JP2024083356A - Gas barrier laminate - Google Patents

Abstract

The present invention provides a transparent gas barrier laminate using a resin substrate, which has good water vapor barrier properties.
[Solution] A gas barrier laminate comprising 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, wherein 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 silicon (Si) atoms in the transparent oxide film layer to the total number of atoms of silicon (Si) and the Group 6 element (A) is 0.80 or less, or the transparent oxide film layer contains both tungsten (W) and molybdenum (Mo), and the atomic ratio Si/(Si+A) is 0.50 or less (however, excluding transparent oxide film layers in which Mo is 0.1 to 10 mass %).
[Selected Figure] Figure 1

Description

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

A gas barrier laminate is a laminate that has the property of not allowing oxygen, water vapor, etc. to pass through (gas barrier properties), and is widely used in a variety of fields that require blocking various gases, such as precision electronic parts, electronics materials, and packaging for food and medicine, etc.

The required gas barrier properties vary depending on the application, but generally, it is said that a high water vapor barrier property of 0.01 g/( ^m2 ·day) or less is required for sealing films for displays such as organic electroluminescence (EL) and electronic paper, and in recent years, there has been an increasing demand for even higher levels of water vapor barrier properties. In addition, these films are required to be transparent.

In recent years, there has been a trend towards using resins instead of glass as substrates in fields such as organic electroluminescence (EL) and electronic paper, for reasons such as flexibility, damage prevention, and weight reduction. However, resin substrates have poor gas barrier properties against oxygen gas and water vapor, which can lead to problems with deterioration of these elements and electronic components.

For this reason, various products have been developed to achieve high gas barrier properties and transparency using resin substrates, and 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 nanoscale on a resin substrate.

In addition, as a method for producing gas barrier laminates, physical film formation methods such as induction heating, resistance heating, electron beam deposition, and sputtering are being considered because they are easy to use for large-area production and roll-to-roll processing.

To achieve higher gas barrier properties, it is necessary to form a dense gas barrier layer made of an inorganic compound, and dense inorganic compound films can generally be easily produced by sputtering.

In addition, to achieve higher transparency, it is necessary to have low reflection at the interface between the resin substrate and the inorganic compound film and high light transmittance for visible light. Therefore, it is necessary to form an inorganic compound film with a refractive index close to that of the resin substrate.

For example, the following Patent Document 1 describes a transparent resin substrate (gas barrier laminate) that is highly transparent and has high water vapor barrier performance. In this gas barrier laminate, a transparent oxide film that contains tin oxide and silicon (Si) as an additive element in a ratio of 46 atomic % to 63 atomic % relative to the total of Si and Sn, is an amorphous film, and has a refractive index of 1.75 or less at a wavelength of 633 nm, is formed as a gas barrier layer on at least one surface of a resin substrate by a direct current (DC) pulse sputtering method.

However, it is stated that the water vapor transmission rate of the gas barrier laminate is less than 0.01 g/( ^m2 ·day) as measured by the Mocon method in accordance with JIS K7129, and this gas barrier laminate certainly has high water vapor gas barrier properties. However, in order to meet the higher standards of water vapor barrier properties that have been demanded in recent years, further improvement is required.

Patent No. 4788463

Therefore, the present invention aims to provide a transparent gas barrier laminate using a resin substrate that has good water vapor barrier properties.

One aspect of the present invention for solving the above problems is a gas barrier laminate comprising 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, in which 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 silicon (Si) atoms in the transparent oxide film layer to the total number of silicon (Si) and Group 6 element (A) atoms is 0.80 or less, or contains both tungsten (W) and molybdenum (Mo) and the ratio of the number of atoms Si/(Si+A) is 0.50 or less (excluding transparent oxide film layers in which Mo is 0.1 to 10 mass %).

The present invention provides a transparent gas barrier laminate using a resin substrate that has good water vapor barrier properties.

