradimethylaminosilane, and tris(dimethylamino)silane; silazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, and tetramethyldisilazane; cyanate silanes such as tetraisocyanate silane; halosilanes such as triethoxyfluorosilane; alkenyl silanes such as diallyldimethylsilane and allyltrimethylsilane; Alkyl silanes, whether unsubstituted or substituted, such as di-t-butylsilane, 1,3-disilane, bis(trimethylsilyl)methane, tetramethylsilane, trimethylsilyl)methane, trimethylsilyl)silane, and benzyltrimethylsilane; silyl ynees, such as bis(trimethylsilyl)acetylene, trimethylsilylacetylene, and 1-(trimethylsilyl)-1-propyne; silylenes, such as 1,4-bistrimethylsilyl-1,3-butadiyne and cyclopentadienyltrimethylsilane; arylalkyl silanes, such as phenyldimethylsilane and phenyltrimethylsilane; alkynylalkyl silanes, such as propargyltrimethylsilane; and alkenylalkyl silanes, such as vinyltrimethylsilane. Disilanes such as hexamethyldisilane; siloxanes such as octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, and hexamethylcyclotetrasiloxane; N,O-bis(trimethylsilyl)acetamide; bis(trimethylsilyl)carbodiimide, etc. These ions can be used alone or in combination of two or more.

[0062] Among them, since it is easier to inject and obtain a gas barrier layer with particularly good gas barrier properties, it is particularly preferred to be an ion selected from at least one of the groups of hydrogen, nitrogen, oxygen, argon, helium, neon, xenon and krypton.

[0063] The method of ion implantation is not particularly limited, and methods such as irradiating ions accelerated by an electric field (ion beam) and implanting ions into plasma are examples. Among these, the latter method of implanting plasma ions is particularly preferred because it easily produces a thin film with gas barrier properties.

[0064] The plasma ion implantation method is preferably (I) a method of implanting ions present in plasma generated by using an external electric field into a silicon-containing polymer layer, or (II) a method of implanting ions present in plasma generated by an electric field obtained by applying a negative high voltage pulse to the aforementioned layer without using an external electric field into a silicon-containing polymer layer.

[0065] In the aforementioned method (I), the pressure during ion implantation (the pressure during plasma ion implantation) is preferably 0.01~1 Pa. When the pressure during plasma ion implantation is in such a range, ions can be implanted uniformly and efficiently, and the target gas barrier layer can be formed efficiently.

[0066] The method described in (II) above does not require a high pressure reduction, making the processing operation simple and significantly shortening the processing time. Furthermore, it can uniformly process the entire aforementioned layer, and when a negative high-voltage pulse is applied, ions in the plasma can be continuously injected into the silicon-containing polymer layer with high energy. Moreover, without the need for special means such as radio frequency (RF) or microwave high-frequency power sources, simply applying a negative high-voltage pulse to the layer is sufficient to uniformly inject high-quality ions into the silicon-containing polymer layer.

[0067] Regardless of either method (I) or (II) mentioned above, when a negative high-voltage pulse is applied, that is, when ion implantation is performed, the pulse width is preferably 1 to 15 μsec. When the pulse width is in this range, ions can be implanted more easily and efficiently.

[0068] Furthermore, the applied voltage during plasma generation is preferably -50 to -1 kV, more preferably -30 to -1 kV, and particularly preferably -20 to -5 kV. When ion implantation is performed with an applied voltage of -1 kV or less, insufficient ion implantation (dosage) is prevented, and the desired performance is easily ensured. On the other hand, when ion implantation is performed with a voltage of -50 kV or more, it is easier to prevent the film from becoming charged during ion implantation, and it is also easier to suppress undesirable conditions such as film coloring.

[0069] The types of ions used for plasma ion implantation may be the same as those exemplified as the ions implanted as described above.

[0070] When injecting ions from plasma into a silicon-containing polymer layer, a plasma ion implantation device is used. Specifically, examples of plasma ion implantation devices include (i) a device that applies a negative high-voltage pulse to a silicon-containing polymer layer (hereinafter referred to as the "layer to be implanted") with a feedthrough, superimposed with high-frequency power, uniformly surrounding the ion-implanted layer with plasma, thereby attracting, implanting, colliding with, and accumulating ions in the plasma (Japanese Patent Application Laid-Open No. 2001-26887), and (ii) a device that installs an antenna in a cavity, applies high-frequency power to generate plasma, and after the plasma reaches the vicinity of the ion-implanted layer, alternately applies positive and negative ions to the ion-implanted layer. A device that uses a positive pulse to attract and collide electrons in the plasma, thereby heating the layer to be implanted with ions, and controls the temperature by controlling the pulse constant, and simultaneously applies a negative pulse to attract and implant ions in the plasma (Japanese Patent Application Publication No. 2001-156013), (iii) a plasma ion implantation device that uses an external electric field such as a microwave high-frequency power source to generate plasma and applies a high-voltage pulse to attract and implant ions in the plasma, and (iv) a plasma ion implantation device that implants ions in the generated plasma by applying a high-voltage pulse without using an external electric field.

