Gas barrier laminate

Abstract

To provide a transparent gas barrier laminate using a resin substrate and having good water vapor barrier properties.SOLUTION: A gas barrier laminate comprises a resin substrate and a transparent oxide film layer containing silicon (Si) and a Group 6 element (referred to as A) formed on one or both surfaces of the resin substrate. The Group 6 element (A) of the transparent oxide film layer contains only tungsten (W) and the ratio Si / (Si+A) of the number of atoms of the silicon (Si) to the total number of atoms of the silicon (Si) and the Group 6 element (A) in the transparent oxide film layer is 0.80 or less, or the Group 6 element (A) of the transparent oxide film layer contains both tungsten (W) and molybdenum (Mo) and the ratio Si / (Si+A) is 0.50 or less (except for the transparent oxide film layer containing 0.1 to 10 mass% of Mo).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a gas barrier laminate using a resin substrate.

Background Art

[0002] A gas barrier laminate is a laminate having a property of not allowing oxygen, water vapor, etc. to pass through (gas barrier property), and is widely used in various fields that require blocking of various gases, such as packaging of precision electronic components, electronics members, foods, and pharmaceuticals.

[0003] The required gas barrier property varies depending on the application. Generally, in a sealing film for displays such as organic electroluminescence (EL) and electronic paper, a high water vapor barrier property of 0.01 g / (m 2 ·day) or less is required, and in recent years, there has been an increasing demand for an even higher level of water vapor barrier property. In addition, these films are required to have transparency.

[0004] In recent years, in the fields of organic EL and electronic paper, etc., due to reasons such as flexibility, damage prevention, and weight reduction, resin is increasingly used as a substrate instead of glass. However, since a resin substrate has a low gas barrier property against oxygen gas and water vapor, deterioration of these elements and electronic members becomes a problem.

[0005] Therefore, in order to achieve high gas barrier property and transparency using a resin substrate, various things have been developed. In recent years, many gas barrier laminates have been proposed in which metal oxide films such as silicon oxide and aluminum oxide, and oxynitride films of various metals are provided on a resin substrate on a nanoscale.

[0006] In addition, as a method for manufacturing a gas barrier laminate, physical film formation methods such as induction heating method, resistance heating method, electron beam evaporation method, and sputtering method have been studied because they are easy to achieve large area and roll-to-roll development.

[0007] In order to achieve higher gas barrier properties, it is necessary to form a dense gas barrier layer composed of an inorganic compound. A dense inorganic compound film can generally be easily manufactured by a sputtering method.

[0008] In addition, in order to achieve higher transparency, it is required that there is less reflection at the interface between the resin substrate and the inorganic compound film and that the light transmittance in visible light is high. Therefore, it is necessary to form an inorganic compound film having a refractive index close to that of the resin substrate.

[0009] For example, Patent Document 1 below describes a transparent resin substrate (gas barrier laminate) having high transparency and high water vapor barrier performance. In such a gas barrier laminate, a transparent oxide film containing tin oxide and silicon (Si) as an additive element in a proportion of 46 atomic% or more and 63 atomic% or less with respect to the total of Si and Sn, being an amorphous film, and having a refractive index at a wavelength of 633 nm of 1.75 or less is formed as a gas barrier layer on at least one surface of a resin substrate by a direct current (DC) pulse sputtering method.

[0010] However, such a gas barrier laminate is described as having a water vapor transmission rate measured by the Mocon method of less than 0.01 g / (m 2 ·day) according to the JIS standard K7129 method. Although it certainly has high water vapor gas barrier properties, in fact, further improvement is required to meet the higher level of water vapor barrier properties required in recent years.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0012] Therefore, an object of the present invention is to provide a transparent gas barrier laminate using a resin substrate, which has good water vapor barrier properties.

Means for Solving the Problems

[0013] One aspect of the present invention for solving the above problems is a gas barrier laminate including a resin substrate and a transparent oxide film layer containing silicon (Si) and a Group 6 element (referred to as A) formed on one or both sides of the resin substrate. The Group 6 element (A) of the transparent oxide film layer contains only tungsten (W), and the ratio of the number of silicon (Si) atoms in the transparent oxide film layer to the total number of silicon (Si) and Group 6 element (A) atoms, Si / (Si + A), is 0.10 or more 0.80 or less, or contains both tungsten (W) and molybdenum (Mo), and the atomic ratio Si / (Si + A) is 0.10 or more 0.50 or less (however, excluding those in which Mo in the transparent oxide film layer is 0.1 to 10% by mass).

Effects of the Invention

[0014] According to the present invention, it is possible to provide a transparent gas barrier laminate using a resin substrate, which has good water vapor barrier properties.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0016] <First Embodiment> Hereinafter, the first embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1, the gas barrier laminate according to the present embodiment includes a resin substrate 11 and the resin substrate It is composed of a transparent oxide film layer 13 formed on one side of 11. In practice, a configuration in which the transparent oxide film layer 13 is laminated on both sides of the resin substrate 11 may also be used. Here, in the following description, the transparent oxide film layer formed (laminated) on the resin substrate 11 and the transparent oxide film layer 13 are synonymous.

[0017] (Resin substrate) The material of the resin substrate 11 is not particularly limited, and known materials can be used. For example, polyolefin-based (such as polyethylene, polypropylene, etc.), polyester-based (such as polyethylene terephthalate, polyethylene naphthalate, etc.), polyimide-based, polyamide-based (such as nylon-6, nylon-66, etc.), polystyrene, ethylene vinyl alcohol, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, polyethersulfone, acrylic, cellulose-based (such as triacetyl cellulose, diacetyl cellulose, etc.), etc. can be mentioned, but it is not particularly limited. In practice, it is desirable to appropriately select according to the use and required physical properties. For packaging that protects contents that extremely dislike moisture, such as electronic components and optical components, it is desirable to use a resin substrate 11 that itself has a high gas barrier property, such as polyethylene naphthalate, polyimides, polyethersulfone, etc., but it is not limited to these examples.

[0018] Also, the thickness of the resin substrate 11 is not limited, but depending on the application, about 12 μm to 300 μm is easy to use. The resin substrate 11 with a thickness within this range is flexible and can also be wound into a roll, so it is preferable.

[0019] Also, the form of the resin substrate 11 may be a long material or a single-sheet material, but a long resin substrate 11 can be preferably used. The length in the longitudinal direction of the long resin substrate 11 is not particularly limited, but for example, a long film of 10 m or more is preferably used. Note that the upper limit of the length is not limited, and for example, it may be about 10 km.

[0020] In addition, the surface of the resin substrate 11 may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, and a lubricant as needed. Further, in order to enhance the adhesion, the surface of the resin substrate 11 may be subjected to physical treatments such as corona treatment, frame treatment, plasma treatment, and easy adhesion treatment, or chemical treatment modification treatments such as chemical treatment with an acid or an alkali. The surface of the resin substrate 11 contributes to the denseness in the initial growth stage of vacuum deposition and is desirably smooth.