1 is a cross-sectional view of a gas barrier laminate according to a first embodiment of the present invention. FIG. 2 is a cross-sectional view of a gas barrier laminate according to a second embodiment of the present invention. FIG. 4 is a cross-sectional view of a gas barrier laminate according to a third embodiment of the present invention.

First Embodiment
A first embodiment of the present invention will be described below with reference to the drawings.
As shown in Fig. 1, the gas barrier laminate according to this embodiment is composed of a resin substrate 11 and a transparent oxide film layer 13 formed on one side of the resin substrate 11. In practice, the transparent oxide film layer 13 may be laminated on both sides of the resin substrate 11. 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.

(Resin substrate)
The material of the resin substrate 11 is not particularly limited, and known materials can be used. For example, polyolefins (polyethylene, polypropylene, etc.), polyesters (polyethylene terephthalate, polyethylene naphthalate, etc.), polyimides, polyamides (nylon-6, nylon-66, etc.), polystyrene, ethylene vinyl alcohol, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, polyethersulfone, acrylic, celluloses (triacetyl cellulose, diacetyl cellulose, etc.), etc. can be mentioned, but are not particularly limited to these. In practice, it is desirable to select appropriately depending on the application and required physical properties, and for packaging that protects contents that are extremely averse to moisture, such as electronic components and optical components, it is desirable to use a resin substrate 11 that itself has high gas barrier properties, such as polyethylene naphthalate, polyimides, and polyethersulfone, but is not limited to these examples.

The thickness of the resin substrate 11 is not limited, but a thickness of about 12 μm to 300 μm is suitable depending on the application. A resin substrate 11 having a thickness within this range is preferred because it is flexible and can be wound into a roll.

The resin substrate 11 may be in the form of a long material or a sheet material, but a long resin substrate 11 is preferably used. The longitudinal length of the long resin substrate 11 is not particularly limited, but a long film of, for example, 10 m or more is preferably used. There is no upper limit to the length, and it may be, for example, about 10 km.

The surface of the resin substrate 11 may contain additives such as antistatic agents, UV absorbers, plasticizers, and slip agents as necessary. Furthermore, in order to enhance adhesion, the surface of the resin substrate 11 may be subjected to physical treatments such as corona treatment, frame treatment, plasma treatment, and adhesion enhancing treatment, or chemical treatment modification treatments such as chemical treatment with acid or alkali. The surface of the resin substrate 11 contributes to the denseness in the initial growth stage of vacuum film formation, and is desirably smooth.

(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) that is 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). It is more preferable to include both molybdenum (Mo) and tungsten (W). Among the group 6 elements, the inclusion of an element different in size from silicon (Si) forms a dense film, and therefore it is believed that the effect of tungsten (W), which has a large atomic number and a large size, is large, is large, but the details are unclear. 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 device that can periodically apply a voltage to the electrodes. Furthermore, it is preferable to use a sputtering method using a magnetron sputtering device that can periodically apply a voltage to the electrodes, and during the off time of the voltage application, a pulse with a different positive and negative polarity from the voltage application is applied (a pulse voltage is applied). It is also preferable to use a sputtering method using a magnetron sputtering device in which two electrodes are positioned in parallel, and positive and negative voltages can be applied alternately to each electrode, with each electrode alternately serving as a cathode and an anode. It is also preferable to use a sputtering method using a magnetron sputtering device equipped with a cylindrical electrode having a rotating mechanism. When forming a transparent oxide layer by these sputtering methods, it is preferable to set the film formation pressure in the range of 0.05 Pa to 5.00 Pa.

