JP2011136584A - Gas barrier film, device, and manufacturing method for the gas barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier film having excellent gas barrier properties, a device using the gas barrier film, and a manufacturing method for the gas barrier film. <P>SOLUTION: The gas barrier film 1 comprises: a plastic film 2 containing an oligomer content of ≤1 mass%; an organic layer 3 provided on the plastic film 2 and made of an ultraviolet curable resin; and an inorganic layer 4 provided on the organic layer 3. The organic layer 3 has a thickness larger than the maximum height difference on the surface of the plastic film. Consequently, the gas barrier film 1 has superior gas barrier properties. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a gas barrier film, an apparatus using the gas barrier film, and a method for producing the gas barrier film.

  The solar cell module back surface protection sheet is required to have a predetermined gas barrier property and durability such as heat resistance, light resistance, hydrolysis resistance, moisture resistance and the like that can withstand a harsh natural environment for a long period of time.

  Patent Document 1 discloses a gas barrier film having a vapor deposition layer made of an inorganic compound on at least one surface of a film substrate having weather resistance and hydrolysis resistance, and a heat resistant film substrate disposed on the gas barrier film, The back surface protection sheet for solar cell modules having

  More specifically, in this document, polyethylene terephthalate (PET), a barrier film in which a vapor-deposited inorganic oxide film is provided on one side of a polyethylene terephthalate (PET) film substrate, is hydrolyzed and deteriorated at high temperatures and high humidity. In particular, the water vapor (moisture) barrier is reduced, and the long-term durability of the solar cell is difficult to maintain. And in order to solve this problem, the film base material which has heat resistance is laminated | stacked on the gas barrier film.

  Actually, in Example 1 of the document, a film base material (PET # 50) having heat resistance is provided on the film base material (PEN # 12) side of the gas barrier film, and heat resistance is provided on the vapor deposition layer (VM) side. A film base material (PET # 188) having a solid content is laminated by a dry lamination lamination method using a two-component curable polyurethane adhesive having a solid content of 30% by weight.

JP 2008-227203 A (Claim 1, paragraph 0008, paragraph 0085)

  However, when this inventor examined about the back surface protection sheet for solar cell modules described in patent document 1, as for the back surface protection sheet, the film base material which has heat resistance turns into a gas-barrier film through an adhesive agent. It has been found that there is a problem that the gas barrier property becomes insufficient in order to adopt the configuration of being attached.

  That is, the film base material having heat resistance is excellent not only in heat resistance but also in mechanical strength, weather resistance, and hydrolysis resistance. By using such a film base material, the gas barrier property of the back surface protection sheet for solar cell modules is used. Improvement is expected. However, in patent document 1, the film base material which has heat resistance is adhere | attached on both surfaces of the gas barrier film with the 2 liquid-curing type polyurethane-type adhesive agent, and it becomes easy to infiltrate a water | moisture content from the said adhesive agent. . As a result, there is a problem that the gas barrier property expected for a heat-resistant film substrate is not sufficiently exhibited.

Actually, the inventors of the present invention have examined the gas barrier property, and in order to actually use it as a back surface protection sheet for a solar cell module, it is 10 ⁻² g / m ² · day level (0.01 g / m ² · day). The following gas barrier properties were found to be required. However, as shown in Table 3 in paragraph 0104 of Patent Document 1, the back surface protective sheet for solar cell module described in the same document achieves only a water vapor barrier property of about 0.15 g / m ² · day. It is not suitable for actual use.

  The present invention has been made to solve the above problems, and a first object thereof is to provide a gas barrier film having excellent gas barrier properties.

  The present invention has been made to solve the above problems, and a second object of the present invention is to provide an apparatus using a gas barrier film having excellent gas barrier properties.

  The present invention has been made to solve the above problems, and a third object of the present invention is to provide a method for producing a gas barrier film capable of producing a gas barrier film having excellent gas barrier properties. is there.

  The present inventor does not attach a heat resistant film base material that has excellent hydrolysis resistance and can be expected to improve gas barrier properties to a gas barrier film via an adhesive by a dry laminating method as in Patent Document 1. Therefore, it was examined whether it could be used as the base material of the gas barrier film. More specifically, an investigation was made as to whether or not a gas barrier film could be formed by directly forming an inorganic layer containing an inorganic material on the heat-resistant film substrate.

  And in the process of such examination, when the amount of oligomer of the film base material is reduced in order to improve hydrolysis resistance (hereinafter referred to as “plastic film”, when the film base material with reduced oligomer amount is meant. It has been found that the surface roughness of this plastic film is increased and the maximum height difference on the film surface is on the order of μm. On the other hand, since the inorganic layer made of silicon oxide or the like has a thickness of several tens to several hundreds of nanometers, the surface roughness of the plastic film becomes rough, so that the inorganic layer cannot completely cover the plastic film surface. . As a result, the portion that was not covered with the inorganic layer could not obtain sufficient gas barrier properties, and the use of a plastic film with improved hydrolysis resistance is expected to improve gas barrier properties. We faced a new challenge of getting worse.

  Therefore, as a result of further diligent studies by the present inventors to overcome the above problems, the plastic film surface roughness is covered and flattened between the inorganic film and the plastic film having improved hydrolysis resistance. It was found that the above problem can be solved by providing an organic layer to complete the present invention.

The gas barrier film of the present invention according to the first aspect for solving the above-mentioned problem comprises a plastic film having an oligomer content of 1% by mass or less and an ultraviolet curable resin provided on the plastic film. It has an organic layer and an inorganic layer provided on the organic layer, and the thickness of the organic layer is larger than the maximum height difference on the surface of the plastic film.

According to this invention, the amount of oligomer contained is 1% by mass or less, the organic layer made of an ultraviolet curable resin provided on the plastic film, and the inorganic layer provided on the organic layer The thickness of the organic layer is larger than the maximum height difference on the surface of the plastic film, so that it becomes easier to form an inorganic layer with good film quality by reducing the amount of oligomer in the plastic film, and the amount of oligomer Even if the maximum height difference on the surface of the plastic film becomes large due to the reduction in the thickness, the organic layer is flattened so as to cover the maximum height difference, and the inorganic layer is provided on the flattened organic layer. As a result, a gas barrier film that is particularly excellent in gas barrier properties can be provided.

The gas barrier film of the present invention according to the second aspect for solving the above-mentioned problem comprises a plastic film having an oligomer content of 1% by mass or less and an ultraviolet curable resin provided on the plastic film. It has an organic layer and an inorganic layer provided on the organic layer, and the thickness of the organic layer is 1.7 μm or more and 10 μm or less.

According to this invention, in addition to the configuration and function and effect of the gas barrier film according to the first aspect, the thickness of the organic layer made of the ultraviolet curable resin is 1.7 μm or more and 10 μm or less. The maximum height difference on the film surface is more reliably covered with the organic layer, and the gas barrier property of the gas barrier film can be more reliably improved.

  In a preferred embodiment of the gas barrier film of the present invention, the plastic film is made of polyethylene terephthalate.

  According to the present invention, since the plastic film is made of polyethylene terephthalate, the polyethylene terephthalate has a property of being easily crystallized, and this property becomes more obvious by reducing the amount of oligomer. As a result, the plastic film formed of polyethylene terephthalate with a reduced amount of oligomer tends to have a rough surface, and the significance of smoothing the surface with an organic layer increases.

