WO2017014246A1

WO2017014246A1 - Gas barrier film and method for producing same

Info

Publication number: WO2017014246A1
Application number: PCT/JP2016/071322
Authority: WO
Inventors: 森　孝博
Original assignee: コニカミノルタ株式会社
Priority date: 2015-07-23
Filing date: 2016-07-20
Publication date: 2017-01-26
Also published as: TW201716242A; TWI627063B; JPWO2017014246A1

Abstract

The present invention is a gas barrier film which comprises, on a resin base, a gas barrier layer that contains silicon atoms, a metal M1 other than silicon, an element M2 other than silicon and the metal M1, and oxygen atoms. If [Si] (atom%) is the ratio of the amount of the silicon atoms relative to the total amount of the silicon atoms, the metal M1, the element M2, the oxygen atoms, nitrogen atoms and carbon atoms in the gas barrier layer, [M1] (atom%) is the ratio of the amount of the metal M1 relative to the total amount of the silicon atoms, the metal M1, the element M2, the oxygen atoms, nitrogen atoms and carbon atoms in the gas barrier layer, and [M2] (atom%) is the ratio of the amount of the element M2 relative to the total amount of the silicon atoms, the metal M1, the element M2, the oxygen atoms, nitrogen atoms and carbon atoms in the gas barrier layer, this gas barrier film sequentially has a region (C) that satisfies formula (c), a region (B) that satisfies formula (b) and a region (A) that satisfies formula (a) in this order from the resin base side.

Description

Gas barrier film and method for producing the same

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

Gas barrier films are used as substrate films and sealing films in flexible electronic devices, particularly flexible organic EL devices. The gas barrier film used for these is required to have high gas barrier properties.

Generally, a gas barrier film is manufactured by forming an inorganic barrier layer on a base film by a vapor deposition method such as vapor deposition, sputtering, or CVD. In recent years, a manufacturing method for forming a gas barrier layer by applying energy to a precursor layer formed by applying a solution on a substrate has been studied. In particular, studies using a polysilazane compound as a precursor have been widely conducted, and studies are being conducted as a technique that achieves 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.

As a gas barrier layer having a high gas barrier property that has a water vapor transmission rate (WVTR) of 10 ⁻² g / m ² / day or less, application studies of a silicon oxide gas barrier layer by sputtering film formation have been frequently made. 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. Moreover, in a very severe environment of high temperature and high humidity such as 85 ° C. and 85% RH, there is a concern that the gas barrier property may deteriorate with time.

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 Japanese translations of PCT publication No. 2009-503157 (US Patent Application Publication No. 2010/1666977), a solution containing polysilazane and a catalyst is applied onto a substrate, and then the solvent is removed to form a polysilazane layer. A method of forming a gas barrier layer on a substrate by irradiating the polysilazane layer with VUV radiation containing a wavelength component of less than 230 nm and UV radiation containing a wavelength component of 230 to 300 nm in an atmosphere containing water vapor Is disclosed.

However, the gas barrier layer formed by modifying polysilazane described in the above Japanese translation of PCT publication No. 2009-503157 (US Patent Application Publication No. 2010/1666977) with excimer light has a low temperature of about 40 ° C. Although the gas barrier property is good, it has been found that the gas barrier property decreases with time in a very severe environment of high temperature and high humidity such as 80 ° C. and 85% RH.

Thus, there has been a demand for a gas barrier film that can be used as an electronic device while suppressing the performance degradation of the gas barrier layer in a high temperature and high humidity environment.

Also, the manufacturing method described in JP-T-2009-503157 (US Patent Application Publication No. 2010/1666977) has a problem that the productivity and the production stability are insufficient.

Therefore, an object of the present invention is to provide a gas barrier film excellent in durability in a high temperature and high humidity environment.

Another object of the present invention is to provide a method for producing a gas barrier film excellent in productivity and production stability.

According to one aspect of the present invention, a gas barrier film having a gas barrier layer containing a silicon atom, a metal M1 other than silicon, an element M2 other than silicon and the metal M1, and an oxygen atom on a resin substrate. The ratio of the amount of the silicon atom to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer is [Si] (unit: atom %), And the ratio of the amount of the metal M1 to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer [M1] (unit: atom) %) And the element relative to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer. When the ratio of the amount of M2 is [M2] (unit: atom%), the region (C) satisfying the following formula (c) and the region (B) satisfying the following formula (b) from the resin base material side. And a gas barrier film having a region (A) satisfying the following formula (a) in this order.

According to another aspect of the present invention, there is provided a method for producing the gas barrier film, wherein the first layer containing the silicon atom, the element M2, and the oxygen atom is formed on the resin base material. And a step of forming a second layer containing the metal M1 and the oxygen atom on the first layer.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view of a vacuum ultraviolet irradiation apparatus used in the examples, 1 is an apparatus chamber, 2 is a Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet light of 172 nm, and 3 also serves as an external electrode. An excimer lamp holder, 4 is a sample stage, 5 is a sample on which a polysilazane compound coating layer is formed, 6 is a light shielding plate, and V is a moving speed of the sample stage.

The present invention is a gas barrier film having, on a resin substrate, a gas barrier layer containing a silicon atom, a metal M1 other than silicon, an element M2 other than silicon and the metal M1, and an oxygen atom, The ratio of the amount of the silicon atom to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer is [Si] (unit: atom%), and The ratio of the amount of the metal M1 to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer is [M1] (unit: atom%), and Ratio of the amount of the element M2 to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer Is [M2] (unit: atom%), from the resin substrate side, the region (C) satisfying the following formula (c), the region (B) satisfying the following formula (b), and the following formula ( It is a gas barrier film having a region (A) satisfying a) in this order.

The gas barrier film of the present invention having such a configuration is excellent in durability in a high temperature and high humidity environment. Moreover, the manufacturing method of the gas barrier film of this invention is excellent in productivity and production stability.

The details of the reason why the above-described effect can be obtained by the gas barrier film of the present invention are unknown, but the following mechanism is conceivable. The following mechanism is based on speculation, and the present invention is not limited to the following mechanism.

Area (A) is an area where a lot of metal M1 exists. It has been found that when the region (A) satisfies the relationship of the above formula (a), the region (A) has a property of being excellent in scratch resistance as compared with a region made of an oxide or oxynitride containing silicon (Si) as a main component. . Then, by arranging the region (A) among the regions (A) to (C) on the side farthest from the resin base material, it functions as a protective layer in the gas barrier film manufacturing process and deteriorates the gas barrier property. It has the effect of suppressing.