[0021] (Transparent oxide film layer) The transparent oxide film layer 13 is a transparent oxide film containing silicon (Si) and a Group 6 element (referred to as A) provided to impart gas barrier properties to the entire gas barrier laminate. The Group 6 element is more preferably molybdenum (Mo) or tungsten (W), and even more preferably tungsten (W). Further, it is more preferable to contain both molybdenum (Mo) and tungsten (W). Among the Group 6 elements, a dense film is formed by incorporating an element having a different size from silicon (Si), and therefore, it is considered that the effect of tungsten (W) having a large atomic number and a large size is large, but the details are unknown. As a method for forming the transparent oxide film layer 13, various sputtering methods can be used. Among the sputtering methods, it is preferable to use a sputtering method using a magnetron sputtering apparatus capable of periodically applying a voltage to the electrodes. Further, it is preferable to use a sputtering method using a magnetron sputtering apparatus capable of periodically applying a voltage to the electrodes and applying a pulse having a positive / negative different from that of the voltage application during the off-time of the voltage application (applying a pulse voltage). Also, it is preferable to use a sputtering method using a magnetron sputtering apparatus in which two electrodes are arranged in parallel, a voltage can be alternately applied to each electrode with positive / negative, and each of the electrodes alternately serves as a cathode and an anode. Further, it is preferable to use a sputtering method using a magnetron sputtering apparatus provided with a cylindrical electrode having a rotating mechanism. Also, when forming the transparent oxide layer by these sputtering methods, it is preferable to set the film formation pressure in the range of 0.05 Pa or more and 5.00 Pa or less.

[0022] The transparent oxide film layer 13 is formed such that the ratio of the number of silicon (Si) atoms to the total number of silicon (Si) and Group 6 element (A) atoms (Si / (Si + A)) is 0.10 or more and 0.98 or less, and the ratio of the number of oxygen (O) atoms to the total number of silicon (Si) and Group 6 element (A) atoms (O / (Si + A)) is 0.80 or more and 3.00 or less. Considering the refractive index and gas barrier properties, the ratio of the number of silicon (Si) atoms to the total number of silicon (Si) and Group 6 element (A) atoms (Si / (Si + A)) is more preferably 0.20 or more and 0.95 or less. When the Group 6 element (A) is tungsten (W), considering the refractive index, transparency, and gas barrier properties, the ratio of the number of silicon (Si) atoms to the total number of silicon (Si) and tungsten (W) atoms (Si / (Si + W)) is more preferably 0.25 or more and 0.95 or less, and even more preferably 0.30 or more and 0.80 or less. When the Group 6 element (A) is molybdenum (Mo), considering the refractive index, transparency, and gas barrier properties, the ratio of the number of silicon (Si) atoms to the total number of silicon (Si) and molybdenum (Mo) atoms (Si / (Si + Mo)) is more preferably 0.50 or more and 0.85 or less. It is more preferable to include both molybdenum (Mo) and tungsten (W) as the Group 6 element (A). Considering the refractive index, transparency, and gas barrier properties, the ratio of the number of silicon (Si) atoms to the total number of silicon (Si), molybdenum (Mo), and tungsten (W) atoms (Si / (Si + Mo + W)) is more preferably 0.25 or more and 0.95 or less. As a method for determining whether the transparent oxide film layer 13 is within the above composition range, a conventionally known method can be used. For example, it can be evaluated based on the results obtained by an analytical device such as an XPS (X-ray photoelectron spectrometer).

[0023] By setting the film composition of the transparent oxide film layer 13 within the above range, the refractive index n becomes 1.45 or more and 2.00 or less, and a refractive index n close to that of the resin base material 11 can be obtained. Therefore, reflection at the interface between the resin base material 11 and the transparent oxide film layer 13 is reduced, and the light transmittance in visible light can be increased. The refractive index of the transparent oxide film layer 13 can be measured and evaluated by measuring the refractive index of a film having the same composition as the transparent oxide film layer 13 with a refractometer (ellipsometer).

[0024] Also, the film thickness of the transparent oxide film layer 13 is preferably 5 nm or more and 500 nm or less. If it is less than 5 nm, the entire resin base material 11 cannot be covered with the transparent oxide film layer 13, and sufficient gas barrier properties cannot be obtained. Also, if it exceeds 500 nm, cracks are likely to occur, and the gas barrier properties may deteriorate. Furthermore, the cost increases due to an increase in the amount of material used, a longer film formation time, etc., which is not preferable from an economic point of view. That is, it is preferable that the optical film thickness nd represented by the product of the film thickness d and the refractive index n is 7 nm or more and 1000 nm or less.

[0025] Also, by setting the composition of the transparent oxide film layer 13 within the above range and the optical film thickness within the above range, the light absorption rate of the transparent oxide film layer 13 at a wavelength of 400 nm can be made 10% or less. For this reason, sufficient transparency can be obtained at all wavelengths in the visible light region. When the Group 6 element (A) is tungsten (W), if the ratio of the number of silicon (Si) atoms to the total number of silicon (Si) and tungsten (W) atoms (Si / (Si + W)) is less than 0.10, light at a wavelength of 400 nm is absorbed and sufficient transparency cannot be obtained. Also, when the optical film thickness exceeds 1000 nm, visible light may be absorbed and sufficient transparency may not be obtained. That is, it is preferable that the light absorption rate at a wavelength of 400 nm is 10% or less, and more preferably 5% or less. The light absorption rate of the transparent oxide film layer 13 can be measured and evaluated with an ultraviolet-visible spectrophotometer.

[0026] Also, the arithmetic mean roughness of the surface of the transparent oxide film layer 13 is preferably 5.0 nm or less. The surface roughness of the transparent oxide film layer is related to the internal structure of the transparent oxide film layer. In a film with a small surface roughness, a dense structure is formed, so it is considered that gas barrier properties are imparted, but the details are unknown. Also, when defects such as cracks that reduce the gas barrier properties occur in the transparent oxide film layer 13, the surface roughness increases. For this reason, the arithmetic mean roughness of the surface of the transparent oxide film layer 13 is preferably 5.0 nm or less, and more preferably 3.0 nm or less. The surface roughness of the transparent oxide film layer 13 can be measured and evaluated by an atomic force microscope.

[0027] Further, in addition to silicon (Si) and a metal element of Group 6 element (A), the transparent oxide film layer 13 may further contain at least one element selected from Mg, Al, Ca, Sc, Ti, V, Zn, Ga, Ge, Sr, Y, Zr, Nb, In, Sn, Ba, Hf, Ta. By the transparent oxide film layer 13 containing at least one element selected from Mg, Al, Ca, Sc, Ti, V, Zn, Ga, Ge, Sr, Y, Zr, Nb, In, Sn, Ba, Hf, Ta in addition to silicon (Si) and a Group 6 element (A), it becomes possible to improve gas barrier properties, improve adhesion to the resin base material 11, improve temperature and humidity durability, adjust the refractive index n, and the like. Further, the transparent oxide film layer 13 may further contain nitrogen in addition to the group of the metal elements, and may be a transparent oxynitride film layer.

