JP5895855B2 - Method for producing gas barrier film - Google Patents

Description

  The present invention relates to a method for producing a gas barrier film. More specifically, the present invention relates to a method for producing a gas barrier film having good gas barrier performance and high durability.

  Various studies have been made on a film having a property of blocking permeation of water vapor and oxygen, that is, a film having a so-called gas barrier property (hereinafter also referred to as “gas barrier film”). A gas barrier film generally has a thin film (gas barrier layer; hereinafter, also simply referred to as “barrier layer”) containing a metal oxide such as aluminum oxide, magnesium oxide or silicon oxide on the surface of a substrate or film made of a thermoplastic resin. It is formed. And such a gas barrier film is used in the application which wraps the goods which need interruption | blocking of various gas, in order to prevent the quality change by various gases, such as water vapor | steam and oxygen. In addition to the packaging applications described above, it is also used for sealing electronic devices such as solar cells, liquid crystal display elements, and organic EL elements in order to prevent deterioration due to various gases. The gas barrier film using a film as a base material is superior in flexibility compared to the case where a glass substrate is used as a base material, and is suitable for roll production, reducing the weight and handling of electronic devices. This is an advantage.

  As a method for producing such a gas barrier film, a barrier is mainly formed on a substrate such as a film by a thermal evaporation method, a plasma CVD method (Chemical Vapor Deposition), a sputtering method, or the like. A method of forming a layer is known (for example, Patent Document 1).

  Among these methods, a technique for producing a gas barrier film having a certain gas barrier property by cooling the substrate when a silicon oxide film is formed on the film substrate by a plasma CVD method has been proposed ( Patent Document 2).

JP 2011-116124 A JP 2008-274385 A

  Patent Document 2 discloses a technique of laminating a silicon oxide film in a state where a film that is a thermoplastic resin base material is in contact with a cooled main roll.

  However, the present inventors have found that even with the above technique, the gas barrier performance is still insufficient, and the durability of the gas barrier film is low.

  This invention is made | formed in view of the said situation, and it aims at providing the manufacturing method of the gas-barrier film which has favorable gas-barrier performance and high durability.

  As a result of intensive studies to solve the above problems, the present inventors have cooled the substrate immediately before forming the barrier layer to a predetermined temperature, and then formed the barrier layer by plasma CVD. It has been found that the above-mentioned problems can be solved by controlling the film forming roller temperature to be a predetermined value or higher, and the present invention has been completed.

  That is, the above objects are achieved by the following means.

  1. While conveying the base material containing the thermoplastic resin to the film forming roller, the step (1) of cooling the surface temperature (t1) of the base material to 10 ° C. or less using a cooling member, and the surface temperature (t2) are as follows: And a step (2) of forming a barrier layer on the substrate by a plasma CVD method using the film forming roller satisfying the relationship of the formula (1).

  2. Simultaneously with the step (1), the step (3) of forming an organic layer on the substrate is performed. The manufacturing method of the gas-barrier film of description.

  3. In the step (3), by forming a curable resin layer made of an electron beam curable resin material on the substrate disposed on the cooling member, and irradiating the curable resin layer with an electron beam Forming an organic layer; 2. The manufacturing method of the gas-barrier film of description.

  4). The barrier layer includes at least silicon, oxygen, and carbon. ~ 3. The manufacturing method of the gas-barrier film in any one of.

  5. In the step (1), the base material is wound so that the surface on which the barrier layer is formed is convex. ~ 4. The manufacturing method of the gas-barrier film in any one of.

  According to the present invention, it is possible to provide a method for producing a gas barrier film having good gas barrier properties and high durability.

It is a schematic diagram of the manufacturing apparatus used suitably for the manufacturing method of the gas barrier film which concerns on one Embodiment of this invention. It is a schematic diagram of the manufacturing apparatus used suitably for the manufacturing method of the gas barrier film which concerns on other embodiment of this invention.

The present invention relates to a method for producing a gas barrier film in which a barrier layer having gas barrier properties is formed on a substrate. In addition, about "gas barrier property" as used in the field of this invention, the water-vapor-permeability (water-vapor-permeability) (60 +/- 0.5 degreeC, relative humidity (90 +/- 2)% measured by the method based on JISK7129-1992. When RH) is 1 × 10 ⁻³ g / (m ² · 24 h) or less, it is defined as having gas barrier properties. Moreover, the oxygen permeability (oxygen permeability) measured by a method according to JIS K 7126-1987 of the gas barrier film is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less (1 atm is 1. 01325 × 10 ⁵ Pa).

  In the production method of the present invention, at least the step (1) for cooling the substrate and the step (2) for forming the barrier layer are performed in this order. Specifically, the present invention is a step (1) of cooling the surface temperature (t1) of the substrate to 10 ° C. or lower using a cooling member while conveying the substrate containing the thermoplastic resin to the film forming roller. And a step (2) of forming a barrier layer on the substrate by a plasma CVD method using the film-forming roller having a surface temperature (t2) satisfying the relationship of the following formula (1): It is a manufacturing method of a film.

  The manufacturing method of the present invention relates to a technique for forming a barrier layer by a roll-type plasma CVD method, and can be performed using, for example, a manufacturing apparatus as shown in FIG. In the present invention, a cooling member such as the cooling roller 51, film forming rollers 39 and 40, and optional transport rollers 33, 34, and 35 are used to transport the base material 2 and a barrier is formed by a plasma CVD method. Layer 3 is formed. Note that an organic layer (not shown) may be formed before the barrier layer 2 is formed.

  Thus, in this invention, the film-forming roller for conveying a base material and performing film-forming is used. At this time, in the step (1), the surface temperature (t1) of the substrate is cooled to 10 ° C. or less before the substrate is conveyed to the film forming roller. Subsequently, in the step (2), the barrier layer is formed after controlling the surface temperature (t2) of the film forming roller for forming the barrier layer to satisfy the relationship of the above formula (1).

  The present inventors have found that a gas barrier film having good gas barrier performance (for example, low water vapor transmission rate and oxygen transmission rate) and high durability can be obtained by the method for producing a gas barrier film through each of the above steps. It is up to the headline and the present invention.

  The mechanism for exerting the operational effects of the configuration of the present invention described above is presumed as follows.

  According to the present invention, since the substrate is cooled before the barrier layer is formed by the plasma CVD method, the following effects can be obtained. That is, as an effect of cooling, there is an effect that it is possible to suppress the diffusion of a low molecular component such as a plasticizer existing inside the thermoplastic resin base material, a monomer or an oligomer as a raw material of the base material to the base material surface. is there. A plasticizer is a compound that can be added to various thermoplastic resin base materials (plastic base materials) to give the base material flexibility or facilitate molding, for example, phthalic acid. Type, adipic acid type, phosphoric acid type, trimellitic acid type and the like. When these components are diffused and oriented on the substrate surface before laminating the barrier layer, the adhesion at the interface between the substrate and the barrier layer is lowered, and as a result, the durability of the gas barrier film is lowered. There is. Moreover, when a plasticizer, a raw material monomer, etc. diffuse to the substrate surface, the barrier performance under high temperature and high humidity storage may be greatly reduced. Therefore, by controlling the substrate temperature before forming the barrier layer below a predetermined temperature, diffusion of plasticizers, raw material monomers, etc. can be suppressed, and as a result, the above phenomenon can be suppressed. Can do.

  Moreover, the effect of improving the adhesiveness of a base material and a barrier layer is also acquired by cooling a base material. That is, since the stress difference between the base material and the barrier layer after the barrier layer is formed can be relaxed, the adhesion between the base material and the barrier layer is improved. As a result, a gas barrier film having high durability can be obtained.

