JP2017095759A - Method for producing gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a gas barrier film having excellent durability under a high temperature and high humidity environment and excellent adhesiveness when sealing a device.SOLUTION: There is provided a method for producing a gas barrier film which comprises: a step 1 of forming a first layer 32 containing a non-transition metal (M1) on a substrate 1; a step 2 of forming a second layer 33 containing a transition metal (M2) so as to be in contact with the first layer by a physical vapor deposition method; and a step 3 of forming a third layer 34 containing a transition metal (M2') by a physical vapor deposition method on the second layer 33, wherein the third layer is an outermost layer and in the step 2 and step 3, when the vapor deposition rate of forming the second layer 33 is defined as DR2(nm/sec) and the vapor deposition rate of forming the third layer 34 is defined as DR3 (nm/sec), R, which is a ratio of the DR2 (nm/sec) to the DR3 (nm/sec), satisfies the following expression. 1.1≤R≤5.0 (Expression 1)SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for producing a gas barrier film.

  Gas barrier films are used as substrate films and sealing films in flexible electronic devices, particularly flexible organic EL devices. High barrier properties are required for gas barrier films used in these.

  In general, a gas barrier film is produced by forming an inorganic barrier layer on a base film by a physical vapor deposition method such as a vacuum vapor deposition method or a sputtering method and a vapor phase film formation method such as a chemical vapor deposition method.

As a gas barrier layer having a high gas barrier property having a water vapor transmission rate (WVTR) of 1.0 × 10 ⁻² g / m ² · day or less, a layer containing a non-transition metal has been studied. As an example of such a gas barrier layer, many studies have been made on application of a silicon oxide gas barrier layer by sputtering film formation. In these studies, studies have been made to use a target in which various metals are combined in order to stabilize the film formation conditions. For example, a technique has been found in which aluminum or boron is added to silicon to prevent arc generation or target cracking. However, although the film forming conditions are stable, the improvement of the gas barrier property itself is poor, and a sufficient gas barrier property has not been obtained.

  In recent years, a manufacturing method in which a gas barrier layer is formed by applying energy to a precursor layer formed by applying a solution on a substrate has been studied. In particular, studies using polysilazane as a precursor have been widely conducted, and studies are being conducted as a technique for achieving both high productivity by coating and gas barrier properties. In particular, the modification of the polysilazane layer using excimer light having a wavelength of 172 nm has attracted attention.

  For example, in Patent Document 1, after applying a solution containing polysilazane and a catalyst onto a substrate, then removing the solvent to form a polysilazane layer, the polysilazane layer is less than 230 nm in an atmosphere containing water vapor. Disclosed is a method for forming a gas barrier layer on a substrate by irradiation with VUV radiation containing a wavelength component and UV radiation containing a wavelength component of 230-300 nm.

Special table 2009-503157

  However, as described in Patent Document 1 above, the gas barrier layer formed by modifying polysilazane with excimer light has a high temperature and humidity of 85 ° C. and 85% RH. It was found that the gas barrier property was lowered. In addition, in the process of sealing an electronic device or the like with a gas barrier film through an adhesive, the gas barrier film may have poor adhesion.

  Therefore, an object of the present invention is to provide a means for producing a gas barrier film which is excellent in durability under a high temperature and high humidity environment and excellent in adhesion at the time of device sealing.

  The above-described problems of the present invention are solved by the following means.

  Forming a first layer containing the non-transition metal (M1) using a non-transition metal (M1) or a compound containing the non-transition metal (M1) on a substrate; and on the first layer Step 2 of forming the second layer containing the transition metal (M2) by using a compound containing the transition metal (M2) or the transition metal (M2) by physical vapor deposition so as to be in contact with the first layer Then, a third layer containing the transition metal (M2 ′) is formed on the second layer by a physical vapor deposition method using a compound containing the transition metal (M2 ′) or the transition metal (M2 ′). And the third layer is an outermost layer. In the step 2 and the step 3, the deposition rate for forming the second layer is DR2 (nm / second), and the third layer is formed. DR3 (nm / second) when the deposition rate for forming is DR3 (nm / second) The DR2, which is the ratio of (nm / sec) R satisfies the following formula 1, method for producing a gas barrier film that;

  According to the present invention, a means for producing a gas barrier film excellent in durability under a high temperature and high humidity environment is provided. Moreover, according to this invention, the means to manufacture the gas barrier film excellent in the adhesiveness at the time of device sealing is provided.

In the manufacturing method which concerns on one form of this invention, it is a schematic diagram which shows a preferable example of the manufacturing apparatus used for formation of a 2nd layer and a 3rd layer. It is a schematic diagram which shows a preferable example of the gas barrier film manufactured with the manufacturing method which concerns on one form of this invention.

  One embodiment of the present invention includes a step 1 of forming a first layer containing a non-transition metal (M1) on a base material using a non-transition metal (M1) or a compound containing a non-transition metal (M1); On the first layer, a second layer containing a transition metal (M2) is formed using a transition metal (M2) or a compound containing a transition metal (M2) by physical vapor deposition so as to be in contact with the first layer. And forming a third layer containing a transition metal (M2 ′) on the second layer by a physical vapor deposition method using a compound containing a transition metal (M2 ′) or a transition metal (M2 ′). And the third layer is the outermost layer. In steps 2 and 3, the deposition rate for forming the second layer is DR2 (nm / second), and the deposition for forming the third layer is performed. When the speed is DR3 (nm / sec), the ratio of DR2 (nm / sec) to DR3 (nm / sec) That R satisfies the following equation 1, relates to a method for producing a gas barrier film;

  The inventors have at least three layers: a layer containing a non-transition metal on a substrate, a second layer containing a transition metal in contact with the layer containing the non-transition metal, and a third layer containing a transition metal as the outermost layer. In addition, the deposition rate of the second layer and the third layer is such that the adhesion with the adhesive layer at the time of gas barrier property / gas barrier property film sealing in a high temperature and high humidity environment (hereinafter, It has been found that it contributes to the sealing adhesion. Further, by setting the ratio of the deposition rate for forming the second layer to the deposition rate for forming the third layer within a specific range, the gas barrier property / sealing adhesive property in a high temperature and high humidity environment is remarkably improved. As a result, the present invention has been completed.

  The present inventors presume the mechanism by which the problem is solved by this configuration as follows.

  In a structure having a layer containing a non-transition metal (M1) and a layer containing a transition metal (M2) in contact with the layer containing the non-transition metal (M1), in the layer containing the non-transition metal (M1) A composite composition region containing the non-transition metal (M1) and the transition metal (M2) is formed in the vicinity of the interface between the layer containing the non-transition metal (M1) and the layer containing the transition metal (M2). Formation of such a composite composition region improves gas barrier properties. This is because the bond between the non-transition metal (M1) and the transition metal (M2) is more likely to occur than the bond between the non-transition metals or the transition metal (M2). It is thought that this is because a simple structure is formed.

  Here, as one method for producing a gas barrier film having such a composite composition region, a method of forming a layer containing a transition metal (M2) by a physical vapor deposition method may be mentioned. Vapor-deposited particles comprising a transition metal (M2) or a compound containing a transition metal (M2) by forming a layer containing a transition metal (M2) by physical vapor deposition so as to be in contact with a layer containing a non-transition metal (M1) Is implanted into a layer containing a non-transition metal (M1) in a state having a kinetic energy of a certain level or more. At this time, the vapor deposition particles enter the layer containing the non-transition metal (M1), and the layer containing the non-transition metal (M1) and the layer containing the transition metal (M2) in the layer containing the non-transition metal (M1). A composite composition region containing a non-transition metal (M1) and a transition metal (M2) is formed in the vicinity of the interface.

  At this time, the higher the vapor deposition rate, the higher the kinetic energy of the vapor deposition particles. Therefore, the distance that the vapor deposition particles enter the layer containing the non-transition metal increases. For this reason, it is easy to form a composite composition region having a sufficient thickness by increasing the deposition rate when forming the layer containing the transition metal (M2) on the layer containing the non-transition metal (M1). Thus, it is considered that higher gas barrier properties can be obtained.

  On the other hand, when the deposition rate of the transition metal is increased in order to form the composite composition region, the film surface density decreases and the film surface smoothness also decreases. When an adhesive layer is formed on such a film surface to seal an electronic device, the adhesiveness is low. This is thought to be due to cohesive failure due to insufficient cohesive force on the rough film surface or interface failure due to insufficient adhesiveness at the adhesive layer interface due to a decrease in smoothness.

  In this embodiment, when forming the outermost layer on the layer (second layer) containing the transition metal (M2) formed at a high deposition rate, it is more relative than the second layer. The transition metal (M2 ′) is deposited at a low deposition rate. By performing the deposition rate of the third layer formed on the second layer relatively lower than that of the second layer, a film having high smoothness and high density can be formed on the outermost surface. By increasing the denseness of the deposited layer, cohesive failure due to insufficient cohesive force can be suppressed, and by increasing the smoothness of the film surface, insufficient adhesion at the interface between the gas barrier film surface and the adhesive layer It is considered that the interfacial breakage due to the can be suppressed.

  Further, by forming a layer (third layer) containing a transition metal (M2 ′) on the outermost surface, durability in a high temperature and high humidity environment can be further improved. This is because during storage, the third layer comes into contact with oxygen first, and the third layer is oxidized prior to the other layers, so that the first layer and the second layer, and further the above composite It is considered that this is because the composition region is suppressed from being deteriorated by oxygen penetration and the gas barrier performance is lowered. Furthermore, after sealing to an electronic device or the like, a layer (third layer) containing a transition metal (M2 ′) is formed on the outermost surface, so that water and oxygen from the outside can be removed from the substrate from the first. By passing through the composite composition region of the layer and the second layer, it is possible to delay the oxidation deterioration of these regions in order, and it is considered that the gas barrier performance under high temperature and high humidity conditions is further improved. Note that the above mechanism is based on speculation, and its correctness does not affect the technical scope of the present invention.

  Hereinafter, preferred embodiments of the present invention will be described. In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, the operation and physical properties are measured under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

〔Base material〕
Although it does not restrict | limit especially as a base material used for 1 form of this invention, It is preferable to use a resin base material. Specific examples of the resin base material 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, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modification Examples include a base material containing a thermoplastic resin such as a polycarbonate resin, a fluorene ring-modified polyester resin, or an acryloyl compound. These resin substrates can be used alone or in combination of two or more.

  More preferable specific examples of the thermoplastic resin that can be used as the substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic. Polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C, manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 190 ° C), cycloolefin copolymer (COC: Compound described in JP 2001-15058 A: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C., manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: JP 2000-227603 Compound described in the report: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP 2000-227603 A: 205 ° C.), acryloyl compound (compound described in JP 2002-80616 A: 300 ° C. or higher), etc. (in parentheses indicate Tg).