[0028] (Regarding the sputtering method) As a means for forming the transparent oxide film layer 13, various sputtering methods can be used. Preferably, a sputtering method using a magnetron sputtering apparatus capable of periodically applying a voltage to the electrodes is used. According to this sputtering method, since the voltage is periodically applied, an off-time for voltage application is provided, thereby eliminating the charge on the target surface. Therefore, damage to the film caused by arcing can be suppressed, and it is possible to stably form a high-quality film. Further preferably, a sputtering method using a magnetron sputtering apparatus capable of periodically applying a voltage to the electrodes and applying a pulse having a positive / negative different from that during voltage application during the off-time of voltage application is used. According to this sputtering method, an off-time for voltage application is provided, and furthermore, since the voltage during that off-time is positive / negative inverted compared to during voltage application, the charge on the target surface is more easily eliminated. Therefore, damage to the film caused by arcing can be further suppressed, and it is possible to stably form a high-quality film. Also preferably, a sputtering method using a magnetron sputtering apparatus in which two electrodes are positioned in parallel, a voltage can be alternately applied to each electrode with positive / negative, and each of the electrodes alternately serves as a cathode and an anode is used. This sputtering method is a method of forming the transparent oxide film layer 13 by installing a target of a material on two electrodes installed in a vacuum chamber, colliding an ionized rare gas element (usually argon is used) obtained by applying a high voltage with the target, ejecting the atoms on the target surface, and depositing the target element on the resin substrate 11. In this sputtering method, since the anode and the cathode are alternately switched between the two targets, when one target is discharging and forming a film, the other target has a weak opposite charge, thereby eliminating the charge on the target surface. Therefore, damage to the film caused by arcing can be suppressed, and it is possible to stably form a high-quality film. It is also preferable to use a sputtering method using a magnetron sputtering apparatus provided with a cylindrical electrode having a rotating mechanism. According to this sputtering method, the target shape is also cylindrical like the electrode, and since the entire surface of the target becomes an erosion region by rotating, the utilization rate of the target is high.In addition, since the entire surface of the target becomes clean and arcing can be suppressed, continuous operation for a long time is possible. Furthermore, damage to the film caused by arcing can be suppressed, and it is possible to stably form a high-quality film. Also, two cylindrical electrodes having a rotating mechanism may be arranged in parallel, and voltages can be alternately applied to the positive and negative of each electrode, and each of the electrodes alternately serves as a cathode and an anode, which is a magnetron. It may also be a sputtering apparatus. At this time, by flowing a predetermined amount of oxygen gas into the chamber, the element ejected from the target reacts with oxygen to form the transparent oxide film layer 13. Further, at this time, by flowing nitrogen gas simultaneously with the oxygen gas, a transparent oxynitride film layer may be formed. Also, as the target, a target made of an alloy of Si and a Group 6 element (A) is used. The target described above may further contain at least one element selected from Mg, Al, Ca, Sc, Ti, V, Zn, Ga, Ge, Sr, Y, Zr, Nb, In, Sn, Ba, Hf, and Ta in addition to Si and the Group 6 element (A).

[0029] Even when using a magnetron sputtering apparatus capable of periodically applying a voltage to the electrodes, even when using a magnetron sputtering apparatus in which two electrodes are located in parallel, voltages can be alternately applied to the positive and negative of each electrode, and each of the electrodes alternately serves as a cathode and an anode, and even when using a magnetron sputtering apparatus equipped with a cylindrical cathode having a rotating mechanism, the power supply for applying a voltage to the electrodes is not particularly specified and may be AC or DC, but a DC pulse power supply is desirable. This is because making the voltage waveform to be applied a pulse wave is effective in relaxing the charge-up at the anode during the off-time of the voltage application. The frequency of the DC pulse power supply is not particularly limited and can be set as appropriate. Preferably, it is preferably 1 kHz or more and 100 kHz or less, and more preferably 10 kHz or more and 50 kHz or less.

[0030] Even when using a magnetron sputtering apparatus capable of periodically applying a voltage to the electrodes, where two electrodes are positioned in parallel and a voltage can be alternately applied to each electrode with positive and negative polarities, and each electrode alternately serves as a cathode and an anode, and even when using a magnetron sputtering apparatus equipped with a cylindrical cathode having a rotating mechanism, it is preferable to set the film-forming pressure in the range of 0.05 Pa or more and 5.00 Pa or less when forming the transparent oxide layer. By performing film formation within this range of film-forming pressure, a film with few surface defects can be obtained.

[0031] The gas barrier laminate according to this embodiment is configured by laminating the above-described transparent oxide film layer 13 on the resin substrate 11. As a result, the water vapor transmission rate under the measurement conditions of 40°C and 90% R.H. can be made 0.01 g / (m 2 ·day) or less. Also, by making the transparent oxide film layer 13 a dense film, the helium transmission rate under the measurement conditions of 40°C and 0% R.H. can be made 1200 cc / (m 2 ·day·atm) or less. Further, the neon transmission rate under the measurement conditions of 40°C and 0% R.H. can be made 2.0 cc / (m 2 ·day·atm) or less. Also, by using the sputtering method using the above-described magnetron sputtering apparatus, it is possible to suppress film defects due to arcing and manufacture a gas barrier laminate provided with a dense transparent oxide film layer 13. Therefore, according to this embodiment, a gas barrier laminate having good gas barrier properties and a method for manufacturing the same can be realized.

[0032] <Second Embodiment> Hereinafter, a second embodiment of the present invention will be described. The gas barrier laminate according to this embodiment is one in which an undercoat layer 12 is further provided between the resin substrate 11 and the transparent oxide film layer 13 of the gas barrier laminate shown in FIG. 1, like the gas barrier laminate shown in FIG. 2. Also, a configuration in which the undercoat layer 12 and the transparent oxide film layer 13 are sequentially laminated on both sides of the resin substrate 11 may be used.

[0033] The undercoat layer 12 is provided on the resin base material 11 to enhance the adhesion between the resin base material 11 and the transparent oxide film layer 13, prevent the occurrence of peeling of the transparent oxide film layer 13, and further protect it from mechanical damages such as scratches and abrasions. The material of the undercoat layer 12 is not particularly limited, but thermosetting resins, thermoplastic resins, ultraviolet curable resins, electron beam curable resins, etc. can be used.

[0034] Examples of the thermosetting resin for forming the undercoat layer 12 include thermosetting urethane resins composed of acrylic polyol resins and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, etc. Among them, by using a composite of an acrylic polyol resin containing a hydroxy group and an isocyanate-based compound having at least two or more NCO groups in the molecule, the adhesion between the resin base material 11 and the transparent oxide film layer 13 can be enhanced.

[0035] An acrylic polyol resin is a polymer compound obtained by polymerizing a (meth)acrylic acid derivative monomer, or a polymer compound obtained by copolymerizing a (meth)acrylic acid derivative monomer and other monomers, etc., which has hydroxy groups at the terminal and side chains and reacts with the NCO groups of the isocyanate-based compound. The (meth)acrylic acid derivative monomer has hydroxy groups at the terminal and side chains. Examples of the (meth)acrylic acid derivative monomer include hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc.

[0036] The above-mentioned other monomers are copolymerizable with (meth)acrylic acid derivative monomers having hydroxy groups at both the terminal and the side chain. Examples of the above-mentioned other monomers include (meth)acrylic acid derivative monomers having an alkyl group in the side chain such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, etc., (meth)acrylic acid derivative monomers having a carboxy group in the side chain such as (meth)acrylic acid, (meth)acrylic acid derivative monomers having an aromatic ring or a cyclic structure in the side chain such as benzyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. In addition to (meth)acrylic acid derivative monomers, styrene monomers, cyclohexyl maleimide monomers, phenyl maleimide monomers, etc. are conceivable. The above-mentioned other monomers may themselves have hydroxy groups at both the terminal and the side chain.

[0037] The acrylic polyol resin is preferably a polymer compound obtained by polymerizing a (meth)acrylic acid derivative monomer having a carboxy group in the side chain such as (meth)acrylic acid. When forming the undercoat layer 12, a gas barrier laminated film having a higher water vapor barrier property can be obtained by forming it using a composite of an acrylic polyol resin obtained by polymerizing a monomer having a carboxy group and an isocyanate-based compound.