  And according to this invention, it does not form a barrier layer continuously in the state which cooled the base material, but forms a barrier layer using the film-forming roller by which the surface temperature was controlled to predetermined temperature. (This is different from the technique described in Patent Document 2.) Therefore, the above effect can be obtained by cooling immediately before the formation of the barrier layer, and the barrier layer can be formed under conditions most suitable when the barrier layer is formed by the plasma CVD method. That is, if the cooling is continuously performed from before the formation of the barrier layer to after the formation, the above-described cooling effect can be obtained, but the plasma surface density near the substrate surface is lowered due to the low substrate surface temperature, and the dense barrier layer The conditions suitable for forming the film cannot be achieved, and the performance of the barrier layer decreases. On the other hand, according to the present invention, the temperature and further the transport speed of the substrate can be finely controlled independently of the cooling step so that the barrier layer becomes a film having a dense structure. As a result, the barrier property of the barrier layer itself is improved, and the barrier property of the entire gas barrier film can be improved. Therefore, according to the present invention, not only the above-described effects can be obtained by cooling the base material, but also a dense barrier layer that cannot be formed if the base material is excessively cooled at the time of forming the barrier layer. Thus, the gas barrier property can be improved. However, the above mechanism is estimation and does not limit the scope of the present invention.

  The method for producing a gas barrier film of the present invention may further include a step (3) of forming an organic layer disposed between the substrate and the barrier layer. As described above, by further including the step (3), in the obtained gas barrier film, the organic layer is interposed between the base material and the barrier layer, and as a result, the adhesion between the base material and the barrier layer. And the barrier performance can be improved.

  And such a process (3) may be performed before the said process (1), and may be performed simultaneously, but it is preferable to perform simultaneously from a viewpoint of improving gas barrier property. That is, it is preferable to perform the step (3) of forming an organic layer on the substrate simultaneously with the step (1).

  Thus, by performing the step (1) and the step (3) at the same time, the organic layer is formed in a state where the substrate is cooled, and the material of the organic layer is more easily adhered to the substrate. In addition, when an organic layer is formed by depositing a monomer as a material for the organic layer on the substrate and then polymerizing the monomer on the substrate, heat is generated with the polymerization reaction. Therefore, in order to prevent the thermoplastic resin base material from being damaged by the generated heat, it is preferable to perform the steps (1) and (3) at the same time and relax the heat transmitted to the base material.

<The manufacturing method of the gas-barrier film which concerns on one Embodiment>
In the method for producing a gas barrier film according to this embodiment, as described above, at least the step (1) of cooling the base material and the step (2) of forming a barrier layer, as well as the step of forming an organic layer ( 3) The step (4) of forming a bleed-out prevention layer and the step (5) of forming an anchor coat layer can also be optionally performed.

  Hereinafter, steps (1) to (5) will be described in detail with reference to FIG. FIG. 1 is a schematic view of a production apparatus suitably used in a method for producing a gas barrier film according to an embodiment of the present invention. The embodiments described below are provided with various technically preferable limitations for carrying out the present invention, but the scope of the invention is not limited to the following embodiments and illustrated examples.

  In the present specification, “X to Y” indicating a range means “X or more and Y or less”, and “weight” and “mass”, “wt%” and “mass%”, “part by weight” and “ “Part by mass” is treated as a synonym. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

[Step (1) (Substrate cooling step)]
In the step (1) in the present invention, the substrate is cooled before the barrier layer described in detail below is formed.

  The base material used in the present invention preferably contains a thermoplastic resin as a main component and has flexibility. More preferably, a base material made of a thermoplastic resin is used, and as such a base material, a plastic film or sheet is generally used, and a film or sheet made of a colorless and transparent resin is preferably used. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a barrier layer, an organic layer and the like, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring Film made of thermoplastic resin such as modified polycarbonate resin, fluorene ring modified polyester resin, acryloyl compound, silsesquioki having organic-inorganic hybrid structure Resistant transparent film was down a basic skeleton (product name Shirupurasu, manufactured by Nippon Steel Chemical Co., Ltd.), and further a resin film or the like formed by laminating the above-mentioned film material 2 or more layers and the like.

  More preferable specific examples of the thermoplastic resin that can be used as the substrate include, for example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyester (for example, Cosmo Shine (registered by Toyobo Co., Ltd.)) from the viewpoint of cost and availability. (Trademark) A4300), cycloaliphatic polyolefin (for example, ZEONOR (registered trademark) 1600 manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr), polyethersulfone (PES), polysulfone (PSF), cycloolefin copolymer (COC: special Compound described in Japanese Patent Application Laid-Open No. 2001-150584), polyimide (for example, Neoprim (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: compound described in Japanese Patent Application Laid-Open No. 2000-227603) ), Alicyclic-modified polycarbonate (IP-PC: compound described in 2000-227603 JP-), acryloyl compound (compound described in 2002-80616 JP-), and the like.

  When the gas barrier film produced according to the present invention is used as an electronic device such as an organic EL element, the plastic film is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do. However, even when the gas barrier film produced according to the present invention is used for display, transparency is not necessarily required when it is not installed on the observation side.

  The thickness of the plastic film used for the gas barrier film produced according to the present invention is not particularly limited because it is appropriately selected depending on the application, but is typically 1 to 800 μm, preferably 5 to 500 μm, more preferably. The thickness is 10 to 250 μm, more preferably 25 to 150 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. As the functional layer, besides those described above, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably employed.

  The substrate preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.

  In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

  The base material used in the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Further, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  It is preferable and necessary to perform various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, on at least the side of the substrate on which the barrier layer according to the present invention is provided. More preferably, the above processes are combined.

  Hereinafter, the preferable method of cooling the base material which concerns on the process (1) of this invention is demonstrated.

  As described in detail below, the gas barrier film according to the present invention preferably forms a barrier layer on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity. Further, an apparatus that can be used when the barrier layer is manufactured by the plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and between the pair of film forming rollers. It is preferable that the apparatus has a configuration capable of discharging. For example, when the manufacturing apparatus shown in FIG. 1 is used, it is possible to manufacture by a roll-to-roll method using the plasma CVD method. It becomes.

  The manufacturing apparatus 100 shown in FIG. 1 includes an unillustrated delivery roller, transport rollers 33, 34, and 35, a cooling roller 51, film forming rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and the like. The magnetic field generators 43 and 44 installed in the film forming rollers 39 and 40 and a winding roller (not shown) are provided. In the manufacturing apparatus 100 used in the present invention, the cooling roller 51 is disposed upstream of the film forming rollers 39 and 40 (upstream with respect to the direction in which the base material 2 is conveyed). The “direction in which the base material is conveyed” is indicated by an arrow in FIG.

  Further, in such a manufacturing apparatus 100, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are disposed in the vacuum chamber 10. . Further, in such a manufacturing apparatus 100, the vacuum chamber 10 is connected to a vacuum pump 11, which is a vacuum exhaust means, via an exhaust port 12, and the pressure in the vacuum chamber 10 is determined by the vacuum pump 11 and the gas supply pipe 41. Can be adjusted as appropriate. The vacuum pump 11 can evacuate the inside of the vacuum chamber 10 to a vacuum state or a low pressure state according to vacuum.

  The manufacturing apparatus 100 also has an organic material supply device 61 and an active energy ray irradiation device 62 used in the step (3), which are optional elements described in detail below, in the vacuum chamber 10.

  In the said manufacturing apparatus 100, a process (1) is performed when the base material 2 contact | abuts on the surface of the cylindrical cooling roller 51 as a cooling member, and, thereby, the base material 2 is cooled. In this step (1), the temperature of the cooling roller 51 is controlled so that the surface temperature (t1) of the base material is 10 ° C. or lower. More specifically, the surface temperature (t1) of the base material is the temperature of the base material at a point immediately before the base material 2 is detached from the cooling roller 51 (point A in FIG. 1). Since the cooling roller 51 has a width, more specifically, it indicates the temperature at the center point in the axial direction of the cooling roller 51 (the depth direction in FIG. 1) immediately before the base material 2 is detached from the cooling roller 51. . The surface temperature (t1) of this substrate is cooled to 10 ° C. or less, more preferably 0 ° C. or less, and still more preferably −10 ° C. or less by the cooling roll 51. In addition, the lower limit value of the surface temperature (t1) of the substrate is not particularly limited, but is preferably -80 ° C, more preferably -40 ° C.