The transparent oxide film layer 13 is formed so that the ratio (Si/(Si+A)) between the number of silicon (Si) atoms and the total number of silicon (Si) and group 6 elements (A) is 0.10 or more and 0.98 or less, and the ratio (O/(Si+A)) between the number of oxygen (O) atoms and the total number of silicon (Si) and group 6 elements (A) is 0.80 or more and 3.00 or less. In consideration of the refractive index and gas barrier properties, the ratio (Si/(Si+A)) between the number of silicon (Si) atoms and the total number of silicon (Si) and group 6 elements (A) is more preferably 0.20 or more and 0.95 or less. In addition, when the Group 6 element (A) is tungsten (W), in consideration of the refractive index, transparency, and gas barrier properties, the ratio (Si/(Si+W)) between the number of silicon (Si) atoms and the total number of silicon (Si) and tungsten (W) atoms is more preferably 0.25 or more and 0.95 or less, and more preferably 0.30 or more and 0.80 or less. In addition, when the Group 6 element (A) is molybdenum (Mo), in consideration of the refractive index, transparency, and gas barrier properties, the ratio (Si/(Si+Mo)) between the number of silicon (Si) atoms and the total number of silicon (Si) and molybdenum (Mo) atoms is more preferably 0.50 or more and 0.85 or less. It is more preferable that both molybdenum (Mo) and tungsten (W) are contained as the Group 6 element (A), and 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. A method for determining whether the transparent oxide film layer 13 is within the above composition range can be used using a conventionally known method, and can be evaluated, for example, from the results obtained by an analysis device such as an XPS (X-ray photoelectron spectroscopy).

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 substrate 11 can be obtained. Therefore, reflection at the interface between the resin substrate 11 and the transparent oxide film layer 13 is small, and the light transmittance of 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 using a refractometer (ellipsometer).

The 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 transparent oxide film layer 13 cannot cover the entire resin substrate 11, and sufficient gas barrier properties cannot be obtained. If it exceeds 500 nm, cracks are likely to occur and the gas barrier properties may deteriorate. Furthermore, costs increase due to an increase in the amount of material used and a longer film formation time, which is not preferable from an economic point of view. In other words, it is preferable that the optical thickness nd, which is expressed as the product of the thickness d and the refractive index n, is 7 nm or more and 1000 nm or less.

In addition, by setting the composition of the transparent oxide film layer 13 within the above range and the optical thickness within the above range, the optical absorptance of the transparent oxide film layer 13 at a wavelength of 400 nm can be set to 10% or less. Therefore, sufficient transparency can be obtained at all wavelengths in the visible light range. When the Group 6 element (A) is tungsten (W), if the ratio (Si/(Si+W)) of the number of silicon (Si) atoms to the total number of silicon (Si) and tungsten (W) atoms is less than 0.10, light with a wavelength of 400 nm is absorbed and sufficient transparency cannot be obtained. In addition, even if the optical thickness exceeds 1000 nm, visible light may be absorbed and sufficient transparency may not be obtained. In other words, the optical absorptance at a wavelength of 400 nm is preferably set to 10% or less, and more preferably to 5% or less. The optical absorptance of the transparent oxide film layer 13 can be measured and evaluated using an ultraviolet-visible light spectrophotometer.

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 13 is related to the internal structure of the transparent oxide film layer, and a film with small surface roughness has a dense structure, which is thought to impart gas barrier properties, but the details are unclear. In addition, the surface roughness increases when defects that reduce gas barrier properties, such as cracks, occur in the transparent oxide film layer 13. 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 using an atomic force microscope.

In addition, 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, and Ta in addition to silicon (Si) and metal elements of Group 6 elements (A). By containing 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 silicon (Si) and Group 6 elements (A), the gas barrier properties, adhesion to the resin substrate 11, temperature and humidity durability, and refractive index n can be improved. In addition, the transparent oxide film layer 13 may further contain nitrogen in addition to the metal element group, and may be a transparent oxynitride film layer.