  Since the gas barrier film produced by the production method according to one embodiment of the present invention can be used as an electronic device such as an organic EL element, the resin substrate is preferably transparent. That is, the light transmittance is preferably 80% or more, more preferably 85% or more, and further 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.

  Moreover, the unstretched film may be sufficient as the resin base material quoted above, and a stretched film may be sufficient as it. The resin base material can be manufactured by a conventionally known general method. About the manufacturing method of these base materials, the matter described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately employed.

  As the resin base material, a commercially available product may be used. For example, Lumirror (registered trademark) U48 manufactured by Toray Industries, Inc., which is a commercially available polyethylene terephthalate film, may be used.

  The surface of the resin substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments may be combined as necessary. May go. The resin base material may be subjected to an easy adhesion treatment.

  The resin substrate may be a single layer or a laminated structure of two or more layers. When the resin base material has a laminated structure of two or more layers, the resin base materials may be the same type or different types.

  The thickness of the substrate according to an embodiment of the present invention (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 μm, and more preferably 20 to 150 μm.

[Formation of first layer containing non-transition metal (M1)]
In the method for producing a gas barrier film according to the present invention, a first layer containing a non-transition metal (M1) is formed on a substrate using a non-transition metal (M1) or a compound containing a non-transition metal (M1). Step 1 is essential. The first layer is a layer having a function of imparting a certain gas barrier property to the gas barrier film.

  In the present invention, as a raw material for forming the first layer, a non-transition metal (M1) simple substance or a compound containing a non-transition metal (M1) may be used.

  Moreover, as a raw material for forming a 1st layer, the other metal or compound may further be contained. Examples of the forming method using such a raw material include a case of performing layer formation by co-evaporation or application of a composition solution. At this time, the raw material for forming the first layer further includes a raw material capable of forming the second and third layers described later, that is, a compound containing a transition metal (M2) or a transition metal (M2). It may be. In this case, the layer classification is determined as follows. First, only the first layer is separately formed under the same conditions as the production of the gas barrier film. Next, the molar amounts of the non-transition metal (M1) and the transition metal (M2) present in the layer as elements are confirmed. When the amount of the non-transition metal (M1) is larger than the amount of the transition metal (M2), the formation of the layer is treated as the formation of the first layer.

  Here, the compound containing the non-transition metal (M1) is not particularly limited, and examples thereof include organic metal compounds, oxides, nitrides, oxynitrides, oxycarbides and the like. Among these, the compound containing the non-transition metal (M1) is preferably an oxide or an oxynitride. In addition, the suitable example of the compound containing a non-transition metal (M1) in case a non-transition metal (M1) is Si is mentioned later.

  Although it does not restrict | limit especially as a non-transition metal (M1), From a gas-barrier viewpoint, the metal selected from the non-transition metal (M1) selected from the metal of the 12th group of the long period type periodic table 14th group It is preferable that Among these, it is more preferable that Si, Al, Zn, In, or Sn is included, it is more preferable that Si, Sn, or Zn is included, and it is particularly preferable that Si is included. In addition, although a non-transition metal (M1) can be used individually or in combination of 2 or more types, it is preferable to use it independently. Thus, it is most preferable that the non-transition metal (M1) is only Si.

  The first layer formed by step 1 includes a non-transition metal (M1). The non-transition metal (M1) contained in the first layer may be a simple substance or a compound containing the non-transition metal (M1). The first layer preferably contains a non-transition metal (M1) and at least one of oxygen (O) and nitrogen (N), and contains the non-transition metal (M1), oxygen (O) and nitrogen (N). It is more preferable to include. The kind of preferable non-transition metal (M1) is the same as that of the non-transition metal (M1) in the raw material for forming the above-mentioned 1st layer.

  The thickness of the first layer is not particularly limited, but is preferably 10 to 500 nm and more preferably 30 to 300 nm from the viewpoint of gas barrier properties.

  The method for forming the first layer is not particularly limited, but it is preferable to use a vapor deposition method or a coating method. Among these, the coating method is more preferable from the viewpoint of productivity.

(Vapor deposition method)
The vapor deposition method is not particularly limited. For example, physical vapor deposition such as sputtering, vapor deposition, or ion plating, chemical vapor deposition (plasma CVD), or chemical vapor deposition such as ALD (Atomic Layer Deposition). Law. Among these, the physical vapor deposition method is preferable and the sputtering method is more preferable because the film formation is possible without damaging the lower layer and the productivity is high.

  For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used. In addition, a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used. By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable. As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. By introducing oxygen, nitrogen, carbon dioxide, carbon monoxide into the process gas, thin films of non-transition metal (M1) or non-transition metal (M1) oxides, nitrides, nitride oxides, carbonates, etc. Can be made. Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, film material, film thickness, and the like.

(Coating method)
In step 1, it is preferable to form the first layer by applying a coating solution containing a compound containing a non-transition metal (M1). Unlike the case where it is formed by the vapor phase film formation method, the film formation by the coating method does not include foreign matters such as particles at the time of film formation, so that a gas barrier layer with few defects can be obtained and the gas barrier performance is improved. To do.

  Here, as a compound containing a non-transition metal (M1), a silicon-containing compound is preferably used. For example, polysiloxane, polysilsesquioxane, polysilazane, polysiloxazan, polysilane, polycarbosilane, alkoxysilane, etc. It is preferable that it is an inorganic precursor containing the non-transition metal (M1). Among these, the compound containing the non-transition metal (M1) is more preferably polysilazane. When the compound containing the non-transition metal (M1) is polysilazane, the composition of the gas barrier layer finally obtained by storage over time until the second layer is formed can be suppressed, and productivity and production can be suppressed. This is because the stability is improved.

When the compound containing the non-transition metal (M1) is alkoxysilane, a sol-gel method may be used as the coating method for forming the first layer as described in JP-A-2005-231039. The coating liquid used when forming the modified layer by the sol-gel method preferably contains alkoxysilane and at least one of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer. Further, the coating liquid preferably contains a sol-gel method catalyst, an acid, water, and an organic solvent. In the sol-gel method, a modified layer is obtained by polycondensation using such a coating solution. Specific examples of the alkoxysilane include, for example, tetramethoxysilane (Si (OCH ₃ ) ₄ ), tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), and tetrapropoxysilane (Si (OC ₃ H ₇ ) _4. ), Tetrabutoxysilane (Si (OC ₄ H ₉ ) ₄ ) and the like can be used.

<Polysilazane>
Polysilazane is a polymer having a silicon-nitrogen bond, and ceramics such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y having bonds such as Si—N, Si—H, and N—H. It is a precursor inorganic polymer.

  The polysilazane is not particularly limited, but polysilazane having the following structure is preferably used.

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R ₁ , R ₂ and R ₃ may be the same or different.

  In the general formula (I), n is an integer, and the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. Is preferred.

In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

  On the other hand, the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard. The ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, these perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

  Polysilazane is commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as the first layer-forming coating solution. As a commercially available product of polysilazane solution, NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, etc. manufactured by AZ Electronic Materials Co., Ltd. Is mentioned. These polysilazane solutions can be used alone or in combination of two or more.

  Another example of the polysilazane that can be used in one embodiment of the present invention is not limited to the following. Glycidol-added polysilazane (JP-A-6-122852) obtained by reacting with alcohol, alcohol-added polysilazane (JP-A-6-240208) obtained by reacting alcohol, and metal obtained by reacting metal carboxylate Carboxylate-added polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal fine particles are added. Obtained metal fine particle Polysilazane (JP 7-196986) etc., include polysilazane ceramic at low temperatures. In addition, for details of polysilazane, paragraphs “0024” to “0040” of JP2013-255910A, paragraphs “0037” to “0043” of JP2013-188942A, and JP2013-103A are known. No. 151123, paragraphs “0014” to “0021”, JP 2013-052569 A paragraphs “0033” to “0045”, JP 2013-129557 A paragraphs “0062” to “0075”, JP 2013 It can be adopted with reference to paragraphs “0037” to “0064” of JP-A-226758.

<Preparation of coating solution>
The solvent for preparing the coating liquid for forming the first layer is not particularly limited as long as it can dissolve the compound containing the non-transition metal (M1). However, when polysilazane is used as the compound containing a non-transition metal (M1), it does not contain water and reactive groups (for example, hydroxyl group or amine group) that easily react with polysilazane, and does not contain polysilazane. Inert organic solvents are preferred, and aprotic organic solvents are more preferred. Specifically, the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene Hydrogen solvents; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Dibutyl ether, dioxane, tetrahydrofuran, mono- and polyalkylene glycol dialkyl ethers (diglymes) ), And ethers such as alicyclic ethers. The solvent is selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of the compound containing the non-transition metal (M1) in the coating solution is not particularly limited and varies depending on the film thickness of the first layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably It is 4-50 mass%.

  The coating solution preferably contains a catalyst from the viewpoint of accelerating the modification when the modification is performed by vacuum ultraviolet rays. The catalyst applicable to the present invention is preferably a basic catalyst, and in particular, an amine catalyst, a metal catalyst such as a Pt compound, a Pd compound, and an Rh compound, and an N-heterocyclic compound are exemplified. Of these, it is preferable to use an amine catalyst. The amine catalyst is not particularly limited, and for example, N, N, N ′, N′-tetramethyl-1,6-diaminohexane or the like can be used. The concentration of the catalyst added at this time is preferably 0.1 to 10% by mass, more preferably 0.1 to 7% by mass, based on the compound containing the non-transition metal (M1) in the coating solution. It is a range. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.

  As long as the effect of this invention is not impaired, another additive can be used for a coating liquid as needed.

<Application method>
As a method of applying the coating liquid for forming the first layer, a conventionally known appropriate wet coating method can be employed. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method and the like. It is done.

  The coating thickness can be appropriately set according to the preferred thickness and purpose.

  After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable first layer can be obtained. The remaining solvent can be removed later.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 50-200 degreeC. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

  In the said manufacturing method, the process of removing a water | moisture content may be included with respect to the coating film obtained by apply | coating a coating liquid. As a method for removing moisture, a form of dehumidification while maintaining a low humidity environment is preferable. Since the humidity in the low humidity environment varies depending on the temperature, the relationship between the temperature and the humidity shows a preferable form by the definition of the dew point temperature. A preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −5 ° C. or lower (temperature 25 ° C./humidity 10%), and the time for maintaining is the film of the first layer. It is preferable to set appropriately depending on the thickness. Specifically, it is preferable that the dew point temperature is −5 ° C. or lower and the maintained time is 1 minute or longer. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher and preferably −40 ° C. or higher. This is a preferred form from the viewpoint of promoting the dehydration reaction of the first layer converted to silanol by removing moisture before the reforming process or when the reforming process is performed.

<Reforming treatment>
In step 1, it is preferable to further modify the coating film obtained by applying the coating solution to form the first layer. Here, when the compound containing the non-transition metal (M1) is a silicon-containing compound, the modification treatment refers to a conversion reaction of the silicon-containing compound to silicon oxide, silicon oxynitride, or the like, and specifically, gas barrier properties. The process which forms the inorganic thin film of the level which can contribute for a film to express gas barrier property as a whole.