  A specific method for cooling the surface temperature (t1) of the substrate to the above temperature will be described in detail below. As an example of the structure of the cooling roller 51, the surface is coated with titanium, stainless steel, chrome plating, cemented carbide, or the like, and the cooling roller 51 includes a mechanism capable of circulating a coolant. It is done. And by circulating a refrigerant | coolant through the inside, the surface temperature of the cooling roller 51 is 10 degrees C or less, More preferably, it is 0 degrees C or less, More preferably, it is cooled to -10 degrees C or less. The temperature of the cooling roller 51 depends on the material of the substrate 2 and the conveyance speed, but is preferably 2 to 3 ° C. lower than the surface temperature (t1) of the target substrate. In addition, the lower limit value of the surface temperature of the cooling roller 51 is not particularly limited, but is preferably −90 ° C., more preferably −50 ° C. As the refrigerant used at this time, known ones can be used. For example, alcohols such as methanol, ethanol and isopropyl alcohol, organic solvents such as acetone, and antifreeze solutions such as saline are used. Moreover, a well-known thing can be used as a mechanism which distribute | circulates a refrigerant | coolant.

  In order to set the surface temperature (t1) of the substrate within the above temperature range, a contact-type or non-contact-type temperature measuring means (not shown) is attached in the vicinity of the point A in FIG. The surface temperature (t1) of the base material is measured by measuring the surface temperature (t1) of the base material using this temperature measuring means, and the temperature of the refrigerant flowing through the cooling roller 51 is controlled from the measurement result. Adjusted appropriately.

  The cooling roller 51 may be disposed on the upstream side of the film forming roller 39 on the most upstream side with respect to the conveyance direction of the base material 2. At this time, the base material that contacts the cooling roller 51 However, it is preferable that the cooling roller 51 is disposed so that the surface on which the barrier layer 3 described later is formed is convex. That is, the step (1) is performed in a state where the cooling roller 51 is brought into contact with the back surface side of the base material 2 so as to be wound, and the subsequent film-forming surface of the barrier layer 3 is convex (that is, in a bulged state). It is preferable. Thus, the gas barrier film is controlled by causing the base material 2 containing the thermoplastic resin to generate a so-called “wrapping” and generating a compressive stress on the film forming surface side when the substrate 2 is stretched horizontally. 1 durability is improved.

  Thus, as the cooling roller 51 used when the base material 2 is cooled in a state where the film formation surface of the barrier layer 3 is convex, a known roller can be used as appropriate. The diameter of the cooling roller 51 is preferably in the range of 40 to 2000 mmφ, more preferably in the range of 50 to 1500 mmφ, and more preferably in the range of 150 to 1000 mmφ from the viewpoints of cooling efficiency, vacuum chamber space, and the like. More preferably, it is in the range, and particularly preferably in the range of 200 to 700 mmφ. If the diameter of the cooling roller 51 is 40 mmφ or more, the substrate 2 can be sufficiently cooled. On the other hand, if the cooling roller 51 is 2000 mmφ or less, it is preferable because it is practical in terms of device design.

  Moreover, it is preferable in the curvature radius of the cooling roller 51 being 20-1000 mm, and it is more preferable in it being 40-500 mm. By setting the curvature radius to 20 mm or more, a contact area for cooling the substrate 2 is ensured, and a sufficient cooling effect can be obtained. Further, it is preferable to set the radius of curvature to 1000 mm or less because it becomes easy to control the temperature at the time of forming the barrier layer 3 and the size of the entire apparatus does not become unnecessarily large. Although FIG. 1 shows an example in which one cooling roller 51 is provided as a cooling member, it is needless to say that a plurality of cooling rollers may be provided. At this time, the surface temperature (t1) of the substrate is just before the substrate is detached from the cooling roller that is most downstream in the conveyance direction of the substrate, and the temperature at the center point in the axial direction of the cooling roller is Shall point to.

  Furthermore, it is preferable that the diameter (curvature radius) of the cooling roller 51 is substantially the same as that of film forming rollers 39 and 40 described later. The ratio of the film forming rollers 39 and 40 to the diameter of the cooling roller 51 is preferably 70% to 230%, and more preferably 75% to 125%. Such a configuration is preferable because the occurrence of the above-mentioned curling is further suppressed.

[Step (2) (Barrier layer forming step)]
A preferred method for forming the barrier layer according to the step (2) of the present invention will be described.

  The method for producing a gas barrier film of the present invention includes a step (2) of forming a barrier layer on at least one surface of a substrate by a plasma CVD method. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

  Further, when plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers, and a pair of film forming rollers 39 and 40 are used as shown in FIG. More preferably, the substrate 2 is disposed on each of the pair of film forming rollers 39, 40, and plasma is generated by discharging between the pair of film forming rollers 39, 40. By adopting such an aspect, the surface portion of the base material 2 existing on the other film forming roller 40 is formed while the surface portion of the base material 2 existing on the one film forming roller 39 is formed at the time of film formation. Can be formed simultaneously, and the barrier layer 3 can be formed efficiently.

  In the present invention, the surface temperature (t2) of the film formation roller during film formation is controlled within a certain range. The surface temperature (t2) of the film forming roller more specifically faces the discharge region (film forming region) of the film forming roller 39 located on the most upstream side in the transport direction of the base material 2. It is the surface temperature of the part opposite to the part. In other words, when the discharge region is formed between the pair of film forming rollers 39 and 40 as shown in FIG. 1, the opposite side to the point where the distance between the pair of film forming rollers 39 and 40 is the shortest. This is the temperature of the film forming roller 39 at point (point B in FIG. 1). Since the film forming rollers 39 and 40 have a width, in more detail, the film forming rollers 39 and 40 are on the surface opposite to the point where the distance between the pair of film forming rollers 39 and 40 is the closest, The temperature at the center point in the axial direction (the depth direction in FIG. 1) of the film forming roller 39 disposed on the most upstream side with respect to the transport direction is indicated.

  In the present invention, the surface temperature (t2) of the film forming roller is controlled so that the temperature difference ((t2)-(t1)) from the cooled substrate surface temperature (t1) is greater than 10 ° C. . At this time, (t2)-(t1) is preferably greater than 20 ° C, more preferably greater than 30 ° C, and even more preferably greater than 40 ° C. By making (t2)-(t1) greater than 10 ° C., the substrate is transported from the cooling roller 51 to the film forming roller 39, and the film reaches the film forming roller 39 when film formation is performed. It is possible to make the conditions suitable for forming a dense barrier layer by plasma CVD without causing the temperature of 2 to be too low. In addition, the upper limit of the value of (t2) − (t1) is preferably about 200 ° C., more preferably 150 ° C., and further preferably 100 ° C.

  In this way, by controlling the surface temperature (t2) of the film forming roller to satisfy the relationship of the above formula (1), the substrate surface temperature at the time of forming the barrier layer is changed to a dense barrier layer by the plasma CVD method. The range is suitable for forming. If the surface temperature (t2) of the film forming roller is made equal to the temperature of the cooling roller ((t2) − (t1) ≦ 10), the plasma density of the substrate surface in the film forming region decreases, and as a result, It becomes difficult to form a dense barrier layer. On the other hand, by controlling the surface temperature (t2) of the film forming roller as described above, a temperature condition suitable for forming a dense barrier layer by plasma CVD can be realized, and the resulting gas barrier film The gas barrier property is improved.

  The specific temperature of the surface temperature (t2) of the film forming roller varies in an appropriate range depending on the type of the substrate 2 to be used, but is 0 to 150 ° C, more preferably 15 to 80 ° C, and further preferably 20 to 60. It is more preferable that it is ° C. By setting the temperature to 150 ° C. or lower, the influence on the base material 2 containing the thermoplastic resin at the time of plasma deposition can be alleviated, and 0 ° C. or higher (however, the surface temperature (t2) of the film forming roller is the above formula (1)) By assuming that the above relationship is satisfied, a gas barrier film having good gas barrier properties can be obtained.