(About 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 device capable of periodically applying a voltage to an electrode is used. According to this sputtering method, since a voltage is periodically applied, an off time of the voltage application is provided, and the charging of the target surface is eliminated. Therefore, damage to the film caused by arcing can be suppressed, and a high-quality film can be stably formed. Furthermore, preferably, a sputtering method using a magnetron sputtering device capable of periodically applying a voltage to an electrode and applying a pulse of a different polarity from that of the voltage application during the off time of the voltage application is used. According to this sputtering method, an off time of the voltage application is provided, and further, the voltage during the off time is reversed in polarity from that during the application, so that the charging of the target surface is more easily eliminated. Therefore, damage to the film caused by arcing can be more suppressed, and a high-quality film can be stably formed. Also, preferably, a sputtering method using a magnetron sputtering device is used, in which two electrodes are positioned in parallel, and a positive and negative voltages can be applied alternately to each electrode, and each electrode alternately plays the role of a cathode and an anode. In this sputtering method, a target of a material is placed on two electrodes installed in a vacuum chamber, and a high voltage is applied to cause an ionized rare gas element (usually argon) to collide with the target, ejecting atoms on the target surface, and the target element is attached to the resin substrate 11, thereby forming a transparent oxide film layer 13. In this sputtering method, the anode and cathode are alternately switched between the two targets, so that while one target is discharging and forming a film, the other target is weakly charged in the opposite direction, thereby eliminating the charging of the target surface. Therefore, damage to the film caused by arcing can be suppressed, and a high-quality film can be stably formed. In addition, it is also preferable to use a sputtering method using a magnetron sputtering device equipped with a cylindrical electrode having a rotating mechanism. According to this sputtering method, the target shape is cylindrical like the electrode, and the entire surface of the target becomes an erosion region by rotation, so the utilization rate of the target is high. In addition, the entire surface of the target becomes clean, and arcing can be suppressed, so that the device can be operated continuously for a long time. Furthermore, damage to the film caused by arcing can be suppressed, and a high-quality film can be stably formed. In addition, the cylindrical electrodes having a rotating mechanism may be arranged in parallel in two, and a magnetron sputtering device may be used in which positive and negative voltages can be applied alternately to each electrode, and each electrode alternately plays the role of a cathode and an anode. At this time, a predetermined amount of oxygen gas is flowed into the chamber, and the element displaced from the target reacts with oxygen to form a transparent oxide film layer 13. Furthermore, at this time, a transparent oxynitride film layer may be formed by flowing nitrogen gas simultaneously with the oxygen gas. In addition, a target made of an alloy of Si and a group 6 element (A) is used as the target. The above-described target may further contain, in addition to Si and the Group 6 element (A), 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.

Whether a magnetron sputtering device capable of periodically applying a voltage to an electrode is used, whether a magnetron sputtering device is used in which two electrodes are positioned in parallel and a voltage can be applied alternately between positive and negative, with each electrode acting alternately as a cathode and an anode, or whether a magnetron sputtering device equipped with a cylindrical cathode having a rotating mechanism is used, the power source for applying a voltage to the electrodes is not particularly specified and may be either alternating current (AC) or DC, but it is preferable to use a DC pulse power source. This is because a pulse wave for the applied voltage waveform is more effective in mitigating charge-up at the anode during off-time of voltage application. The frequency of the DC pulse power source is not particularly limited and can be set as appropriate. It is preferably 1 kHz or more and 100 kHz or less, and more preferably 10 kHz or more and 50 kHz or less.

When using a magnetron sputtering device capable of periodically applying a voltage to an electrode, when using a magnetron sputtering device in which two electrodes are positioned in parallel and alternating positive and negative voltages can be applied to each electrode, with each electrode alternately serving as a cathode and an anode, or when using a magnetron sputtering device equipped with a cylindrical cathode having a rotating mechanism, it is preferable to set the deposition pressure when depositing the transparent oxide layer in the range of 0.05 Pa to 5.00 Pa. By depositing the film within this deposition pressure range, a film with few surface defects can be obtained.