  The conversion reaction of the silicon-containing compound into silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method. The reforming treatment is not particularly limited, and various known methods can be used. Specific examples include plasma treatment, ultraviolet irradiation treatment, and heat treatment. The modification process can be performed at a relatively low temperature (about 200 ° C. or less), has little influence on the resin base material, and the modification process is performed efficiently. It is preferable that

  Furthermore, after forming the first layer, it has a step of storing in a high-temperature and high-humidity environment by performing vacuum ultraviolet irradiation until the second layer is formed after forming the first layer. Even if it has, the composition of the gas barrier layer finally obtained hardly changes compared with the manufacturing method which does not have the process to preserve | save, and production stability improves more. Therefore, in actual production, there are fewer restrictions on the coating process, the modification process, and the like, and there are fewer restrictions on the substrate conveyance speed in the coating process, the modification process, etc., and the productivity is further improved.

  The present invention can obtain a particularly remarkable effect when polysilazane is used as a compound containing a non-transition metal (M1) and is formed through such a modification step. This reason is presumed to be because the effect of suppressing the reforming reaction occurring in the unmodified portion remaining in the modified layer when the deposited particles are injected into the modified layer of polysilazane is high.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, it can be processed in an ultraviolet baking furnace equipped with an ultraviolet ray generation source. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. Further, when the object is a long film, it can be converted to ceramics by continuously irradiating ultraviolet rays in a drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. The time required for ultraviolet irradiation is preferably 0.1 seconds to 10 minutes, more preferably 0.5 seconds to 3 minutes, although it depends on the resin substrate used and the composition and concentration of the first layer. .

  Modification by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and only bonds photons called photon processes to bond atoms. In this method, a film containing silicon oxynitride is formed at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together. Here, as temperature in heat processing, it is preferable that it is 40-150 degreeC. If the heat treatment temperature is 40 ° C. or higher, the reforming can be further promoted. Moreover, generation | occurrence | production of a deformation | transformation of a resin base material etc. can be suppressed more as heat processing temperature is 150 degrees C or less.

  The vacuum ultraviolet source may be any source that generates light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp), and low-pressure mercury having an emission line at about 185 nm. Vapor lamps, as well as medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having a maximum emission at about 222 nm.

  Among these, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  As the vacuum ultraviolet irradiation processing apparatus, for example, an excimer irradiation apparatus MODEL: MEUT-1-500 manufactured by M.D.Com Co., Ltd. can be used.

  Oxygen is required for the reaction at the time of vacuum ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. In addition, it is preferably performed in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). More preferably. Also, the water vapor concentration during the conversion process is preferably in the range of 1,000 to 4,000 volume ppm.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

In vacuum ultraviolet radiation, preferably the intensity of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is a ^{1mW / cm 2 ~10W / cm 2} , more preferably 30mW / cm ² ~200mW / cm 2 and further preferably ^{50mW / cm 2 ~160mW / cm 2} . If it is 1 mW / cm ² or more, the reforming efficiency is improved, and if it is 10 W / cm ² or less, ablation that can occur in the coating film and damage to the substrate can be reduced.

When subjected to vacuum ultraviolet irradiation, irradiation energy of the vacuum ultraviolet in the surface of the coating film (dose) is preferably less than 0.1 J / cm ² or more ^{10J / cm 2, 0.2~5J / cm} 2 It is more preferable that If the irradiation energy amount is within this range, even if it has a step of storing in a high-temperature and high-humidity environment until the second layer is formed after the first layer is formed, finally, The composition of the obtained gas barrier layer hardly changes, and the production stability is further improved. Further, in actual production, there are fewer restrictions on the coating process and the modification process, and there are fewer restrictions on the substrate conveyance speed in the coating process and the modification process, and the productivity is further improved.

  Moreover, it is preferable that the distance of an irradiation surface and a light source is 0.5-10 mm. When the distance between the irradiation surface and the light source is 0.5 mm or more, scratches caused by contact between the substrate surface and the light source can be further reduced when the substrate is continuously processed while being conveyed. In addition, when the distance between the irradiation surface and the light source is 10 mm or less, it is possible to further suppress a decrease in the amount of light due to the vacuum ultraviolet absorbing gas existing between the substrate surface and the light source.

The vacuum ultraviolet ray used may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.

[Formation of Second Layer Containing Transition Metal (M2) and Third Layer Containing Transition Metal (M2 ′)]
The method for producing a gas barrier film according to the present invention uses a compound containing a transition metal (M2) or a transition metal (M2) on the first layer by physical vapor deposition so as to be in contact with the first layer. Step 2 of forming a second layer containing a transition metal (M2) and a compound containing a transition metal (M2 ′) or a transition metal (M2 ′) on the second layer by physical vapor deposition And step 3 of forming a third layer containing a transition metal (M2 ′). Here, the third layer is disposed in the outermost layer. The order in which the third layer is formed is not particularly limited as long as it is on the second layer and the outermost layer, but it is preferably formed so as to be in contact with the second layer.

  By forming the second layer containing the transition metal (M2) so as to be in contact with the first layer, the gas barrier property is improved. The reason why this function is realized is that, as described above, when the second layer is formed, a composite having a high-density structure of the metal compound in the vicinity of the interface between the second layer and the first layer. It is presumed that the composition region is formed. In addition, by forming the third layer including the transition metal (M2 ′) in the outermost layer, the third layer is oxidized first when oxygen enters from the outside. It is considered that the durability in a high-temperature and high-humidity environment is further improved because oxidation of the layer 2 and the composite composition region is suppressed.

  In the present invention, the second layer is formed using a transition metal (M2) or a compound containing a transition metal (M2). That is, as a raw material for forming the second layer, the transition metal (M2) itself may be used, or a compound containing a metal element (a compound containing a transition metal (M2)) may be used. The third layer is formed using a transition metal (M2 ′) or a compound containing a transition metal (M2 ′). That is, as a raw material for forming the third layer, a transition metal (M2 ′) itself or a compound containing a metal element (compound containing a transition metal (M2 ′)) may be used.

  Hereinafter, the transition metal (M2) and the transition metal (M2 ′) are also simply referred to as a transition metal, a compound containing the transition metal (M2), and a compound containing the transition metal (M2 ′) simply as a compound containing a transition metal.

  In the present specification, the transition metal represents a Group 3 element to a Group 11 element in the long-period periodic table. The transition metal is not particularly limited, and any transition metal can be used, but Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru , Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au It is preferable to contain. Among these, Nb, Ta, V, Zr, Ti, Hf, Y, La, and Ce are more preferable as the transition metal from the viewpoint of obtaining a further improvement effect of gas barrier properties. From the same viewpoint, it is more preferable that the metal is selected from Group 5 metals of the long-period periodic table, that is, a metal selected from Nb, Ta, and V, more preferably Nb. Particularly preferred. Moreover, although a transition metal can be used individually or in combination of 2 or more types, it is preferable to use it independently. Therefore, it is most preferable that the transition metal is only Nb.

  Here, the transition metal (M2) contained in the raw material for forming the second layer and the transition metal (M2 ′) contained in the raw material for forming the third layer may be the same. May be different. However, the viewpoint that the transition metal (M2) contained in the second layer and the transition metal (M2 ′) contained in the third layer have an effect of improving the gas barrier property in a further high-temperature and high-humidity environment. Therefore, they are preferably the same, and are both metals selected from Group 5 of the long-period periodic table, that is, more preferably Nb, Ta, and V, and even more preferably Nb. It is considered that a further effect of improving the gas barrier property is obtained due to the combination that the bond between the non-transition metal (M1) and the transition metal (M2) is more likely to occur and the lower layer oxidation suppression effect is high.

Here, the compound containing a transition metal as a raw material for forming the second layer or the third layer is not particularly limited, and examples thereof include organometallic compounds, oxides, nitrides, oxynitrides, and acids. Carbide etc. are mentioned. Among these, the compound containing a transition metal is preferably an oxide. The transition metal oxide is preferably an oxygen-deficient transition metal oxide, and particularly preferably an oxygen-deficient niobium oxide. Here, the oxygen-deficient niobium oxide is not particularly limited, but, for example, one having a composition of Nb ₁₂ O ₂₉ can be used.

Here, the oxygen-deficient transition metal oxide is a metal oxide MO _x1 where x1 <x2 when the stoichiometrically obtained transition metal oxide is MO _x2 (M is a transition metal). Refers to transition metal oxide. For example, taking the oxide of Nb (niobium) as an example, the Nb stoichiometric oxide is niobium pentoxide, which is NbO _2.5 , so x2 = 2.5. is there. Nb can take the composition of niobium trioxide, but x2 in the present invention means x2 of a stoichiometric compound having the highest degree of oxidation. If the transition metal M2 is stacked under the condition of oxygen deficiency, it is difficult for the non-transition metal M1 included in the first layer and the metal M2 included in the second layer to bond with oxygen alone. A bond is likely to occur between the non-transition metal M1 included in the first layer and the metal M2 included in the second layer.

  As the transition metal (M′2) oxide, an oxygen-deficient transition metal oxide is preferably used, and an oxygen-deficient niobium oxide is particularly preferable. By forming a deposited film using such a raw material, a region having an oxidation degree lower than the stoichiometric oxidation degree exists in the outermost layer. For this reason, it is thought that it is easy to receive the oxidation by the oxygen which penetrate | invaded from the outside, oxidative degradation of another layer is suppressed, and a higher gas barrier performance is exhibited under high temperature and high humidity conditions.

  Further, the raw material for forming the second layer and the third layer may further contain other metals or compounds. As a forming method using such a raw material, for example, co-deposition is performed. At this time, the raw material for forming the second layer and the third layer includes the raw material capable of forming the first layer, that is, the non-transition metal (M1) or the non-transition metal (M1). Further compounds may be included. In this case, the layer classification is determined as follows. First, only the second layer or the third layer is separately formed under the same conditions as in the production of the gas barrier film. Next, the molar amounts of the non-transition metal (M1) and the transition metal (M2) present in the layer as elements are confirmed. When the molar amount of the transition metal (M2) is larger than the molar amount of the non-transition metal (M1), the formation of such a layer is handled as the formation of the second layer or the third layer. However, in the present invention, it is preferable that the raw material for forming the second layer or the third layer does not contain a non-transition metal (M1) or a compound containing a non-transition metal (M1). .

  Further, the second layer and the third layer formed by the step 2 and the step 3 include a transition metal. The transition metal contained in the second layer and the third layer may be in the state of a single metal element or a compound containing a transition metal (for example, an oxide, nitride, oxynitride of transition metal, or Acid carbide). The second layer and the third layer preferably contain a transition metal and oxygen (O). Preferred transition metal types are the same as those of the transition metal in the raw material for forming the second layer and the third layer.