  A specific method for controlling the surface temperature (t2) of the film forming roller to the above temperature will be described in detail below. As an example of the configuration of the film forming rollers 39, 40, the surface thereof is coated with titanium, stainless steel, chrome plating, cemented carbide or the like, and a mechanism capable of circulating a refrigerant or a heat medium therein is provided. What is provided. Then, the surface temperature of the film forming rollers 39 and 40 is controlled to be within the above range by circulating the refrigerant or the heat medium therein. As the refrigerant and heat medium used at this time, known ones can be used. For example, alcohol such as methanol, ethanol, isopropyl alcohol, water, silicone oil, or the like is used. Moreover, a well-known thing can be used as a mechanism which distribute | circulates a refrigerant | coolant or a heat medium.

  In order to keep the surface temperature (t2) of the film forming roller within the above range, a contact-type or non-contact-type temperature measuring means (not shown) is attached in the vicinity of the point B in FIG. Using this temperature measuring means, the surface temperature (t2) of the film forming roller is measured, and from this measurement result, the temperature of the refrigerant or heat medium circulated inside the film forming roller 39 is controlled, thereby The surface temperature (t2) is adjusted appropriately. In addition, when using a pair of film-forming rollers 39 and 40 like FIG. 1, the film-forming rollers 39 and 40 are connected in series (in a state where the film-forming rollers are connected by a common coolant or heat medium flow path). ) The temperature may be controlled by flowing a refrigerant or a heat medium, or the temperature may be individually controlled. At this time, it is preferable that the temperatures of the film forming rollers 39 and 40 are controlled to be equal. By making the temperature of the pair of film forming rollers 39 and 40 equal, the film forming condition by one film forming roller and the film forming condition by the other film forming roller can be made equal, and a more uniform barrier layer can be formed. Can be formed.

  The interval from step (1) to step (2) described above depends on the transport speed of the substrate, but is preferably 1 second to 5 minutes, and more preferably 2 seconds to 1 minute. More specifically, the time required for the base material that has passed the point (point A) immediately before leaving the cooling roller 51 to abut on the film forming roller 39 on the most upstream side in the transport direction of the base material 2 is 1 It is preferably 2 seconds to 5 minutes, more preferably 2 seconds to 1 minute. By setting it to 5 minutes or less, the productivity of the gas barrier film is improved. Moreover, by setting it as 1 second or more, the space | interval of the cooling roller 51 used for a process (1) and the film-forming roller 39 used for a process (2) can fully be ensured from the point of apparatus design. It is advantageous. Further, if the interval from the cooling roller 51 to the film forming roller 39 is 1 second or more in terms of time, the condition for forming a dense barrier layer can be realized without the temperature of the substrate 2 during film formation being too low. .

  Although the conveyance speed (line speed) of the base material 2 can be suitably adjusted according to the kind of source gas, the pressure in a vacuum chamber, etc., it is preferable to set it as the range of 0.25-100 m / min. More preferably, the range is 3 to 30 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient thickness as a barrier layer, without impairing productivity.

  As described above, as a more preferable aspect of the present embodiment, the barrier layer according to the present invention is formed by plasma CVD using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is characterized by doing. This is excellent in flexibility (flexibility) when mass production is performed using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode, and has both mechanical strength, particularly durability, and barrier performance. This is because the barrier layer can be manufactured efficiently. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

  As described above, in the manufacturing apparatus 100 having the pair of film formation rollers (the film formation roller 39 and the film formation roller 40), the pair of film formation rollers can function as a pair of counter electrodes. Each film forming roller is connected to a plasma generating power source 42. Therefore, in such a manufacturing apparatus 100, it is possible to discharge into the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming roller 39,40) so that the center axis may become substantially parallel on the same plane. In this way, by arranging the pair of film forming rollers (film forming rollers 39 and 40), the film forming rate can be doubled. And according to such a manufacturing apparatus, it is possible to form the barrier layer 3 on the surface of the base material 2 by the CVD method, and the barrier layer component is formed on the surface of the base material 2 on the film forming roller 39. While depositing, the barrier layer component can also be deposited on the surface of the substrate 2 also on the film forming roller 40, so that the barrier layer can be efficiently formed on the surface of the substrate 2.

  Inside the film forming roller 39 and the film forming roller 40, magnetic field generators 43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  In the magnetic field generators 43 and 44 provided in the film formation roller 39 and the film formation roller 40, respectively, the magnetic field generation apparatus 43 provided in one film formation roller 39 and the magnetic field generation provided in the other film formation roller 40 are provided. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between the devices 44 and the magnetic field generators 43 and 44 form a substantially closed magnetic circuit. By providing such magnetic field generators 43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surface of each of the film forming rollers 39 and 40, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

  The magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity. By providing such magnetic field generators 43 and 44, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 43 and 44 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 2 is excellent in that the barrier layer 3 that is a deposited film can be efficiently formed.

  As the film forming roller 39 and the film forming roller 40, known rollers can be appropriately used. As such film forming rollers 39 and 40, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rollers 39 and 40 is preferably in the range of 100 to 1000 mmφ, particularly in the range of 150 to 700 mmφ from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 100 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated, and it will be possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

  In such a manufacturing apparatus 100, the base material 2 is conveyed on a pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) so that the surfaces of the base material 2 face each other. By disposing the base material 2 in this manner, when the plasma is generated by performing discharge in the facing space between the film formation roller 39 and the film formation roller 40, the base existing between the pair of film formation rollers is present. Each surface of the material 2 can be formed simultaneously. That is, according to such a manufacturing apparatus, a barrier layer component is deposited on the surface of the substrate 2 on the film forming roller 39 and further deposited on the film forming roller 40 by plasma CVD. Therefore, the barrier layer can be efficiently formed on the surface of the substrate 2.

  As the unillustrated delivery roller and transport rollers 33, 34, and 35 used in the manufacturing apparatus 100, known rollers can be appropriately used. The winding roller (not shown) is not particularly limited as long as the gas barrier film 1 having the barrier layer 3 formed on the substrate 2 can be wound, and a known roller is appropriately used. Can do.

  Further, as the gas supply pipe 41 and the vacuum pump 11, those capable of supplying or discharging the source gas or the like at a predetermined speed can be appropriately used.

  The gas supply pipe 41 as a gas supply means is preferably provided on one side of a facing space (discharge region; film formation region) between the film formation roller 39 and the film formation roller 40, and is a vacuum exhaust means. The vacuum pump 10 is preferably provided on the other side of the facing space. As described above, by disposing the gas supply pipe 41 as the gas supply means and the vacuum pump 11 as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 39 and the film formation roller 40. It is excellent in that it can be supplied and the film formation efficiency can be improved.

  Furthermore, as the plasma generating power source 42, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. Moreover, as such a plasma generating power source 42, it becomes possible to perform plasma CVD more efficiently, so that the applied power can be set to 100 W to 10 kW, and the AC frequency is set to 50 Hz to 500 kHz. More preferably, it is possible to do this. As the magnetic field generators 43 and 44, known magnetic field generators can be used as appropriate.

  Using such a manufacturing apparatus 100 shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport of the film (base material) The barrier layer can be formed by appropriately adjusting the speed. Specifically, using the manufacturing apparatus 100 shown in FIG. 1, a film-forming gas (raw material gas or the like) is supplied into the vacuum chamber 10 while discharging is performed between the pair of film-forming rollers (film-forming rollers 39 and 40). When generated, the film forming gas (raw material gas or the like) is decomposed by plasma, and the barrier layer 3 is formed on the surface of the base material 2 on the film forming roller 39 and on the surface of the base material 2 on the film forming roller 40. Is formed by plasma CVD. In such film formation, the substrate 2 is conveyed by the delivery roller 32, the cooling roller 51, and further the film formation roller 39, respectively, so that the base film 2 is formed by a continuous roll-to-roll film formation process. A barrier layer 3 is formed on the surface of the material 2.

  In the step (2), the barrier layer 3 is preferably formed so as to contain at least silicon, oxygen and carbon. Thus, the gas barrier property of a barrier layer improves by containing silicon, oxygen, and carbon in the barrier layer formed. In order to form the barrier layer having the above-described structure, it is preferable to use a gas containing an organosilicon compound and oxygen as the film forming gas (raw material gas). The oxygen content is preferably less than the theoretical oxygen amount necessary for complete oxidation of the total amount of the organosilicon compound in the film forming gas.