The gas barrier laminate according to this embodiment is constructed by laminating the transparent oxide film layer 13 described above on a resin substrate 11. This allows the water vapor transmission rate to be 0.01 g/( ^m2 ·day) or less under measurement conditions of 40°C and 90% R.H. Furthermore, by making the transparent oxide film layer 13 a dense film, the helium transmission rate to be 1200 cc/( ^m2 ·day·atm) or less under measurement conditions of 40°C and 0% R.H. Furthermore, the neon transmission rate to be 2.0 cc/( ^m2 ·day·atm) or less under measurement conditions of 40°C and 0% R.H. Furthermore, by using the sputtering method using the magnetron sputtering device described above, it is possible to suppress defects in the film due to arcing and to manufacture a gas barrier laminate having a dense transparent oxide film layer 13. Therefore, according to this embodiment, a gas barrier laminate having good gas barrier properties and a manufacturing method thereof can be realized.

Second Embodiment
A second embodiment of the present invention will now be described.
The gas barrier laminate according to this embodiment, like the gas barrier laminate shown in Fig. 2, further comprises an undercoat layer 12 provided between the resin substrate 11 and the transparent oxide film layer 13 of the gas barrier laminate shown in Fig. 1. Alternatively, the gas barrier laminate may have a structure in which the undercoat layer 12 and the transparent oxide film layer 13 are sequentially laminated on both sides of the resin substrate 11.

The undercoat layer 12 is provided on the resin substrate 11 in order to increase the adhesion between the resin substrate 11 and the transparent oxide film layer 13, prevent peeling of the transparent oxide film layer 13, and protect the transparent oxide film layer 13 from mechanical damage such as scratches and abrasions. The material of the undercoat layer 12 is not particularly limited, but may be a thermosetting resin, a thermoplastic resin, an ultraviolet-curable resin, an electron beam-curable resin, or the like.

Thermosetting resins forming the undercoat layer 12 include thermosetting urethane resins consisting of acrylic polyol resins and isocyanate prepolymers, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, etc. Among these, the undercoat layer 12 is formed using a composite of an acrylic polyol resin containing a hydroxyl group and an isocyanate compound having at least two or more NCO groups in the molecule, which can increase the adhesion between the resin substrate 11 and the transparent oxide film layer 13.

An acrylic polyol resin is a polymeric compound obtained by polymerizing a (meth)acrylic acid derivative monomer, or a polymeric compound obtained by copolymerizing a (meth)acrylic acid derivative monomer with another monomer, which has hydroxy groups at the end and side chains and reacts with the NCO group of an isocyanate compound. A (meth)acrylic acid derivative monomer has hydroxy groups at the end and side chains. Examples of (meth)acrylic acid derivative monomers include hydroxyethyl (meth)acrylate and hydroxybutyl (meth)acrylate.

The above other monomers can be copolymerized with (meth)acrylic acid derivative monomers having hydroxy groups at the end and at the side chain. Examples of the above other monomers include (meth)acrylic acid derivative monomers having an alkyl group at 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 at the side chain, such as (meth)acrylic acid, and (meth)acrylic acid derivative monomers having an aromatic ring or a cyclic structure at the side chain, such as benzyl (meth)acrylate and cyclohexyl (meth)acrylate. Other than (meth)acrylic acid derivative monomers, styrene monomers, cyclohexylmaleimide monomers, and phenylmaleimide monomers are possible. The above other monomers may themselves have hydroxy groups at the end and at the side chain.

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

There are no particular limitations on the hydroxyl group-containing acrylic polyol resin that can be used in the undercoat layer 12, but it is desirable that the hydroxyl group value is 50 mgKOH/g or more and 250 mgKOH/g or less. Here, the hydroxyl group value (mgKOH/g) is an index of the amount of hydroxyl groups in the acrylic polyol resin, and indicates the number of mg of potassium hydroxide required to acetylate the hydroxyl groups in 1 g of the acrylic polyol resin. In addition, there are no particular limitations on the weight average molecular weight of the acrylic polyol resin, but specifically, it is preferably 3,000 or more and 200,000 or less. In particular, it is preferably 5,000 or more and 100,000 or less. Furthermore, it is more preferably 5,000 or more and 40,000 or less.