The region (B) is a region having a high gas barrier property. In the region (B), it is considered that a compound having a bond between Si and the metal M1 (hereinafter also referred to as Si-M1 bond) is contained in a high ratio, and by forming the Si-M1 bond, It is considered that a dense structure is obtained and a high gas barrier property is obtained. In addition, since the region (B) where the Si-M1 bond is formed has higher moisture and heat resistance than SiO ₂ , the region (B) has excellent durability to maintain a good gas barrier property even when stored in a high temperature and high humidity environment. Although the element M2 may exist in the region (B), it is considered that the element M2 inhibits the formation of the Si-M1 bond. Therefore, in the region (B), by satisfying the relationship of the above formula (b), It is considered that the gas barrier properties are further improved. And since area | region (B) is arrange | positioned between area | region (A) and area | region (C), it has the effect of suppressing that gas barrier property deteriorates by the influence of the unevenness | corrugation of a resin base material.

Among the regions (A) to (C), the region (C) closest to the resin base material is a region mainly containing silicon but containing a relatively large amount of the element M2. When the region (C) contains a relatively large amount of the element M2, that is, by satisfying the relationship of the above formula (c), composition change when stored in a high temperature and high humidity environment is suppressed, and durability in a high temperature and high humidity environment is achieved. Excellent in properties. Moreover, it has the effect of reducing the unevenness | corrugation of the above resin base materials.

Furthermore, according to the method for producing a gas barrier film of the present invention, even if it has a step of storing in a high-temperature and high-humidity environment during the production process, the composition stability is hardly changed and the production stability becomes stable. It also has excellent productivity.

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”. In the present specification, unless otherwise specified, measurement of operation and physical properties is performed under the conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

[Resin substrate]
Specific examples of the resin substrate according to the present invention include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, and polyamideimide resin. , 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 , A base material containing a thermoplastic resin such as an alicyclic modified 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-A No. 2001-150584: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C. manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: JP No. 2000-227603 Described compound: 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.) And the like) (Tg is shown in parentheses).

Since the gas barrier film according to the present invention is used as an electronic device such as an organic EL element, the resin substrate is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.

However, even when the gas barrier film according to the present invention is used for display, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.

Further, the resin base material listed above may be an unstretched film or a stretched film. The resin substrate can be produced by a conventionally known general method. Regarding the method for producing these base materials, the items described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately employed.

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 resin base material according to 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.

[Gas barrier layer]
The gas barrier film of the present invention has a gas barrier layer containing a silicon atom, a metal M1 other than silicon, an element M2 other than silicon and metal M1, and an oxygen atom. The gas barrier layer may further contain nitrogen atoms.

[Metal M1]
The metal M1 other than silicon is not particularly limited, but a transition metal is preferable.

Here, the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and more specifically, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr ), Manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc) ), Ruthenium (Ru), palladium (Pd), silver (Ag), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu) ), Gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbi (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au) Etc. These transition metals may be used alone or in combination of two or more.

Among these, Nb, Ta, V, Zr, Ti, Hf, Y, La, or Ce is preferable as M1 from the viewpoint that a good gas barrier property can be obtained. Furthermore, among these, it is considered from the various examination results that Nb, Ta, and V, which are metals of Group 5 of the long-period periodic table, are likely to be bonded to Si contained in the gas barrier layer. Further preferably, it can be used. When the metal M1 is a Group 5 metal (particularly Nb), a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 metal (particularly Nb) is particularly likely to occur. Furthermore, from the viewpoint of optical characteristics, the metal M1 is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.

[Element M2]
Examples of the element M2 include elements other than silicon and metal M1, and at least one element selected from the group consisting of elements of Group 1 to Group 14 of the long-period periodic table. As further specific examples of the element M2, aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), magnesium (Mg), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), potassium (K), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), germanium (Ge), etc. Preferably mentioned. Among these, at least one selected from the group consisting of boron (B), aluminum (Al), titanium (Ti), and zirconium (Zr) is more preferable, and aluminum (Al) and boron (B) are more preferable. Aluminum (Al) is particularly preferable.

By including these elements M2, the moisture and heat resistance of the gas barrier film can be further improved. In addition, the element M2 may be used independently and 2 or more types may be used together.

It is confirmed that the gas barrier layer contains silicon atoms, metals M1, elements M2, and oxygen atoms by performing XPS (X-ray Photoelectron Spectroscopy) composition analysis of the gas barrier layer as follows. Can do.

<< XPS analysis conditions >>
・ Device: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profiles: in terms of SiO ₂ sputter thickness, repeat the measurement at a predetermined thickness intervals, - obtaining the depth depth profile Quantification relative sensitivity coefficients background determined by Shirley method, from the peak area obtained Quantified using the method. For data processing, MultiPak manufactured by ULVAC-PHI was used. The elements to be analyzed were Si, metal M1, element M2, O, N, and C.

In the present invention, the measurement resolution (predetermined thickness interval) of the depth profile may be 3 nm or less, 2 nm or less, or 1 nm or less. In the embodiment of the present invention, the measurement resolution of the depth profile is 1 nm.

The gas barrier layer according to the present invention includes, from the resin substrate side, a region (C) that satisfies the above formula (c), a region (B) that satisfies the above formula (b), and a region (A) that satisfies the above formula (a). In this order.

[Area (A)]
The region (A) is a region that satisfies the above formula (a). The thickness of the region (A) is preferably 1 nm or more from the viewpoint that a certain amount of thickness is necessary to function as a protective layer and from the viewpoint of obtaining a visible light reflectance suitable as a film for optical applications. It is 15 nm or less, more preferably 3 nm or more and 10 nm or less. The thickness of the region (A) can be measured by the following method using XPS composition analysis.

That is, when the gas barrier layer is analyzed in the depth direction from the surface layer side by XPS, the starting point is the measurement point where [M1]> [Si] ≧ [M2], and [Si] ≧ [M1]> The region up to the measurement point immediately before the measurement point that is [M2] is defined as the region (A). When the sputtering depth in terms of SiO _{2 with} respect to one measurement point is d (unit: nm), the number of measurement points (A) n measured as the region (A) is multiplied by d [(A). n × d (nm)] is the thickness of the region (A).

The thickness of the regions (A) to (C), and [B] and [C] described later can be measured by the XPS composition analysis described above.

[Area (B)]
The region (B) is a region that satisfies the above formula (b). The thickness of the region (B) is preferably 5 nm or more and 50 nm or less, more preferably 10 nm or more and 30 nm or less, from the viewpoint of gas barrier properties and productivity. The thickness of the region (B) can be measured by the following method using XPS composition analysis.

That is, when the gas barrier layer is analyzed in the depth direction from the surface layer side by XPS, the starting point is [Si] ≧ [M1]> [M2], and [Si]> [M2] ≧ The region (B) is defined up to the measurement point immediately before the measurement point that becomes [M1]. When the sputtering depth in terms of SiO ₂ for one measurement point is d (unit: nm), the number of measurement points (B) n measured as the region (B) is multiplied by d [(B). n × d (nm)] is the thickness of the region (B).