  An apparatus of the present invention for solving the above problems is an apparatus using the gas barrier film of the present invention, wherein the apparatus is a display device or a power generation device.

According to this invention, it is an apparatus using the gas barrier film of the present invention, and since this apparatus is a display device or a power generation device, it is 10 ⁻² g / m ² · day level (0.01 g / m ² · The gas barrier film of the present invention is used for a display device or a power generation device that requires a high gas barrier property (day or less), and an apparatus using the gas barrier film having excellent gas barrier property can be provided.

The method for producing a gas barrier film of the present invention for solving the above-mentioned problems is a plastic film preparation step of preparing a plastic film having an oligomer amount of 1% by mass or less, a maximum height difference on the surface of the plastic film on the plastic film. An organic layer forming step of forming a thicker organic layer with an ultraviolet curable resin, and an inorganic layer forming step of forming an inorganic layer on the organic layer.

According to the present invention, a plastic film preparing step for preparing a plastic film having an oligomer amount of 1% by mass or less, and an organic layer thicker than the maximum height difference on the surface of the plastic film is formed on the plastic film with an ultraviolet curable resin . Since it has an organic layer forming step and an inorganic layer forming step for forming an inorganic layer on the organic layer, a reduction in the amount of oligomers in the plastic film facilitates the formation of an inorganic layer with good film quality and the formation of oligomers. Even if the maximum height difference on the surface of the plastic film increases due to the reduction in the amount, the organic layer formed by the UV-curing type tree covers the maximum height difference and is flattened, and an inorganic layer is formed on the flattened organic layer. A layer will be provided. As a result, a method for producing a gas barrier film capable of producing a gas barrier film having excellent gas barrier properties can be provided.

  According to the gas barrier film of the present invention, a gas barrier film having excellent gas barrier properties can be provided.

  According to the apparatus of the present invention, an apparatus using a gas barrier film having excellent gas barrier properties can be provided.

  According to the method for producing a gas barrier film of the present invention, a method for producing a gas barrier film capable of producing a gas barrier film having excellent gas barrier properties can be provided.

It is typical sectional drawing which shows an example of the gas barrier film of this invention. It is a graph which shows the relationship between the amount of oligomers contained in a plastic film, and water vapor transmission rate.

  Next, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

(Gas barrier film)
FIG. 1 is a schematic cross-sectional view showing an example of the gas barrier film of the present invention.

  The gas barrier film 1 has a plastic film 2 having an oligomer content of 1% by mass or less, an organic layer 3 provided on the plastic film 2, and an inorganic layer 4 provided on the organic layer 3. The thickness of the organic layer 3 is larger than the maximum height difference (not shown) on the surface of the plastic film 2. As a result, the inorganic layer 4 having good film quality is easily formed by reducing the amount of oligomer in the plastic film 2, and the organic layer 3 is formed even if the maximum height difference on the surface of the plastic film 1 is increased by reducing the amount of oligomer. Flattening is performed to cover the maximum height difference, and the inorganic layer 4 is provided on the flattened organic layer 3. As a result, the gas barrier film 1 that is particularly excellent in gas barrier properties can be provided. Hereinafter, each member which comprises the gas barrier film 1 is demonstrated.

  The amount of oligomer contained in the plastic film 2 is 1% by mass or less. From the viewpoint of better forming the inorganic layer 4, the oligomer amount is preferably 0.8% by mass or less, and more preferably 0.7% by mass or less. The plastic film 2 having a small amount of oligomer may be called a hydrolysis resistant film. If an oligomer is present in the plastic film 2, it is generated as a gas when the inorganic layer 4 is vacuum-deposited, so that the film formation is hindered, the film thickness of the inorganic layer 4 tends to be thin, and good film quality is difficult to obtain. Become. Therefore, in the present invention, by reducing the amount of oligomer, inhibition of the formation of the inorganic layer 4 is suppressed, and the thickness and film quality of the inorganic layer 4 are easily improved. The amount of oligomer contained is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. If the amount of oligomer is too small, the flexibility of the plastic film itself is lowered, which may make it difficult to apply to the roll process or cause a problem in the subsequent process.

  The oligomer contained in the plastic film 2 is a generic term for, for example, unreacted monomers, oligomers, and low molecular compounds such as reaction double products when forming the plastic film 2, and is not necessarily pure oligomers. It is not limited to. More specifically, all substances (substances contributing to weight reduction) detected as oligomer components by the oligomer content measurement method described later are oligomers as referred to in the present invention.

  The measurement of the content of the oligomer contained in the plastic film 2 can include various methods. Preferably, the plastic film as a sample is immersed in heated xylene for 24 hours, and the weight of the sample is changed. And a method of measuring oligomer components extracted into xylene. More specifically, the method described in JP-A-11-288622 may be used. That is, 16 film samples cut into 50 mm squares are dried in a hot air oven at 140 ° C. for 2 hours, and the weight (weight before extraction) is measured. It is then extracted with boiling xylene (500 ml) for 24 hours using a Soxhlet extractor. The extracted sample is taken out and washed for 6 minutes with an ultrasonic cleaner containing water three times, and lightly wipes off xylene adhering to the surface with gauze. The sample extracted at the end was dried in a hot air oven at 160 ° C. for 8 hours, the weight (weight after extraction) was measured, and the amount of oligomer was determined as follows: “Oligomer amount (%) = 100 × (weight before extraction−weight after extraction) ) / Weight before extraction ”.

  The material of the plastic film 2 is not particularly limited as long as it is plastic. As a material of the plastic film 2, a polyester resin can be preferably mentioned from the viewpoint of versatility and industrial property. Examples of such polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and copolymers thereof, polycyclohexanedimethylene terephthalate (PCT). Among the polyester resins, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and copolymers thereof are preferable, polyethylene terephthalate and copolymers thereof are more preferable, and polyethylene terephthalate is particularly preferable. That is, the material of the plastic film 2 is particularly preferably polyethylene terephthalate. Polyethylene terephthalate has the property of being easily crystallized, and this property becomes more apparent by reducing the amount of oligomers. As a result, the plastic film 2 formed of polyethylene terephthalate with a reduced amount of oligomer tends to have a rough surface, and the significance of smoothing the surface with the organic layer 3 increases.

  Specific examples of polyethylene terephthalate with a reduced amount of oligomer include, for example, X10S (trade name) manufactured by Toray Industries, Inc., VN, VW, VK (all trade names) manufactured by Teijin DuPont Films, Ltd., and Mitsubishi Plastics, Inc. P100 (product name) made by the company, etc. can be mentioned.

  The thickness of the plastic film 2 is not particularly limited as long as a predetermined rigidity can be imparted to the gas barrier film 1, and is usually 10 μm or more, preferably 50 μm or more, and usually 5 mm or less, preferably 3 mm or less. The thickness is preferably 1 mm or less, more preferably 500 μm or less, and particularly preferably 300 μm or less. When the thickness of the plastic film 2 is 300 μm or less, the unevenness of the thickness is easily reduced when the plastic film 2 is stretched in the film forming process of the plastic film preparation process. Further, when the thickness of the plastic film 2 is 300 μm or less, the rigidity is lowered, and the inorganic layer 4 is cracked or scratched when the inorganic layer 4 is formed in a roll-to-roll method and then wound into a roll shape. Less likely to occur. Further, when the gas barrier film 1 is used as a back surface protection sheet for a solar cell module, the market demand for low-priced products is particularly strong. If the thickness of the plastic film 2 is 300 μm or less, It is also possible to reduce costs by reducing the amount used.