  In the present invention, the second layer and the third layer are formed by a physical vapor deposition method (PVD method). The physical vapor deposition is a method of depositing a thin film of a target substance on the surface of the substance in a gas phase by a physical method. The physical vapor deposition method can be roughly divided into an evaporation system and a sputtering system. Film formation by sputtering of a transition metal simple substance or transition metal oxide film, nitride film, oxynitride film or oxycarbide film is bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering using an intermediate frequency region, Ion beam sputtering, ECR sputtering, or the like can be used. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used. When sputtering a transition metal element or a transition metal oxide film, nitride film, nitrogen oxide film, or carbonation film, the above-described transition metal element or a compound containing a transition metal can be used as the target. As the inert gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a transition metal simple substance or a transition metal oxide, nitride, nitride oxide, or carbonate thin film can be formed. When the film is formed by RF (high frequency) sputtering, it is preferable to use a ceramic target containing an oxide or nitride of a transition metal, such as Nb, Ta, V, Zr, Ti, Hf, Y, La, or Ce. . Examples of film forming conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, and these can be appropriately selected according to the sputtering apparatus, the material of the film, the film thickness, and the like. In addition, vacuum evaporation (heating method: resistance heating, electron beam, high frequency induction, laser, etc.), molecular beam evaporation (MBE), ion plating, ion beam evaporation etc. It may be used.

  In the method for producing a gas barrier film according to the present invention, in step 2 and step 3, the deposition rate for forming the second layer is DR2 (nm / second), and the deposition rate for forming the third layer is DR3 (nm / second). R) (DR2 / DR3), which is a ratio of DR2 (nm / second) to DR3 (nm / second), satisfies the following formula 1.

  When R is 1.1 or less, DR3 is relatively similar to DR2 or has a high deposition rate. As described above, DR2 needs to have a high deposition rate to form a composite composition region. Therefore, if R is 1.1 or less, DR3 also necessarily has a high deposition rate. When the deposition rate is increased, the denseness of the formed film is lowered and the smoothness of the surface is lowered, so that the sealing adhesiveness is deteriorated. This is because the surface of the gas barrier film is prone to cohesive failure due to insufficient cohesion, and since the smoothness is low, when the adhesive layer is laminated, the adhesiveness at the interface of the adhesive layer is lowered, and interface failure is liable to occur. it is conceivable that.

  On the other hand, if R exceeds 5.0, the film thickness of the third layer becomes thin, so that the irregularities on the surface of the second layer cannot be smoothed, and the sealing adhesiveness is considered to deteriorate. .

  Further, when R exceeds 1.1, DR3 has a lower deposition rate than DR2, so that the denseness of the film is increased, and water or oxygen that has entered from the outside flows from the substrate to the first layer, It is possible to delay the oxidative degradation of these regions in order through the composite composition region of the second layer, and further suppress the intrusion of water and oxygen in the third layer. It is considered that the performance is further improved. In addition, even when oxygen enters from the film surface after the gas barrier film is manufactured and before sealing, the third layer tends to be oxidized and deteriorated first, and the first layer, the second layer, and the composite composition region It is considered that the oxidative deterioration can be further suppressed, and the gas barrier performance under high temperature and high humidity conditions is further improved.

  On the other hand, when R is 5.0 or less, the thickness of the third layer to be formed is sufficiently thick, and the effect of suppressing the oxidative degradation of the lower gas barrier layer is sufficiently exhibited. It is considered that the gas barrier performance under the conditions is further improved.

  From the same viewpoint, R (DR2 / DR3) is preferably 1.5 ≦ R ≦ 4.5, and more preferably 2.0 ≦ R ≦ 3.5.

  Here, the vapor deposition rate (nm / second) can be calculated by dividing the vapor deposition time (second) from the film thickness (nm) of the deposited film. That is, DR2 (nm / second) can be calculated by dividing the vapor deposition time t2 (second) for forming the second layer from the film thickness T2 (nm) of the second layer. DR3 (nm / second) can be calculated by dividing the deposition time t3 (second) for forming the third layer from the film thickness T3 (nm) of the third layer. The vapor deposition time refers to the time required to form the film thickness T2 (nm) or T3 (nm) of the vapor deposition film. The film thickness and deposition time are rounded off to the first decimal place, and R is calculated to the first decimal place. R is calculated to the second decimal place and rounded to the first decimal place. The obtained value is adopted.

  Here, the second layer and the third layer may have the same composition, and may be formed by continuous vapor deposition while maintaining a vacuum state as will be described later. Thus, it may be difficult to measure and calculate T2 (nm) and T3 (nm) from the manufactured gas barrier film itself. As a result, T2 (nm) and T3 (nm) are formed in advance using a base material in which the vapor deposition particles do not easily enter the second layer and the third layer under the film forming conditions. It can be obtained by measuring. In addition, in the case of the film thickness measurement and vapor deposition rate calculation in this specification, the glass substrate is used as a base material for a measurement. A commercially available glass substrate can also be used, for example, Corning's Willow Glass or the like.

  DR2 (nm / second) and DR3 (nm / second) are not particularly limited within the range of the deposition rate that can be achieved by a known deposition method, and the effects of the present invention can be obtained. About DR2, it is preferable that it is a vapor deposition rate so that a composite composition area | region may be formed in the 1st layer and 2nd layer interface. Such a deposition rate can be appropriately set by those skilled in the art. However, DR2 (nm / second) is preferably 0.5 nm / second or more and 1000 nm / second or less. Within such a range, it is possible to obtain an effect of improving gas barrier properties under further high temperature and high humidity conditions. The reason for this is that by selecting an appropriate vapor deposition rate, generation of heat in the vicinity of the vapor deposition surface of the layer containing the non-transition metal (M1) can be further reduced, and the layer of the layer containing the non-transition metal (M1) This is considered to be because the chemical reaction of the forming substance and the shrinkage of the layer containing the non-transition metal (M1) resulting from the chemical reaction and the generation of gas can be further suppressed. And it is thought that it is because the stress of the layer containing the non-transition metal (M1) generated due to these can be further reduced. Furthermore, since the deposition rate is moderate, it is considered that the composite region can be formed thick and uniform. From the same viewpoint, it is more preferably 1 nm / second to 300 nm / second, more preferably 1.5 nm / second to 300 nm / second, more preferably 2.0 nm / second to 100 nm / second. More preferably. Further, DR3 (nm / second) is preferably 0.1 nm / second or more and 500 nm / second or less. Within such a range, it is possible to obtain a gas barrier property improving effect and a further adhesion improving effect under further high temperature and high humidity conditions. From the same viewpoint, it is more preferably 0.2 nm / second or more and 300 nm / second or less, and more preferably 0.3 nm / second or more and 100 nm / second or less.

  Here, when the substrate is being transported, the deposition time (seconds) is the deposition surface length (m), which is the length in the transport direction in which deposition particles deposited from one deposition source are deposited on the deposition surface, It can be calculated by dividing the transport speed (m / min) of the substrate by the value (m / second) appropriately converted to a unit, and the deposition speed is the deposition film thickness (nm) by the deposition time (second). It can be calculated by dividing.

  T2 (nm) is not particularly limited, but is preferably 2.0 nm or more and 20.0 nm or less, and more preferably 3.0 nm or more and 10.0 nm or less. When the thickness is 2.0 nm or more and 20.0 nm or less, an effect of improving gas barrier properties under further high temperature and high humidity conditions can be obtained. In particular, if the second layer is formed under the same film forming conditions except for the vapor deposition rate, it is equivalent to a higher vapor deposition rate as the film thickness increases. For this reason, when T2 (nm) is 2.0 nm or more, the distance that the vapor deposition particles enter the layer containing the non-transition metal (M1) becomes larger, and a uniform composite composition region with a larger film thickness is formed. It is speculated that the effect of improving gas barrier properties under high temperature and high humidity conditions can be obtained. In addition, when T2 (nm) is 20.0 nm or less, the amount of the vapor deposition particles in the second layer is moderately suppressed. Therefore, the vapor deposition particles include the non-transition metal (M1) in the plane. The distance into the inside, the uniformity of the number of vapor deposition particles entering the first layer containing the non-transition metal (M1) in the plane is higher, the in-plane uniformity of the composite composition region is further increased, It is presumed that an effect of improving gas barrier properties under high temperature and high humidity conditions can be obtained.

  Further, T3 (nm) is not particularly limited, but when t2 = t3 within the preferable range of T2, the deposition rate ratio is the film thickness ratio, so that the range of R is satisfied. What is necessary is just to set suitably, It is preferable that it is 0.4 nm or more and 18.0 nm or less, It is more preferable that it is 0.6 nm or more and 9.0 nm or less, 0.8 nm or more and 3.5 nm or less Is particularly preferred. When the thickness is 0.4 nm or more, it is possible to obtain an effect of improving gas barrier properties and a further effect of improving adhesiveness under further high temperature and high humidity conditions. The reason for this is that the thickness of the third outermost layer to be formed is sufficiently thick, so that the effect of suppressing oxidation deterioration can be sufficiently exerted, and the unevenness on the surface of the second layer can be smoothed. This is probably because of this. Further, when it is 18 nm or less, it is possible to obtain an effect of improving gas barrier properties and a further effect of improving adhesiveness under further high temperature and high humidity conditions. The reason for this is considered to be that the vapor deposition rate becomes appropriate, the denseness of the film increases, and the smoothness of the film surface also increases.

  Assuming that the deposition time for forming the second layer is t2 (seconds) and the deposition time for forming the third layer is t3 (seconds), t2 (seconds) and t3 (seconds) are not particularly limited. It is preferably 1 second or more and 20.0 seconds or less, more preferably 0.5 seconds or more and 10.0 seconds or less, and further preferably 1.0 seconds or more and 5.0 seconds or less.

In Step 2 and Step 3, the pressure (vacuum degree) in the vacuum chamber for forming the second layer or the third layer can be adjusted as appropriate. However, the pressure further improves the gas barrier property. From the viewpoint of obtaining, it is preferably 10 Pa or less, more preferably in the range of 1 × 10 ⁻⁸ Pa to 10 Pa, and further preferably 0.01 to 1.0 Pa.

In Steps 2 and 3, the second layer and the third layer are preferably formed by continuous vapor deposition while maintaining a vacuum state from the viewpoint of obtaining a further improvement effect of gas barrier properties. In the present specification, the vacuum state means that the pressure in the vacuum chamber is 10 Pa or less. The reason why it is preferable to perform continuous deposition while maintaining a vacuum state is that when the second layer and the third layer are continuously deposited at a pressure of 10 Pa or less, the second layer and the third layer are formed before the third layer is formed. This is considered to be because the surface or the inside can be prevented from being exposed to the outside air such as oxygen or moisture. As a result, by preventing the deterioration in the second layer, the transition metal (M2) and other elements are prevented from forming an unintended bonding state, and the non-transition metal (M1) and the transition metal are suppressed. This is probably because the bond with (M2) is more likely to occur. From the same viewpoint, the pressure in the vacuum chamber for continuously forming the second layer and the third layer is more preferably in the range of 1 × 10 ⁻⁸ Pa to 10 Pa. More preferably, the pressure is set to 01 to 1.0 Pa.