[Region (C)]
The region (C) is a region that satisfies the above formula (c). The thickness of the region (C) is preferably 1 nm or more and 500 nm or less, more preferably 10 nm or more and 200 nm or less, from the viewpoint of reducing durability in a high temperature and high humidity environment and unevenness of the resin base material. The thickness of the region (C) can be measured by the following method using XPS composition analysis.

When analyzing the gas barrier layer in the depth direction from the surface layer side by XPS, the measurement point originated from the surface of the resin base material, starting from the measurement point where [Si]> [M2] ≧ [M1] was first established. A region (C) is defined up to the measurement point immediately before the measurement point at which the measurement point (measurement point due to the surface of the other layer when another layer is provided between the gas barrier layer and the resin base material) is obtained. To do. The definition of the depth range is calculated in the same way as above. Whether or not the measurement point is due to the surface of the resin substrate (measurement point due to the surface of the other layer) is appropriately determined from the composition of the resin substrate (other layer) used.

As a method for obtaining the gas barrier film of the present invention having such regions (A) to (C), the following method for producing the gas barrier film of the present invention can be mentioned. Details will be described later.

<[B] and [C]>
The average value of the ratio ([M2] / [Si]) between [M2] and [Si] in the region (B) is [B], and the ratio between [M2] and [Si] in the region (C) When the average value of ([M2] / [Si]) is [C], it is preferable that [C]> [B]. By satisfying such a relationship, gas barrier properties and durability under a high temperature and high humidity environment are improved.

Note that the mechanism of [C]> [B] is not clear, but is estimated as follows. Taking (1-2) coating method of the manufacturing method according to the present invention as an example, the first layer formed by the coating method is originally [M2] / [Si] is the thickness of the first layer. It is constant over the entire area of direction. However, when the second layer is formed on the first layer, the metal M1 in the second layer diffuses into the first layer while extracting oxygen from the first layer. At that time, since the first layer has an oxygen deficient composition, it is considered that a Si-M1 bond or a Si-M2 bond is formed. However, since the Si-M1 bond is easier to form than the Si-M2 bond, the Si-M2 bond is formed preferentially, and the phenomenon that Si diffuses into the second layer also occurs. A layer containing a mixed oxide as a main component and having a reduced M2 content is formed on the surface layer side. In the layer having the Si—M1 mixed oxide as a main component and the M2 content reduced, a region where [Si] ≧ [M2] is the region (B). Thereby, it is considered that [C]> [B] as described above.

[B] is preferably 0 to 0.2, more preferably 0 to 0.1. [C] is preferably 0.001 to 0.5, and more preferably 0.002 to 0.2. Furthermore, when [C]> [B], [C] / [B] is preferably 1.2 to 20, and more preferably 1.5 to 10.

Examples of the method for obtaining a gas barrier film satisfying the relationship [C]> [B] include the following method for producing a gas barrier film of the present invention. In the manufacturing method described later, this can be achieved by laminating the second layer containing the metal M1 on the first layer containing Si and the element M2 by a specific method. Specifically, the lamination is preferably performed under the condition that the metal M1 is oxygen deficient (a state where the amount of oxygen or nitrogen bonded to the maximum valence of the metal M1 is insufficient). When the metal M1 is laminated under conditions that cause oxygen vacancies, a bond is formed between the Si contained in the first layer and the metal M1 contained in the second layer (because the Si and the metal M1 are likely to form a bond). Conceivable). At this time, the first layer of Si diffuses into the second layer, and the second layer of metal M1 diffuses into the first layer. On the other hand, the element M2 in the first layer is less likely to form a bond with the metal M1 than Si, and thus the element M2 is difficult to diffuse to the second layer side. Thereby, the gas-barrier film which satisfy | fills the relationship of [C]> [B] is obtained.

<Boundaries of regions (A), (B), (C)>
At the boundary between the region (A) and the region (B), [Si] = [M1]. [Si] and [M1] at the boundary between the region (A) and the region (B) are preferably 10 atom% or more and 25 atom% or less, and 12 atom% or more and 20 atom% or less from the viewpoint of good gas barrier properties. It is more preferable that

[Si] and [M1] at the boundary between the region (A) and the region (B), and [M1] and [M2] at the boundary between the region (B) and the region (C) are XPS composition analysis. It is obtained by interpolating between the measurement points obtained in (1).

[M1] = [M2] at the boundary between the region (B) and the region (C). [M1] and [M2] at the boundary between the region (B) and the region (C) are preferably 0 atom% or more and 15 atom% or less, and preferably 0 atom% or more and 5 atom% or less from the viewpoint of good heat and moisture resistance. It is preferable that it is 0 atm% or more and 1 atom% or less.

[Si] and [M1] at the boundary between the region (A) and the region (B), and [M1] and [M2] at the boundary between the region (B) and the region (C) are the first layer. The [M2] / [Si] ratio and the film formation conditions of the second layer can be controlled.

<Oxygen deficient region>
In the gas barrier film according to the present invention, the region (B) of the gas barrier layer has the following condition <B> when oxygen is O, nitrogen is N, and the composition of the gas barrier layer is SiM1 _x O _y N _z. It is preferable to satisfy.

・ Condition <B>
Region [b] satisfying the following formula (1) when y> 0, z ≧ 0, the maximum valence of Si is 4, and the maximum valence of metal M1 is b [X] (XPS composition analysis) At least one measurement point).

The above condition <B> indicates that the gas barrier layer contains the oxygen deficient composition of the complex oxide of Si and the metal M1 over a predetermined thickness.

As described above, the composition of the composite oxide of Si and metal M1 according to the present invention is represented by SiM1 _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 Si is 4, the maximum valence of metal M1 is b, the valence of O is 2, and the valence of N is 3. When the composite oxide (including a partly nitrided) has a stoichiometric composition, (2y + 3z) / (4 + bx) = 1.0. This formula means that the total number of bonds of Si and metal M1 and the total number of bonds of O and N are the same. In this case, both Si and metal M1 are bonded to either O or N. Will be. In the present invention, when two or more kinds are used in combination as the metal M1, the composite valence calculated by weighted averaging the maximum valence of each element according to the abundance ratio of each element is “maximum valence”. It shall be adopted as the value of b.

On the other hand, when (2y + 3z) / (a + bx) <1 as in the region [b] according to the present invention, the total number of O and N bonds is greater than the total number of bonds of Si and metal M1. This means that there is a shortage, and this state is the “oxygen deficiency” of the composite oxide. In the oxygen deficient state, the remaining bonds of Si and metal M1 have the possibility of bonding to each other. When the metals of Si and metal M1 are directly bonded to each other, they are bonded to each other through O or N. It is considered that a denser and higher density structure is formed than in the case, and as a result, the gas barrier property is improved.