  As the film forming gas (such as source gas) supplied from the gas supply pipe 41 to the facing space, source gas, reaction gas, carrier gas, and discharge gas may be used alone or in combination of two or more. The source gas in the film-forming gas used for forming the barrier layer 3 can be appropriately selected and used according to the material of the barrier layer 3 to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of characteristics such as handling of the compound and gas barrier properties of the resulting barrier layer. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the barrier layer 3.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By not excessively increasing the ratio of the reactive gas, the barrier layer 3 formed is excellent in that excellent barrier properties and bending resistance can be obtained. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

Hereinafter, as the film forming gas, hexamethyldisiloxane (organosilicon compound, HMDSO, (CH ₃ ) ₆ Si ₂ O) as a raw material gas and oxygen (O ₂ ) as a reactive gas are used. Taking a case of producing a silicon-oxygen-based thin film as an example, a suitable ratio of the raw material gas and the reactive gas in the film forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen system When the thin film is produced, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and silicon dioxide is generated.

  In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. However, in the present invention, in order to improve the gas barrier property of the formed barrier layer, the amount of oxygen is set to 1 mole of hexamethyldisiloxane so that the reaction of the reaction formula (1) does not proceed completely. The stoichiometric ratio is preferably less than 12 moles. In the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas Even if the (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane (flow rate), the reaction cannot actually proceed completely, and the oxygen content is reduced. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is changed to the hexamethyldioxide raw material. (It may be about 20 times the molar amount (flow rate) of siloxane). Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that were not completely oxidized were taken into the barrier layer, and the resulting gas barrier film was excellent. It becomes possible to exhibit gas barrier properties and bending resistance. From the viewpoint of use as a flexible substrate for devices that require transparency, such as organic EL elements and solar cells, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas The lower limit of (flow rate) is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.

  Moreover, although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5 Pa-50 Pa.

  In such a plasma CVD method, in order to discharge between the film forming roller 39 and the film forming roller 40, an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used. The power to be applied to the power source can be adjusted as appropriate according to the type of raw material gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated at the time of film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.

  The thickness of the barrier layer is not particularly limited, but is preferably in the range of 100 to 1000 nm, preferably 150 to 800 nm, and more preferably 250 to 600 nm.

[Step (3) (Organic layer forming step)]
The method for producing a gas barrier film of the present invention may include a step (3) for forming an organic layer between the substrate and the barrier layer. That is, the method for producing a gas barrier film of the present invention may include a step (3) before forming the barrier layer.

  A preferred method for forming the organic layer (underlying layer, primer layer) according to the step (3) of the present invention will be described.

  The organic layer is formed for the purpose of improving the adhesion (adhesion) between the substrate and the barrier layer. In addition, the organic layer is used for flattening the rough surface of the substrate on which protrusions and the like exist, or for filling the unevenness and pinholes generated in the barrier layer with the protrusions existing on the substrate to flatten the surface. It may be provided. Such an organic layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer.

  The organic layer also contains a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and examples thereof include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more. The curable resin may be a commercially available product or a synthetic product.

  In the step (3), as described above, when the organic layer is formed through the polymerization reaction of the curable resin material, the step (1) and the step ( It is preferable to perform 3) simultaneously. More specifically, it is preferable that the step (1) and the step (3) are simultaneously performed in a certain part on the substrate.

  The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam. Is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and among them, an electron beam curable resin that is cured by electron beam irradiation is preferable.

  In the step (3), the method for forming a curable resin layer made of a curable resin material that is cured by active energy rays or heat is not particularly limited. Examples thereof include a method of applying a coating liquid containing a curable resin material on a substrate using a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dry coating method such as a vapor deposition method. Among these, it is preferable to use a spray method because it is particularly suitable for continuous film formation under vacuum conditions. Further, among the spray methods, an ultrasonic spray method and an electrospray method are preferable.

  In the ultrasonic spray method, the vibration of the piezoceramic is transmitted to the ultrasonic spray nozzle (atomizer), where the liquid film is vibrated to form fine particles and sprayed. The liquid is supplied without being pressurized, Fine particles (particles of curable resin material) can be sprayed.

  The electrospray method is a method that utilizes a phenomenon in which a liquid is sprayed due to electric field concentration by applying a high voltage to a container with a sharp tip. Such an electrospray deposition method (ESD method) is a method of depositing and fixing on a substrate or the like using electrostatic force while spraying a curable resin material to form nano-sized particles.

  Thus, the ultrasonic spray method and the electrospray method are methods that do not require a solvent and are particularly preferable because they are suitable for forming a denser organic film under vacuum conditions.

  After forming the curable resin layer (coating film) that becomes the precursor of the organic layer on the surface of the substrate 2 as described above, visible light, infrared light, ultraviolet light, X-rays, α-rays, β-rays, γ-rays, electrons A method is preferred in which the curable resin layer is cured by irradiation and / or heating with an active energy ray such as a wire. As a method of irradiating active energy rays, for example, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like is preferably used to irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm. Alternatively, a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator can be used. Among these, a method of irradiating an electron beam as an active energy ray is preferable from the viewpoint of ease of device design and improvement of barrier properties of the film. That is, in the step (3), a curable resin layer made of an electron beam curable resin material is formed on the substrate 2 disposed on the cooling roller 51 as a cooling member, and an electron beam is applied to the curable resin layer. It is preferable to form an organic layer by irradiation.

  In order to form the organic layer by the above method, the manufacturing apparatus 100 of FIG. 1 has a resin material supply device 61 for supplying a curable resin material to the surface of the base material 2 cooled on the cooling roller 51. Is provided. The resin material supply device 61 is a device for spraying the curable resin material and depositing it on the base material 2, and is specifically an ultrasonic spray unit (ultrasonic sprayer). As the resin material supply device 61, one having a known configuration can be adopted.

  And in the conveyance direction of the base material 2, the active energy ray which irradiates active energy rays, such as an electron beam, with respect to the curable resin layer formed on the base material 2 in the downstream of the resin material supply apparatus 61. An irradiation device 62 is provided. The active energy ray irradiating device 62 irradiates the base material 2 with the above-described ultraviolet rays, electron beams or the like in order to polymerize the curable resin material on the base material 2. As this active energy ray irradiation apparatus 62, what has a well-known structure is employable.

  In addition, when performing a process (3) and a process (1) simultaneously, the said resin material supply apparatus 61 and the active energy ray irradiation apparatus 62 are within the range facing the range which the cooling roller 51 and the base material 2 contact | abut. It is preferable to be disposed. That is, it is preferable to perform the process from the application process of the curable resin to the active energy ray irradiation process on the cooling roller 51. Thus, when curable resin is apply | coated on the base material 2 cooled, the adhesiveness of the base material 2 and curable resin material (namely, organic layer) will improve. Furthermore, since the polymerization reaction is performed on the cooled base material 2, the heat of polymerization can be relaxed and the base material 2 can be prevented from being damaged by the heat.

  Examples of the active energy ray-curable material used for forming the organic layer include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, and polyester. Examples include compositions containing polyfunctional acrylate monomers such as acrylates, polyether acrylates, polyethylene glycol acrylates, and glycerol methacrylates. Specifically, curable bifunctional acrylate NK ester A-DCP (tricyclodecane dimethanol diacrylate) from Shin-Nakamura Chemical Co., Ltd., UV curable organic / inorganic hybrid hard coat material OPSTAR (registered by JSR Corporation) Trademark) series (compounds obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) and the like can be used.

  It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no restriction in particular.

  Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene Oxide modified pentaerythritol triacrylate, propylene oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

  It is preferable that the composition containing an active energy ray-curable material contains a photopolymerization initiator.

  Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoy Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoin peroxide And combinations of photoreducing dyes such as eosin and methylene blue and reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more. .

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nitto Boseki Co., Ltd. Inorganic / organic nanocomposite material SSG coating, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicon resin, polyamidoamine-epichlorohydrin resin And the like.