[0071] Among these, the plasma ion implantation apparatus of (iii) or (iv) is preferred because the processing operation is simple and the processing time can be greatly shortened, making it suitable for continuous use. Regarding the methods of using the aforementioned plasma ion implantation apparatus of (iii) and (iv), those described in International Publication No. WO2010 / 021326 can be cited.

[0072] In the plasma ion implantation apparatus described in (iii) and (iv) above, the plasma generation means that generates plasma is combined with a high-voltage pulse power supply. Therefore, no special means such as high-frequency power sources such as RF or microwave are required. Only by applying a negative high-voltage pulse, plasma is generated, and ions in the plasma are continuously injected into the silicon-containing polymer layer. This allows for the mass production of silicon-containing polymer layers with ion implantation-modified portions on the surface, i.e., gas barrier composites with gas barrier layers.

[0073] The thickness of the ion-implanted portion can be controlled by the type of ion or the implantation conditions such as the applied voltage and processing time. It is determined by the thickness of the silicon-containing polymer layer and the intended use of the gas barrier laminate, and is usually 5~1,000 nm.

[0074] The implantation of ions can be confirmed by elemental analysis at a distance of 10 nm from the surface of the silicon-containing polymer layer using X-ray photoelectron spectrophotometry (XPS).

[0075] The gas barrier properties of the gas barrier layer can be confirmed by the low water vapor transmission rate of the gas barrier layer. The water vapor transmission rate of the gas barrier layer at 40°C and 90% relative humidity is typically below 1.0 g / m² / day, preferably below 0.8 g / m² / day, more preferably below 0.5 g / m² / day, and even more preferably below 0.1 g / m² / day. The water vapor transmission rate can be determined using known methods.

[0076] 1-5. First Gas Barrier Layer The first gas barrier layer of the gas barrier film described above is not particularly limited in material, as long as it has gas barrier properties. One example of the first gas barrier layer is, similar to the second gas barrier layer, a layer formed by a coating containing a silicon-containing polymer compound. Other examples include inorganic films such as silicon oxide formed by dry film deposition methods such as chemical vapor deposition.

[0077] The first gas barrier layer may contain at least one of a metal, a metal oxide, a metal nitride, and a metal carbide. Here, "metal" includes the concept of half-metals, preferably metal oxides, nitrides, and carbides; more preferably half-metal oxides, nitrides, and carbides; and even more preferably silicon oxides, nitrides, and carbides. Oxides, nitrides, and carbides also include those that have been combined, such as oxynitrides, etc.

[0078] The aforementioned inorganic films are not particularly limited; for example, inorganic vapor-deposited films can be listed. Inorganic vapor-deposited films can include vapor-deposited films of inorganic compounds or metals. As raw materials for vapor-deposited films of inorganic compounds, the aforementioned metal oxides, nitrides, and carbides can include inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride, and titanium nitride; inorganic carbides; inorganic nitride oxides such as silicon nitride oxide; inorganic nitride oxides; inorganic nitride carbides; and inorganic nitride carbides. Raw materials for vapor-deposited films of metals can include aluminum, magnesium, zinc, and tin. These can be used alone or in combination of two or more. Of these, from the viewpoint of gas barrier properties, inorganic vapor-deposited films made from metal oxides, metal nitrides, or metals are preferred; furthermore, from the viewpoint of transparency, inorganic vapor-deposited films made from metal oxides or metal nitrides are preferred. Furthermore, inorganic vapor-deposited films can be single-layered or multi-layered.

[0079] The thickness of the inorganic vapor-deposited film, from the viewpoint of gas barrier properties and operability, is preferably in the range of 10~2,000 nm, more preferably 20~1,000 nm, more preferably 30~500 nm, and even more preferably 40~300 nm.

[0080] Methods for forming inorganic vapor-deposited films include PVD (physical vapor deposition) methods such as vacuum vapor deposition, sputtering, and ion plating, or CVD methods such as thermal CVD (chemical vapor deposition), plasma CVD, and photo-CVD.

[0081] The gas barrier layer obtained by modifying the layer containing the silicon-containing polymer compound can be the same as the second gas barrier layer. The thickness of the first gas barrier layer is preferably 10 to 1,500 nm, more preferably 20 to 1,000 nm, even more preferably 30 to 600 nm, and even more preferably 40 to 300 nm.

[0082] 1-6. Release sheet and protective film release sheet are those that are peeled off in specific steps when storing, transporting or storing gas barrier laminates, etc., and play the role of protecting the substrate film.

[0083] The peeling sheet is preferably in the form of a thin sheet or a thin film. The thin sheet or thin film is not limited to long shapes, but also includes short flat plates.

[0084] The release sheet may include paper substrates such as cellophane, coated paper, and high-quality paper; laminated paper on which thermoplastic resins such as polyethylene or polypropylene are laminated; paper substrates that have been filled with cellulose, starch, polyvinyl alcohol, acrylic-styrene resin, etc.; or plastic films such as polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polyethylene or polypropylene; and glass, etc.