In the present invention, the region [b] is a region satisfying x <1. In this region, since both Si and the metal M1 are involved in the direct bonding between the metals, the region [b] satisfying this condition is considered to contribute to the improvement of the gas barrier property. Note that it is considered that the closer the abundance ratio of Si and metal M1 is, the more the gas barrier property can be improved, so the region [b] preferably includes a region satisfying 0.5 <x <1. It is more preferable to include a region that satisfies 6 <x <1, and it is further preferable to include a region that satisfies 0.7 <x <1.

Here, as described above, it was confirmed that if the region [b] satisfying (2y + 3z) / (4 + bx) <1.0 is present, the effect of improving the gas barrier property is exhibited, but the region [b] Preferably satisfies (2y + 3z) / (4 + bx) ≦ 0.98, more preferably satisfies (2y + 3z) / (4 + bx) ≦ 0.95, and (2y + 3z) / (4 + bx) ≦ 0. More preferably, 92 is satisfied. Here, as the value of (2y + 3z) / (4 + bx) in the region [b] 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 film used for an application where transparency is desired, (2y + 3z) / (4 + bx) ≧ 0.7 is preferable, and (2y + 3z) / (4 + bx) ≧ 0.75. Is more preferable, and (2y + 3z) / (4 + bx) ≧ 0.8 is more preferable.

In the present invention, the thickness of the region [b] where good gas barrier properties can be obtained is preferably 2 nm or more, more preferably 3 nm or more, and more preferably 4 nm or more as the sputtering thickness in terms of SiO _2. More preferably, it is more preferably 5 nm or more.

[Method for producing gas barrier film]
Although the manufacturing method of the gas barrier film of the present invention is not particularly limited, (1) a step of forming a first layer containing a silicon atom, an element M2, and an oxygen atom on a resin substrate; (2) the first And a step of forming a second layer containing metal M1 and oxygen atoms on one layer.

Hereinafter, the preferable manufacturing method will be described.

[Step of forming first layer]
As a method of forming the first layer containing silicon atoms, element M2, and oxygen atoms, a method including vapor phase film-forming or applying and drying a coating liquid containing a compound containing polysilazane and element M2 (Hereinafter, also simply referred to as a coating method). Among these, the coating method is preferable from the viewpoint of productivity.

(1-1) Vapor Deposition Method The vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, and ion plating, plasma CVD (chemical), and the like. Examples thereof include chemical vapor deposition methods such as vapor deposition method and ALD (Atomic Layer Deposition). Among them, 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. When DC sputtering or DMS sputtering is performed, a thin film of an element M2 oxide can be formed by using a target containing the element M2 as a target and further introducing oxygen into the process gas. In the case of forming a film by RF sputtering, an oxide target of the element M2 can be used. 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. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, carbon monoxide, or the like into the process gas, a thin film such as an oxide, nitride, nitride oxide, or carbonate of the element M2 can be formed. 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.

Examples of the target including the element M2 include a plurality of targets described in, for example, JP 2000-026961 A, JP 2009-215651 A, JP 2003-160862 A, JP 2012-007218 A, and the like. A target containing any of these elements can be used.

(1-2) Coating Method Another method for forming the first layer includes a method of coating and drying a coating solution containing polysilazane and a compound containing the element M2.

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

Specifically, the polysilazane preferably has the following structure.

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.

Alternatively, polysilazane has a structure represented by the following general formula (II).

In the general formula (II), R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} may be the same or different. In the general formula (II), n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that Note that n ′ and p may be the same or different.

Among the polysilazanes of the above general formula (II), R _{1 ′} , R _{3 ′} and R _{6 ′} each represent a hydrogen atom, and R _{2 ′} , R _{4 ′} and R _{5 ′} each represent a methyl group; R _{1 '} , R _3' and R _{6 '} each represents a hydrogen atom, R _2' , R _{4 '} each represents a methyl group, and R _5' represents a vinyl group; R _{1 '} , R _3' , R ₄ A compound in which _' and R _6' each represent a hydrogen atom and R _{2 '} and R ₅ ' each represents a methyl group is preferred.

Alternatively, polysilazane has a structure represented by the following general formula (III).

In the general formula (III), R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} may be the same or different.

In the general formula (III), n ″, p ″ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ″, p ″, and q may be the same or different.

Of the polysilazanes of the above general formula (III), R _{1 ″} , R _{3 ″} and R _{6 ″} each represent a hydrogen atom, and R _{2 ″} , R _{4 ″} , R _{5 ″} and R _{8 ″} each represent a methyl group. , R _{9 ″} represents a (triethoxysilyl) propyl group, and R _{7 ″} represents an alkyl group or a hydrogen atom.

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

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

Other examples of the polysilazane that can be used in the present invention include, but are not limited to, for example, a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827), a glycidol reacted Glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting alcohol (Japanese Patent Laid-Open No. 6-240208), metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal obtained by adding metal fine particles Fine particle added policy Zhang such (JP-A-7-196986), and a polysilazane ceramic at low temperatures.

<Compound containing element M2>
Examples of the compound containing the element M2 used in the coating method include, for example, aluminum isopropoxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, Aluminum tri-n-butylate, aluminum tri-sec-butylate, aluminum ethyl acetoacetate diisopropylate, acetoalkoxy aluminum diisopropylate, calcium isopropylate, titanium tetraisopropoxide (titanium (IV) isopropylate), zirconium tetraacetylacetate Nate, aluminum diisopropylate monoaluminum tert-butylate, aluminum trisethyl acetoacetate, Luminium oxide isopropoxide trimer, zirconium (IV) isopropylate, tris (2,4-pentanedionato) titanium (V), tetrakis (2,4-pentandedionato) zirconium (IV), tris (2,4- Pentandionato) cobalt (III), tris (2,4-pentandionato) iron (III), bis (2,4-pentadionato) palladium (II), tris (2,4-pentandionato) iridium (III ), Tris (2,4-pentanedionato) aluminum (III), bis (2,4-pentanedionato) nickel (II), bis (2,4-pentandedionato) copper (II), bis (2 , 4-Pentandionato) Zinc (II), Tris (2,4-pentandionato) Manganese (III), Tris ( , 4-pentandionato) chromium (III), tris (2,4-pentandionato) indium (III), tris (2,4-pentandionato) calcium (III), magnesium ethoxide, sodium ethoxide, Potassium ethoxide, trimethylgallium, di-n-butyldimethoxytin, tetraethyllead, manganese (III) acetylacetonate, diethyldiethoxygermane, berylliumacetylacetonate, trimethylborate, triethylborate, trin-propylborate , Triisopropyl borate, tri-n-butyl borate, tri-tert-butyl borate, strontium isopropoxide, barium diisopropoxide, barium tert-butoxide, barium acetylacetonate, thallium ethoxide, and titanium Examples include lithium acetylacetonate. These compounds may be used alone or in combination of two or more.