  In Step 2 and Step 3, the method of forming the second layer and the third layer is not particularly limited, but it is preferable to use a roll-to-roll method from the viewpoint of improving productivity. Further, in the step 2 and the step 3, the second layer and the third layer are transferred in a roll-to-roll manner with a substrate and a laminate of the first layer (hereinafter also referred to as a vapor deposition substrate) having a constant conveyance speed ( It is more preferable that the film is transported at a line speed). By forming the second layer and the third layer while the deposition substrate is conveyed at a constant rate, the deposition time and film thickness of each of the second layer and the third layer are controlled, and the deposition rate This makes it easier to set up and confirm, and to improve productivity.

  The conveyance speed of the vapor deposition substrate is not particularly limited and can be appropriately adjusted according to the vapor deposition method, pressure, and the like, but the conveyance speed is preferably 0.5 m / min or more and 100 m / min or less. Productivity can be improved more as a conveyance speed is 0.5 m / min or more. Moreover, the further improvement effect of gas barrier property can be acquired as a conveyance speed is 100 m / min or less. It is considered that a further improvement effect of the gas barrier property can be obtained by forming a vapor deposition film having a sufficient thickness and reducing minute defects in the vapor deposition film. Moreover, as for the conveyance speed of a vapor deposition base material, it is more preferable that they are 1 m / min or more and 50 m / min or less. When the conveyance speed is 50 m / min or less, a remarkable gas barrier property improvement effect can be more easily obtained. The reason for this is considered that the amount of the vapor deposition particles entering the layer containing the non-transition metal is increased, and the formation of the composite composition region containing the non-transition metal and the transition metal is further promoted. Moreover, when the conveyance speed is within such a range, it becomes easier to control the deposition time and film thickness of each of the second layer and the third layer, and to set and check the deposition speed, thereby further improving productivity. be able to. From the same viewpoint, the conveyance speed of the vapor deposition substrate is more preferably 4 m / min or more and 20 m / min or less.

  In addition, it is one preferable form of the present invention to produce a gas barrier film by a roll-to-roll method including not only steps 2 and 3 but also step 1 described above.

  Note that the gas barrier film according to an embodiment of the present invention is a roll-to-roll method in which the deposition base is constant from the viewpoints of ease of film thickness control and deposition rate control, productivity, and freedom of equipment selection. The deposition time t2 (second) for forming the second layer is the same as the deposition time t3 (second) for forming the third layer. It is particularly preferred to produce. As a preferred example of such a manufacturing method, the equipment and structure of the region for forming the second layer is the same as the equipment and structure of the region for forming the third layer in the roll-to-roll method. A method using a certain apparatus is mentioned. This is because when the base material is transported at a constant transport speed in such an apparatus, the time required for the deposition base material to pass through the region for forming the second layer, and the deposition base material for the third layer. This is because the time for passing through the region for formation is the same.

  In such a manufacturing method, the vapor deposition rate is represented by the thickness of the vapor deposition film deposited per unit time. Thus, when t2 (seconds) and t3 (seconds) are the same, the deposition rate is proportional to the film thickness only. That is, R, which is the ratio of the deposition rate DR2 (nm / second) for forming the second layer to the deposition rate DR3 (nm / second) for forming the third layer, is the thickness T3 (nm of the third layer). ) With respect to the ratio of the film thickness T2 (nm) of the second layer. More specifically, as a manufacturing method under such conditions, the deposition time for forming the second layer is t2 (seconds), the deposition time for forming the third layer is t3 (seconds), When the film thickness is T2 (nm) and the film thickness T3 (nm) of the third layer, t2 (seconds) and t3 (seconds) satisfy the following formula 2, and DR2 (nm / second) and T2 (nm) Satisfies the following formula 3, and DR3 (nm / sec) and T3 (nm) can be expressed as a method for producing a gas barrier film satisfying the following formula 4. Such a production method is a particularly preferred embodiment of the present invention.

  The second layer and the third layer are formed of the reaction gas type, the target type, the pressure, the transport speed of the film (deposition substrate), the diameter of the film forming roller provided in the apparatus, and the evaporation source and the evaporation surface. It can be manufactured as a layer having desired characteristics by appropriately adjusting the opening length in the conveying direction regulated by the adhesion-preventing plate installed therebetween.

  Here, the deposition rate DR2 (nm / second) for forming the second layer and the deposition rate DR3 (nm / second) for forming the third layer are not particularly limited, but from the viewpoint of simplicity of control, It is preferable to control by controlling the sputtering power supply power.

  In Step 2 and Step 3, the physical vapor deposition method used is preferably a sputtering method from the viewpoint of achieving further improvement in gas barrier properties and sealing adhesiveness under high temperature and high humidity conditions.

  A sputtering apparatus that can be used in one embodiment of the present invention is not particularly limited, and a known apparatus can be used. As a sputtering apparatus for performing continuous vapor deposition while maintaining a vacuum state in a roll-to-roll system, for example, an apparatus described in JP 2012-237047 A (a roll-to-roll sputtering apparatus having a magnetron sputtering cathode) 5, the apparatus shown in FIG. 5, the apparatus shown in Japanese Patent Application Laid-Open No. 2015-074810, apparatus names SmartWeb XL 1400 12 cathode system, SmartWeb XL 1400 6 system, etc., manufactured by Applied Material. A known apparatus can be used.

  The power source used for the sputtering method is not particularly limited, but a DC power source, a DC pulse power source, or an MF power source is preferably used from the viewpoint of the deposition rate. As these power supplies, for example, DC power supplies DPG-10, DPG-10H, DPG-20 and DPG-20H manufactured by ULVAC, Inc., DC pulse power supplies of Advanced Energy, Inc., Pinplus Plus + (trademark) 5K, 10K, 5K Dual, TF power source MF Generators TruPlasma MF Series 7000 etc. can be used.

As a method for forming the second layer and the third layer, it is preferable to use a reactive sputtering method among the sputtering methods. The reactive sputtering method is a technique in which a reactive gas such as oxygen or nitrogen is allowed to flow in a chamber during sputtering to deposit a product of a component and gas contained in a target constituent material as a thin film. The reactive sputtering method is preferable because the film composition becomes uniform and the gas barrier property becomes high. In the reactive sputtering method, the aforementioned various transition metals or compounds containing each transition metal can be used as a target. As described above, as described above, it is preferable to use an oxide of a transition metal, more preferably an oxygen-deficient transition metal oxide, and particularly preferably an oxygen-deficient niobium oxide. As the inert gas, He, Ne, Ar, Kr, Xe or the like can be used, and Ar is preferably used. Further, oxygen, nitrogen, carbon dioxide, carbon monoxide, ammonia, H ₂ O, acetylene can be used as the reaction gas, and oxygen is preferably used.

  Although the content of the reactive gas in the sputtering gas in the reactive sputtering method is not particularly limited, the partial pressure of the reactive gas is preferably 1 to 50%, more preferably 3 to 30% with respect to the total pressure of the sputtering gas. More preferably, it is more preferably 5 to 20%.

In the reactive sputtering method, the input power (sputter power supply power) to the target is appropriately set, but is preferably 0.1 to 30 W, more preferably 1 to 10 W / cm ² , and ² to 6 W. / Cm ² is more preferable, and 2.5 to 4.5 W / cm ² is particularly preferable.

  Further, in the reactive sputtering method, the gas pressure at the time of film formation varies depending on the type of apparatus and the like, and thus cannot be generally specified, but is preferably 0.01 to 1.0 Pa, preferably 0.1 to 1.0 Pa. It is more preferable that it is 0.2-0.8 Pa.

  Note that the thickness of the oxide film formed by the reactive sputtering method can be controlled by the film conveyance speed at the time of film formation, the power and voltage applied to the target, the oxygen concentration, and the opening shape (film formation area). .

  FIG. 1 is a schematic diagram showing a preferable example of a manufacturing apparatus used for forming the second layer and the third layer in the manufacturing method according to one embodiment of the present invention. Specifically, FIG. 1 is a schematic diagram showing a sputtering apparatus for performing continuous vapor deposition while maintaining a vacuum state by a roll-to-roll method.

  Hereinafter, an apparatus used in one embodiment of the present invention will be described with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios. In addition, this invention is not limited only to one form demonstrated below.

  The sputtering apparatus 1 in FIG. 1 includes a vacuum chamber 2, a supply-side transfer system chamber 3, and a storage-side transfer system chamber 4. The sputtering apparatus 1 includes transport rollers 7 and 8, a film forming roller 11, and a cathode 12 in a vacuum chamber 2, and the vacuum chamber 2 includes a reactive gas supply device 19 and an inert gas supply device 20. And the vacuum pump 18 are connected. Here, the vacuum chamber 2 can appropriately adjust the pressure in the vacuum chamber 2 by the vacuum pump 18. Further, the cathode 12 is connected to a discharge power supply (not shown). In addition, the sputtering apparatus 1 includes a transport roller 6 and a delivery roller 5 in the supply-side transport system chamber 3, and a transport roller 9, a take-up roller 10, and the like in the storage-side transport system chamber 4. It is equipped with. The supply-side transfer system chamber 3 and the storage-side transfer system chamber 4 are each connected to a vacuum pump 18, and the pressure in the supply-side transfer system chamber 3 and the storage-side transfer system chamber 4 is changed by the vacuum pump, respectively. It is possible to adjust appropriately independently. Further, the sputtering apparatus 1 includes a load lock 21 between the vacuum chamber 2 and the supply-side transfer system chamber 3, and includes a load lock 22 between the vacuum chamber 2 and the storage-side transfer system chamber 4. ing. With the load locks 21 and 22, even if the supply-side transport system chamber 3 and the storage-side transport system chamber 4 are opened to the atmosphere by roll exchange or the like, the vacuum state in the vacuum chamber 2 can be maintained while the film is passed. Can be held.

  The delivery roller 5 is loaded with a vapor deposition base material 15 (here, the vapor deposition base material 15 represents a base material or a laminate including the first layer and the base material) wound in a roll shape. It rotates, and the vapor deposition base material 15 is sent out. The fed deposition base material 15 passes through the load roller 21 through the transport roller 6, and further reaches the film forming roller 11 through the transport roller 7. A reaction gas (for example, oxygen or nitrogen) supplied from a reaction gas supply device 19 to a target 13 (for example, an oxygen-deficient niobium oxide target) held on a cathode 12 connected to a discharge power source (not shown). , And an inert gas (for example, argon) supplied from the inert gas supply device 20 is introduced and mixed, and sputtering for forming the second layer and the third layer is sequentially performed. A laminated body 16 including a laminated structure including the second layer and the third layer is formed on the laminated film 17.