[0038] The acrylic polyol resin containing a hydroxy group that can be used for the undercoat layer 12 is not particularly limited, but it is desirable that the hydroxy value is 50 mgKOH / g or more and 250 mgKOH / g or less. Here, the hydroxy value (mgKOH / g) is an index of the amount of hydroxy groups in the acrylic polyol resin, and indicates the number of mg of potassium hydroxide required to acetylate the hydroxy groups in 1 g of the acrylic polyol resin. Further, the weight average molecular weight of the acrylic polyol resin is not particularly limited, but specifically, it is preferably 3000 or more and 200000 or less. In particular, it is preferably 5000 or more and 100000 or less. Furthermore, it is more preferably 5000 or more and 40000 or less.

[0039] Isocyanate compounds are those having two or more NCO groups in their molecules. Examples of monomeric isocyanates include aromatic isocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), aliphatic isocyanates such as hexamethylene diisocyanate (HDI), bis(isocyanatomethyl)cyclohexane (H6XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI), etc. Further, polymers or derivatives of these monomeric isocyanates can also be used. For example, there are trimeric nurate types, adduct types reacted with 1,1,1-trimethylolpropane, etc., biuret types reacted with biuret, etc. The isocyanate compounds may be arbitrarily selected from the above-mentioned isocyanate compounds or their polymers and derivatives, and can be used alone or in combination of two or more.

[0040]

[0041] As an example of the undercoat layer 12, a solution composed of a composite of the above acrylic polyol resin and the above isocyanate compound and a solvent is applied onto the resin base material 11 and reaction-cured to form it. The equivalent ratio (NCO / OH) of the NCO group of the isocyanate compound to the hydroxy group of the acrylic polyol resin is preferably 0.3 or more and 2.5 or less. The solvent used here may be any solvent that dissolves the above acrylic polyol resin and isocyanate compound. Examples of the solvent include methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, dioxolane, tetrahydrofuran, etc. In actuality, these solvents can be used alone or in combination of two or more.

[0042] ​Examples of the thermoplastic resin for forming the undercoat layer 12 include, for example, polyols having two or more hydroxy groups such as acrylic polyol, polyester polyol, polycarbonate polyol, polyether polyol, polycaprolactone polyol, epoxy polyol, etc., polyvinyl resins such as polyvinyl acetate and polyvinyl chloride, polyvinylidene chloride resin, polystyrene resin, polyethylene resin, polypropylene resin, polyurethane resin, etc., which are appropriately selected from these. Further, these may be mixed at an arbitrary ratio. The hydroxy value of the polyol is not particularly limited, but it is preferably 10 mgKOH / g or more and 250 mgKOH / g or less.

[0043] Examples of the ultraviolet curable resin or electron beam curable resin for forming the undercoat layer 12 include, as the organic polymer resin, although not particularly limited, it is desirable to contain at least a resin having a hydroxy value in the range of 10 or more and 100 mgKOH / g or less. Further, as the organic polymer resin, although not particularly limited, it is desirable to contain at least a resin having an acid value in the range of 10 or more and 100 mgKOH / g or less. Here, the acid value (mgKOH / g) indicates the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of the sample. Further, it is desirable to contain at least a thermoplastic resin as the organic polymer resin. When the hydroxy value or acid value is less than 10 mgKOH / g, the chemical bonding force between the functional group and the surface of the transparent oxide film layer 13 becomes weak, and the adhesion to the transparent oxide film layer 13 tends to be low. When the hydroxy value or acid value exceeds 100 mgKOH / g, precipitates containing hydroxy groups generated by the decomposition of the undercoat layer 12 in durability tests such as the damp heat test tend to inhibit the adhesion between the undercoat layer 12 and the transparent oxide film layer 13.

[0044] Examples of monomers that can be used in the ultraviolet curable resin or electron beam curable resin for forming the undercoat layer 12 include monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, N-vinylpyrrolidone, etc., and polyfunctional monomers such as trimethylolpropane (meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol (meth)acrylate, etc. Examples of oligomers that can be used in this ultraviolet curable resin or electron beam curable resin include urethane acrylate, epoxy acrylate, polyester acrylate, etc.

[0045] When two or more kinds selected from thermosetting resins, thermoplastic resins, ultraviolet curable resins, and electron beam curable resins are used in combination as the organic polymer resin for forming the undercoat layer 12, the blending ratio is not particularly limited.

[0046] The undercoat layer 12 may further contain additives as necessary in addition to the organic polymer resin. Examples of additives include antioxidants, weathering agents, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, silane coupling agents, etc.

[0047] The film thickness of the undercoat layer 12 is preferably 0.05 μm or more and 10.0 μm or less. In particular, it is preferably 0.05 μm or more and 5.0 μm or less. If it is thinner than 0.05 μm, the adhesion between the resin substrate 11 and the transparent oxide film layer 13 will be insufficient. If it is thicker than 10.0 μm, the influence of internal stress will be large, the transparent oxide film layer 13 cannot be laminated neatly, the barrier property will not be sufficiently exhibited, and furthermore, the transparency and coating accuracy will also be insufficient.

[0048] As a method for forming the undercoat layer 12, a normal coating method can be used. For example, well-known methods such as dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, gravure offset method, organic vapor deposition method, etc. can be used. As the drying method, a method of applying heat such as hot air drying, hot roll drying, high-frequency irradiation, infrared irradiation, UV irradiation, electron beam irradiation, etc. can be used alone or in combination of two or more kinds. Further, a film previously coated on another resin substrate by the above forming method may be transferred to the resin substrate 11 using a transfer method such as adhesive transfer, thermal transfer, UV transfer, etc.

[0049] <Third Embodiment> Hereinafter, the third embodiment of the present invention will be described. The gas barrier laminate according to this embodiment is one in which an overcoat layer 14 is further provided on the transparent oxide film layer 13 of the gas barrier laminate shown in FIG. 3, like the gas barrier laminate shown in FIG. 2. Further, the same effect can be obtained by providing the overcoat layer 14 on the transparent oxide film layer 13 of the gas barrier laminate shown in FIG. 1.

[0050] The overcoat layer 14 is a layer containing an organic polymer resin, and is provided to protect the transparent oxide film layer 13 and prevent the occurrence of cracks due to rubbing and bending.

[0051] The organic polymer resin contained in the overcoat layer 14 can be appropriately selected. For example, one or more selected from thermosetting resins, thermoplastic resins, ultraviolet curable resins, and electron beam curable resins can be used. The ratio of the organic polymer resin in the overcoat layer 14 is not particularly limited and can be appropriately set.

[0052] Examples of the thermosetting resin for forming the overcoat layer 14 include thermosetting urethane resins composed of acrylic polyol resins and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. Among them, by using a composite of an acrylic polyol resin containing a hydroxy group and an isocyanate-based compound having at least two or more NCO groups in the molecule, the adhesion between the overcoat layer 14 and the transparent oxide film layer 13 can be enhanced.

[0053] The acrylic polyol resin is a polymer compound obtained by polymerizing (meth)acrylic acid derivative monomers, or a copolymerization of (meth)acrylic acid derivative monomers and other monomers Among them, those having hydroxy groups at the terminals and side chains, which react with the NCO groups of isocyanate-based compounds. The (meth)acrylic acid derivative monomers have hydroxy groups at the terminals and side chains. Examples of the (meth)acrylic acid derivative monomers include hydroxyethyl (meth)acrylate and hydroxybutyl (meth)acrylate.