The compound containing the element M2 is preferably a metal alkoxide compound, and among the metal alkoxide compounds, a compound having a branched alkoxy group is more preferable from the viewpoint of reactivity, solubility, and the like, a 2-propoxy group, or More preferred is a compound having a sec-butoxy group. Moreover, the compound which has an ethoxy group from a viewpoint of gas barrier performance, adhesiveness, etc. is more preferable.

Furthermore, metal alkoxide compounds having an acetylacetonate group are also preferred. The acetylacetonate group is preferable because it has an interaction with the central element of the alkoxide compound due to the carbonyl structure, so that handling is easy. More preferably, a compound having a plurality of alkoxide groups or acetylacetonate groups is more preferable from the viewpoint of reactivity and film composition.

As the metal alkoxide compound, a commercially available product or a synthetic product may be used. Specific examples of commercially available products include, for example, AMD (aluminum diisopropylate mono-sec-butylate), ASBD (aluminum sec-butylate), ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH-TR (aluminum tris) Ethyl acetoacetate), aluminum chelate M (aluminum alkyl acetoacetate / diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate / monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) , Kawaken Fine Chemical Co., Ltd.), Preneact (registered trademark) AL-M (acetoalkoxyaluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.), Olga Tsu box series (manufactured by Matsumoto Fine Chemical Co., Ltd.) and the like.

In addition, when using a metal alkoxide compound, it is preferable to mix with the coating liquid containing polysilazane in inert gas atmosphere. This is to prevent the metal alkoxide compound from reacting with moisture and oxygen in the atmosphere and causing intense oxidation.

<First layer forming coating solution>
The solvent for preparing the coating solution for forming the first layer is not particularly limited as long as it can dissolve the compound containing polysilazane and the element M2, but water and reactive groups that easily react with polysilazane ( For example, an organic solvent that does not contain a hydroxyl group or an amine group and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable. Specifically, the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc. 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; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. 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 polysilazane in the coating solution for forming the first layer is not particularly limited and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, More preferably, it is 10 to 40% by mass.

The coating solution for forming the first layer preferably contains a catalyst from the viewpoint of promoting modification by vacuum ultraviolet rays. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on polysilazane. 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.

In the first layer forming coating solution, the following additives may be used as necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, particularly urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyester resins or modified polyester resins, epoxy resins, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

<Method of Applying First Layer Forming Coating Solution>
As a method of applying the first layer forming coating solution, a conventionally known appropriate wet coating method may 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.

The drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C. 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.

The manufacturing method may include a step of removing moisture from the coating film obtained by applying the first layer forming coating solution. 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. The preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), the more preferable dew point temperature is −5 ° C. or lower (temperature 25 ° C./humidity 10%), and the time for maintaining is the thickness of the first layer It is preferable to set appropriately. Specifically, it is preferable that the dew point temperature is −5 ° C. or lower and the maintaining 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 water before or during the reforming treatment.

<Vacuum UV irradiation>
After the first layer is formed as described above, the second layer may be formed continuously. However, before forming the second layer, the first layer is irradiated with vacuum ultraviolet rays to form polysilazane silicon oxynitride, etc. It is preferable to carry out the conversion reaction into If the first layer containing the element M2 is formed, the composition of the gas barrier layer that is finally obtained by storage over time until the second layer is formed can be suppressed without irradiation with vacuum ultraviolet rays. , Productivity and production stability are improved. However, after forming the first layer, by performing vacuum ultraviolet irradiation, it was assumed that it had a process of storing in a high temperature and high humidity environment until the second layer was formed after the first layer was formed. However, the composition of the gas barrier layer finally obtained is hardly changed compared to a production method having no storage step, and production stability is further improved. 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.

UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate 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 depends on the resin substrate used and the composition and concentration of the first layer, but is preferably 0.1 second to 10 minutes, more preferably 0.5 seconds to 3 minutes.

<Vacuum UV irradiation treatment: Excimer irradiation treatment>
The modification by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms only to photons called photon processes. 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.

The vacuum ultraviolet ray source in the present invention may be any source that generates light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator (for example, Xe excimer lamp) having a maximum emission at about 172 nm, and an emission line at about 185 nm. Low pressure mercury vapor lamps with medium pressure and medium and high pressure mercury vapor lamps with wavelength components of 230 nm or less, and excimer lamps with 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.

Also, 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.

¡Excimer lamps have high light generation efficiency and can be lit 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 irradiation object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

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 irradiation with vacuum ultraviolet rays 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.

The gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas 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 irradiation, the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane coating is preferably 1 mW / cm ² to 10 W / cm ² , more preferably 30 mW / cm ² to 200 mW / 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 vacuum ultraviolet irradiation is performed, the amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the surface of the coating film is preferably 0.1 J / cm ² or more and less than 1 J / cm ² , preferably 0.2 to 0.8 J / cm ^2. more preferably cm ^2. If the amount of irradiation energy is within this range, even if it has a step of storing in a high-temperature and high-humidity environment between the formation of the first layer and the formation of the second layer, it is finally obtained. The composition of the 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.

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.

The content of the element M2 in the first layer is preferably 0.001 to 50% by mass, and more preferably 0.1 to 40% by mass with respect to the mass of the entire first layer.

In addition, the content of the element M2 in the first layer is preferably 5 to 20 mol%, more preferably 5 to 10 mol% with respect to 100 mol% of silicon (Si).

The thickness of the first layer formed as described above is preferably 10 to 500 nm, and more preferably 30 to 300 nm.

[Method for forming second layer]
The method for forming the second layer containing the metal M1 and oxygen atoms is preferably a vapor deposition method from the viewpoint of easily forming the regions (A) and (B). The vapor deposition method is not particularly limited, and specific examples include the method described in (1-1) above.

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. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a transition metal compound thin film such as an oxide, nitride, nitride oxide, or carbonate of metal M1 can be formed. Examples of film formation conditions in the vapor phase film formation method include applied power, discharge current, discharge voltage, time, and the like. These may be appropriately selected according to the apparatus used, the material of the film, the film thickness, and the like. it can.

As a target used in the vapor deposition method, a target containing an oxide of metal M1 is preferable.

Among the formation methods of the second layer, a sputtering method used as a target containing an oxide of the metal M1 is preferable because the film formation rate is higher and the productivity is higher.

The set thickness of the second layer is preferably 1.5 to 30 nm, and preferably 3 to 20 nm.