[0085] Furthermore, from the viewpoint of ease of operation, the release sheet can also be a paper substrate or a plastic film with a release agent layer. When forming the release agent layer, conventionally known release agents such as polysiloxane release agents, fluorinated release agents, alkyd release agents, and olefin release agents can be used to form the release agent layer.

[0086] The protective film plays a role in protecting the gas barrier layer during storage, transportation, etc., of the gas barrier composite, and is peeled off in a specific step. The protective film is preferably in the form of a sheet or film. The sheet or film shape is not limited to elongated shapes, but also includes short, flat shapes. The protective film is usually attached to the surface of the gas barrier layer after its formation, thus preventing unintentional detachment from the gas barrier layer. From this perspective, it is preferable to have an adhesive layer provided on a substrate. In this case, the adhesive layer is provided on the surface of the protective film on the gas barrier layer side. By having an adhesive layer, the protective film can be peelably attached to the gas barrier layer. The substrate of the protective film can be made of the same material / thickness as the release liner.

[0087] The adhesive constituting the adhesive layer may include, for example, adhesives containing the following: acrylic adhesives, carbamate adhesives, polysiloxane adhesives, rubber adhesives, adhesives containing polyolefin polymers, and adhesives containing polyolefin copolymers. The adhesive layer preferably contains at least one of a polyolefin polymer and a polyolefin copolymer. Examples of polyolefin polymers include polyethylene and polypropylene; examples of polyolefin copolymers include ethylene-vinyl acetate copolymers and ethylene-(meth)acrylic acid copolymers. Furthermore, a protective film containing a commercially available polyolefin adhesive can be used as the protective film (β), such as Sunytect PAC-3-50THK and Sunytect PAC-2-70 manufactured by Sun A Chemical Research Co., Ltd.

[0088] 1-7. Other Configuration Examples of Gas Barrier Films The gas barrier film of the embodiments of the present invention is not limited to that shown in FIG. 1, and may also include other gas barrier layers between the first gas barrier layer and the second gas barrier layer. Furthermore, the gas barrier film of the embodiments of the present invention may include one or more other layers, between the substrate film or the undercoating layer on the substrate film and the first gas barrier layer, or on the second gas barrier layer, without impairing the purpose of the present invention. Moreover, even when other layers are present on the second gas barrier layer in the gas barrier film of the embodiments of the present invention, there is a possibility of scratches occurring on the second gas barrier film after the formation of the second gas barrier layer until the placement of the other layers. Therefore, the effects of the present invention can be obtained even with a gas barrier film configured in this way. Examples of other layers include conductive layers, impact absorption layers, and adhesive layers. Furthermore, the placement of the other layers is not limited to those described above.

[0089] Materials constituting the conductive layer may include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specifically, examples include antimony-doped tin oxide (ATO); fluorine-doped tin oxide (FTO); semi-conductive metal oxides such as tin oxide, germanium-doped zinc oxide (GZO), zinc oxide, indium oxide, indium tin oxide (ITO), and zinc indium oxide (IZO); metals such as gold, silver, chromium, and nickel; mixtures of these metals and conductive metal oxides; inorganic conductive materials such as copper iodide and copper sulfide; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole.

[0090] There are no particular restrictions on the method for forming the conductive layer. Examples include vapor deposition, sputtering, ion plating, thermal CVD, and plasma CVD.

[0091] The thickness of the conductive layer can be appropriately selected according to its application. It is usually 10nm to 50μm, and preferably 20nm to 20μm.

[0092] The impact-absorbing layer is used to protect the gas barrier layer when an impact is applied to it. The material forming the impact-absorbing layer is not particularly limited, and examples include acrylic resins, urethane resins, polysiloxane resins, olefin resins, and rubber materials.

[0093] There are no particular limitations on the method for forming the impact-absorbing layer. For example, a method can be described in which an impact-absorbing layer forming solution containing the material for forming the aforementioned impact-absorbing layer and other components such as a desired solvent is coated onto the layer to be laminated, the resulting coating is dried, and heating is performed as needed. Alternatively, the impact-absorbing layer can be separately formed on a release substrate, and the resulting film can be transferred onto the layer to be laminated for lamination. The thickness of the impact-absorbing layer is typically 1 to 100 μm, preferably 5 to 50 μm.

[0094] The adhesive layer is a layer used when attaching a gas barrier laminate to an adherend. The material forming the adhesive layer is not particularly limited, and known adhesives or heat sealants such as acrylic, polysiloxane, and rubber adhesives may also be used.

[0095] Furthermore, a hard coating or the like may also be provided on the surface of the substrate film opposite to the side where the first gas barrier layer is provided, but it is preferable not to provide a hard coating on that surface. Examples of hard coatings include a layer composed of a cured product of a line-curing resin, and the same line-curing resin as used in the aforementioned undercoating can be used. Because no hard coating is provided on the surface of the substrate film opposite to the side where the first gas barrier layer is provided, a gas barrier film can be obtained with high productivity. On the other hand, a substrate film without a hard coating on the surface opposite to the side where the first gas barrier layer is provided has poorer heat resistance than a substrate film with a hard coating on that surface. However, the aforementioned first and second gas barrier films are manufactured by not heating the substrate film to 110°C or higher, thus a gas barrier film that does not exhibit thermal deformation even with such a substrate film can be obtained.