  Next, the laminate film 17 passes through the load roller 22 via the transport roller 8, and further reaches the take-up roller 10 via the transport roller 9, and the laminate film 17 is wound up in a roll shape. Here, the laminate film 17 becomes a gas barrier film.

  In the apparatus 1, a partition wall 14 is disposed to prevent the mixture of sputtering particles and the deposition atmosphere gas such as a reaction gas or an inert gas. In the apparatus 1, six cathodes are arranged. However, other cathodes may be arranged between the partition walls as described above, and sputtering may be performed from a plurality of locations. By performing sputtering from a plurality of locations, the throughput per vacuum chamber can be improved, so that the film formation cost can be suppressed and the tact time can be reduced with a small additional apparatus cost.

  In the case where the second layer and the third layer are formed using the device 1, the second layer and the third layer are formed using at least two of the six cathodes. . The positions of the two cathodes for forming the second layer and the third layer are not particularly limited, but it is preferable to select two cathodes arranged adjacent to each other. In addition to the second layer and the third layer, when forming a layer, the remaining cathode can be used. When seven or more layers are formed, for example, a structure in which two vacuum chambers 2 are coupled in series may be employed.

  Further, in the apparatus 1, a vacuum state is provided between each partition wall, and a vacuum is formed between each wall so that a film formation atmosphere such as a film formation atmosphere gas such as a reaction gas or an inert gas can be controlled independently. A pump 18, a reactive gas supply device 19, and an inert gas supply device 20 are provided. However, the film formation atmosphere may be controlled as a whole of the vacuum chamber 2, and in this case, at least the vacuum pump 18, the reactive gas supply device 19, and the inert gas supply device 20 are placed at arbitrary positions in the vacuum chamber 2. It is sufficient to have one.

  As the delivery roller 5, the transport rollers 6, 7, 8, 9 and the film forming roller 11, known rollers can be used as appropriate. Further, the winding roller 10 is not particularly limited as long as it can wind the laminated film 17 in which the laminated body 16 is formed on the vapor deposition substrate 15, and a known roller is appropriately used. Can do.

  As the load lock 21 and the load lock 22, each chamber is arbitrarily airtightly maintained so that the pressures in the vacuum chamber 2, the supply-side transfer system chamber 3, and the storage-side transfer system chamber 4 can be appropriately adjusted independently. Anything that can do. Accordingly, the load lock 21 and the load lock 22 are not particularly limited, and known load locks can be used as appropriate. Known load locks include, for example, a load lock valve having two roller gates facing inside and a film other than the roller gate, such as the apparatus described in Japanese Patent Application Laid-Open No. 2015-074810. And a load lock valve provided with a flexible member having a shape that can be kept airtight.

  As the reactive gas supply device 19, the inert gas supply device 20, and the vacuum pump 18, those capable of supplying or discharging a gas or the like at a predetermined speed can be appropriately used.

  As the target 13, when a transition metal element or a transition metal oxide film, nitride film, oxynitride film, or carbonation film is sputtered, the above-described transition metal element or a compound containing a transition metal can be used. .

[Formation of layers having various functions (other layers)]
In the method for producing a gas barrier film according to one embodiment of the present invention, a step of forming layers having various functions may be further provided.

<Anchor coat layer>
In the manufacturing method according to one aspect of the present invention, an anchor coat layer is formed on the surface of the base material on the side on which the first layer is formed for the purpose of improving the adhesion between the base material and the first layer. You may have the process further.

  As anchor coating agents used for the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, etc. are used alone Or in combination of two or more.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5.0 g / m ² (dry state).

  The anchor coat layer can also 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. Alternatively, by forming an anchor coat layer as described in Japanese Patent Application Laid-Open No. 2004-314626, when an inorganic thin film is formed thereon by a vapor phase method, the gas generated from the substrate side is blocked to some extent. Thus, an anchor coat layer can be formed for the purpose of controlling the composition of the inorganic thin film.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

<Hard coat layer>
The manufacturing method which concerns on one form of this invention may have further the process of forming a hard-coat layer in the surface of the base material of the both sides of a base material or the side which forms a 1st layer. Examples of the material contained in the hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more.

  The active energy ray-curable resin 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 cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray. A layer containing a cured product of the functional resin, that is, a hard coat layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable. A commercially available product may be used as the ultraviolet curable resin, for example, Z731L manufactured by Aika Industry Co., Ltd., Z7527 manufactured by JSR Corporation, or the like. You may use the commercially available resin base material in which the hard-coat layer is formed previously.

  Although it does not restrict | limit especially as a kind of hard-coat layer, For example, a clear hard-coat layer can be used.

  The thickness of the hard coat layer is preferably from 0.1 to 15 μm, more preferably from 0.5 to 5 μm, from the viewpoint of smoothness and bending resistance.

  Here, although the drying temperature in the case of forming a hard-coat layer using the solution for hard-coat layer formation is not restrict | limited, It is preferable that it is 40-120 degreeC.

Here, the ultraviolet irradiation means is not particularly limited, but irradiation with a high-pressure mercury lamp is preferable. Further, the amount of ultraviolet irradiation energy is not particularly limited, but is preferably 0.3 to 5 J / cm ² .

<Smooth layer>
The manufacturing method which concerns on one form of this invention may further have the process of forming a smooth layer between a base material and a 1st layer. The smooth layer used in the present invention flattens the rough surface of the resin base material where protrusions and the like exist, or flattens the unevenness and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the resin base material. To be provided. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

  Examples of the photosensitive material for the smooth layer include a resin composition containing an acrylate compound having a radical-reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, and urethane acrylate. And a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. Specifically, a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Co., Ltd., Nanohybrid Silicone manufactured by ADEKA Corporation, and Unidic manufactured by DIC Corporation. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), various silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd. Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

  The method for forming the smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

  The thickness of the smooth layer is preferably in the range of 1 to 10 μm and more preferably in the range of 2 to 7 μm from the viewpoint of improving the heat resistance of the film and facilitating balance adjustment of the optical properties of the film.

  The smoothness of the smooth layer is a value expressed by the surface roughness defined by JIS B 0601: 2001, and the ten-point average roughness Rz is preferably 10 nm or more and 30 nm or less. If it is this range, even if it is a case where a gas barrier layer is apply | coated by the application type, even if it is a case where a coating means contacts the smooth layer surface by application methods, such as a wire bar and a wireless bar, applicability | paintability will be impaired. In addition, it is easy to smooth the unevenness after coating.

[Gas barrier film]
FIG. 2 is a schematic view showing a preferred example of a gas barrier film produced by the production method according to one embodiment of the present invention.

  Hereinafter, a gas barrier film manufactured by a manufacturing method according to an embodiment of the present invention will be described with reference to the accompanying drawings. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios. In addition, the gas barrier film manufactured by the manufacturing method of this invention is not limited only to one form demonstrated below.

  A gas barrier film 30 manufactured by a manufacturing method according to an embodiment of the present invention includes a first layer 32 containing a non-transition metal (M1) on a base material 31, and a transition metal in contact with the first layer 32. A second layer 33 containing (M2), and a third layer 34 containing a transition metal (M2 ′) in contact with the second layer 33, and the first layer 32 and the first layer 2 has a composite composition region 32b containing a non-transition metal (M1) and a transition metal (M2) in the vicinity of the interface with the second layer 33. Here, it is considered that the composite composition region 32 b is formed by depositing vapor deposition particles into the first layer 32 when the second layer 33 and the third layer 34 are formed. That is, the first layer 32 includes a composite composition region 32b and a region 32a other than the composite composition region.

  In the above description, the second layer and the third layer are in contact with each other. However, as long as the third layer is the outermost layer, the shape is not limited to this, and the second layer and the third layer Other layers may be interposed between them. However, it is preferable that the second layer and the third layer are in contact with each other from the viewpoint of thinning the film.

  The first layer 32 formed by Step 1 includes a non-transition metal (M1). The non-transition metal (M1) contained in the first layer 32 may be a single metal element state or a compound containing a metal element (compound containing a non-transition metal (M1)). Good. Further, the second layer 33 and the third layer 34 formed by the step 2 and the step 3 contain a transition metal (M2 or M2 ′). The transition metal (M2 or M2 ′) contained in the second layer 33 and the third layer 34 may be a single metal element or a compound containing a metal element (transition metal (M2 or M2 ′)). ) Containing compound). And the composite composition area | region 32b containing a non-transition metal (M1) and a transition metal is formed by the process 2 and the process 3. As a result, the composite composition region 32b and the region 32a other than the composite composition region exist in the layer containing the non-transition metal (M1). Here, the definition and preferred examples of each term are the same as those described for the formation of each layer.

The gas barrier property of the gas barrier film after high-temperature and high-humidity storage was measured by the MOCON method using a MOCON water vapor transmission rate measuring apparatus Aquatran (manufactured by MOCON) with a water vapor transmission rate (WVTR) (g / m ² · day). as the value is preferably less than 0.005g ^/ m 2 · day, more preferably less than 0.001g ^/ m 2 · day. Moreover, since it is better that the water vapor transmission rate is lower, the lower limit is not particularly limited. For example, from the viewpoint of productivity, it is preferably 0.0001 g / m ² · day or more. In addition, the detailed measuring method of the gas-barrier property after high-temperature, high-humidity preservation | save of a gas-barrier film is described in an Example.

  The gas barrier film produced by the production method of the present invention includes a first layer containing a non-transition metal (M1), a second layer containing a transition metal (M2) in contact with the first layer, and an outermost layer. And a third layer containing a transition metal (M2 ′). In the first layer, a compound (for example, oxide) in which a non-transition metal (M1) and a transition metal (M2) are compounded in the vicinity of the interface between the first layer and the second layer. It is preferable that the composition region is configured to continuously exist in the thickness direction with a thickness of a predetermined value or more (specifically, 5 nm or more).

(Composite composition area)
The composite composition region is defined as follows. That is, when the composition distribution in the thickness direction of the laminated structure (hereinafter also referred to as a gas barrier layer) composed of the first layer, the second layer, and the third layer is analyzed by the XPS method, the non-transition metal (M1) is The non-transition metal (M1) and the transition metal (M2) coexist at the interface between the first layer containing and the second layer containing the transition metal (M2), and the transition metal (M2) / non- If there is a region where the value of the atomic ratio of the transition metal (M1) is in the range of 0.02 to 50 and the thickness is 5 nm or more, it is defined as a composite composition region.

<Composition analysis by XPS and measurement of composite composition thickness>
For the “composite composition region”, the composition content and the layer thickness can be obtained by the following composition analysis by XPS. Hereinafter, a method for measuring a composite composition region by XPS analysis will be described.