  The thickness of the plastic film can be evaluated by measuring the thickness at the time of acquisition. On the other hand, the thickness of the plastic film after the gas barrier film was formed was processed by a focused ion beam processing apparatus (FIB: Hitachi, FB-2000) to expose the cross section of the plastic film. Then, it can measure by observing the cross section with a scanning electron microscope (SEM: Hitachi Ltd. make, S-5000H, acceleration voltage 1.5kV). At this time, arbitrary six places on the cross section of the plastic film are measured, and an average value is adopted.

  Although not shown in FIG. 1, the plastic film 2 has a rough surface due to the reduced amount of oligomer. The mechanism by which the unevenness of the surface of the plastic film 2 is increased by reducing the amount of oligomer in the plastic film 2 is not clear, but the plastic film 2 having a large surface unevenness tends to be whitened. As expected.

  The phenomenon that the plastic film 2 is whitened is considered to occur because the molecular chain in the plastic film 2 is partially crystallized and the refractive index of light of the crystal part is different from that of the amorphous part. And it is thought that the crystal | crystallization part becomes convex shape or a concave shape by this crystal | crystallization part growing etc., and surface unevenness | corrugation is induced. Here, the ease of crystallization varies depending on the molecular shape of the polymer constituting the plastic film 2. Molecular structures are simple and regular ones are easy to crystallize. For example, when a polyethylene terephthalate plastic film 2 is used, the polyethylene terephthalate belongs to a crystalline plastic and originally has a property of being easily crystallized. For this reason, the transparent polyethylene terephthalate film is devised at the time of film molding. For example, the amorphous polyethylene terephthalate film is obtained by rapidly cooling after setting the temperature to the melting point or higher. Thus, since the polyethylene terephthalate itself has the property of being easily crystallized, it is considered that the plastic film 2 formed of polyethylene terephthalate with a reduced amount of oligomer is more easily crystallized. This is because it is considered that regularity is improved together with the resin composition purity by reducing the amount of unreacted components such as oligomers, and the characteristics of the original crystalline plastic are more easily expressed. In other words, in order to reduce the amount of oligomers, the polyethylene terephthalate pellets once obtained are often further treated by a method such as solid phase polymerization to reduce unreacted components, so the resin composition purity It is considered that regularity is improved and crystallization, that is, whitening easily occurs.

  As described above, since the amount of oligomer is reduced, the plastic film 2 has a predetermined surface roughness. Further, the surface roughness of the plastic film 2 has a relationship that is substantially proportional to the thickness of the plastic film 2. Specifically, as the thickness of the plastic film 2 increases, the maximum height difference between the peaks and valleys on the surface of the plastic film 2 tends to increase. Considering these points, the maximum height difference of the peaks and valleys on the surface of the plastic film 2 is usually 0.7 μm or more and 5 μm or less. For example, as will be described later in the examples, in the plastic film 2 having a thickness of 300 μm or less, the maximum height difference is 1.6 μm at the maximum, so that the thickness of the organic layer 3 is set to 1.7 μm or more. It is preferable.

  The measurement of the maximum height difference as the surface roughness is, for example, 0.13 mm × 0.17 mm using a surface shape measuring device (SP-500 manufactured by Toray Engineering Co., Ltd.) with a lens magnification of 50 times and a resolution of 1376 × 1040 pixels. The range may be measured, and the difference between the maximum value and the minimum value may be evaluated as the maximum height difference. On the other hand, the measurement of the maximum height difference as the surface roughness of the plastic film after constituting the gas barrier film is performed by processing the gas barrier film with a focused ion beam processing apparatus (FIB: Hitachi, FB-2000), After the section of the plastic film is exposed, the section may be observed with a scanning electron microscope (SEM: manufactured by Hitachi, S-5000H, acceleration voltage 1.5 kV). Measure any six points on the cross section of the plastic film, and adopt the maximum height difference value.

  The surface of the plastic film 2 may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, heat treatment, chemical treatment, and easy adhesion treatment. As a specific method of such surface treatment, a conventionally known method can be appropriately used.

  The manufacturing method of the plastic film 2, specifically, the manufacturing method of the plastic film 2 containing a predetermined oligomer amount will be described later.

  The organic layer 3 is formed so as to cover the surface roughness of the plastic film 2. That is, the organic layer 3 is formed so that the thickness is larger than the maximum height difference on the surface of the plastic film 2.

  The material constituting the organic layer 3 is not particularly limited as long as it is an organic material, and examples thereof include a thermosetting resin and an ultraviolet curable resin. Among these, in view of industrial productivity, it is preferable to use an ultraviolet curable resin. That is, since the thermosetting resin requires heating at, for example, about 160 ° C. for curing, it is necessary to use the plastic film 2 having heat resistance, and the selection of the material of the plastic film 2 is slightly narrowed. In addition, since the thermosetting resin requires a certain curing time (for example, about 30 minutes), it may be difficult to secure a sufficient drying time in a roll-to-roll production process. In this case, in order to cure more reliably, it may be put into a heating oven in a state of being wound on a roll. However, since it is in a wound state wound on a roll, there are blocking problems and the outside of the roll and the vicinity of the center of the roll. And uneven curing tends to occur. On the other hand, the UV curable resin can be sufficiently cured by irradiating with the necessary exposure amount, so that the curing can be completed in a short time, and a good organic layer 3 is formed on the plastic film 2 for industrial production. It becomes easy.

  When the organic layer 3 is composed of an ultraviolet curable resin, the organic layer 3 is formed by applying an ultraviolet curable resin composition on the plastic film 2 and irradiating the coating film with ultraviolet rays to cure the ultraviolet curable resin. A film is formed. Although the detail about the formation method of the organic layer 3 is mentioned later, the material used for an ultraviolet curable resin composition is demonstrated below.

  Although there is no restriction | limiting in particular in the ultraviolet curable resin composition used for formation of the organic layer 3, It is preferable to use resin which has an acrylic monomer as a main component. Specific examples of the resin mainly composed of an acrylic monomer include those having an acrylate functional group, such as a polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal having a relatively low molecular weight. Examples include oligomers or prepolymers such as resins, polybutadiene resins, polythiol polyene resins, (meth) acrylates of polyfunctional compounds such as polyhydric alcohols, and reactive diluents. Specific examples thereof include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone, and polyfunctional monomers such as polymethylolpropane tri (meth) acrylate. , Hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, and the like. In this specification, “(meth) acrylate” means acrylate or methacrylate.

  The ultraviolet curable resin composition used for forming the organic layer 3 further includes acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthones, and photopolymerization initiators. As a sensitizer, n-butylamine, triethylamine, tri-n-butylphosphine, or the like can be mixed and used. There is no restriction | limiting in particular in content of the polymerization initiator and photosensitizer in an ultraviolet curable resin composition, What is necessary is just a content which is a grade with which favorable hardening is performed. In addition, the ultraviolet curable resin composition may contain a solvent such as toluene or methyl ethyl ketone from the viewpoint of adjusting the viscosity of the coating solution. These solvents may be mixed and used at an arbitrary ratio within the scope of the gist of the present invention.