[0096] 1-8. Roller-shaped gas barrier film In one embodiment of the present invention, the gas barrier film is roller-shaped, and the number of scratches with an aspect ratio of 2 or greater on the surface of the aforementioned second gas barrier layer is 200 or less per 1 m². FIG2 is a cross-sectional schematic diagram showing an example of a roller-shaped gas barrier film. The roller-shaped gas barrier film 100A shown in FIG2 has a roller-shaped portion 100A1 wound around a cylindrical or rod-shaped core material 20. Furthermore, a pull-out portion 100A2 is formed by pulling out the front end of the roller-shaped portion 100A1.

[0097] As described above, the gas barrier film of this embodiment can suppress the formation of scratches. Therefore, the number of scratches with an aspect ratio of 2 or higher on the surface of the second gas barrier layer is less than 200 per m². Scratches are mainly caused by contact with the guide roller during the manufacturing process described above. Therefore, it can be assumed that they occur at the same frequency at any position in the coating direction of the roller-shaped film. Therefore, the observation of the number of scratches can be performed at any randomly selected part in the coating direction. Furthermore, scratches caused by the guide roller tend to extend along the coating direction. Therefore, when more accurately grasping only the situation of scratches caused by the guide roller, the aspect ratio of the scratches of the observed object is preferably 3 or higher, and more preferably 4 or higher. The number of scratches with an aspect ratio of 2 or higher on the surface of the second gas barrier layer is more preferably less than 150, more preferably less than 130, and more preferably less than 120 per m².

[0098] In the roller-shaped gas barrier film 100A shown in FIG. 2, the roller-shaped portion 100A1 is formed with the first gas barrier layer 11 and the second gas barrier layer 12 located further outward than the substrate film 10. Therefore, it is not easy to apply pressure to the first gas barrier layer 11 and the second gas barrier layer 12 in the roller-shaped portion 100A1. It is also possible to form the roller-shaped portion with the first gas barrier layer 11 and the second gas barrier layer 12 located further inward than the substrate film 10. In this case, during the storage or transportation of the roller-shaped gas barrier film, it is easy to prevent the second gas barrier layer 12 or the first gas barrier layer 11 from peeling off due to contact with external objects.

[0099] 2. Method for manufacturing a gas barrier film The method for manufacturing a gas barrier film according to an embodiment of the present invention comprises the following steps.

[0100] ･A coating step in which a composition containing a silicon-containing polymer compound is coated onto the first gas barrier layer of a laminate having a first gas barrier layer and a substrate film to form a coating film;･A heating step in which the coating film is heated;･An ultraviolet irradiation step in which the coating film is irradiated with ultraviolet light after the heating step begins;･An ultraviolet irradiation step in which the coating film is subjected to a modification treatment different from the treatment performed in the ultraviolet irradiation step after the ultraviolet irradiation step to obtain a modification step of the second gas barrier layer.

[0101] In the above-described method for manufacturing a gas barrier film, during the formation of the second gas barrier layer, an ultraviolet irradiation step is performed after the heating of the coating used to form the second gas barrier layer begins and before the modification step. This allows the conversion reaction of the silicon-containing polymer compound in the second gas barrier layer to proceed appropriately. Therefore, a hard gas barrier film that is not easily scratched can be obtained.

[0102] Figure 3 shows an example of the manufacturing steps of the gas barrier composite according to an embodiment of the present invention. Figures 3(a) to 3(c) show the steps of forming the first gas barrier layer on the substrate film. Figure 3(d) shows the above-described coating step, Figure 3(e) corresponds to the above-described heating step, Figure 3(f) corresponds to the above-described ultraviolet irradiation step, and Figure 3(g) corresponds to the above-described modification step. Hereinafter, each step will be described using an example where a gas barrier layer obtained by modifying a layer containing a silicon-containing polymer compound is used as the first gas barrier layer, with appropriate reference to the figures.

[0103] 2-1. Preparation of the substrate film The substrate film can also be used directly, but it is preferable to form a primer coating on the substrate film as the substrate film (symbol 10 in FIG3(a)). When forming the primer coating, firstly, a primer coating before curing is formed on the substrate film using a curable resin composition.

[0104] The method of coating the curable resin composition onto the substrate film is not particularly limited, and known coating methods such as spin coating, spray coating, bar coating, knife coating, roller coating, blade coating, die coating, and gravure coating can be used.

[0105] The method for drying the obtained coating is not particularly limited, and conventionally known drying methods such as hot air drying, hot roller drying, and infrared irradiation can be used.

[0106] The drying temperature of the coating is usually 30~150℃, preferably 50~120℃. The drying time is usually 1~10 minutes, preferably 2~7 minutes. The thickness of the dried coating is not particularly limited, and the reason why it is almost the same as the thickness of the hardened coating is that it can be the same as the thickness of the primer layer mentioned above.