[Layers with various functions (other layers)]
In the gas barrier film of the present invention, layers having various functions can be provided.

<Anchor coat layer>
An anchor coat layer may be formed on the surface of the resin substrate on the side where the gas barrier layer according to the present invention is formed for the purpose of improving the adhesion between the resin substrate and the gas barrier layer.

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).

Also, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like. 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>
A hard coat layer may be provided on the surface (one side or both sides) of the resin substrate. 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 is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or 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, ie, 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. You may use the commercially available resin base material in which the hard-coat layer is formed previously.

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.

<Smooth layer>
The gas barrier film of the present invention may have a smooth layer between the resin substrate and the gas barrier 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 coat 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 Coat, Nanohybrid Silicone manufactured by ADEKA, and Unidic manufactured by DIC. (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, 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 specified by JIS B 0601: 2001, and the 10-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.

[Electronic device]
The gas barrier film according to 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 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 effect 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.

[Production of resin base material]
As the resin base material, a 100 μm-thick polyethylene terephthalate film (Lumirror (registered trademark) (U48), manufactured by Toray Industries, Inc.) with 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 resin 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 resin substrate so that the dry film thickness was 0.5 μm, and then dried at 80 ° C., and then under high pressure in the air. Curing was performed using a mercury 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 resin substrate on the side where the gas barrier layer is to be formed as follows. A UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a resin substrate so as to have a dry film thickness of 2 μm, then dried at 80 ° C., and then using a high-pressure mercury lamp in the air. Then, curing was performed under the condition of an irradiation energy amount of 0.5 J / cm ² . In this way, a resin substrate with a clear hard coat layer was obtained. Hereinafter, in this example and the comparative example, this resin substrate with a clear hard coat layer is simply referred to as a resin substrate for convenience.

(Examples 1-1 to 1-3, Comparative Examples 1-1 to 1-4)
On the resin base material, the first layer and the second layer were formed as follows to produce a gas barrier film.

[Deposition of the first layer]
A first layer was formed on one surface of the resin base material using a magnetron sputtering apparatus (manufactured by Canon Anelva Co., Ltd .: Model EB1100).

The following targets and film formation conditions were used as targets, Ar and O ₂ were used as process gases, and film formation was performed by DC sputtering. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. In each film formation condition, the composition was adjusted by adjusting the oxygen partial pressure. In addition, in film formation using a glass substrate in advance, the condition of the composition is determined by adjusting the oxygen partial pressure, and the condition in which the composition near the depth of 10 nm from the surface layer becomes the target composition is found. Applied. Regarding the film thickness, film thickness change data with respect to the film formation time is obtained in the range of 100 to 300 nm, the film formation time per unit time is calculated, and then the film formation time is set to the set film thickness. The film thickness was adjusted by setting.

<Target>
T1: A silicon target containing no M2 was produced by the method described in Comparative Example 1 of JP2012-007218A. However, the target shape was a plate shape;
T2: A target containing 1.5% by mass of boron with respect to silicon as M2 was produced by the method described in Example 1 of JP2012-007218A. However, the target shape was a plate shape;
T3: According to the same method as that of the target 1 of the present invention described in “Aspects of the Invention” of JP-A-2003-160862, M2 contains 5% by mass of aluminum, 12% by mass of phosphorus, and the balance (almost 95 A target having a mass%) of silicon was produced. Since the phosphorus content was very small, no analysis was performed on phosphorus in the composition analysis described below.

<Film formation conditions>
T1-1: T1 was used as a target, and in the above XPS analysis, the oxygen partial pressure was adjusted so that the composition of the layer was SiO ₂ . Also, the film formation time was set so that the film thickness was 120 nm;
T1-2: Performed in the same manner as T1-1 except that the film formation time was set so that the film thickness was 100 nm;
T2-1: Performed in the same manner as T1-1 except that T2 was used as a target and the film formation time was set to 120 nm in the T2 condition determination;
T2-2: The same as T2-1, except that the film formation time was set so that the film thickness was 100 nm;
T3-1: Performed in the same manner as T1-1 except that T3 was used as a target and a film formation time was set at which the film thickness was 120 nm in the T3 condition determination;
T3-2: Performed in the same manner as T3-1 except that the film formation time was set so that the film thickness was 100 nm.

<Film stability evaluation>
Continuous film formation was performed for 1 hour under the above film formation conditions, and the presence or absence of arc generation was confirmed. When no arc was generated, the film formation stability was good (◯), and when the arc was generated, the film formation stability was poor (x).

[Deposition of second layer]
A second layer was formed on the first layer. For film formation, the same apparatus as that used for film formation of the first layer was used, and the film composition and film thickness were set by the same method as that for film formation of the first layer.

<Target>
T4: A commercially available oxygen-deficient niobium oxide target was used. The composition was Nb ₁₂ O ₂₉ .

<Film formation conditions>
T4-1: T4 was used as a target, and the oxygen partial pressure was 12%. Also, the film formation time was set so that the film thickness was 15 nm;
T4-2: Performed in the same manner as T4-1 except that the film formation time was set so that the film thickness was 10 nm;
T4-3: Performed in the same manner as T4-1 except that the film formation time was set so that the film thickness was 5 nm.

(Examples 2-1 to 2-15, Comparative Examples 2-1 to 2-7)
On the resin base material, the first layer and the second layer were formed as follows to produce a gas barrier film.

[Deposition of the first layer]
The coating liquid (S1 to S9) containing polysilazane as shown below is applied on one surface of the resin substrate, dried to form a coating film, and then modified by vacuum ultraviolet irradiation under the conditions shown below The first layer was formed (S1-1, S2-1, S2-3 to 9-1) or without modification (S1-2, S2-2).

The coating solution (S1 to S9) was applied on the resin base material by spin coating so as to have a dry film thickness shown in Table 2 below, and dried at 80 ° C. for 2 minutes. Next, vacuum ultraviolet irradiation treatment was performed on the dried coating film under the film forming conditions shown in Table 2 using the vacuum ultraviolet irradiation apparatus of FIG. 1 having an Xe excimer lamp with a wavelength of 172 nm. At this time, the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The stage temperature for installing the sample was set to 80 ° C.

In FIG. 1, reference numeral 1 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber. The oxygen concentration can be maintained at a predetermined concentration. 2 is an Xe excimer lamp having a double tube structure that irradiates 172 nm vacuum ultraviolet light (excimer lamp light intensity: 130 mW / cm ² ), 3 is an excimer lamp holder that also serves as an external electrode, and 4 is a sample stage. The sample stage 4 can reciprocate horizontally in the apparatus chamber 1 at a predetermined speed (V in FIG. 1) by a moving means (not shown). The sample stage 4 can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 5 denotes a sample on which a polysilazane compound coating layer is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 3 mm. Reference numeral 6 denotes a light-shielding plate which prevents the application of the sample from being irradiated with vacuum ultraviolet rays during aging of the Xe excimer lamp 2.