  The thickness of the organic layer 3 is preferably 1.7 μm or more and 10 μm or less. Thereby, the maximum height difference on the surface of the plastic film 2 is more reliably covered with the organic layer 3, and the gas barrier property of the gas barrier film 1 can be easily improved more reliably. For example, as will be described later in the examples, in the plastic film 2 having a thickness of 300 μm or less, the maximum height difference is 1.6 μm at the maximum, so that the thickness of the organic layer 3 is set to 1.7 μm or more. It is preferable. For example, when the organic layer 3 is an ultraviolet curable resin layer formed of an ultraviolet curable resin, the thickness is preferably greater than or equal to the maximum height difference of the plastic film 2 and the upper limit may be 10 μm or less. . The thickness of the organic layer 3 is determined by processing the gas barrier film 1 with a focused ion beam processing apparatus (FIB: FB-2000 manufactured by Hitachi, Ltd.) to expose the cross section of the organic layer, and then scanning the cross section with the scanning electron. It can be measured by observing with a microscope (SEM: manufactured by Hitachi, S-5000H, acceleration voltage 1.5 kV). At this time, arbitrary six places on the cross section of the organic layer are measured, and an average value is adopted.

  If the thickness of the organic layer 3 is smaller than the maximum height difference of the surface roughness of the plastic film 2, the surface of the plastic film 2 cannot be sufficiently flattened, and the plastic film 2 cannot be completely covered. It becomes difficult to form the inorganic layer 4 uniformly on the entire surface of the layer 3, and the gas barrier property of the portion where the inorganic layer is not formed tends to be insufficient. From such a viewpoint, it is preferable that the thickness of the organic layer 3 is 1.7 μm or more. On the other hand, considering the occurrence of curling of the plastic film 2 and cracking of the organic layer 3, the thickness of the organic layer 3 is preferably 10 μm or less.

  The inorganic layer 4 is formed as a layer that blocks gas such as water vapor. The material for forming the inorganic layer 4 is not particularly limited as long as it is an inorganic compound. For example, a metal, an inorganic oxide, an inorganic oxynitride, an inorganic nitride, an inorganic oxide carbide, an inorganic oxycarbonitride, or the like can be used. Can be mentioned. The inorganic layer 4 may be used by mixing the above materials at an arbitrary ratio within the scope of the present invention. If a thin film is formed from these materials, it is easy to block the permeation of water vapor and the permeation of oxygen, so that a gas barrier function can be effectively provided.

  More specifically, the inorganic compound constituting the inorganic layer 4 contains one or more selected from silicon, aluminum, magnesium, titanium, tin, indium, or cerium from the viewpoint of gas barrier properties. It is preferable. More specifically, from the viewpoint of gas barrier properties, as the inorganic oxide, for example, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, or indium alloy oxide is preferable. As the nitride, silicon oxynitride is preferable, as the inorganic nitride, silicon nitride, aluminum nitride, or titanium nitride is preferable, and as the metal of the substrate thin film, aluminum, silver, tin, chromium, Nickel or titanium is preferred. The inorganic layer 4 may be used by mixing the above materials at an arbitrary ratio within the scope of the present invention.

  The thickness of the inorganic layer 4 varies depending on the inorganic compound used, but is usually 5 nm or more, preferably 10 nm or more, from the viewpoint of ensuring gas barrier properties. Further, the thickness of the inorganic layer 4 is usually 5000 nm or less, preferably 500 nm or less, more preferably 300 nm or less, from the viewpoint of suppressing the occurrence of cracks and the like. The inorganic layer 4 is not necessarily limited to a single layer, and may be a laminate of two or more layers. In this case, the same materials may be combined or different materials may be combined. Good.

  Details of the method of forming the inorganic layer 4 will be described later.

  As described above, the gas barrier film 1 is formed of the plastic film 2, the organic layer 3, and the inorganic layer 4, and other layers are appropriately disposed between the plastic film 2, the organic layer 3, and the inorganic layer 4. It may be inserted, laminated on the surface of the plastic film 2 where the organic layer 3 is not formed, or laminated on the inorganic layer 4. Examples of such an optional layer include a primer layer and an overcoat layer. A conventionally well-known thing can be used suitably for such a primer layer and an overcoat layer.

The gas barrier film 1 includes a plastic film 2 with a reduced amount of oligomer, an organic layer 3 having a thickness that covers the maximum height difference on the surface of the plastic film 2, and an inorganic layer 4 that contributes to gas barrier properties. Therefore, a high gas barrier property is achieved. Specifically, a high gas barrier property of 10 ⁻² g / m ² · day level (0.01 g / m ² · day or less) can be achieved. The gas barrier property can be evaluated by, for example, measuring a water vapor transmission rate. As a measurement method, for example, a water vapor transmission rate measuring device under the conditions of measurement temperature: 37.8 ° C. and humidity: 100% RH (Method of measurement using MOCON, trade name: AQUATRAN).

(apparatus)
The device of the present invention is a device using the gas barrier film of the present invention described above, and is a display device or a power generation device. As a result, the gas barrier film of the present invention is used for a display device or a power generation device that requires a high gas barrier property of 10 ⁻² g / m ² · day level (0.01 g / m ² · day or less). Thus, an apparatus using a gas barrier film having excellent gas barrier properties can be provided.

  The display device has a property that display performance deteriorates due to intrusion of water vapor or the like, and it is necessary to use a gas barrier film. Examples of such a display device include a liquid crystal display device and an organic EL display device. The liquid crystal display device and the organic EL display device may appropriately use a conventionally known configuration, and may be appropriately sealed by a gas barrier film using a conventionally known method.

  The power generation device has a property that power generation performance deteriorates due to intrusion of water vapor or the like, and it is necessary to use a gas barrier film. Examples of such a power generation device include a solar cell device (solar cell module). A conventionally well-known structure can be used suitably for a solar cell apparatus, and the sealing by a gas barrier film should just use a conventionally well-known method suitably. More specifically, the gas barrier film is usually used as a back surface protection sheet of a solar cell device. This is because the back protective sheet is required to have a gas barrier property for blocking the entry of water vapor (moisture) and oxygen from the outside. When the gas barrier property is insufficient, the output of the solar cell may decrease, for example, the filler constituting the solar cell device may be peeled off or discolored due to permeation of water vapor (moisture), or the wiring may be corroded. Therefore, the significance of using the gas barrier film of the present invention having particularly excellent gas barrier properties is great.

  There is another advantage of using the gas barrier film of the present invention in a power generation device, more specifically in a solar cell device. That is, since the gas barrier film of the present invention reduces the amount of oligomer of the plastic film, it may be whitened by the formation of partial crystals that cause surface irregularities. By such whitening, the sunlight irradiated to the solar cell device is irregularly reflected, the irradiation efficiency is improved, and the power generation efficiency of the solar cell device tends to be improved. From such a standpoint, the gas barrier film of the present invention is preferably used for a power generation device represented by a solar cell device.