[0054] The above-mentioned other monomers are copolymerizable with the (meth)acrylic acid derivative monomers having hydroxy groups at the terminals and side chains. Examples of the above-mentioned other monomers include (meth)acrylic acid derivative monomers having an alkyl group in the side chain such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and t-butyl (meth)acrylate, (meth)acrylic acid derivative monomers having a carboxy group in the side chain such as (meth)acrylic acid, and (meth)acrylic acid derivative monomers having an aromatic ring or a cyclic structure in the side chain such as benzyl (meth)acrylate and cyclohexyl (meth)acrylate. Other than the (meth)acrylic acid derivative monomers, styrene monomers, cyclohexyl maleimide monomers, phenyl maleimide monomers, etc. are conceivable. The above-mentioned other monomers may themselves have hydroxy groups at the terminals and side chains.

[0055] The acrylic polyol resin is preferably a polymer compound obtained by polymerizing a (meth)acrylic acid derivative monomer having a carboxy group in its side chain such as (meth)acrylic acid. When forming the undercoat layer 12, by forming it using a composite of an acrylic polyol resin obtained by polymerizing a monomer having a carboxy group and an isocyanate compound, a gas barrier laminated film having a higher water vapor barrier property can be obtained.

[0056] Regarding the acrylic polyol resin containing a hydroxy group in the overcoat layer 14, although it is not particularly limited, it is desirable that the hydroxy value is 50 mgKOH / g or more and 250 mgKOH / g or less. Also, the weight average molecular weight of the acrylic polyol resin is not particularly limited, but specifically, it is preferably 3000 or more and 200000 or less. In particular, it is preferably 5000 or more and 100000 or less. Further, it is more preferably 5000 or more and 40000 or less.

[0057] The isocyanate compound is one having two or more NCO groups in its molecule. Examples of monomeric isocyanates include aromatic isocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), aliphatic isocyanates such as hexamethylene diisocyanate (HDI), bis(isocyanatomethyl)cyclohexane (H6XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI), etc. Also, polymers or derivatives of these monomeric isocyanates can be used. For example, there are trimeric nurate type, adduct type reacted with 1,1,1-trimethylolpropane, etc., biuret type reacted with biuret, etc.

[0058] The isocyanate compound can be arbitrarily selected from the above-mentioned isocyanate compounds or their polymers and derivatives, and can be used alone or in combination of two or more.

[0059] As an example, the overcoat layer 14 is formed by applying a solution composed of a composite of the above acrylic polyol resin and the above isocyanate compound and a solvent onto the resin substrate 11 and subjecting it to reaction curing. The equivalent ratio (NCO / OH) of the NCO group of the isocyanate compound to the hydroxy group of the acrylic polyol resin is preferably 0.3 or more and 2.5 or less. Here, the solvent used may be any solvent that dissolves the above acrylic polyol resin and isocyanate compound. Examples of the solvent include methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, dioxolane, tetrahydrofuran, and the like. In practice, these solvents can be used alone or in combination of two or more kinds. As for the thermosetting resin forming the overcoat layer 14, in addition to the above, it is particularly preferable to contain at least one selected from the group consisting of a water-soluble polymer having a hydroxy group and an alkoxysilane and its hydrolyzate.

[0060]

[0061] The water-soluble polymer having a hydroxy group is preferably polyvinyl alcohol, polycarboxylic acid, starch, or celluloses. In particular, when polyvinyl alcohol (hereinafter referred to as PVA) is used in the coating agent of the present invention, the gas barrier property is excellent. Since PVA is a polymer containing the most hydroxy groups in the monomer unit, it has a very strong hydrogen bond with the hydroxy group of the organosilicon compound after hydrolysis. The PVA mentioned here generally refers to what is obtained by saponifying polyvinyl acetate, and includes so-called partially saponified PVA in which several tens of % of the acetate groups remain to completely saponified PVA in which only a few % of the acetate groups remain. The molecular weight of PVA has a wide variety from a degree of polymerization of 300 to several thousand, but there is no problem with the effect no matter which molecular weight is used. However, generally, a high-saponification-degree and high-molecular-weight PVA with a high degree of polymerization is preferable because of its high water resistance.

[0062] ​In addition, as the alkoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltriethoxysilane, methyltrimethoxysilane, etc. can be used. Further, as the hydrolysis product of the alkoxysilane, those prepared by dissolving the alkoxysilane in an alcohol such as methanol, adding an aqueous solution of an acid such as hydrochloric acid to the solution, and subjecting it to a hydrolysis reaction can be mentioned. By the hydrolysis reaction, the alkoxy group bonded to the silicon atom becomes a hydroxy group, and a siloxane bond is formed by dehydration condensation of the hydroxy groups, and a dense and strong network polymer film can be formed. Therefore, an overcoat layer 14 excellent in heat resistance, water resistance, moisture resistance, flexural resistance, tensile resistance, etc. can be obtained.

[0063] In addition, in order to improve the adhesion to the transparent oxide film layer 13, a silane coupling agent may be added. Examples of the silane coupling agent include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, those having a mercapto group such as 3-mercaptopropyltrimethoxysilane, those having an NCO group such as 3-isocyanatopropyltriethoxysilane, etc., and these silane coupling agents can be used alone or in combination of two or more.

[0064] As the thermoplastic resin for forming the overcoat layer 14, for example, polyols having two or more hydroxy groups such as acrylic polyol, polyester polyol, polycarbonate polyol, polyether polyol, polycaprolactone polyol, epoxy polyol, etc., polyvinyl resins such as polyvinyl acetate and polyvinyl chloride, polyvinylidene chloride resin, polystyrene resin, polyethylene resin, polypropylene resin, polyurethane resin, etc. are appropriately selected. Further, these may be mixed at an arbitrary ratio. The hydroxy value of the polyol is not particularly limited, but it is preferably 10 mgKOH / g or more and 250 mgKOH / g or less.

[0065] As the ultraviolet curable resin or electron beam curable resin for forming the overcoat layer 14, although not particularly limited as the organic polymer resin, it is desirable to contain at least a resin having a hydroxy value in the range of 10 or more and 100 mgKOH / g or less. Further, as the organic polymer resin, although not particularly limited, it is desirable to contain at least a resin having an acid value in the range of 10 or more and 100 mgKOH / g or less. Further, it is desirable to contain at least a thermoplastic resin as the organic polymer resin. When the hydroxy value or acid value is less than 10 mgKOH / g, the chemical bonding force between the functional group and the surface of the transparent oxide film layer 13 becomes weak, and the adhesion to the transparent oxide film layer 13 tends to be low. When the hydroxy value or acid value exceeds 100 mgKOH / g, deposits containing hydroxy groups generated by the decomposition of the overcoat layer 14 in durability tests such as a damp heat test tend to inhibit the adhesion between the overcoat layer 14 and the transparent oxide film layer 13. As such, although not particularly limited, it is desirable to contain at least a resin having an acid value in the range of 10 or more and 100 mgKOH / g or less. Further, it is desirable to contain at least a thermoplastic resin as the organic polymer resin. When the hydroxy value or acid value is less than 10 mgKOH / g, the chemical bonding force between the functional group and the surface of the transparent oxide film layer 13 becomes weak, and the adhesion to the transparent oxide film layer 13 tends to be low. When the hydroxy value or acid value exceeds 100 mgKOH / g, deposits containing hydroxy groups generated by the decomposition of the overcoat layer 14 in durability tests such as a damp heat test tend to inhibit the adhesion between the overcoat layer 14 and the transparent oxide film layer 13.