[0107] Next, the obtained primer layer before curing is cured to form a cured primer layer. The method for curing the primer layer before curing is not particularly limited, and known methods can be used. For example, when using a curable resin composition containing a thermal polymerization initiator, a cured primer layer can be obtained by heating. The heating temperature is usually 30~150°C, preferably 50~100°C.

[0108] Furthermore, when using a curable resin composition containing a photopolymerization initiator, a cured base coating can be obtained by irradiating it with electromagnetic waves, which serve as active energy lines. The electromagnetic waves can be irradiated using a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like.

[0109] The wavelength of the electromagnetic wave is preferably in the ultraviolet region of 200-400 nm, more preferably 350-400 nm. The irradiation dose is typically 50-1,000 mW / cm², and the light intensity is typically 50-5,000 mJ / cm², more preferably 200-5,000 mJ / cm². The irradiation time is typically 0.1-1,000 seconds, more preferably 1-500 seconds, and even more preferably 10-100 seconds. Considering the heat load of the light irradiation process, irradiation may be repeated multiple times to meet the aforementioned light intensity.

[0110] Alternatively, a hardened base coating can be obtained by irradiating with an electron beam, which serves as the active energy line. When irradiating with an electron beam, an electron beam accelerator or the like can be used. The irradiation dose is typically in the range of 10 to 1,000 krad. The irradiation time is typically 0.1 to 1,000 seconds, preferably 1 to 500 seconds, and even more preferably 10 to 100 seconds.

[0111] The curing of the layer composed of a curable resin composition can also be carried out in an inert gas environment such as nitrogen, as needed. By carrying out curing in an inert gas environment, it is easy to avoid obstacles to curing caused by oxygen or moisture.

[0112] 2-2. Formation of the first gas barrier layer (coating step) A coating film for forming the first gas barrier layer is formed directly on the substrate film or on the undercoating layer of the substrate film using a solution containing the aforementioned silicon compound, in other words, the first gas barrier layer before curing (symbol 11a in FIG. 3(b)). When coating the solution for forming the gas barrier layer, known devices such as spin coaters, blade coaters, and gravure coaters can be used.

[0113] (Heating Step) Next, the coating of the composition is dried and hardened by heating. The heating and drying methods can be conventionally known methods such as hot air drying, hot roller drying, or infrared irradiation. The heating temperature is typically 80~110°C, preferably 90~105°C. The heating time is typically tens of seconds to tens of minutes, preferably 60 seconds to 5 minutes, and more preferably 90 seconds to 3 minutes.

[0114] (Modification Step) In this embodiment, the first gas barrier layer is a layer obtained by modifying a layer containing a silicon-containing polymer compound. Therefore, the first gas barrier layer (symbol 11 in FIG3(c)) can be formed by the step of forming a layer containing a silicon-containing polymer compound on a resin layer and the step of modifying the layer containing the silicon-containing polymer compound. The details of the modification process are as described above.

[0115] At this time, before the modification treatment, the first gas barrier layer tends to have water vapor easily penetrate from the substrate film side, making the conversion reaction easier to proceed. Therefore, even if no special steps are set before the modification treatment during manufacturing, the ratio of oxygen atoms to nitrogen atoms, expressed as [average moles of oxygen atoms] / [average moles of nitrogen atoms], tends to increase when nitrogen atoms, oxygen atoms, and silicon atoms are present. Furthermore, when the first gas barrier layer composed of an inorganic film is formed by vapor deposition or the like, the second gas barrier layer is usually formed without the above-mentioned heating step, but depending on the type of the first gas barrier layer, a modification treatment may also be performed.

[0116] 2-3. Formation of the Second Gas Barrier Layer (Coating Step) On the first gas barrier layer formed on the substrate film, a coating film for forming the second gas barrier layer is formed using a solution containing the aforementioned silicon compound, in other words, the second gas barrier layer before curing (symbol 12a in FIG. 3(d)). The specific process of the coating step is the same as that described in the formation of the first gas barrier layer.

[0117] (Heating Step) Next, the coating of the composition is dried and hardened by heating (symbol 12b in FIG3(e) indicates the heated coating). The specific process or conditions of the heating step are the same as those described in the formation of the first gas barrier layer. That is, the heating temperature is usually 80~110°C, preferably 90~105°C. The heating time is usually tens of seconds to tens of minutes, preferably 60 seconds to 5 minutes, and more preferably 90 seconds to 3 minutes.

[0118] (Ultraviolet Irradiation Step) After the heating step begins, the above coating is irradiated with ultraviolet light (symbol 12c in Figure 3(f) indicates the coating after ultraviolet irradiation). The ultraviolet light used in this step has a wavelength exceeding 200 nm, which is different from vacuum ultraviolet light. The ultraviolet irradiation step can be started after the heating step or during the heating step. The specific process of ultraviolet irradiation is as described above.