(Method for producing gas barrier film)
In the method for producing a gas barrier film of the present invention, a plastic film preparing step of preparing a plastic film having an oligomer amount of 1% by mass or less, and an organic layer thicker than the maximum height difference on the surface of the plastic film is formed on the plastic film. An organic layer forming step, and an inorganic layer forming step of forming an inorganic layer on the organic layer. This makes it easier to form an inorganic layer with good film quality by reducing the amount of oligomer in the plastic film, and even if the maximum height difference on the surface of the plastic film is increased by reducing the amount of oligomer, the organic layer has this maximum height difference. Is flattened, and an inorganic layer is provided on the flattened organic layer. As a result, a method for producing a gas barrier film capable of producing a gas barrier film having excellent gas barrier properties can be provided. Hereinafter, each step will be described.

  First, the plastic film preparation process will be described.

  The plastic film preparation step is a step of preparing a plastic film having an oligomer amount of 1% by mass or less. More specifically, in the plastic film preparation step, the predetermined plastic film is manufactured and prepared, or the predetermined plastic film is manufactured by a film maker and the like is purchased and prepared. Done. A method for producing a plastic film with a reduced amount of oligomer is not particularly limited. For example, when a thermoplastic resin typified by a polyester resin is used as the material of the plastic film, the following steps may be performed. Specifically, after the step of reducing oligomer components such as a thermoplastic resin (oligomer component reduction step), a step of forming the film by melting the thermoplastic resin (film forming step) may be performed. Hereinafter, the said oligomer component reduction process and a film formation process are demonstrated.

The raw material used for the oligomer component reduction step is formed from a thermoplastic resin. Here, an antimony compound such as antimony trioxide Sb ₂ O ₃ is usually used as a polymerization catalyst for synthesizing this thermoplastic resin. From the viewpoint that the raw material obtained from the low regeneration rate of the oligomer, the magnitude of the catalyst deactivation effect, etc. is likely to be low oligomer, the polymerization catalyst is at least selected from Ge, Ti, Co, Zn, Al It is preferable to use a catalyst containing one kind of compound such as germanium oxide or titanium oxide.

  The repeating unit of the raw material thermoplastic resin used in the oligomer component reducing step is preferably 80 or more, and more preferably 120 or more. Further, the intrinsic viscosity of the thermoplastic resin is preferably 0.5 (dl / g) or more, more preferably 0.6 (dl / g) or more as a measured value in orthochlorophenol (OCP), It is particularly preferable to set it to 0.7 (dl / g) or more in which oligomer components are reduced by polymerization.

  In the oligomer component reduction step, the raw material prepared as described above is used in a pellet form or a powder form. More specifically, the raw material may be in the form of a 2 to 4 mm square pellet, but in order to reduce the specific surface area and more easily remove the oligomer component, it is 1 μm or more, 1 mm It is preferable to use a raw material having a large specific surface area such as the following powder. By using such a powdery raw material, the processing time for reducing / removing the oligomer component tends to be shortened, and the extraction efficiency can be easily improved. When the raw material is used in the form of powder, the average particle diameter of the powder is preferably as fine as possible from the point of extraction of the oligomer, and in terms of handleability, it is preferable to set it as 10 μm or more and 500 μm or less from the viewpoint that the rougher is easier to handle. More preferred. The measurement of the average particle diameter when the raw material is used as a powder is not particularly limited, but the static scattering method using an argon laser or a helium laser can be exemplified as the most practical measurement method. Further, there is no particular limitation on the pulverization method used for pulverizing the pellet-form raw material to obtain a powder-form raw material, but usually a cooling pulverization method (freezing pulverization method) is used. As the freeze pulverization method, for example, a known colloid mill, jet pulverizer, ball mill, roll mill, impact fine pulverizer, etc. may be used alone or in combination as appropriate.

  In the oligomer component reduction step, removal of the oligomer component from the raw material is attempted. The method for reducing and removing the oligomer component is not particularly limited, but it is preferable to treat the prepared raw material in a supercritical gas state from the viewpoint of reducing the environmental load while improving the production efficiency. Since supercritical gas is a good solvent for oligomers, the amount of oligomer can be reduced by treatment in supercritical gas. Here, the supercritical state refers to a state having both gas-like diffusion performance and liquid-like extraction performance at a certain temperature or higher and a certain pressure or higher. In the case of carbon dioxide, the supercritical state is 72 at 31.3 ° C. or higher. It becomes a supercritical gas state at 9 atmospheres or more. The gas to be used is not particularly limited, but those having a critical temperature of 300 ° C. or lower and a critical pressure of 500 atm or lower are preferable. For example, carbon monoxide, carbon dioxide, ammonia, nitrogen, water, methanol, ethanol, ethane, propane , Butane, benzene, diethyl ether and the like. Of these gases, carbon dioxide and ethane are preferred in that the supercritical temperature is low.

  In the oligomer component reduction step, as described above, the supercritical gas functions as a good solvent for the oligomer, but the oligomer can be further extracted by coexisting the supercritical gas and the raw material together with an entrainer that does not dissolve the thermoplastic resin. It becomes easy to perform well. Although there is no restriction | limiting in particular as an entrainer to be used, What is necessary is just to select suitably according to the thermoplastic resin to be used. For example, in the case of a polyethylene terephthalate resin, it is preferable to use halogenated hydrocarbons such as chloroform; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as dioxane and tetrahydrofuran as the entrainer. Among these entrainers, it is more preferable to use dioxane from the viewpoints of improvement of production efficiency, reduction of environmental load, ease of handling, and the like. The mixing ratio of the entrainer is not particularly limited, but is preferably 10% or more with respect to the supercritical gas from the viewpoint of better oligomer extraction.

  When a supercritical gas is used in the oligomer component reduction step, the processing temperature is set to a supercritical temperature or higher. Here, when the raw material to be used is a thermoplastic resin, from the viewpoint of easy handling of the raw material, the processing temperature is set to a supercritical temperature or higher, and the thermoplastic resin has a melting point Tm or lower and a glass transition temperature Tg or higher. It is preferable to do. In addition, the system pressure in the case of using a supercritical gas may be not less than the critical pressure, but it is preferable to perform the treatment at as high a pressure as possible from the viewpoint of improving the extraction rate. For example, when carbon dioxide is used as the gas, it may be about 100 atm, but is preferably 300 atm or more, and more preferably 400 atm or more. With such a range, the extraction speed can be easily increased. The treatment time with the supercritical gas depends on the amount of extraction, but considering industrial production, it is set to 1 hour or more and 10 hours or less.

  When processing with supercritical gas in the oligomer component reduction process, this supercritical gas processing may use a closed processing system, and a system that can continuously input and discharge raw materials, supercritical gas, etc. The processing apparatus may be used. From the standpoint of facilitating good industrial production, it is preferable to perform the treatment in a system in which raw materials and supercritical gas can be continuously charged and discharged. More specifically, the resin raw material can be continuously charged and discharged into the treatment kettle, and the extracted gas is discharged from the treatment kettle while supplying fresh supercritical gas and entrainer mixed gas. After the oligomer is recovered and purified, it is preferable to use a circulation type processing apparatus that is used as a supercritical gas.