[0066] Examples of the monomers that can be used in the ultraviolet curable resin or electron beam curable resin for forming the overcoat layer 14 include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone, etc., and polyfunctional monomers such as trimethylolpropane (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, etc. can be used. Examples of the oligomers that can be used in this ultraviolet curable resin or electron beam curable resin include urethane acrylate, epoxy acrylate, polyester acrylate, etc.

[0067] When two or more kinds selected from thermosetting resins, thermoplastic resins, ultraviolet curable resins, and electron beam curable resins are used in combination as the organic polymer resin for forming the overcoat layer 14, the blending ratio is not particularly limited.

[0068] The overcoat layer 14 may further contain additives as required in addition to the organic polymer resin. Examples of the additives include antioxidants, weathering agents, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, silane coupling agents, and the like.

[0069] The film thickness of the overcoat layer 14 is not particularly limited and can be set as appropriate. Preferably, it is desirably 0.05 μm or more and 10.0 μm or less. If it is thinner than 0.05 μm, the protection of the transparent oxide film layer 13 will be insufficient, and if it is thicker than 10.0 μm, the influence of internal stress will be large and cracks will occur.

[0070] As a method for forming the overcoat layer 14, the same normal coating method as that for the undercoat layer 12 can be used. For example, well-known methods such as dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, gravure offset method, organic vapor deposition method, etc. can be used. As the drying method, a method of applying heat such as hot air drying, hot roll drying, high-frequency irradiation, infrared irradiation, UV irradiation, electron beam irradiation, etc. can be used alone or in combination of two or more kinds. Further, a film previously coated on another resin substrate by the above forming method may be transferred to the transparent oxide film layer 13 using a transfer method such as adhesive transfer, thermal transfer, UV transfer, etc.

Examples

[0071] Hereinafter, the gas barrier laminate according to the present invention will be described more specifically by way of examples and comparative examples of the present invention, but the present invention is not limited to these examples.

[0072] In Example 1, Example 20, Example 21, Example 22, Example 23, and Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, a transparent oxide film layer 13 is provided on one side of the resin substrate 11. In Example 2, Example 3, Example 6, Example 7, Example 8, Example 9, Example 10, Example 1 1. Example 1 2. Example 1 3. Example 1 4. Example 1 5. Example 1 6. Example 1 7. Example 1 8. Example 1 9. Example 1, and Comparative Example 5, an undercoat layer 12 is further provided between the resin base material 11 and the transparent oxide film layer 13. In Example 4 and Example 5, an overcoat layer 14 is further provided on the transparent oxide film layer 13. That is, Example 1, Example 20, Example 21, Example 22, Example 23, and Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4 correspond to the gas barrier laminate shown in FIG. 1. Example 2, Example 3, Example 6, Example 7, Example 8, Example 9, Example 10, Example 11, Example 12, Example 13, Example 14, Example 15, Example 16, Example 17, Example 18, Example 19, and Comparative Example 5 correspond to the gas barrier laminate shown in FIG. 2. Example 4 and Example 5 correspond to the gas barrier laminate shown in FIG. 3.

[0073] <Example 1> [Arrangement step of resin base material] As the resin base material 11, a biaxially stretched PET film (manufactured by Toray Industries, Inc., product name "Lumirror T60") with a thickness of 50 μm was used.

[0074] [Lamination step of transparent oxide film layer] On one side of the resin base material 11, the transparent oxide film layer 13 was formed by a sputtering method (referred to as Method A) using a magnetron sputtering apparatus in which two electrodes are arranged in parallel and a voltage can be alternately applied to each electrode, and each of the electrodes alternately serves as a cathode and an anode. As the film formation conditions, the film formation pressure was 0.30 Pa, and the power density was 3.3 W / cm 2Specifically, an alloy target of Si and W (atomic composition ratio Si:W = 90:10) was used as the target. As the means for supplying power to the two electrodes, an MF power supply was used. At that time, a rectangular voltage with a frequency of 40 kHz was applied to the two electrodes positioned in parallel. As the gases, argon gas and oxygen gas were used. At this time, the flow rate of the oxygen gas was controlled by detecting the emission intensity of the plasma and the voltage value of the discharge so that the state of the target surface was a transition state in the middle of the transition from the metal mode to the oxide mode. A gas barrier laminate was obtained by forming a transparent oxide film layer 13 with a film thickness of 100 nm.

[0075] <Example 2> [Resin Substrate Arrangement Step] Similar to Example 1, as the resin substrate 11, a biaxially stretched PET film with a thickness of 50 μm (manufactured by Toray Industries, Inc., product name "Lumirror T60") was used.

[0076] [Solution Preparation and Coating Step for Undercoat Layer] As the solution for the undercoat layer 12, an acrylic polyol (weight average molecular weight 10×10 3 ) obtained by copolymerizing hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) as monomers was used as the main agent, and a 5% solution of methyl ethyl ketone in which an HDI nurate type isocyanate curing agent was blended in an amount of 1 equivalent to the amount of hydroxy groups in the main agent was prepared. Then, the prepared solution was coated on the resin substrate 11, and an undercoat layer 12 with a thickness of 300 nm after drying was laminated.

[0077] [Lamination Step of Transparent Oxide Film Layer] A gas barrier laminate was obtained by forming a transparent oxide film layer 13 with a film thickness of 100 nm on the undercoat layer 12 under the same sputtering conditions as in Example 1, except that an alloy target of Si and Mo (atomic composition ratio Si:Mo = 80:20) was used.

[0078] <Example 3> A gas barrier laminate was obtained in the same manner as in Example 2, except that an alloy target of Si and Mo (atomic composition ratio Si:Mo = 50:50) was used.

[0079] <Example 4> [Resin substrate arrangement step] In the same manner as in Example 1 and Example 2, a biaxially stretched PET film with a thickness of 50 μm (manufactured by Toray Industries, Inc., product name "Lumirror T60") was used as the resin substrate 11.

[0080] [Preparation and coating process of the solution for the undercoat layer] In the same manner as in Example 2, an undercoat layer 12 with a dry thickness of 300 nm was laminated on the resin substrate 11.

[0081] [Lamination process of the transparent oxide film layer] A transparent oxide film layer 13 with a film thickness of 100 nm was formed on the undercoat layer 12 under the same sputtering conditions as in Example 1, except that an alloy target of Si and Cr (atomic composition ratio Si:Cr = 70:30) was used.

[0082] [Preparation and coating process of the solution for the overcoat layer] As the solution for the overcoat layer 14, a hydrolyzed solution of tetraethoxysilane (TEOS) and an aqueous solution of polyvinyl alcohol (PVA) were mixed so that the solid content ratio after drying was 70:30 to prepare a solution with a solid content of 5% by mass. Then, the prepared solution was coated on the transparent oxide film layer 13 using spin coating, and a gas barrier laminate was obtained by laminating an overcoat layer 14 with a dry thickness of 300 nm.

[0083] <Example 5> A gas barrier laminate was obtained in the same manner as in Example 4, except that an alloy target of Si and W (atomic composition ratio Si:W = 60:40) was used.