The energy applied to the surface of the sample coating layer in the vacuum ultraviolet irradiation step was measured using a 172 nm sensor head using an ultraviolet integrated light meter (C8026 / H8025 UV POWER METER) manufactured by Hamamatsu Photonics Co., Ltd. In the measurement, the sensor head is installed in the center of the sample stage 4 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 1 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as in the process, and the sample stage 4 was moved at a speed of 0.5 m / min for measurement. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 2, an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.

Based on the irradiation energy obtained by this measurement, the amount of irradiation energy shown in Table 2 was adjusted by adjusting the moving speed of the sample stage. The vacuum ultraviolet irradiation was performed after aging for 10 minutes.

<Coating solution>
S1: Dibutyl ether solution containing 20% by mass of perhydropolysilazane (Merck Co., Ltd., NN120-20) and amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) ) And a dibutyl ether solution of 20% by mass of perhydropolysilazane (manufactured by Merck & Co., Inc., NAX120-20) at a ratio of 4: 1 (mass ratio), and further a solid content concentration of 3% by mass with dibutyl ether. The coating solution S1 was prepared by dilution. The coating solution was prepared in a glove box. The following preparation is similar;
S2: An aluminum compound solution was prepared by diluting aluminum ethyl acetoacetate diisopropylate with dibutyl ether so that the solid concentration was 3% by mass. S1 and the aluminum compound solution are mixed so that the Al / Si atomic ratio is 0.01, heated to 80 ° C. with stirring, held at 80 ° C. for 2 hours, and then gradually lowered to room temperature (25 ° C.). Chilled. In this way, a coating solution S2 was prepared;
S3: A coating solution S3 was prepared in the same manner as S2, except that S1 and the aluminum compound solution prepared in S2 were mixed so that the Al / Si atomic ratio was 0.1;
S4: Coating solution S4 was prepared in the same manner as S2, except that S1 and the aluminum compound solution prepared in S2 were mixed so that the Al / Si atomic ratio was 0.15;
S5: A coating solution S5 was prepared in the same manner as S2, except that S1 and the aluminum compound solution prepared in S2 were mixed so that the Al / Si atomic ratio was 0.005;
S6: Coating solution S6 was prepared in the same manner as S2, except that S1 and the aluminum compound solution prepared in S2 were mixed so that the Al / Si atomic ratio was 0.03;
S7: A boron compound solution was prepared by diluting triisopropyl borate with dibutyl ether so that the solid concentration was 3% by mass. S1 and boron compound solution are mixed so that the B / Si atomic ratio is 0.01, heated to 80 ° C. with stirring, held at 80 ° C. for 2 hours, and then gradually brought to room temperature (25 ° C.). Chilled. In this way, a coating solution S7 was prepared;
S8: A titanium compound solution was prepared by diluting titanium isopropoxide with dibutyl ether so that the solid concentration was 3% by mass. S1 and the titanium compound liquid were mixed so that the Ti / Si atomic ratio was 0.01, the temperature was raised to 80 ° C. with stirring, the temperature was maintained at 80 ° C. for 2 hours, and then gradually increased to room temperature (25 ° C.). Chilled. In this way, a coating solution S8 was prepared;
S9: A zirconium compound solution was prepared by diluting zirconium tetraacetylacetonate with dibutyl ether so that the solid concentration was 3% by mass. S1 and the zirconium compound liquid were mixed so that the Zr / Si atomic ratio was 0.01, the temperature was raised to 80 ° C. with stirring, the temperature was maintained at 80 ° C. for 2 hours, and then gradually increased to room temperature (25 ° C.). Chilled. In this way, a coating solution S9 was prepared;
<Film formation conditions>
S1-1: Using the coating solution S1, coating and drying were performed according to the above-described method so that the dry film thickness was 100 nm. Thereafter, the above-described vacuum ultraviolet irradiation was performed under the condition of 0.8 J / cm ² ;
S1-2: The same as S1-1 except that the vacuum ultraviolet irradiation was not performed;
S2-1: The same as S1-1 except that the coating solution S2 was used;
S2-2: Performed in the same manner as S2-1 except that the vacuum ultraviolet irradiation was not performed;
S2-3: The same as S2-1 except that the vacuum ultraviolet irradiation was performed under the condition of 0.3 J / cm ² ;
S2-4: The same as S2-1 except that the vacuum ultraviolet irradiation was performed under the condition of 0.5 J / cm ² ;
S3-1: Performed in the same manner as S1-1 except that the coating solution S3 was used;
S4-1: The same as S1-1 except that the coating solution S4 was used;
S5-1: The same as S1-1 except that the coating solution S5 was used;
S6-1: The same as S1-1 except that the coating solution S6 was used;
S7-1: The same as S1-1 except that the coating solution S7 was used;
S8-1: Performed in the same manner as S1-1 except that the coating liquid S8 was used;
S9-1: Performed in the same manner as S1-1 except that the coating liquid S9 was used.

[Deposition of second layer]
A second layer was formed on the first layer. For film formation, a magnetron sputtering apparatus (Canon Anelva Co., Ltd .: Model EB1100) was used, and the film composition and film thickness were set by the same method.

<Target>
T4: A commercially available oxygen-deficient niobium oxide target was used. The composition was Nb ₁₂ O ₂₉ ;
T5: A commercially available Ta target was used.

<Film formation conditions>
T4-1: T4 was used as a target, and the oxygen partial pressure was set to 12% by volume. Also, the film formation time was set so that the film thickness was 15 nm;
T4-2: Performed in the same manner as T4-1 except that the film formation time was set so that the film thickness was 10 nm;
T4-3: Performed in the same manner as T4-1 except that the film formation time was set so that the film thickness was 5 nm;
T4-4: The same as T4-1 except that the film formation time was set so that the film thickness was 2 nm;
T4-5: The same as T4-1, except that the film formation time was set so that the film thickness was 1 nm;
T4-6: Film formation was performed without introducing oxygen using T4 as a target. Also, the film formation time was set so that the film thickness was 5 nm;
T4-7: The same as T4-6, except that the film formation time was set so that the film thickness was 2 nm;
T5-1: T5 was used as a target, and the oxygen partial pressure was 18% by volume. The film formation time was set so that the film thickness was 15 nm.

[Evaluation methods]
[Measurement of composition distribution in the thickness direction (gas barrier layer composition)]
The composition distribution profile in the thickness direction of the gas barrier layer was measured by XPS analysis. The XPS analysis conditions are as follows.