[0119] (Modification Step) By performing a modification step after the ultraviolet irradiation step, a second gas barrier layer (symbol 12 in Figure 3(g)) is formed. Details of the modification treatment are as described above. From the viewpoint of appropriately carrying out the conversion reaction of silicon-containing polymers, the time from the end of the ultraviolet irradiation step to the start of the modification step is preferably 6 to 144 hours, more preferably 12 to 120 hours, and even more preferably 15 to 108 hours.

[0120] When the gas barrier film is in the form of a roller, a preferred method for performing the modification treatment is to transport the roller-shaped film, on which a layer containing a silicon-containing polymer compound is formed on a substrate film or on a base coating layer of the substrate film, in a certain direction while sequentially performing a heating step and an ultraviolet irradiation step, thereby modifying the silicon-containing polymer compound layer after these steps to manufacture the gas barrier film. According to this manufacturing method, roller-shaped gas barrier films can be continuously manufactured.

[0121] 2-4. After other steps, a protective film is applied, as needed, to the second gas barrier layer or to the side of the substrate film opposite to the first gas barrier layer. This step, for example, involves sequentially pressing the protective film, with the adhesive layer facing the surface to be adhered, in a manner that prevents air bubbles from being trapped. [Example]

[0122] Next, specific embodiments of the present invention will be described, but the present invention is not limited by such examples. The following process will be used to evaluate and measure / calculate the thermal shrinkage rate of the film substrate used in the gas barrier films produced in the following embodiments and comparative examples, the thermal deformation of each gas barrier film, the elemental ratio of the second gas barrier layer of each gas barrier film, the surface elastic modulus of the coating film used to form the second gas barrier layer during the manufacture of each gas barrier film, the water vapor permeability of each gas barrier film, and the number of scratches on each gas barrier film.

[0123] [Heat Shrinkage Rate of Substrate Film] Based on JIS K7133, test pieces of the PET film used in the Examples and Comparative Examples were prepared. The test pieces were heated under the same conditions as those in the Examples and Comparative Examples, or heated and irradiated with ultraviolet light, in accordance with (i) heating at 100°C for 2 minutes, (ii) heating at 100°C for 2 minutes followed by ultraviolet irradiation, and (iii) heating at 120°C for 2 minutes. The change in the distance between the marks on the test pieces before and after heating was measured according to JIS K7133, and the change in heating dimension for the same specification was obtained as the heat shrinkage rate. The measurement was performed four times, and the average value was taken.

[0124] [Surface elastic modulus of the coating for forming the second gas barrier layer] In Examples 1-3 and Comparative Example 3, the coating for forming the second gas barrier layer, which is mainly composed of ultraviolet-irradiated perhydropolysilazane, was coated on the first gas barrier layer and taken in the state before plasma ion implantation. In Comparative Examples 1 and 2, the coating for forming the second gas barrier layer, which is mainly composed of ultraviolet-unirradiated perhydropolysilazane, was coated on the first gas barrier layer and taken in the state before plasma ion implantation. The surface elastic modulus of the coating of each sample was measured using a "Dimension Icon" manufactured by BRUKER under the following conditions: probe: RTESA-525, measurement area: 1 μm□, and indentation amount: 10 nm.

[0125] [Thermal Deformation of Gas Barrier Films] Roller-shaped gas barrier films prepared from the Examples and Comparative Examples were cut into sheet samples of 210 × 297 mm at randomly selected locations along the coating direction of the roller. The samples were extracted from the center of the roller in the width direction (perpendicular to the coating direction). The sheet samples were placed on a platform with a fluorescent lamp mounted on top, and the reflection of the fluorescent lamp was visually observed. The degree of thermal deformation was evaluated according to the following criteria: G: No significant deformation observed under fluorescent lamp; NG: Significant deformation observed under fluorescent lamp.

[0126] [Elemental Ratio of the Second Gas Barrier Layer Obtained by X-ray Photoelectron Spectrophotometry (XPS)] For sheet-like samples obtained in the same manner as the thermal deformation of the aforementioned gas barrier thin film, the molar ratio of each atom contained in the second gas barrier layer 2 of the sheet-like sample was measured in the thickness direction (averaged at 15 equally spaced points across the entire thickness of the second gas barrier layer 2), and the value of [average molar % of oxygen atoms] / [average molar % of nitrogen atoms] was calculated. ･Apparatus name: PHI Quantera SXM, manufactured by ULVAC-PHI ･X-ray beam diameter: 100um ･Power: 25W ･Voltage: 15kV ･Extraction angle: 45° ･Sputtering gas: Argon

[0127] [Water Vapor Transmission Rate (WVTR)] The gas barrier films prepared in the examples and comparative examples were cut into circular test pieces with an area of ​​50 cm². The water vapor transmission rate (g / m² / day) was measured using a water vapor transmission rate measuring device (manufactured by MOCON, device name: AQUATRAN2) at 40°C and 90% relative humidity with a gas flow rate of 20 sccm. Furthermore, the detection limit of the measuring device was 0.05 mg / m² / day.