An isocyanate compound has 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), and tetramethylxylylene diisocyanate (TMXDI), and aliphatic isocyanates such as hexamethylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H12MDI). Polymers or derivatives of these monomeric isocyanates can also be used. For example, there are trimer nurate types, adduct types reacted with 1,1,1-trimethylolpropane, and biuret types reacted with biuret.

The isocyanate compound may be selected from the above-mentioned isocyanate compounds or their polymers and derivatives, and one or more of them may be used in combination.

One example of the undercoat layer 12 is formed by applying a solution consisting of a composite of the above-mentioned acrylic polyol resin and the above-mentioned isocyanate compound and a solvent onto the resin substrate 11 and reacting and curing 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-mentioned acrylic polyol resin and the isocyanate compound. Examples of the solvent include methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, dioxolane, tetrahydrofuran, etc. In practice, these solvents can be used alone or in combination of two or more.

The thermoplastic resin forming the undercoat layer 12 is appropriately selected from polyols having two or more hydroxyl groups, such as acrylic polyol, polyester polyol, polycarbonate polyol, polyether polyol, polycaprolactone polyol, and epoxy polyol, polyvinyl resins such as polyvinyl acetate and polyvinyl chloride, polyvinylidene chloride resin, polystyrene resin, polyethylene resin, polypropylene resin, and polyurethane resin. Furthermore, these may be mixed in any ratio. The hydroxyl value of the polyol is not particularly limited, but is preferably 10 mgKOH/g or more and 250 mgKOH/g or less.

As the ultraviolet-curable resin or electron beam-curable resin forming the undercoat layer 12, it is desirable to include at least a resin having a hydroxyl value in the range of 10 to 100 mgKOH/g as an organic polymer resin, although it is not particularly limited thereto. In addition, it is desirable to include at least a resin having an acid value in the range of 10 to 100 mgKOH/g as an organic polymer resin, although it is not particularly limited thereto. Here, the acid value (mgKOH/g) indicates the number of mg of potassium hydroxide required to neutralize the free fatty acid, resin acid, etc. contained in 1 g of sample. It is also desirable to include at least a thermoplastic resin as an organic polymer resin. If the hydroxyl value or acid value is less than 10 mgKOH/g, the chemical bonding strength 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. If the hydroxyl value or acid value exceeds 100 mgKOH/g, precipitates containing hydroxyl groups produced by decomposition of the undercoat layer 12 during durability tests such as a moist heat resistance test tend to inhibit adhesion between the undercoat layer 12 and the transparent oxide film layer 13.

Monomers that can be used in the ultraviolet curable resin or electron beam curable resin that forms the undercoat layer 12 include, for example, monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, and N-vinylpyrrolidone, as well as 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, and neopentyl glycol (meth)acrylate. Oligomers that can be used in this ultraviolet curable resin or electron beam curable resin include, for example,
Examples include urethane acrylate, epoxy acrylate, and polyester acrylate.

When two or more types of organic polymer resins selected from thermosetting resins, thermoplastic resins, ultraviolet curable resins, and electron beam curable resins are used in combination as the organic polymer resins forming the undercoat layer 12, the mixing ratio is not particularly limited.

The undercoat layer 12 may further contain additives other than the organic polymer resin as necessary. Examples of additives include antioxidants, weathering agents, heat stabilizers, lubricants, crystal nucleating agents, UV absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, and silane coupling agents.

The 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 effect of internal stress will be large, the transparent oxide film layer 13 will not be laminated neatly, the barrier properties will not be expressed sufficiently, and further, the transparency and coating accuracy will be insufficient.

The undercoat layer 12 can be formed by a conventional coating method. For example, well-known methods such as dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset, and organic deposition can be used. As the drying method, one or more heat application methods such as hot air drying, heat roll drying, high frequency irradiation, infrared irradiation, UV irradiation, and electron beam irradiation can be used in combination. In addition, a film that has been coated in advance on another resin substrate by the above forming method can be transferred to the resin substrate 11 by a transfer method such as adhesive transfer, heat transfer, and UV transfer.