  Solvents used when forming an organic layer using a coating solution in which a curable material is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol Terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carb Acetic esters such as tall acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate , Diethylene glycol dialkyl ether, dipropylene Glycol dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The organic layer can contain additives such as a thermoplastic resin, an antioxidant, an ultraviolet absorber, and a plasticizer, if necessary, in addition to the above-described materials. In addition, an appropriate resin or additive may be used for improving the film formability and preventing the occurrence of pinholes in the film. Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof and the like. Examples include resins, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, and polycarbonate resins.

  The smoothness of the organic layer is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 80 nm or less.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of μm many times.

The coating amount of the curable resin material for forming the organic layer is preferably about 0.1 to 5 g / m ² (dry state). The thickness of the organic layer is not particularly limited, but is preferably in the range of 0.5 to 10 μm, preferably 1 to 5 μm.

[Step (4) (Bleed-out prevention layer forming step)]
The method for producing a gas barrier film of the present invention may further include a step (4) of forming a bleed-out prevention layer. When the step (3) is performed, the step (4) is preferably performed before the step (3), and more preferably performed before the step (1).

  A preferred method for forming the bleed-out preventing layer according to the step (4) of the present invention will be described.

  The bleed-out prevention layer is a phenomenon in which the plasticizer existing inside the thermoplastic resin base material and low molecular components such as monomers and oligomers that are raw materials of the base material diffuse to the base material surface and contaminate the contact surface. It can be provided on the surface of the substrate for the purpose of suppressing (so-called bleed out). In addition, the bleed-out prevention layer suppresses a phenomenon in which, when a film having an organic layer on a substrate is heated, unreacted oligomers migrate from the film substrate to the surface and contaminate the contact surface. For the purpose, it can be provided on the opposite side of the substrate with the organic layer. The bleed-out prevention layer may basically have the same configuration as the organic layer as long as it has this function. Therefore, the bleed-out prevention layer can be formed by a method similar to the method for forming the organic layer described above.

  As with the organic layer, the bleedout prevention layer preferably contains a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and examples thereof include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more. The curable resin may be a commercially available product or a synthetic product.

  Examples of the active energy ray-curable resin used for forming the bleedout prevention layer include resins that can be cured by irradiating active energy rays such as ultraviolet rays and electron beams, among these, An ultraviolet curable resin that is cured by ultraviolet irradiation is preferred.

  In the step (4), the method for forming a curable resin layer (coating film) made of a curable resin material that is cured by active energy rays or heat and the method for curing the curable resin layer are not particularly limited, Since it is the same as the formation method of the curable resin layer in the step (3) and its curing method, its detailed description is omitted.

  Although a specific configuration for forming the bleed-out prevention layer is not shown in FIG. 1, the bleed-out prevention layer may be formed in the manufacturing apparatus 100, or the base material may be attached to the manufacturing apparatus 100. Before setting 2, a bleed-out prevention layer may be formed on one surface of the substrate 2 in advance. When the bleed-out prevention layer is formed in the manufacturing apparatus 100, the base material 2 is transported to the cooling roller 51 on the back surface side of the base material 2 (the side opposite to the surface on which the barrier layer 3 is formed). A mechanism similar to the resin material supply device 61 and the active energy ray irradiation device 62 may be further provided on the upstream side in the direction.

  Compounds that can be included in the bleed-out prevention layer include polyunsaturated organic compounds having two or more polymerizable unsaturated groups in the molecule, or unit price unsaturated having one polymerizable unsaturated group in the molecule. Hard coating agents such as organic compounds can be listed.

  Here, as the polyunsaturated organic compound, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meta ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpro Ntetora (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of unit unsaturated organic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl. (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-eth Ciethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by weight or more, preferably 4 parts by weight or more, more preferably 6 parts by weight or more and 20 parts by weight or less, preferably 100 parts by weight of the solid content of the hard coating agent. It is desirable that they are mixed in a proportion of 18 parts by weight or less, more preferably 16 parts by weight or less.

  In addition, the bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.

  Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof. Vinyl resins such as polyvinyl formal, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicon resin etc. are mentioned.

  In addition, as an ionizing radiation curable resin, an ionizing radiation (ultraviolet ray or electron beam) is irradiated to an ionizing radiation curable coating material in which one or more of a photopolymerizable prepolymer or a photopolymerizable monomer is mixed. Those that cure can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl). ) -1-propane, α-acyloxime ester, thioxanthone and the like.

  The bleed-out prevention layer as described above is prepared as a coating solution by blending a hard coat agent and other components as necessary, and appropriately using a diluting solvent as necessary. After coating by a conventionally known coating method, it can be formed by irradiating with ionizing radiation and curing. As a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer is one of the transparent polymer films. When it is provided on this surface, curling of the barrier film can be easily suppressed.

[Step (5) (Anchor coat layer forming step)]
In the method for producing a gas barrier film of the present invention, when performing the step (3) of forming an organic layer, the method may further include a step (5) of forming an anchor coat layer. At this time, the step (5) is performed before the step (3) of forming the organic layer.

  A preferred method for forming the anchor coat layer according to the step (5) of the present invention will be described.

  The anchor coat layer is provided between the base material and the organic layer, and is formed for the purpose of improving the adhesion (adhesion) between the organic layer and the base material. The anchor coat layer may be formed as an easy adhesion layer. Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One type or two or more types can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) can be used.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). A commercially available base material with an easy-adhesion layer may be used.

  Alternatively, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

<The manufacturing method of the gas-barrier film which concerns on other embodiment>
Hereafter, the manufacturing method of the gas barrier film which concerns on other embodiment is demonstrated in detail, referring FIG. FIG. 2 is a schematic view of a production apparatus suitably used in the method for producing a gas barrier film according to another embodiment of the present invention. In the following description and drawings, the same or corresponding elements as those in FIG.

[Step (1) according to Other Embodiment (Base Material Cooling Step)]
In the description related to the step (1) in the above-described embodiment described with reference to FIG. 1, the aspect in which the base material 2 is cooled using one cooling roller 51 is shown. Among these, one of the features is that the step (1) is performed using a plurality of cooling rollers 51a, 51b, 51c, 51d as cooling members.

  In the manufacturing apparatus 200, the process (1) includes the substrate 2 continuously contacting the surfaces of cylindrical cooling rollers 51 a, 51 b, 51 c, 51 d (hereinafter collectively referred to as “51 ′”). The substrate 2 is cooled by the above. In this embodiment, in such a step (1), the temperature of the cooling roller 51 ′ is controlled so that the surface temperature (t 1) of the base material is 10 ° C. or less. At this time, the surface temperature (t1) of the base material is more specifically the point immediately before the base material 2 is detached from the cooling roller 51d located on the most downstream side in the transport direction of the base material 2 (in FIG. 1). It is the temperature of the base material at point A ′). Since each cooling roller 51 ′ has a width, more specifically, the temperature at the center point in the axial direction of the cooling roller 51d (the depth direction in FIG. 2) immediately before the base material 2 is detached from the cooling roller 51d. Point to. The surface temperature (t1) of the substrate is cooled to 10 ° C. or less, more preferably 0 ° C. or less, and still more preferably −10 ° C. or less by the cooling roll 51 ′. The lower limit value of the surface temperature (t1) of the substrate is not particularly limited, but is preferably -80 ° C, more preferably -40 ° C.

  The individual configuration of each of the cooling rollers 51a, 51b, 51c, and 51d and the temperature control method are the same as those of the cooling roller 51 described above, and thus detailed description thereof is omitted.

  Each cooling roller 51a, 51b, 51c, 51d is disposed further upstream than the film forming roller 39 located on the most upstream side with respect to the conveyance direction of the substrate 2, and the central axis thereof is on the same plane. It arrange | positions so that it may become substantially parallel. As described above, in the step (1), the cooling roller is set so that the conveying direction of the base material 2 and the plane including all the central axes of the cooling rollers 51a, 51b, 51c, 51d arranged in parallel are substantially parallel. 51a, 51b, 51c, 51d may be provided. That is, the substrate 2 may be transported to the film forming roller 39 while being cooled in a flat shape.