<XPS analysis conditions>
・ Device: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement was 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 for 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. For data processing, MultiPak manufactured by ULVAC-PHI was used. The analyzed elements were Si, metal M1, element M2, O, N, and C.

By this XPS composition analysis, the thickness of the regions (A) to (C), the Si ratio at the boundary between the regions (A) and (B), the composition of the region (b), the regions (B) and (C) The M1 ratio, [B], and [C] at the boundary were measured.

<Gas barrier property evaluation>
For each of the samples of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-4, the sample without storage under high temperature and high humidity conditions and a gas barrier film with the gas barrier layer exposed to 85 were used. Samples stored for 24 hours in a high-temperature and high-humidity environment of 85 ° C. at 85 ° C. were prepared, and Ca method evaluation cells were prepared by the methods described below.

For each sample of Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-7, a sample in which the second layer was formed under the following two conditions was prepared, and the Ca A method evaluation cell was produced;
After the first layer is formed, the second layer is formed after storage for 24 hours in an environment of 20 ° C. and 50% RH. After the first layer is formed, the second layer is stored after being stored in an environment of 60% 90% RH for 48 hours. After forming the first layer, after storing for 24 hours in an environment of 20 ° C. and 50% RH, for the sample on which the second layer was formed, a sample without high-temperature and high-humidity storage and a gas barrier film were used. Samples stored for 24 hours in a high-temperature and high-humidity environment of 85 ° C. and 85% RH with the gas barrier layer exposed were prepared, and Ca method evaluation cells were prepared. That is, three types of samples for gas barrier property evaluation were prepared.

<Evaluation of water vapor permeability of gas barrier film (Ca method)>
According to the following measuring method, the water vapor permeability of each gas barrier film was evaluated.

After the surface of the gas barrier layer of the gas barrier film was UV washed, a thermosetting sheet-like adhesive (epoxy resin) was bonded to the surface of the gas barrier layer with a thickness of 20 μm as a sealing resin layer. This was punched out to a size of 50 mm × 50 mm, then placed in a glove box and dried for 24 hours.

One side of a 50 mm × 50 mm non-alkali glass plate (thickness 0.7 mm) was UV cleaned.

Ca was vapor-deposited with a size of 20 mm × 20 mm through a mask in the center of the glass plate using a vacuum vapor deposition apparatus manufactured by ALS Technology. The thickness of Ca was 80 nm.

The glass plate on which Ca was vapor-deposited was taken out into the glove box, placed so that the sealing resin layer surface of the barrier film to which the sealing resin layer was bonded and the Ca vapor-deposited surface of the glass plate were in contact, and adhered by vacuum lamination. At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down, and cured for 30 minutes to produce an evaluation cell.

In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample was similarly 85. It was stored in a high-temperature and high-humidity environment at 85 ° C. and it was confirmed that no corrosion of metallic calcium occurred even after 100 hours.

(Measurement of transmission density)
The transmission density was measured using the evaluation cell. For transmission density measurement, a black and white transmission density meter TM-5 manufactured by Konica Minolta Co., Ltd. was used. The transmission density was measured at any four points in the cell, and the average value was calculated. The same applies hereinafter.

After measuring the initial value of the transmission density of each evaluation cell, the evaluation cell is stored in an 85 ° C. and 85% RH environment, and is observed every 1 hour, 5 hours, 10 hours, and thereafter every 5 hours. The transmission density was measured. The observation time when the transmission density became less than 50% of the initial value was determined, and evaluated using the following indices.

Indicator Time for transmission density to be less than 50% 0: less than 1 hour 1: 1 to less than 5 hours 2: 5 to 10 hours 3: 10 to 25 hours 4: 25 to 50 hours 5:50 Over time.

The compositions and evaluation results of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-4 are shown in Table 1 and Table 2 below. Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2 The composition and evaluation results of −7 are shown in Table 3 and Table 4 below, respectively. “No film formation” in the film formation condition column for the second layer in Tables 1 and 3 indicates that the second layer was not formed. Moreover, the gas barrier layer composition of Table 4 is the result of measuring about the sample which formed the 2nd layer, after storing for 24 hours in 20 degreeC50% RH environment after 1st layer formation.

As is clear from Tables 2 and 4 above, the gas barrier films of Examples 1-1 to 1-3 and Examples 2-1 to 2-15 have gas barrier properties even after being stored in a high temperature and high humidity environment. It turns out that it is hard to deteriorate and is excellent in durability.

Further, as apparent from Table 2 and Table 4 above, according to the manufacturing method of the present invention, the second layer is formed afterwards regardless of the change in the storage environment after the first layer is formed. A gas barrier film having excellent gas barrier properties can be obtained. That is, the production method according to the present invention is excellent in production stability and productivity.

Note that this application is based on Japanese Patent Application No. 2015-146183 filed on July 23, 2015, the disclosure of which is incorporated by reference in its entirety.

Claims

A gas barrier film having a gas barrier layer containing a silicon atom, a metal M1 other than silicon, an element M2 other than silicon and the metal M1, and an oxygen atom on a resin substrate,
The ratio of the amount of the silicon atom to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer is [Si] (unit: atom%),
The ratio of the amount of the metal M1 to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer is [M1] (unit: atom%),
The ratio of the amount of the element M2 to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer was [M2] (unit: atom%). In case,
Gas barrier properties having, from the resin substrate side, a region (C) satisfying the following formula (c), a region (B) satisfying the following formula (b), and a region (A) satisfying the following formula (a) in this order. the film.
The average value of the ratio ([M2] / [Si]) between the [M2] and the [Si] in the region (B) is [B], and the [M2] and the [Si] in the region (C) The gas barrier film according to claim 1, wherein [C]> [B] is satisfied, where [C] is an average value of a ratio with respect to ([M2] / [Si]).
The gas barrier film according to claim 1 or 2, wherein the metal M1 is a metal of Group 5 of the periodic table.
The element M2 according to any one of claims 1 to 3, wherein the element M2 is at least one selected from the group consisting of aluminum (Al), boron (B), zirconium (Zr), and titanium (Ti). Gas barrier film.
A method for producing a gas barrier film according to any one of claims 1 to 4,
Forming a first layer containing the silicon atom, the element M2, and the oxygen atom on the resin substrate;
Forming a second layer containing the metal M1 and the oxygen atom on the first layer;
A method for producing a gas barrier film, comprising:
The manufacturing method according to claim 5, wherein the step of forming the first layer includes applying a solution containing polysilazane and the compound containing the element M2 on the resin base material and drying the solution.
The manufacturing method according to claim 5 or 6, wherein the second layer is formed by a vapor deposition method.
The manufacturing method according to claim 7, wherein the vapor deposition method is a physical vapor deposition method.