Third Embodiment
A third embodiment of the present invention will now be described.
The gas barrier laminate according to this embodiment, like the gas barrier laminate shown in Fig. 3, further comprises an overcoat layer 14 provided on the transparent oxide film layer 13 of the gas barrier laminate shown in Fig. 2. The same effect can also be obtained by providing an overcoat layer 14 on the transparent oxide film layer 13 of the gas barrier laminate shown in Fig. 1.

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 or bending.

The organic polymer resin contained in the overcoat layer 14 can be appropriately selected, and for example, one or more types selected from thermosetting resins, thermoplastic resins, ultraviolet curing resins, and electron beam curing resins can be used. The proportion of the organic polymer resin in the overcoat layer 14 is not particularly limited and can be set appropriately.

Thermosetting resins that form the overcoat layer 14 include thermosetting urethane resins made of acrylic polyol resins and isocyanate prepolymers, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, and the like. In particular, the overcoat layer 14 can be formed using a composite of an acrylic polyol resin containing a hydroxyl group and an isocyanate compound having at least two or more NCO groups in the molecule, thereby improving the adhesion between the overcoat layer 14 and the transparent oxide film layer 13.

The 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 with other monomers, which has hydroxyl groups at the end and side chains and reacts with the NCO group of an isocyanate compound. The (meth)acrylic acid derivative monomer has hydroxyl groups at the end and side chains. Examples of the (meth)acrylic acid derivative monomer include hydroxyethyl (meth)acrylate and hydroxybutyl (meth)acrylate.

The above other monomers can be copolymerized with (meth)acrylic acid derivative monomers having hydroxy groups at the end and at the side chain. Examples of the above other monomers include (meth)acrylic acid derivative monomers having an alkyl group at 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 at the side chain, such as (meth)acrylic acid, and (meth)acrylic acid derivative monomers having an aromatic ring or a cyclic structure at the side chain, such as benzyl (meth)acrylate and cyclohexyl (meth)acrylate. Other than (meth)acrylic acid derivative monomers, styrene monomers, cyclohexylmaleimide monomers, and phenylmaleimide monomers are possible. The above other monomers may themselves have hydroxy groups at the end and at the side chain.

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

The hydroxyl group-containing acrylic polyol resin of the overcoat layer 14 is not particularly limited, but it is desirable that the hydroxyl group value is 50 mgKOH/g or more and 250 mgKOH/g or less. In addition, the weight average molecular weight of the acrylic polyol resin is not particularly limited, but specifically, it is preferably 3,000 or more and 200,000 or less. In particular, it is preferably 5,000 or more and 100,000 or less. Furthermore, it is more preferably 5,000 or more and 40,000 or less.

An isocyanate compound has 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), and tetramethylxylylene diisocyanate (TMXDI), and aliphatic isocyanates such as hexamethylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H12MDI). Polymers or derivatives of these monomeric isocyanates can also be used. For example, there are trimer nurate types, adduct types reacted with 1,1,1-trimethylolpropane, and biuret types reacted with biuret.

The isocyanate compound may be selected from the above-mentioned isocyanate compounds or their polymers and derivatives, and one or a combination of two or more types may be used.

The overcoat layer 14 is formed, for example, by applying a solution consisting of a composite of the above-mentioned acrylic polyol resin and the above-mentioned isocyanate compound and a solvent onto the resin substrate 11 and reacting and curing 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-mentioned acrylic polyol resin and the isocyanate compound. Examples of the solvent include methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, dioxolane, tetrahydrofuran, etc. In practice, these solvents can be used alone or in combination of two or more.

In addition to the above, the thermosetting resin forming the overcoat layer 14 preferably contains at least one selected from the group consisting of a water-soluble polymer having a hydroxyl group, an alkoxysilane, and a hydrolyzate thereof.