[0084] <Example 6> A gas barrier laminate was obtained in the same manner as in Example 2, except that an alloy target of Si and W (atomic composition ratio Si:W = 10:90) was used.

[0085] <Example 7> A gas barrier laminate was obtained in the same manner as in Example 2, except that an alloy target of Si and W (atomic composition ratio Si:W = 30:70) was used.

[0086] <Example 8> A gas barrier laminate was obtained in the same manner as in Example 2, except that an alloy target of Si and W (atomic composition ratio Si:W = 50:50) was used.

[0087] <Example 9> A gas barrier laminate was obtained in the same manner as in Example 2, except that an alloy target of Si and W (atomic composition ratio Si:W = 75:25) was used and the film formation pressure was set to 0.50 Pa.

[0088] <Example 10> A gas barrier laminate was obtained in the same manner as in Example 2, except that an alloy target of Si and W (atomic composition ratio Si:W = 95:5) was used and the film formation pressure was set to 0.8 Pa.

[0089] <Example 11> A gas barrier laminate was obtained in the same manner as in Example 5, except that the film formation pressure was set to 0.15 Pa as the film formation condition.

[0090] <Example 12> A gas barrier laminate was obtained in the same manner as in Example 2, except that an alloy target of Si, Mo, and W (atomic composition ratio Si:Mo:W = 50:25:25) was used.

[0091] <Example 13> As a method for forming the transparent oxide film layer 13, a sputtering method (referred to as Method B) using a magnetron sputtering apparatus capable of periodically applying a voltage to the electrode and applying a pulse with a positive / negative different from that of the voltage application during the off-time of the voltage application was used. A gas barrier laminate was obtained in the same manner as in Example 2, except that an alloy target of Si and W (atomic composition ratio Si:W = 20:80) was used. At this time, a DC power supply was used as the means for supplying power to the electrode. At that time, a pulse voltage with a frequency of 10 kHz (on-time: 95%, off-time: 5%, a negative voltage is applied during the on-time, and a positive voltage is applied during the off-time) was applied to the electrode. As the film formation conditions, the film formation pressure was 0.35 Pa, and the power density was 3.3 W / cm 2 was set. As the gas , argon gas and oxygen gas were used, and the flow rate of the oxygen gas was adjusted so that an oxide film could be obtained.

[0092] <Example 14> A gas barrier laminate was obtained in the same manner as in Example 13, except that an alloy target of Si and W (atomic composition ratio Si:W = 30:70) was used.

[0093] <Example 15> A gas barrier laminate was obtained in the same manner as in Example 13, except that an alloy target of Si and W (atomic composition ratio Si:W = 50:50) was used.

[0094] <Example 16> A gas barrier laminate was obtained in the same manner as in Example 13, except that an alloy target of Si and W (atomic composition ratio Si:W = 80:20) was used.

[0095] <Example 17> A gas barrier laminate was obtained in the same manner as in Example 13, except that an alloy target of Si and W (atomic composition ratio Si:W = 90:10) was used and the film formation pressure was set to 0.50 Pa.

[0096] <Example 18> As a method for forming the transparent oxide film layer 13, a sputtering method (referred to as Method C) using a magnetron sputtering apparatus equipped with two cylindrical electrodes having a rotating mechanism in parallel, capable of applying voltages alternately positive and negative to each electrode, and each of the electrodes alternately serving as a cathode and an anode, was used. A gas barrier laminate was obtained in the same manner as in Example 2, except that an alloy target of Si and W (atomic composition ratio Si:W = 25:75) was used. At this time, as a means for supplying power to the two electrodes, an MF power supply was used. At that time, a rectangular voltage with a frequency of 40 kHz was applied to the two electrodes arranged in parallel. As the gas, argon gas and oxygen gas were used. At this time, the flow rate of the oxygen gas was controlled by detecting the emission intensity of the plasma and the voltage value of the discharge so that the state of the target surface was in a transition state in the middle of the transition from the metal mode to the oxide mode. As the film formation conditions, the film formation pressure was 0.30 Pa, and the power density was 3.3 W / cm 2 .

[0097] <Example 19> A gas barrier laminate was obtained in the same manner as in Example 18, except that the film formation pressure was set to 0.18 Pa and an alloy target of Si and W (atomic composition ratio Si:W = 60:40) was used.

[0098] <Example 20> A gas barrier laminate was obtained in the same manner as in Example 1, except that a target formed of Si, W, and Al was used.

[0099] <Example 21> A gas barrier laminate was obtained in the same manner as in Example 1, except that a target formed of Si, W, and Hf was used.

[0100] <Example 22> A gas barrier laminate was obtained in the same manner as in Example 1, except that a target formed of Si, W, and Ta was used.

[0101] <Example 23> A gas barrier laminate was obtained in the same manner as in Example 1, except that argon gas, oxygen gas, and nitrogen gas were used as the introduction gases under the sputtering conditions.

[0102] <Comparative Example 1> A gas barrier laminate was obtained in the same manner as in Example 1, except that a target formed of Si (atomic composition ratio Si = 100%) was used.

[0103] <Comparative Example 2> A gas barrier laminate was obtained in the same manner as in Example 1, except that a target formed of W (atomic composition ratio W = 100%) was used.

[0104] <Comparative Example 3> A gas barrier laminate was obtained in the same manner as in Example 1, except that an alloy target of Si and W (atomic composition ratio Si:W = 5:95) was used.

[0105] <Comparative Example 4> A gas barrier laminate was obtained in the same manner as in Example 1, except that an alloy target of Si and Mo (atomic composition ratio Si:Mo = 10:90) was used.

[0106] <Comparative Example 5> A gas barrier laminate was obtained in the same manner as in Example 13, except that an alloy target of Si and Sn (atomic composition ratio Si:Sn = 50:50) was used.

[0107] <Evaluation and Method> [Measurement of the Film Composition of the Transparent Oxide Film Layer of the Gas Barrier Laminate] For the gas barrier laminates prepared in Examples 1 to 19 and Comparative Examples 1 to 5, the film composition was measured using X-ray photoelectron spectroscopy (JPS-9010MX manufactured by JEOL Ltd.). At that time, the composition analysis in the depth direction of the deposited film was repeated four or more times with Ar ions, and the average was obtained to calculate Si / (Si + A) and O / (Si + A). In addition, when tungsten (W) was included as the Group 6 element (A), the outermost surface composition was analyzed because it was affected by reduction by Ar ions.

[0108] [Measurement of Refractive Index of Transparent Oxide Film Layer of Gas Barrier Laminate] For the gas barrier laminates prepared in Examples 1 to 19 and Comparative Examples 1 to 5, the refractive index was measured using an ellipsometer (VUV-VASE) manufactured by J. A. Woollam Co., Ltd.

[0109] [Measurement of Light Absorbance of Transparent Oxide Film Layer of Gas Barrier Laminate] For the gas barrier laminates prepared in Examples 1 to 19 and Comparative Examples 1 to 5, the light absorbance was measured using an ultraviolet-visible spectrophotometer (UV-2450) manufactured by Shimadzu Corporation.

[0110] [Surface Roughness of Transparent Oxide Film Layer of Gas Barrier Laminate] For the gas barrier laminates prepared in Examples 1 to 19 and Comparative Examples 1 to 5, the arithmetic mean surface roughness was measured using a scanning probe microscope (AFM5400L) manufactured by Hitachi High-Technologies Corporation. At that time, the arithmetic mean roughness was analyzed from an image observing a range of 1 μm square per field of view.