  In the film forming step, the resin with a low oligomer content obtained in the oligomer component reducing step is dehydrated, dried and heat-treated as necessary, and then usually melt-formed (melt-extruded) at a melting point Tm or higher of the resin. To form a plastic film. Here, melt extrusion can use arbitrary extruders, such as a uniaxial, a biaxial vent, and a tandem extruder, for example. Also, the base can be of any shape such as a ring die, a T die, a coat hanger die, a fishtail die, and an L die. In the melt extrusion, from the viewpoint of removing foreign substances in the molten raw material, the molten resin is usually extruded while filtering an appropriate filter, for example, a sintered metal, a porous ceramic, sand, a wire mesh, and the like.

  In the film forming step, it is preferable to extrude the molten resin sheet from the base in the vertical direction from the viewpoint of eliminating the base stripes and stable casting, and it is more preferable that the base land direction is also in the vertical direction. Further, the positional relationship between the base and the cast drum is not particularly limited. However, the base is located on the top of the casting drum, and the vertical direction is more tangential to the drum than the top of the casting drum. The position is preferable for thickness uniformity, surface no defect, and the like. For this purpose, the shape of the mouthpiece is preferably a tip type with a sharp tip. The draft ratio when extruding the molten sheet from the die (= the gap between the die lip / the thickness of the extruded sheet) should be 3 or more from the viewpoint that the thickness unevenness is small and a sheet with good flatness can be easily obtained. Is preferably 5 or more, more preferably 20 or less.

  In the film forming step, it is preferable to subsequently stretch the extruded plastic film having a small amount of oligomer component to about 1.5 to 7 times by heating to a Tg or higher using a roll in a roll type longitudinal stretching machine. Next, the sheet is guided to a tenter-type width direction stretching machine for stretching in the width direction, grips both ends of the sheet with a clip, heats the sheet to a Tg or more with hot air, and widens the width of the both end clips to extend the sheet in the lateral direction (width direction). It is also preferable that the film is stretched 2 to 8 times. Further, in order to obtain a sheet having a strong strength in the longitudinal direction, it may be roll-stretched again in the longitudinal direction. Of course, simultaneous biaxial stretching in which the longitudinal direction and the width direction are simultaneously stretched may be performed.

  Next, an organic layer formation process is demonstrated.

  The organic layer forming step is a step of forming an organic layer thicker than the maximum height difference on the surface of the plastic film on the plastic film. The organic layer is preferably formed using an ultraviolet curable resin. The advantage of using the ultraviolet curable resin is that the thermal load on the plastic film during the formation of the organic layer can be reduced as compared with the thermosetting resin, so that the room for selecting the material of the plastic film is widened. In addition, when the organic layer is formed by a roll-to-roll method, the thermosetting resin needs to be further dried after being wound on a roll, and the phenomenon that the organic layer tends to block easily occurs. The occurrence of the above phenomenon can be suppressed in the curable resin. Further, when a thermosetting resin is used, uneven curing tends to occur between the organic layer near the center of the roll and the organic layer near the outside of the roll by the further drying, but an ultraviolet curable resin is used. This makes it easier to control this trend.

  In the organic layer forming step, when an ultraviolet curable resin is used for the organic layer, the ultraviolet curable resin composition is applied on a plastic film, and the coating is irradiated with ultraviolet rays to cure the ultraviolet curable resin. A layer is formed. Here, as the ultraviolet curable resin composition, what is described in the explanation section of the “gas barrier film” may be used, and therefore, the explanation here is omitted to avoid duplication of explanation.

  In the organic layer forming step, the method for applying the ultraviolet curable resin composition is not particularly limited. For example, the roll coating method, the gravure roll coating method, the kiss roll coating method, the reverse roll coating method, the Miya bar coating method. Commonly used coating methods such as a gravure coating method, a spin coating method, and a die coating method can be used.

  In the organic layer forming step, after the ultraviolet curable resin composition is applied on a plastic film, drying is performed as necessary, and ultraviolet curing is further performed. The drying temperature may be room temperature, but when the ultraviolet curable resin composition contains a solvent, it is preferably performed at a temperature equal to or higher than the boiling point of the solvent. Moreover, what is necessary is just to adjust drying time suitably from the viewpoint of removing the solvent contained as needed reliably, considering industrial productivity. Ultraviolet curing may be performed by irradiating ultraviolet rays from an ultraviolet source. Specific examples of the ultraviolet light source in this case include light sources such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp. As the wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm can be used. What is necessary is just to adjust suitably the time which irradiates an ultraviolet-ray from the viewpoint which carries out reliable hardening of an organic layer, considering industrial productivity.

  Next, the inorganic layer forming step will be described.

  The inorganic layer forming step is a step of forming an inorganic layer on the organic layer. Since the material used for the inorganic layer may be the same as that described in the explanation section of the above “gas barrier film”, the explanation here is omitted to avoid duplication of explanation.

  In the inorganic layer forming step, the predetermined material described above is deposited on the organic layer to form the inorganic layer. The method for forming such an inorganic layer is not particularly limited, but from the viewpoint of industrial productivity, for example, physical vapor deposition methods such as vacuum deposition, sputtering, ion plating, etc. (Physical Vapor Deposition method) and plasma The chemical vapor deposition method (Chemical Vapor Deposition method) etc. can be mentioned preferably. The film forming conditions in these various forming methods may be adjusted by appropriately adjusting conventionally known film forming conditions in consideration of the physical properties and thickness of the inorganic layer to be obtained.

  More specifically, the formation of the inorganic layer in the inorganic layer forming step is a vacuum deposition in which an inorganic oxide, an inorganic nitride, an inorganic oxynitride, or a metal is used as a raw material, and these are heated to be deposited on a substrate. The law can be mentioned. Further, an oxidation reaction vapor deposition method in which oxygen gas is introduced into the raw material to be oxidized and vapor-deposited on a base material can be exemplified. Furthermore, the sputtering method which vapor-deposits on a base material can be mentioned by using the said raw material as a target raw material, introducing argon gas and oxygen gas, and sputtering. Then, an ion plating method in which the raw material is heated by a plasma beam generated by a plasma gun and deposited on a substrate can be used. Further, when a silicon oxide vapor deposition film is formed, a plasma chemical vapor deposition method using an organic silicon compound as a raw material can also be used.

  Although the manufacturing method of the gas barrier film of this invention is comprised from a plastic film preparatory process, an organic layer formation process, and an inorganic layer formation process, you may perform processes other than these. Examples of such a process include a primer layer forming process and an overcoat layer forming process. These various steps may be performed by appropriately using conventionally known methods.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

(Example 1)
<Plastic film preparation process>
First, a 50 μm-thick polyester film (PET film, trade name: Lumirror X10S (Lumirror is a registered trademark), oligomer amount: 0.65 mass%) manufactured by Toray Industries, Inc. was used as a plastic film. Here, the amount of oligomer (the amount of oligomer) is based on the website of Toray Industries, Inc. (http://www.toray.jp/films/properties/luminor/lum_x10s.html). On the same homepage, the analysis of the oligomer is described as “xylene 24HR”, which is considered to have been performed in accordance with the following method described in the patent publication of Toray Industries, Inc. (Japanese Patent Laid-Open No. 11-288622). First, 16 film samples cut into 50 mm squares are dried in a hot air oven at 140 ° C. for 2 hours, and the weight (weight before extraction) is measured. It is then extracted with boiling xylene (500 ml) for 24 hours using a Soxhlet extractor. Thereafter, the extracted sample is taken out and washed with an ultrasonic cleaner containing water for 6 minutes three times, and lightly wipes off xylene adhering to the surface with gauze. The sample extracted at the end was dried in a hot air oven at 160 ° C. for 8 hours, the weight (weight after extraction) was measured, and the amount of oligomer was determined as follows: “Oligomer amount (%) = 100 × (weight before extraction−weight after extraction) ) / Weight before extraction ".