[0128] [Number of Scratches] Visual inspection using reflected light (inspection area: 100mm × 200mm) with an LED light source (illuminance: 3,500 ± 500 lx) was conducted on sheet samples obtained in the same manner as the evaluation of thermal deformation of the gas barrier film described above. The number of scratches per 1m² generated in the second gas barrier layer of the gas barrier film was calculated by converting the number of scratches detected from the inspection area to a value per 1m². Furthermore, the specific aspect ratios of the scratches with an aspect ratio of 2 or higher observed were all 5 or higher.

[0129] [Example 1] (1) Preparation of the substrate film with the base coating: A PET film (manufactured by Toyobo Co., Ltd., PET50A4360) with a thickness of 50 μm, a width of 1,000 mm, and a length of 500 m, which has undergone double-sided easy-bonding treatment, was prepared in roller form. A UV-curable acrylate resin composition (manufactured by Arakawa Chemical Co., Ltd., Opstar Z7530) was coated onto the PET film using a die coater, and the resulting coating was dried at 70°C for 1 minute in a dryer attached to the coater. Afterward, the coating was irradiated with ultraviolet light using an electrodeless UV lamp system (manufactured by Heraeus Co., Ltd.) under conditions of illuminance of 250 mW / cm2 and light intensity of 170 mJ / cm2 to cure the UV-curable acrylate resin composition. Thus, a base coating with a thickness of 1,000 nm was formed on one side of the PET film.

[0130] (2) The first gas barrier layer is formed on the surface of the base coating of the substrate film of the obtained base coating by applying a coating agent (Merck Performance Materials, AQUAMICA NL110-20, solvent: xylene, concentration: 20%) with perhydropolysilazane (PHPS) as the main component using a die coater. The resulting uncured coating layer is then cured by heating at 100°C for 2 minutes in a dryer attached to the coater to form a coating film with a thickness of 200 nm. After standing for 12 hours at 23°C and 50% relative humidity, the coating film is subjected to plasma ion implantation under the following conditions using a plasma ion implantation device to form the first gas barrier layer. <Conditions for Plasma Ion Implantation> • Chamber pressure: 0.2 Pa • Plasma generating gas: Argon • Gas flow rate: 100 sccm • RF output: 1,000 W • RF frequency: 1,000 Hz • RF pulse width: 50 μs • RF delay: 25 nm • DC voltage: -6 kV • DC frequency: 1,000 Hz • DC pulse width: 5 μs • DC delay: 50 μs • Duty ratio: 0.5% • Processing time: 200 seconds

[0131] (3) The second gas barrier layer is formed on the surface of the obtained first gas barrier layer by applying a coating agent (Merck Performance Materials, AQUAMICA NL110-20, solvent: xylene, concentration: 20%) with PHPS as the main component using a die coater. The obtained uncured coating layer is heated to 100°C for 2 minutes in a dryer attached to the coater to form a coating film with a thickness of 100 nm. This coating film is irradiated with an electrodeless UV lamp system (Heraeus) at an illuminance of 70 mW / cm2 and a light intensity of 190 mJ / cm2, with ultraviolet light having maximum intensity at 254 nm, 313 nm, and 365 nm, and substantially containing no light with wavelengths below 200 nm. Then, after standing for 12 hours at 23°C and 50% relative humidity, the coating was subjected to plasma ion implantation under the same conditions as when the first gas barrier layer was formed, to form the second gas barrier layer 2. Thus, a gas barrier film was obtained.

[0132] [Example 2] A 250 nm silicon oxide film (SiOx film (x=2.33)) was formed on the surface of the above-mentioned base coating using plasma chemical vapor deposition under the following conditions, thereby forming a first gas barrier layer instead of the first gas barrier layer described above. Otherwise, a gas barrier thin film was obtained in the same manner as in Example 1. <Conditions of plasma chemical vapor deposition> ･Flow rate of hexamethyldisiloxane: 50 sccm ･Flow rate of argon: 15 sccm ･Flow rate of oxygen: 10 sccm ･Inner chamber pressure: 0.3 Pa ･RF power supply: 1,000 W ･Film deposition time: 120 seconds

[0133] [Example 3] When the coating was irradiated with ultraviolet light during the formation of the second gas barrier layer, it was left to stand for 96 hours at 23°C and 50% relative humidity. Otherwise, the gas barrier film was obtained in the same way as in Example 1.

[0134] [Comparative Example 1] The coating was not irradiated with ultraviolet light during the formation of the second gas barrier layer, and the gas barrier film was obtained in the same manner as in Example 1.

[0135] [Comparative Example 2] During the formation of the second gas barrier layer, the coating was not subjected to ultraviolet irradiation, and the uncured coating layer was heated at 120°C for 2 minutes during the formation of the second gas barrier layer. Otherwise, the gas barrier film was obtained in the same manner as in Example 1. In this example, the evaluation result of the thermal deformation of the gas barrier film was poor, so no other evaluation / measurement was performed.

[0136] [Comparative Example 3] After irradiating the coating with ultraviolet light during the formation of the second gas barrier layer, it was left to stand for 168 hours at 23°C and 50% relative humidity. Otherwise, a gas barrier film was obtained in the same manner as in Example 1. In this example, sufficient gas barrier performance was not obtained, so the number of scratches was not evaluated.