[0111] [Measurement of Gas Barrier Property of Gas Barrier Laminate] For the gas barrier laminates prepared in Examples 1 to 23 and Comparative Examples 1 to 5, using a method in accordance with JIS-K7129, the water vapor transmission rate (g / m 2 ·day) under an environment of 40°C and 90% RH (temperature 40°C, relative humidity 90%) was measured using a water vapor transmission rate meter (AQUATRAN-ModelII) manufactured by MOCON, Inc., USA. The helium transmission rate (cc / (m 2 ·day·atm)) and neon transmission rate (cc / (m 2 ·day·atm)) were measured using a differential pressure method in accordance with JIS K 7126A method at 40°C and 0% RH using a pressure sensor type gas measuring device (Delta Palm DP-2MST) manufactured by Technolox.

[0112] [Measurement Results] The measurement results are shown in Tables 1 to 3 below. Table 1 shows the measurement results of Examples 1 to 13, Table 2 shows the measurement results of Examples 14 to 19 and Comparative Examples 1 to 5, and Table 3 shows the measurement results of Example 1 and Examples 20 to 23. [Table 1] [Table 2] [Table 3]

[0113] Comparing Example 1 corresponding to the first embodiment with Comparative Examples 1 to 4, Example 1 in which the target and the transparent oxide film layer 13 contain Si and W as metal elements has better results in terms of water vapor transmission rate, helium transmission rate, and neon transmission rate than Comparative Example 1 in which the target element and the transparent oxide film layer 13 contain only Si as a metal element, Comparative Example 2 containing only W, Comparative Example 3 having only 5% Si content, and Comparative Example 4 containing Si and Mo with only 10% Si content.

[0114] In Examples 13 to 17, the sputtering method is Method B, but similar to Example 2 in which the sputtering method is Method A, good results in terms of water vapor transmission rate, helium transmission rate, and neon transmission rate were obtained.

[0115] In Examples 18 and 19, the sputtering method is Method C, but similar to Example 2 in which the sputtering method is Method A, good results in terms of water vapor transmission rate, helium transmission rate, and neon transmission rate were obtained.

[0116] Comparing Examples 13 to 17 corresponding to the second embodiment, in which the sputtering method is Method B, with Comparative Example 5, Examples 13 to 17 in which the target and the transparent oxide film layer 13 contain Si and W as metal elements have better results in terms of water vapor transmission rate, helium transmission rate, and neon transmission rate than Comparative Example 5 containing Si and Sn.

[0117] Corresponding to the second embodiment, the sputtering method is Method A, and the target and the transparent oxide film layer 13 contain three kinds of metal elements, Si, Mo, and W, as metal elements. Example 12, like Examples 2 and 3 containing only Si and Mo, and Examples 5 to 11 containing only Si and W, obtained good results for water vapor transmission rate, helium transmission rate, and neon transmission rate.

[0118] Examples 4 and 5 corresponding to the third embodiment have an overcoat layer laminated, but like Example 2 corresponding to the second embodiment without the overcoat layer laminated, good results for water vapor transmission rate, helium transmission rate, and neon transmission rate were obtained.

[0119] In Examples 20 to 22, a target containing Si and a metal element other than Group 6 elements as the metal element of the target was used, but like Example 1 using a target containing only Si and Group 6 elements as the metal element of the target, good results for water vapor transmission rate, helium transmission rate, and neon transmission rate were obtained.

[0120] In Example 23, nitrogen gas was used simultaneously with oxygen gas as the reaction gas in the sputtering process, but like Example 1 using only oxygen gas as the reaction gas in the sputtering process, good results for water vapor transmission rate, helium transmission rate, and neon transmission rate were obtained.

[0121] Although the embodiments of the present invention have been described in detail above, actually, it is not limited to the above embodiments, and even if there are changes within the scope not departing from the gist of the present invention, they are included in the present invention.

Industrial Applicability

[0122] The gas barrier laminate according to the present invention is particularly preferably expected to be used in fields such as members related to electronic devices where high gas barrier properties are required.

Explanation of Reference Numerals

[0123] 11…Resin substrate 12… Undercoat layer 13… Transparent oxide film layer 14… Overcoat layer

Claims

1. The present invention comprises a resin substrate and a transparent oxide film layer containing silicon (Si) and a Group 6 element (referred to as A) formed on one or both sides of the resin substrate, The Group 6 element (A) of the transparent oxide film layer is containing only tungsten (W), and a ratio Si / (Si+A) of the number of silicon (Si) atoms in the transparent oxide film layer to the total number of silicon (Si) atoms and the Group 6 element (A) is 0.10 or more and 0.80 or less; or a gas barrier laminate containing both tungsten (W) and molybdenum (Mo) and having an atomic ratio Si / (Si+A) of 0.10 or more and 0.50 or less (excluding those in which the transparent oxide film layer contains 0.1 to 10 mass % Mo).

2. The helium permeability at measurement conditions of 40°C and 0% R.H. is 1200cc / (m ２ 2. The gas barrier laminate according to claim 1, wherein the gas barrier density is 100% or less.

3. Measurement conditions: Neon transmittance at 40°C and 0% R.H. is 2.0 cc / (m ２ 3. The gas barrier laminate according to claim 1, wherein the gas barrier density is 100% or less.

4. A gas barrier laminate according to any one of claims 1 to 3, wherein the ratio (O / (Si+A)) of the number of oxygen (O) atoms to the total number of silicon (Si) and the Group 6 element (A) atoms is 0.80 or more and 3.00 or less.

5. 5. The gas barrier laminate according to claim 1, wherein the transparent oxide film layer has a refractive index n of 1.45 or more and 2.00 or less, and an optical thickness nd represented by the product of a thickness d and the refractive index n is 7 nm or more and 1000 nm or less.

6. 6. The gas barrier laminate according to claim 1, wherein the transparent oxide film layer further contains at least one element selected from Mg, Al, Ca, Sc, Ti, V, Zn, Ga, Ge, Sr, Y, Zr, Nb, In, Sn, Ba, Hf, and Ta.

7. The gas barrier laminate according to claim 1 , wherein the transparent oxide film layer further contains nitrogen (N).

8. 8. The gas barrier laminate according to claim 1, wherein the transparent oxide film layer has a light absorptance of 10% or less at a wavelength of 400 nm.

9. 9. The gas barrier laminate according to claim 1, wherein the transparent oxide film layer has a surface with an arithmetic mean roughness of 5.0 nm or less.

10. 10. The gas barrier laminate according to claim 1, further comprising an undercoat layer between the resin substrate and the transparent oxide film layer, the undercoat layer being formed from at least one of a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and an electron beam curable resin.

11. 11. The gas barrier laminate according to claim 10, wherein the undercoat layer is a layer made of a cured product of a composition containing an acrylic resin having an organic acid group, the composition further containing a polyisocyanate, and the acrylic resin is an acrylic polyol resin.

12. 12. The gas barrier laminate according to claim 1, further comprising an overcoat layer on the outer side of the transparent oxide film layer, the overcoat layer being formed from at least one of a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and an electron beam curable resin.

13. 13. The gas barrier laminate according to claim 12, wherein the overcoat layer is formed containing a water-soluble polymer having a hydroxyl group, and at least one selected from the group consisting of alkoxysilanes and hydrolysates thereof.

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