  In addition, the amount of oligomers for each grade of each plastic film listed on the website of Toray Industries, Inc. (http://www.tour.jp/films/properties/luminor/lum_x10s.html) is shown in Table 1 below. copy.

  Further, the surface roughness (maximum height difference) of the surface of the plastic film was 0.13 mm × 0 under the conditions of a lens shape of 50 times and a resolution of 1376 × 1040 pixels using a surface shape measuring device (SP-500 manufactured by Toray Engineering). A range of .17 mm was measured, and the difference between the maximum value and the minimum value was evaluated as the maximum height difference. As a result, the maximum height difference of the plastic film was 1.3 μm. In addition, the measurement of the maximum height difference as the surface roughness of the plastic film after constituting the gas barrier film is performed by processing the gas barrier film with a focused ion beam processing apparatus (FIB: Hitachi, Ltd., FB-2000), After the section of the plastic film is exposed, the section may be observed with a scanning electron microscope (SEM: manufactured by Hitachi, S-5000H, acceleration voltage 1.5 kV). Measure any six points on the cross section of the plastic film, and adopt the maximum height difference value.

<Organic layer formation process>
On one side of this plastic film, an ultraviolet curable resin composition (ultraviolet curable organic layer ink) adjusted to the following composition was applied by die coating, dried at 120 ° C. for 2 minutes, and then with a wavelength of 260 nm to 400 nm. The organic layer having a thickness of 5 μm was formed by irradiating with ultraviolet rays under the condition of an integrated light quantity of 300 mJ / cm ^{2 in} the range. The thickness of the organic layer is determined by processing the gas barrier film with a focused ion beam processing apparatus (FIB: manufactured by Hitachi, Ltd., FB-2000) to expose the cross section of the organic layer, and then scanning the cross section with a scanning electron microscope. (SEM: manufactured by Hitachi, S-5000H, acceleration voltage 1.5 kV). At this time, arbitrary six places of the cross section of the organic layer were measured, and an average value was adopted.

-Composition of UV curable organic layer ink;
Polyester acrylate oligomer (Toagosei Co., Ltd., Aronix M-8060): 39 parts by weight Mixed solvent of toluene / methyl ethyl ketone (1/1): 60 parts by weight oligo [2-hydroxy-2-methyl- [1- (4 -Methylvinyl) phenyl] propanone] (photopolymerization initiator, manufactured by Lamberti, ESACURE ONE): 1 part by weight

<Inorganic layer forming step>
The inorganic layer was formed by a sputtering film formation method. Specifically, the plastic film on which the organic layer is formed is placed in a chamber of a batch type sputtering apparatus (SPF-530H, manufactured by Anerva Corporation) in a direction to form a film on the organic layer side, and silicon is used as a target material. As mounted. Here, the distance between the target and the plastic film on which the organic layer was formed was set to 50 mm. Nitrogen gas (manufactured by Taiyo Toyo Oxygen Co., Ltd., purity 99.9995% or more) and argon gas (manufactured by Taiyo Toyo Oxygen Co., Ltd., purity 99.9999% or more) were used as additive gases during film formation. The inside of the chamber was decompressed to an ultimate vacuum of 2.5 × 10 ⁻⁴ Pa with an oil rotary pump and a cryopump. Next, nitrogen gas was introduced into the chamber at a flow rate of 15 sccm, and argon gas was introduced at a flow rate of 20 sccm. Then, by controlling the degree of opening and closing of the valve between the vacuum pump and the chamber, the thickness of the organic layer is increased by an RF magnetron sputtering method with an input power of 1.2 kW while keeping the pressure in the chamber at 0.25 Pa. An 80 nm silicon oxynitride layer was formed. Note that sccm is an abbreviation for standard cubic centimeter per minute.

  The layer structure of the gas barrier film obtained as described above is polyester film (PET film) / ultraviolet curable organic layer / inorganic layer (silicon oxynitride layer). The water vapor permeability of this gas barrier film was measured by the following method. That is, it measured using the water-vapor-permeation rate measuring apparatus (The product made by MOCON, brand name: AQUATRAN) on the conditions of measurement temperature: 37.8 degreeC and humidity: 100% RH. The results are shown in Table-2.

  Although the thickness of the plastic film can be evaluated by the thickness data at the time of acquisition, the thickness of the plastic film after constituting the gas barrier film is determined by using a focused ion beam processing apparatus (FIB: manufactured by Hitachi, Ltd., FB-2000), the cross section of the plastic film was exposed, and then the cross section was measured by observing with a scanning electron microscope (SEM: Hitachi, S-5000H, acceleration voltage 1.5 kV). . At this time, arbitrary six places on the cross section of the plastic film were measured, and an average value was adopted.

(Example 2)
In the inorganic layer forming step, the gas barrier film was produced in the same manner as in Example 1 except that the inorganic layer was formed by an ion plating film forming method to obtain an inorganic layer having the following composition. Hereinafter, the inorganic layer forming step as a difference will be described.

Prior to the formation of the inorganic layer, the following ion source evaporation source material was prepared. That is, with respect to 100 parts by weight of Si ₃ N ₄ powder (made by high purity chemical, average particle size: 1 μm) as silicon nitride powder, zinc oxide (ZnO) powder (made by high purity chemical, particle size distribution meter) as conductive material -Average particle diameter measured by Coulter counter method: 0.5 μm, 30 parts by weight of volume resistivity measured by 4 probe method according to JIS-K7194 was added and mixed. Next, the raw material powder was rotated while dropping a 2% cellulose aqueous solution as a binder into the raw material powder to obtain a 10 mmφ spherical body. Thereafter, it was put in a baking furnace and held at 400 ° C. for 1 hour to obtain an evaporation source material for ion plating consisting of a lump having an average particle diameter of 7 mmφ. In addition, as a result of measuring the mass ratio of the obtained evaporation source material with an X-ray spectrometer (XPS / ESCA), the mass ratio of zinc oxide is 30 with respect to silicon dioxide 100, and the mixing ratio of the raw material powder and It was almost the same. Here, ESCA LAB220i-XL manufactured by VG Scientific was used as the X-ray spectroscopic analyzer.

The inorganic layer was formed by an ion plating film formation method. Specifically, in the same manner as in Example 1, a polyester film having a thickness of 50 μm (PET film, trade name: Lumirror X10S, oligomer amount: 0.65 mass%, manufactured by Toray Industries, Inc.) was used as the plastic film. An organic layer was formed on one side. And it set to the hollow cathode type | mold ion plating apparatus in the direction which forms a plastic film in the organic layer side. Next, the produced evaporation source material was put into a crucible in a hollow cathode type ion plating apparatus, and then evacuated. After the degree of vacuum reached 5 × 10 ⁻⁴ Pa, 15 sccm of argon gas was introduced into the plasma gun, and plasma with a current of 110 A and a voltage of 90 V was generated. Plasma was bent in a predetermined direction by maintaining the inside of the chamber at 1 × 10 ⁻³ Pa and a magnetic force, and the evaporation source material according to the present invention was irradiated. It was confirmed that the evaporation source material in the crucible sublimates through a molten state. Ion plating was performed for 5 seconds (evaporation rate: 360 nm / min) to deposit on the substrate, thereby forming a 30 nm thick SiNZnO layer.