[0137] The measurement results of the gas barrier films of each embodiment and comparative example are shown in Table 1.

[0138]

[0139] As can be clearly seen from the results in Table 1, the average molar percentage ratio of oxygen atoms to nitrogen atoms in the second gas barrier layer of the gas barrier films in Examples 1-3 is in the range of 1.0 to 6.0. Furthermore, the gas barrier properties are good, and the number of scratches is low. Also, the substrate film has low thermal shrinkage and good thermal deformation. Furthermore, the coating used for forming the second gas barrier layer after ultraviolet irradiation has a suitable elastic modulus.

[0140] In contrast, the gas barrier film of Comparative Example 1, since it was not subjected to ultraviolet irradiation during the formation of the second gas barrier layer, shows that the average molar percentage ratio of oxygen atoms to nitrogen atoms in the second gas barrier layer is lower than the range of 1.0 to 6.0. Furthermore, it was found that the substrate film has a low thermal shrinkage rate and good thermal deformation evaluation, but the number of scratches is very high. Also, since the coating used to form the second gas barrier layer was not subjected to ultraviolet irradiation, it is understandable that its elastic modulus is lower compared to the example that was subjected to ultraviolet irradiation.

[0141] Furthermore, regarding the gas barrier film of Comparative Example 2, it can be understood that because the heating temperature during the formation of the first gas barrier layer and the second gas barrier layer is higher than the glass transition temperature of the substrate film, and no ultraviolet irradiation was performed during the formation of the second gas barrier layer, the substrate film has a large thermal shrinkage rate and the evaluation of thermal deformation is poor.

[0142] Furthermore, in Comparative Example 3, the gas barrier film, due to the long standing time from the irradiation with ultraviolet light during the formation of the second gas barrier layer to the subsequent modification treatment, indicates that the average molar percentage ratio of oxygen atoms to nitrogen atoms in the second gas barrier layer is higher than the range of 1.0 to 6.0. In other words, it can be understood that the PHPS conversion reaction proceeded excessively, and the modification treatment did not achieve sufficient modification effect, resulting in a decrease in gas barrier properties compared to Examples 1 to 3. [Simplified Explanation of the Diagram]

[0012] [Figure 1] shows a cross-sectional schematic diagram of an example of a gas barrier film. [Figure 2] shows a cross-sectional schematic diagram of an example of a roller-shaped gas barrier film. [Figure 3] shows an explanatory diagram of an example of a method for manufacturing a gas barrier film.

Claims

1. A gas barrier film comprising, in sequence, a substrate film, a first gas barrier layer, and a second gas barrier layer, wherein the substrate film is a resin film with a glass transition temperature of 100°C or less, and the second gas barrier layer is a layer formed by a coating containing a silicon-containing polymer compound, wherein nitrogen atoms, oxygen atoms, and silicon atoms are present in the second gas barrier layer in X-ray photoelectron spectroscopy, and the ratio of oxygen atoms to nitrogen atoms, expressed as [average moles % of oxygen atoms] / [average moles % of nitrogen atoms], is 1.0 to 6.0, and the gas barrier film is manufactured without heating the substrate film to 110°C or higher.

2. A gas barrier film comprising, in sequence, a substrate film, a first gas barrier layer, and a second gas barrier layer, wherein the substrate film comprises a polyethylene terephthalate film layer, and the second gas barrier layer comprises a coating comprising a composition containing a silicon-containing polymer compound, wherein nitrogen atoms, oxygen atoms, and silicon atoms are present in the second gas barrier layer in X-ray photoelectron spectroscopy, and the ratio of oxygen atoms to nitrogen atoms, expressed as [average moles % of oxygen atoms] / [average moles % of nitrogen atoms], is 1.0 to 6.0, and the gas barrier film is manufactured without heating the substrate film to 110°C or higher.

3. The gas barrier film as claimed in claim 1 or 2, wherein the aforementioned gas barrier film is in the shape of a roller, and the number of scratches with an aspect ratio of 2 or greater on the surface of the aforementioned second gas barrier layer is less than 200 per 1m2.

4. The gas barrier film of claim 1 or 2, wherein the aforementioned first gas barrier layer contains at least one of a metal, a metal oxide, a metal nitride, and a metal carbide.

5. The gas barrier film as claimed in claim 1 or 2, wherein the aforementioned substrate film has not undergone heat treatment.

6. The gas barrier film of claim 1 or 2, wherein no hard coating is provided on the surface of the aforementioned substrate film opposite to the side on which the first gas barrier layer is provided.

7. A method for manufacturing a gas barrier thin film, comprising a coating step of coating a composition containing a silicon-containing polymer compound onto the first gas barrier layer of a laminate having a first gas barrier layer and a substrate thin film to form a coating film; a heating step of heating the aforementioned coating film; an ultraviolet irradiation step of irradiating the aforementioned coating film with ultraviolet light after the heating step begins; and a modification step of subjecting the aforementioned coating film to a modification treatment different from the treatment performed in the aforementioned ultraviolet irradiation step after the ultraviolet irradiation step to obtain a second gas barrier layer.

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