  2 shows an example in which four cooling rollers 51a, 51b, 51c, 51d are provided as cooling members, the number of cooling rollers is not limited to this. . In addition, when using a plurality of cooling rollers in this way, each cooling roller may be controlled in temperature by flowing a refrigerant in series (in a state where the cooling rollers are connected by a common refrigerant flow path), Each may be individually temperature controlled.

[Step (2) according to Other Embodiment (Barrier Layer Forming Step)]
Step (2) is the same as step (2) in the embodiment described with reference to FIG.

[Step (3) according to Other Embodiment (Organic Layer Forming Step)]
Another embodiment according to the step (3) will be described in detail with reference to FIG.

  In the embodiment described with reference to FIG. 1 described above, the mode in which the organic layer is formed simultaneously with the cooling of the base material 2 on the cooling roller 51 is shown. One of the features is that an organic layer is formed before passing through 51 '. That is, step (3) may be performed before step (1). At this time, as shown in FIG. 2, the organic layer is preferably applied to the substrate 2 in contact with the transport roller 36. Thus, from the viewpoint of improving the adhesion between the base material and the barrier layer, it is preferable that the organic layer is formed in a state where the surface on which the organic layer is formed is convex (a bulged state). In addition, about the resin material supply apparatus 61 and the active energy ray irradiation apparatus 62 for forming an organic layer, since each structure and the organic layer formation method are the same as that of embodiment by FIG. 1 mentioned above, the detailed description Is omitted.

[Steps of forming other layers according to other embodiments]
The method for producing a gas barrier film according to another embodiment may further include a step of forming a bleed-out prevention layer and an anchor coat layer. In addition, about the formation method of each layer, since it is the same as the above-mentioned respectively, the detailed description is abbreviate | omitted.

<Use of gas barrier film>
Applications of the gas barrier film produced according to the present invention include application to the following electronic devices and optical members.

[Electronic device]
The gas barrier film produced according to the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. Examples of the device include electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device.

  The gas barrier film produced by the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.

(Organic EL device)
An example of an organic EL element using a gas barrier film is described in detail in Japanese Patent Application Laid-Open No. 2007-30387.

(Liquid crystal display element)
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film produced according to the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has the structure which consists of a film | membrane. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The type of the liquid crystal cell is not particularly limited, but more preferably a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment), an EC type, a B type. OCB type (Optically Compensated Bend), IPS type (In-Plane Switching), and CPA type (Continuous Pinwheel Alignment) are preferable.

(Solar cell)
The gas barrier film produced according to the present invention can also be used as a sealing film for solar cell elements. Here, the gas barrier film is preferably sealed so that the barrier layer is closer to the solar cell element. The solar cell element in which the gas barrier film produced according to the present invention is preferably used is not particularly limited, but for example, a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure Type amorphous silicon solar cell elements, III-V compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI compound semiconductor solar elements such as cadmium tellurium (CdTe) Battery element, copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur system (so-called CIGS system), etc. -III-VI compound semiconductor solar cell element, dye-sensitized solar cell element, organic Solar cell elements, and the like. In particular, in the present invention, the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur. It is preferable that it is an I-III-VI group compound semiconductor solar cell element, such as a system (so-called CIGSS system).

(Other)
As other application examples, the thin film transistor described in JP-A-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., described in JP-A-2000-98326. Electronic paper and the like.

[Optical member]
The gas barrier film produced according to the present invention can also be used as an optical member. Examples of the optical member include a circularly polarizing plate.

(Circularly polarizing plate)
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate is 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. .

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Further, in the examples, the display of “part” or “%” is used, but “part by weight” or “% by weight” is expressed unless otherwise specified. Moreover, in the following operation, unless otherwise specified, the measurement of the operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

[Production of gas barrier film]
Example 1
1. Preparation of Substrate As a base material, a thermoplastic resin support, a 100 μm-thick polyester film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.), which is easily bonded on both sides, is used as a base material. Was stored for 96 hours in an environment of a temperature of 25 ° C. and a relative humidity of 55% to adjust the humidity.

2. Formation of bleed-out prevention layer (step (4))
After applying UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7535 manufactured by JSR Corporation on one side of the substrate with a wire bar so that the film thickness after drying becomes 4 μm, 80 ° C., After drying for 3 minutes, curing was performed under a curing condition: 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere and in the air to form a bleed-out prevention layer.

3. Formation of organic layer (step (1) and step (3))
An organic layer was formed on the base material on which the bleed-out prevention layer was formed as described above (the surface on the side where the bleed-out prevention layer was not formed) using the manufacturing apparatus shown in FIG.

  First, the wound body of the substrate was mounted on a feed roll (not shown). The base material fed out from the wound body was wound around a take-up roll (not shown) through a conveyance roller, a cooling roller, a film formation roller, a conveyance roller, a conveyance roller, and a film formation roller in this order.

At this time, a curable bifunctional acrylate tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK-ester A-DCP) from a 60 kHz ultrasonic spray unit (ultrasonic sprayer) while conveying the substrate. ) Was coated on the substrate. At this time, the adhesion amount of the acrylate was 1 g / m ² . Then, conveyance of the base material was advanced, and an organic layer cured at curing conditions: 10 kV, 3.4 mA was formed using an electron beam irradiation unit. At this time, the organic layer is formed when the substrate passes over the cooling roller, and the surface temperature (t1) of the substrate conveyed in the above process (the surface at the point immediately before the substrate is detached from the cooling roller). The temperature was controlled by adjusting the temperature and flow rate of the refrigerant circulating inside the cooling roll so that the measured value was −20 ° C. The diameter of the cooling roller was 200 mm (curvature radius: 100 mm).

  The maximum cross-sectional height Rt (p) representing the surface roughness of the organic layer formed as described above was 20 nm. The surface roughness is calculated from an uneven sectional curve continuously measured with a detector having a stylus having a minimum tip radius using an AFM (Atomic Force Microscope AFM: manufactured by Digital Instruments), and the minimum tip radius is calculated. Was measured many times in the section having a measurement direction of 30 μm with the stylus of No. 1 and obtained from the average roughness with respect to the amplitude of fine irregularities.

4). Formation of barrier layer (step (2))
Further, the substrate is transported, and the above 3. A barrier layer was formed on the organic layer formed in (1). The barrier layer is formed by applying a magnetic field between a pair of film-forming rollers having a diameter of 180 mm and supplying electric power to discharge between the film-forming rollers to generate plasma. A film forming gas (hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas as a reaction gas) is supplied, and a thin film is formed by plasma CVD under the following film forming conditions (plasma CVD conditions). A gas barrier film (Sample 1) was obtained, in which a bleed-out preventing layer was formed on one surface of the material, and an organic layer and a barrier layer were sequentially stacked on the other surface. At this time, the temperature was controlled by adjusting the temperature and flow rate of the water circulating inside so that the surface temperature (t2) of the film forming roller was 30 ° C. In addition, the conveyance speed of a base material shall be 1.0 m / min, and the space | interval from the process (1) (process (3)) to a process (2) (the same part of a base material passes A point of FIG. 1). The time from the first contact to the most upstream film formation roller was 1 minute.

  The thickness of the barrier layer formed as described above was 320 nm.

  The obtained sample was subjected to XPS depth profile measurement under the following conditions to obtain silicon element distribution, oxygen difference element distribution, and carbon element distribution. As a result, the distribution of silicon (Si), oxygen (O), and carbon (C) in the film thickness direction was Si: C: O = 1: 2.1: 0.3.

(Example 2)
In Example 1, a gas barrier film (Sample 2) was produced in the same manner as in Example 1 except that the surface temperature (t1) of the substrate after forming the organic layer was changed to -10 ° C.

(Example 3)
In Example 1, a gas barrier film (Sample 3) was produced in the same manner as in Example 1 except that the surface temperature (t1) of the substrate after forming the organic layer was changed to 0 ° C.

Example 4
In Example 1, a gas barrier film (Sample 4) was produced in the same manner as in Example 1 except that the surface temperature (t1) of the substrate after forming the organic layer was changed to 10 ° C.