  The layer structure of the gas barrier film obtained as described above is polyester film (PET film) / ultraviolet curable organic layer / inorganic layer (SiNZnO layer). The water vapor permeability of this gas barrier film was measured in the same manner as in Example 1. The results are shown in Table-2.

(Example 3)
In the inorganic layer forming step, a gas barrier film was produced in the same manner as in Example 1 except that the inorganic layer was formed by a vacuum vapor deposition film forming method to obtain an inorganic layer having the following composition. Hereinafter, the inorganic layer forming step as a difference will be described.

As in Example 1, a polyester film having a thickness of 50 μm (PET film, Toray Industries, Inc., trade name: Lumirror X10S, oligomer amount: 0.65 mass%) was used as a plastic film, and an organic layer was formed on one side of the plastic film. Formed. And it set to the vacuum evaporation apparatus in the direction which forms a plastic film in the organic layer side. Next, SiO was evaporated by a high-frequency heating method under a vacuum of 1.33 × 10 ⁻³ Pa using a vacuum deposition apparatus, and a SiOx (x = 1.7) layer having a thickness of 40 nm was formed on the organic layer. .

  The layer structure of the gas barrier film obtained as described above is polyester film (PET film) / ultraviolet curable organic layer / inorganic layer (SiOx (x = 1.7)). The water vapor permeability of this gas barrier film was measured in the same manner as in Example 1. The results are shown in Table-2.

Example 4
A gas barrier film was used in the same manner as in Example 1 except that a 125 μm thick polyester film (PET film, trade name: Lumirror X10S, oligomer amount: 0.53 mass%) was used as the plastic film. Manufactured. The amount of oligomer is the same as in Example 1 using data posted on the Toray Industries, Inc. website. Further, when the surface roughness of the plastic film was measured in the same manner as in Example 1, the maximum height difference was 1.5 μm. The water vapor permeability of the obtained gas barrier film was measured in the same manner as in Example 1. The results are shown in Table-2.

(Example 5)
A gas barrier film was obtained in the same manner as in Example 1 except that a 300 μm thick polyester film (PET film, trade name: Lumirror X10S, oligomer amount: 0.37% by mass) was used as the plastic film. Manufactured. The amount of oligomer is the same as in Example 1 using data posted on the Toray Industries, Inc. website. Further, when the surface roughness of the plastic film was measured in the same manner as in Example 1, the maximum height difference was 1.6 μm. The water vapor permeability of the obtained gas barrier film was measured in the same manner as in Example 1. The results are shown in Table-2.

(Example 6)
A gas barrier film was produced in the same manner as in Example 1 except that the thickness of the organic layer was 3 μm. The water vapor permeability of the obtained gas barrier film was measured in the same manner as in Example 1. The results are shown in Table-2.

(Example 7)
A gas barrier film was produced in the same manner as in Example 1 except that the thickness of the organic layer was 2.0 μm. The water vapor permeability of the obtained gas barrier film was measured in the same manner as in Example 1. The results are shown in Table-2.

(Example 8)
A gas barrier film was produced in the same manner as in Example 1 except that the thickness of the organic layer was 1.7 μm. The water vapor permeability of the obtained gas barrier film was measured in the same manner as in Example 1. The results are shown in Table-2.

(Comparative Example 1)
A gas barrier film was produced in the same manner as in Example 1 except that the organic layer was not formed. The water vapor permeability of the obtained gas barrier film was measured in the same manner as in Example 1. The results are shown in Table-2.

(Comparative Example 2)
A gas barrier film was produced in the same manner as in Example 1 except that the thickness of the organic layer was 1 μm. The water vapor permeability of the obtained gas barrier film was measured in the same manner as in Example 1. The results are shown in Table-2.

(Comparative Example 3)
Example except that a polyester film having a thickness of 50 μm (PET film, product name: Lumirror S10, oligomer amount: about 1.6% by mass, manufactured by Toray Industries, Inc.) was used as a plastic film in which the oligomer amount was not reduced. A gas barrier film was produced in the same manner as in Example 1. Similarly to Example 1, the amount of oligomer was obtained using data posted on the Toray Industries, Inc. website, and was further determined using the following method. That is, the Lumirror S10 describes that the amount of oligomer having a thickness of 250 μm (oligomer content) is 1.4% by mass. In Lumirror X10S, when the thickness is 250 μm to 50 μm, From 0.46% by mass to 0.65% by mass, it is increased by about 0.2% by mass. Therefore, it is considered that the amount of oligomer is about 0.2% by mass for Lumirror S10 having a thickness of 50 μm, and the amount of oligomer is set to 1.4 + 0.2 = 1.6% by mass. Moreover, when the surface roughness of the plastic film in which the oligomer amount was not reduced was measured in the same manner as in Example 1, the maximum height difference was 0.6 μm. The water vapor permeability of the obtained gas barrier film was measured in the same manner as in Example 1. The results are shown in Table-2.

FIG. 2 is a graph showing the relationship between the amount of oligomer contained in the plastic film and the water vapor transmission rate. Specifically, among the data shown in Table 2, per gas barrier film (Examples 1, 4 to 8, Comparative Example 3) in which the organic layer has a thickness of 5 μm and the inorganic layer is formed by a sputtering method. It is the graph which plotted the relationship between the amount of oligomers contained in a plastic film, and water vapor transmission rate. From FIG. 2, by setting the amount of oligomer contained in the plastic film to 1.0% by mass or less, the water vapor transmission rate is 10 ⁻² g / m ² / day level or less (0.01 g / m ² / day or less). It can be seen that a very high level of gas barrier properties can be achieved.

1 Gas barrier film 2 Plastic film 3 Organic layer 4 Inorganic layer

Claims (5)

A plastic film having an oligomer content of 1% by mass or less, an organic layer made of an ultraviolet curable resin provided on the plastic film, and an inorganic layer provided on the organic layer;
A gas barrier film, wherein the organic layer has a thickness greater than a maximum height difference on the surface of the plastic film. A plastic film having an oligomer content of 1% by mass or less, an organic layer made of an ultraviolet curable resin provided on the plastic film, and an inorganic layer provided on the organic layer;
A gas barrier film, wherein the organic layer has a thickness of 1.7 μm or more and 10 μm or less.   The gas barrier film according to claim 1 or 2, wherein a material of the plastic film is polyethylene terephthalate.   An apparatus using the gas barrier film according to claim 1, wherein the apparatus is a display device or a power generation device. A plastic film preparation step of preparing a plastic film having an oligomer amount of 1% by mass or less,
On the plastic film, an organic layer forming step of forming an organic layer thicker than the maximum height difference on the plastic film surface with an ultraviolet curable resin ,
An inorganic layer forming step of forming an inorganic layer on the organic layer. A method for producing a gas barrier film, comprising:

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