The element concentration distribution in the thickness direction of the gas barrier layer (hereinafter referred to as depth profile) specifically includes a non-transition metal (M1) distribution curve (for example, silicon distribution curve), a transition metal (M2) distribution curve, oxygen (O), nitrogen (N), carbon (C) distribution curves, etc., by using X-ray photoelectron spectroscopy (XPS) measurement in combination with rare gas ion sputtering such as argon It can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the interior. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of each element (unit: atom%) and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time, the etching time is generally correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the layer thickness direction. As the “distance from the surface of the gas barrier layer in the thickness direction”, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement can be adopted. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

  An example of specific conditions for XPS analysis applicable to the present invention is shown below.

・ Analyzer: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement is repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).

  Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI. The elements to be analyzed are non-transition metal (M1) (for example, silicon (Si)), transition metal (M2), oxygen (O), nitrogen (N), and carbon (C).

The composition ratio is calculated from the obtained data, the non-transition metal (M1) and the transition metal (M2) coexist, and the value of the atomic ratio of the transition metal (M2) / non-transition metal (M1) is The thickness in the range of 0.02 to 50 is obtained. This thickness represents the sputter depth in XPS analysis in terms of SiO ₂ .

  When the thickness is 5 nm or more, it is determined as a “composite composition region”. From the viewpoint of gas barrier properties, there is no upper limit of the thickness of the composite composition region, but from the viewpoint of obtaining a further effect of improving gas barrier properties, it is preferably in the range of 5 to 100 nm, more preferably 8 to 50 nm. Within the range, more preferably within the range of 10 to 30 nm.

  Although details will be described later, the composition of the region other than the composite composition region of the gas barrier layer is not particularly limited as long as this feature is satisfied. The region other than the composite composition region may be, for example, a region such as a non-transition metal (M1) oxide, nitride, oxynitride, or oxycarbide, or a transition metal (M2) oxide or nitridation. It may be a region of an oxide, an oxynitride, an oxycarbide or the like, or may be a composite oxide layer of a non-transition metal (M1) and a transition metal (M2).

<Oxygen deficient region>
The oxygen deficient region represents a region having an oxygen deficient composition. In the gas barrier film produced by the production method according to one embodiment of the present invention, the composite composition region is preferably an oxygen deficient region. When the composite composition region is an oxygen deficient region, the non-transition metal is (M1), the transition metal is (M2), oxygen is O, nitrogen is N, and the composition of the composite composition region is (M1) (M2) _x O _y when a N _z, it is preferable to satisfy the following equation 6.

(In the formula, a is the valence of the non-transition metal (M1). B is the maximum valence of the transition metal (M2).)
Relational expression 6 represents that the composite composition region of the gas barrier layer includes an oxygen deficient composition of a composite oxide of a non-transition metal (M1) and a transition metal (M2).

As described above, the composition of the composite oxide of the non-transition metal (M1) and the transition metal (M2) is preferably represented by (M1) (M2) _x O _y N _z . As is clear from this composition, the composite oxide may partially include a nitride structure. Here, the maximum valence of the non-transition metal (M1) is a, the maximum valence of the transition metal (M2) is b, the valence of O is 2, and the valence of N is 3. When the composite oxide (including one partially nitrided) has a stoichiometric composition, (2y + 3z) / (a + bx) = 1.0. This formula means that the total number of bonds of non-transition metal (M1) and transition metal (M2) is equal to the total number of bonds of O and N. In this case, non-transition metal (M1) And the transition metal (M2) are bonded to either O or N. In addition, when two or more kinds are used together as the non-transition metal (M1), or when two or more kinds are used together as the transition metal (M2), the maximum valence of each element is weighted by the abundance ratio of each element. The composite valence calculated by averaging is adopted as the values of a and b of the “maximum valence”.

  On the other hand, when (2y + 3z) / (a + bx) <1.0, the total number of O and N bonds is insufficient with respect to the total number of bonds of the non-transition metal (M1) and the transition metal (M2). This state is “oxygen deficiency” of the composite oxide. In the oxygen deficient state, the remaining bonds of the non-transition metal (M1) and the transition metal (M2) have a possibility of bonding to each other, and the non-transition metal (M1) and transition metal (M2) metals When they are directly bonded, it is considered that a denser and higher-density structure is formed than when bonded between metals via O or N, and as a result, the gas barrier property is further improved.

  The composite composition region is a region where the value of x satisfies 0.02 ≦ x ≦ 50 (0 <y, 0 ≦ z). This is because, in the description of the composite composition region, the value of the atomic ratio of transition metal (M2) / non-transition metal (M1) is in the range of 0.02 to 50, and the thickness is 5 nm or more. This is the same definition as defined. In this region, since both the non-transition metal (M1) and the transition metal (M2) are involved in the direct bonding between the metals, a composite composition region that satisfies this condition exists at a thickness of a predetermined value or more (5 nm). This is considered to contribute to the improvement of gas barrier properties. In addition, it is considered that the closer the abundance ratio of the non-transition metal (M1) and the transition metal (M2), the more the gas composition can contribute to the improvement of the gas barrier properties. Therefore, the composite composition region is a region satisfying 0.1 ≦ x ≦ 10. More preferably, it includes a thickness of 5 nm or more, more preferably includes a region satisfying 0.2 ≦ x ≦ 5 at a thickness of 5 nm or more, and a region satisfying 0.3 ≦ x ≦ 4 of 5 nm or more. It is particularly preferable to include it.

  The composite composition region is preferably an oxygen deficient region satisfying (2y + 3z) / (a + bx) ≦ 0.9, more preferably an oxygen deficient region satisfying (2y + 3z) / (a + bx) ≦ 0.85, More preferably, the region is an oxygen deficient region that satisfies (2y + 3z) / (a + bx) ≦ 0.8. As the value of (2y + 3z) / (a + bx) in the composite composition region decreases, the effect of improving the gas barrier property increases, but the absorption with visible light also increases. Therefore, in the case of a gas barrier layer used for an application where transparency is desired, 0.2 ≦ (2y + 3z) / (a + bx) is preferable, and 0.3 ≦ (2y + 3z) / (a + bx). More preferably, 0.4 ≦ (2y + 3z) / (a + bx).

In the present invention, the thickness of the composite composition region in which better gas barrier properties are obtained is preferably 5 nm or more, more preferably 8 nm or more, and more preferably 10 nm or more as the sputtering thickness in terms of SiO _2. More preferably, it is more preferably 20 nm or more.

  Ratio of transition metal (M2) and oxygen in film forming raw material, ratio of inert gas and reactive gas during film formation, gas supply amount during film formation, degree of vacuum during film formation, and film formation A composite composition region having an oxygen-deficient composition can be formed by adjusting film formation conditions (preferably, oxygen partial pressure) such as power.

[Electronic device]
The gas barrier film manufactured by the manufacturing method according to one embodiment of the present invention can be preferably applied to an electronic device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. . Examples of the electronic device include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

  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.

[Manufacture of gas barrier film 1]
(Preparation of base material)
As a base material, a polyethylene terephthalate film (Lumilar (registered trademark) U48, manufactured by Toray Industries, Inc.) having a thickness of 100 μm and subjected to easy adhesion treatment on both surfaces was used. A clear hard coat layer having a thickness of 0.5 μm and having an antiblock function was formed on the surface of the substrate opposite to the surface on which the gas barrier layer was formed. That is, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied on a substrate so that the dry film thickness was 0.5 μm, dried at 80 ° C., and then high-pressure mercury in the air. Curing was performed using a lamp under the condition of an irradiation energy amount of 0.5 J / cm ² .

Next, a clear hard coat layer having a thickness of 2 μm was formed on the surface of the substrate on which the gas barrier layer was to be formed as follows. A UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a substrate so that the dry film thickness was 2 μm, then dried at 80 ° C., and then using a high-pressure mercury lamp in the air. Curing was performed under the condition of an irradiation energy amount of 0.5 J / cm ² . In this way, a substrate with a clear hard coat layer was obtained. Hereinafter, in this example and the comparative example, this base material with a clear hard coat layer is simply used as a base material for convenience.

(Formation of first layer containing non-transition metal (M1); Step 1)
<Application of polysilazane solution>
Subsequently, a polysilazane coating film was formed on the prepared substrate. Non-catalytic perhydropolysilazane 20% by weight dibutyl ether solution (Aquamica (registered trademark) NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) and amine catalyst (N, N, N ′, N′-tetramethyl-1, 6-diaminohexane) perhydropolysilazane containing 20% by weight of solid content in dibutyl ether solution (Aquamica (registered trademark) NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) The mixture was used so as to be 1% by mass, and further diluted with dibutyl ether to prepare a 5% by mass dibutyl ether solution of perhydropolysilazane. This solution is applied onto a substrate using a die coater, and then dried with a dryer at a temperature of 50 ° C. and a dew point of 10 ° C. for 1 minute, and then dried at a temperature of 80 ° C. and a dew point of 5 ° C. for 2 minutes. A polysilazane coating film was formed.

<Polysilazane coating modification process>
After drying the polysilazane coating film, a vacuum silage irradiation treatment was performed with the following apparatus and conditions to form a polysilazane modified layer. By spraying N ₂ gas heated in the reforming process step continuously performed on the film substrate heated to 80 ° C. with a dryer, the oxygen concentration is reduced to a predetermined value while the base during the reforming process is performed. The material temperature was kept at 80 ° C. The dew point temperature during the reforming treatment was -20 ° C.
・ Modification processing equipment Eximer irradiation equipment MODEL: MEUT-1-500 manufactured by M.D.
Wavelength: 172nm
Lamp enclosed gas: Xe (uses Xe excimer lamp)
-Modification treatment conditions Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample (irradiated surface) and light source: 2 mm
Film substrate temperature: 80 ° C
Oxygen concentration between the excimer lamp tube surface and the film substrate: 0.1% by volume or more and 0.3% by volume or less On the other hand, vacuum ultraviolet light having a cumulative light amount (irradiation energy amount) of 2.5 J / cm ² was irradiated to form a first layer (film thickness: 150 nm) on the substrate.

(Formation of second layer and third layer containing transition metal (M2); Step 2 and Step 3)
<Deposition by sputtering>
The second layer and the third layer containing the transition metal (M2) were formed by sputtering, which is physical vapor deposition. As a sputtering device, a device name SmartWeb XL 1400 6 cathode system manufactured by Applied Material, which is a reactive sputtering device, was used.

  The second layer and the third layer were formed by a roll-to-roll method in a state in which the deposition base material, which is a laminate of the base material and the first layer, was transported at a constant transport speed of 5 m / min. . Here, the second layer and the third layer are formed in the first cathode and the second process zone (between the partition walls having the cathode) in the transfer path, respectively, and the third to sixth process zones are in a vacuum state. By carrying only as (0.4 Pa or less), the second layer and the third layer were formed by continuous vapor deposition while maintaining the vacuum state. Here, the vapor deposition time t2 (second) for forming the second layer and the vapor deposition time t3 (second) for forming the third layer were the same at 2.0 seconds.