(Comparative Example 1)
In Example 1, a gas barrier film (Sample 5) was produced in the same manner as in Example 1 except that the surface temperature (t1) of the substrate after forming the organic layer was changed to 20 ° C.

(Comparative Example 2)
In Example 1, a gas barrier film (Sample 6) was produced in the same manner as in Example 1 except that the surface temperature (t1) of the substrate after forming the organic layer was changed to 30 ° C.

(Comparative Example 3)
In Example 1, the surface temperature (t1) of the base material after the organic layer was formed was −10 ° C., and the surface temperature (t2) of the film forming roller was changed to −10 ° C. Thus, a gas barrier film (Sample 7) was produced.

(Comparative Example 4)
In Example 2, a gas barrier film (Sample 8) was produced in the same manner as in Example 2 except that the formation method and composition of the barrier layer were changed. Formation of the barrier layer was performed as follows.

  The substrate was conveyed from the cooling roller, and a barrier layer was formed on the previously formed organic layer. The barrier layer is formed by forming a thin film by sputtering on a film formation roller having a diameter of 180 mm under the following film formation conditions, a bleed-out prevention layer on one surface of the substrate, and an organic layer on the other surface. Thus, a gas barrier film (sample 8) formed by sequentially laminating barrier layers was obtained. At this time, the temperature was controlled by adjusting the temperature and flow rate of the water circulating inside so that the surface temperature (t2) of the film forming roller was 30 ° C.

  The thickness of the barrier layer formed as described above was 310 nm.

(Comparative Example 5)
In Comparative Example 4, a gas barrier film (Sample 9) was produced in the same manner as in Comparative Example 4 except that the surface temperature (t2) of the film forming roller was changed to −10 ° C.

(Example 5)
In Example 2, a gas barrier film (sample 10) was produced in the same manner as in Example 2 except that the organic layer was not formed and only the substrate was cooled.

(Comparative Example 6)
In Comparative Example 2, a gas barrier film (Sample 11) was produced in the same manner as Comparative Example 2 except that the organic layer was not formed and only the substrate was cooled.

(Example 6)
In Example 2, a gas barrier film (sample 12) was produced in the same manner as in Example 2 except that the manufacturing apparatus having the structure shown in FIG. 2 was used instead of the manufacturing apparatus having the structure shown in FIG.

  At this time, in the manufacturing apparatus of FIG. 2, four cooling rollers having a diameter of 80 mm (curvature radius: 40 mm) were used, and these were arranged horizontally.

(Example 7)
In Example 2, a gas barrier film (Sample 13) was produced in the same manner as in Example 2 except that the method for forming the organic layer was changed. The organic layer was formed as follows.

For the formation of the organic layer, an ultraviolet curable acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., purple light (registered trademark) UV-7605B) is applied onto the substrate from an ultrasonic spray unit, and this is irradiated with ultraviolet light. This was done by curing. At this time, ultraviolet irradiation was performed using a high-pressure mercury lamp, and the curing treatment was performed so that the irradiation amount was 2000 mJ / cm ² .

(Example 8)
In Example 2, a gas barrier film (sample 14) was produced in the same manner as in Example 2 except that the supply amount of hexamethyldisiloxane (HMDSO) as a source gas was changed to 25 sccm. In addition, when XPS depth profile measurement was performed about this sample, the film thickness average carbon (C) composition rate was not substantially detected.

[Bending durability test]
For the gas barrier films (samples 1 to 14) produced in Examples 1 to 8 and Comparative Examples 1 to 6, the gas barrier properties before and after the bending treatment were evaluated, and the bending durability test was performed. The results are shown in Table 1 below.

  The test was conducted as follows.

(Bending treatment)
Each of the gas barrier films (samples 1 to 14) was stored for 72 hours under an environment of 85 ° C./85% RH, and then repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm.

(Production of gas barrier property (water vapor permeability) evaluation cell)
The water vapor permeation amount of each gas barrier film sample was evaluated as follows.

  Using a vacuum deposition apparatus (JEOL vacuum deposition apparatus JEE-400) on the surface of each gas barrier film sample on the barrier layer side, metallic calcium was deposited on the surface of the gas barrier film sample. After that, in a dry nitrogen gas atmosphere, the metal calcium vapor deposition surface is bonded and bonded to quartz glass having a thickness of 0.2 mm via a sealing ultraviolet curable resin (manufactured by Nagase ChemteX) and irradiated with ultraviolet rays. An evaluation cell was produced.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample Was stored under the same high temperature and high humidity conditions of 40 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

(Evaluation of corrosion of metallic calcium)
For the samples of Examples 1 to 8 and Comparative Examples 1 to 6, cell samples were prepared for those subjected to bending treatment and those not subjected to bending treatment, and each cell sample was subjected to an environment of 40 ° C. and 90% RH. And observed the change from 0 day to 90 days in terms of the occurrence of corrosion points in the calcium deposition region and the state of its expansion.

  The observed calcium corrosion state of each sample was evaluated as follows.

1.0 Day Evaluation A cell sample was prepared, and the presence or absence of a corrosion point was evaluated after 2 hours had passed in a glove box under a nitrogen atmosphere. Table 1 shows the results.

“◯”: The occurrence of corrosion spots was not observed. “×”: The occurrence of corrosion spots was observed.

2. Evaluation on the 90th day 2-1. Number of Corrosion Points About the cell sample 90 days after preparation, the number of corrosion points generated per square centimeter in the calcium vapor deposition region sealed with a gas barrier film was evaluated. Table 1 shows the results.

“5”: Less than 0.1 “4”: 0.1 or more and less than 0.5 “3”: 0.5 or more and less than 2.0 “2”: 2.0 or more and 20.0 Less than “1”: 20.0 or more.

2-2. Corrosion area About the cell sample 90 days after preparation, the total area of corrosion points per square centimeter in the calcium vapor deposition area sealed with a gas barrier film was evaluated. Table 1 shows the results.

“5”: Total area of corrosion points was 0.3% or less of total deposition area. “4”: Total area of corrosion points was 0.3% or more and less than 1.0% of total deposition area. “3”: The total integrated area of the corrosion points was 1.0% or more and less than 3.0% of the total deposition area. “2”: The total integrated area of the corrosion points was 3.0% or more of the total deposition area. It was 0.0% or less “1”: The total integrated area of corrosion points exceeded 10.0% of the total deposition area.

  From Table 1 above, it was shown that the gas barrier film of the present invention has a high gas barrier property before and after bending and also has a high gas barrier property after bending.

100, 200 ... manufacturing equipment,
1 ... Gas barrier film,
2 ... base material,
3 ... barrier layer,
10 vacuum chamber,
11 Vacuum pump,
12 Exhaust port,
33, 34, 35, 36 transport rollers,
39, 40 Deposition roller,
41 gas supply pipe,
42 Power supply for plasma generation,
43, 44 Magnetic field generator,
51, 51 ′, 51a, 51b, 51c, 51d Cooling roller (cooling member),
61 resin material supply device,
62 Active energy ray irradiation apparatus.

Claims (5)

A step (1) of cooling the surface temperature (t1) of the base material to 10 ° C. or lower using a cooling member while transporting the base material containing the thermoplastic resin to the film forming roller;
A step (2) of forming a barrier layer on the substrate by a plasma CVD method using the film forming roller having a surface temperature (t2) satisfying the relationship of the following formula (1): Production method.

  The manufacturing method of the gas barrier film of Claim 1 which performs the process (3) which forms an organic layer on the said base material simultaneously with the said process (1). In the step (3),
Forming a curable resin layer made of an electron beam curable resin material on the substrate disposed on the cooling member, and irradiating the curable resin layer with an electron beam to form the organic layer; Item 3. A method for producing a gas barrier film according to Item 2.   The method for producing a gas barrier film according to claim 1, wherein the barrier layer contains at least silicon, oxygen, and carbon.   The method for producing a gas barrier film according to any one of claims 1 to 4, wherein, in the step (1), the base material is wound so that a surface on which the barrier layer is formed is convex.

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