A commercially available oxygen deficient niobium oxide target (composition is Nb ₁₂ O ₂₉ ) is used as the target, Ar and O ₂ are used as process gases, and a DC power source (DPG-20) manufactured by ULVAC is used. Membrane was performed.

In the formation of the second layer, the sputtering power source power was 7.0 W / cm ² and the gas pressure during film formation was 0.4 Pa. Further, the film was formed by adjusting the oxygen partial pressure to 12%.

In the formation of the third layer, the sputtering power source power was 7.0 W / cm ² and the gas pressure during film formation was 0.4 Pa. Further, the film was formed by adjusting the oxygen partial pressure to 12%.

  The film is wound after the second layer and the third layer are formed, and the first layer, the second layer, and the third layer are provided in this order on the substrate. The gas barrier film 1 having a configuration in which the layers and the second layer and the third layer are in direct contact with each other was formed.

<Calculation of deposition rate and deposition rate ratio>
Here, the deposition rate (nm / second) of each layer was previously determined on the film-forming conditions of each layer on a film-like glass substrate (Corning Willow Glass manufactured by Corning). It was calculated by calculating by removing the deposition time (seconds) from the film thickness (nm). That is, DR2 (nm / second) was calculated by dividing the vapor deposition time t2 (second) for forming the second layer from the film thickness T2 (nm) of the second layer. DR3 (nm / second) was calculated by dividing the deposition time t3 (second) for forming the third layer from the film thickness T3 (nm) of the third layer. From these values, R (DR2 / DR3), which is a ratio of DR2 (nm / second) to DR3 (nm / second), was calculated. Here, since the vapor deposition times are the same in this experiment, R corresponds to the ratio of T2 (nm) to T3 (nm).

[Production of gas barrier film 2]
In the production of the gas barrier film, the gas barrier film 2 was produced in the same manner except that the sputtering power source power during the formation of the third layer was 6.5 W / cm ² .

[Production of gas barrier film 3]
In the production of the gas barrier film, the gas barrier film 3 was produced in the same manner except that the sputtering power source power during the formation of the third layer was 6.0 W / cm ² .

[Production of gas barrier film 4]
In the production of the gas barrier film, the gas barrier film 4 was produced in the same manner except that the sputtering power source power during the formation of the third layer was 4.7 W / cm ² .

[Production of gas barrier film 5]
In the production of the gas barrier film, the gas barrier film 5 was produced in the same manner except that the sputtering power source power during the formation of the third layer was 3.3 W / cm ² .

[Manufacture of gas barrier film 6]
In the production of the gas barrier film, the gas barrier film 6 was produced in the same manner except that the sputtering power source power at the time of forming the third layer was 2.8 W / cm ² .

[Manufacture of gas barrier film 7]
In the production of the gas barrier film, the gas barrier film 7 was produced in the same manner except that the sputtering power source power during the formation of the third layer was 2.1 W / cm ² .

[Production of gas barrier film 8]
In the production of the gas barrier film, the gas barrier film 8 was produced in the same manner as in the formation of the third layer, except that the sputtering power source power was 1.9 W / cm ² .

[Production of gas barrier film 9]
In the production of the gas barrier film 4, the gas barrier film 8 was produced in the same manner except that the conveyance speed of the substrate was 2.5 min / m.

  In the production of the gas barrier films 1 to 9, R (DR2) is a ratio of the deposition rate DR2 (nm / second) for forming the second layer to the deposition rate DR3 (nm / second) for forming the third layer. / DR3) is shown in Table 1.

  Moreover, in each gas barrier film 1-9, the composite composition area | region was formed in the interface of a 1st layer and a 2nd layer. The composite composition region was an oxygen deficient composition.

[Evaluation]
The following evaluation was performed about the gas barrier films 1-9.

(Water vapor transmission rate after storage at high temperature and high humidity (WVTR))
Each of the gas barrier films 1 to 9 was stored in a high-temperature and high-humidity tank having a temperature of 85 ° C. and a relative humidity of 85% RH for one day, and then left in an environment of a temperature of 25 ° C. and a relative humidity of 40% RH for one day. Thereafter, the water vapor transmission rate (g / m ² · day) at a temperature of 38 ° C. and a relative humidity of 90% RH was measured by the MOCON method using a MOCON water vapor transmission rate measuring device Aquatran (manufactured by MOCON). The measured water vapor transmission rate was ranked as the gas barrier properties of the gas barrier films 1 to 9 as follows.

5: water vapor transmission rate, 0.001g ^/ m 2 · day less than 4: Water vapor transmission rate, 0.001g ^/ m 2 · day or more 0.005g ^/ m 2 · day less than 3: water vapor permeability, 0. 005g ^/ m 2 · day or more 0.010 g ^/ m 2 · day less than 2: water vapor permeability, 0.010 g ^/ m 2 · day or more 0.100 g ^/ m 2 · day less than 1: water vapor transmission rate, 0. 100 g / m ² · day or more Note that the smaller the value of the water vapor transmission rate, the higher the gas barrier property, the gas barrier property that can be practically used in rank 3 or higher, and the gas barrier property that is particularly remarkable in rank 4 or higher. These results are shown in Table 1.

(Sealing adhesiveness)
The sealing adhesiveness of each gas barrier film 1-9 was measured. The measurement was performed according to JIS K 5600 5-6 (2004 edition).

  Specifically, 10 × 10 square grid cuts were made on the third layer side, which is the outermost surface of each gas barrier film 1-9, using a cutter knife and a cutter guide with a 1 mm interval. One square has a size of 1 mm square, and the depth of the cut is a depth reaching the base material through the first layer from the third layer side.

  An adhesive tape CT405AP-18 (manufactured by Nichiban Co., Ltd.) having a width of 18 mm was attached on the third layer having the cuts, and the adhesive tape was attached to the gas barrier layer by rubbing the adhesive tape with an eraser. Thereafter, the pressure-sensitive adhesive tape was peeled off in the direction perpendicular to the gas barrier layer, and among 10 × 10 squares, the number of squares where the gas barrier layer was peeled off from the substrate was counted. The sealing adhesion between the base material and the gas barrier layer was evaluated from the number of counted masses as follows.

5: Number of peeled cells is 5 or less 4: Number of peeled cells is 6 or more and 10 or less 3: Number of peeled cells is 11 or more and 15 or less 2: Number of peeled cells is 16 or more and 20 or less 1: Peeled The number of cells is 21 or more. Note that the smaller the number of cells peeled, the higher the sealing adhesiveness, and the sealing adhesiveness of rank 3 or higher is practical. These results are shown in Table 1.

  From the above, it was confirmed that the gas barrier films 3 to 7 and 9 manufactured by the manufacturing method according to the examples have high high-temperature and high-humidity durability and low haze that is excellent in sealing adhesiveness. .

  Moreover, from the results of the gas barrier films 4, 5, and 9, when R (DR2 / DR3) is 2.0 to 3.5, a film that has both particularly high high temperature durability and particularly excellent adhesion. It was confirmed that it could be manufactured.

DESCRIPTION OF SYMBOLS 1 Sputtering apparatus 2 Vacuum chamber 3 Supply side conveyance system chamber 4 Storage side conveyance system chamber 5 Delivery roller 6, 7, 8, 9 Conveyance roller 10 Take-up roller 11 Film formation roller 12 Cathode 13 Target 14 Partition 15 Deposition base material 16 Lamination Body (laminated body including a laminated structure in which the second layer and the third layer are in direct contact)
DESCRIPTION OF SYMBOLS 17 Laminated body film 18 Vacuum pump 19 Reaction gas supply apparatus 20 Inert gas supply apparatus 21, 22 Load lock 30 Gas barrier film 31 Base material 32 1st layer containing a non-transition metal (M1) 32a Area | regions other than a composite composition area | region 32b Composite composition region (oxygen deficient region)
33 Second layer containing transition metal (M2) 34 Third layer containing transition metal (M2).

Claims (12)

Forming a first layer containing the non-transition metal (M1) using a non-transition metal (M1) or a compound containing the non-transition metal (M1) on a substrate;
A second layer containing the transition metal (M2) is formed on the first layer using a compound containing a transition metal (M2) or a transition metal (M2) by physical vapor deposition so as to be in contact with the first layer. Forming a layer of step 2;
Step 3 of forming a third layer containing the transition metal (M2 ′) on the second layer by a physical vapor deposition method using a transition metal (M2 ′) or a compound containing the transition metal (M2 ′). And including
The third layer is the outermost layer;
In the step 2 and the step 3, when the deposition rate for forming the second layer is DR2 (nm / sec) and the deposition rate for forming the third layer is DR3 (nm / sec),
A method for producing a gas barrier film, wherein R which is a ratio of the DR2 (nm / second) to the DR3 (nm / second) satisfies the following formula 1.
In step 2 and step 3,
The deposition time for forming the second layer is t2 (min), the deposition time for forming the third layer is t3 (min),
When the film thickness of the second layer is T2 (nm) and the film thickness T3 (nm) of the third layer,
The t2 (second) and the t3 (second) satisfy the following formula 2, the DR2 (nm / second) and the T2 (nm) satisfy the following formula 3, and the DR3 (nm / second) and the T3 (nm The method for producing a gas barrier film according to claim 1, wherein:
  The method for producing a gas barrier film according to claim 1 or 2, wherein in the step 2 and the step 3, the second layer and the third layer are formed by continuous vapor deposition while maintaining a vacuum state.   In the step 2 and the step 3, the second layer and the third layer are conveyed in a roll-to-roll manner with a laminate including the base material and the first layer being conveyed at a constant conveyance speed. The manufacturing method of the gas-barrier film of any one of Claims 1-3 formed by.   The method for producing a gas barrier film according to claim 4, wherein the transport speed is 1 (m / min) or more and 50 (m / min) or less.   In the said process 2 and the said process 3, the manufacturing method of the gas-barrier film of any one of Claims 1-5 whose said physical vapor deposition method is a sputtering method.   The method for producing a gas barrier film according to any one of claims 1 to 6, wherein the transition metals (M2) and (M2 ') are metals selected from metals of Group 5 of the long-period periodic table. .   The method for producing a gas barrier film according to any one of Claims 1 to 7, wherein the non-transition metal is a metal selected from Group 12 to Group 14 metal of the long-period periodic table.   The gas barrier film according to any one of claims 1 to 8, wherein in the step 1, the first layer is formed by applying a coating liquid containing a compound containing the non-transition metal (M1). Production method.   The method for producing a gas barrier film according to claim 9, wherein the compound containing the non-transition metal (M1) is polysilazane.   The method for producing a gas barrier film according to claim 9 or 10, wherein, in the step 1, the coating layer obtained by applying the coating solution is further subjected to a modification treatment to form the first layer.   The method for producing a gas barrier film according to claim 11, wherein the modification treatment is a vacuum ultraviolet irradiation treatment.