Preferred water-soluble polymers having hydroxyl groups are polyvinyl alcohol, polycarboxylic acid, starch, and cellulose. In particular, when polyvinyl alcohol (hereinafter referred to as PVA) is used in the coating agent of the present invention, the gas barrier properties are excellent. Since PVA is the polymer that contains the most hydroxyl groups in the monomer unit, it forms very strong hydrogen bonds with the hydroxyl groups of the organosilicon compound after hydrolysis. The PVA referred to here is generally obtained by saponifying polyvinyl acetate, and includes so-called partially saponified PVA in which several tens of percent of acetate groups remain, and fully saponified PVA in which only a few percent of acetate groups remain. There are many types of molecular weight PVA, with a degree of polymerization ranging from 300 to several thousand, but there is no problem with the effect regardless of the molecular weight. However, in general, PVA with a high degree of saponification and a high molecular weight with a high degree of polymerization is preferred because it has high water resistance.

As the alkoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltriethoxysilane, methyltrimethoxysilane, etc. can be used. As the hydrolysis product of the alkoxysilane, there can be mentioned one 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 carrying out a hydrolysis reaction. Through the hydrolysis reaction, the alkoxy group bonded to the silicon atom becomes a hydroxyl group, and the hydroxyl group is dehydrated and condensed to form a siloxane bond, forming a dense and strong network polymerized coating. As a result, an overcoat layer 14 having excellent heat resistance, water resistance, moisture resistance, bending resistance, stretch resistance, etc. can be obtained.

A silane coupling agent may be added to improve adhesion to the transparent oxide film layer 13. Examples of silane coupling agents 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, and those having an NCO group such as 3-isocyanatopropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

The thermoplastic resin forming the overcoat layer 14 is appropriately selected from polyols having two or more hydroxyl groups, such as acrylic polyol, polyester polyol, polycarbonate polyol, polyether polyol, polycaprolactone polyol, and epoxy polyol, polyvinyl resins such as polyvinyl acetate and polyvinyl chloride, polyvinylidene chloride resin, polystyrene resin, polyethylene resin, polypropylene resin, and polyurethane resin. Furthermore, these may be mixed in any ratio. The hydroxyl value of the polyol is not particularly limited, but is preferably 10 mgKOH/g or more and 250 mgKOH/g or less.

The ultraviolet curable resin or electron beam curable resin forming the overcoat layer 14 is not particularly limited, but preferably contains at least a resin having a hydroxyl value in the range of 10 to 100 mgKOH/g as an organic polymer resin. Also, it is not particularly limited, but it is preferable that the organic polymer resin contains at least a resin having an acid value in the range of 10 to 100 mgKOH/g. Also, it is preferable that the organic polymer resin contains at least a thermoplastic resin. If the hydroxyl value or acid value is less than 10 mgKOH/g, the chemical bonding strength 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. If the hydroxyl value or acid value exceeds 100 mgKOH/g, precipitates containing hydroxyl groups generated by decomposition of the overcoat layer 14 in durability tests such as a moist heat resistance test tend to inhibit adhesion between the overcoat layer 14 and the transparent oxide film layer 13.

Monomers that can be used in the ultraviolet-curable resin or electron-beam-curable resin that forms the overcoat layer 14 include monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, and N-vinylpyrrolidone, as well as 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, and neopentyl glycol (meth)acrylate. Oligomers that can be used in this ultraviolet-curable resin or electron-beam-curable resin include urethane acrylate, epoxy acrylate, and polyester acrylate.

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

The overcoat layer 14 may further contain additives other than the organic polymer resin as necessary. Examples of additives include antioxidants, weathering agents, heat stabilizers, lubricants, crystal nucleating agents, UV absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, and silane coupling agents.

The thickness of the overcoat layer 14 is not particularly limited and can be set as appropriate. It is preferably 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 effect of internal stress will be large, causing cracks.

As a method for forming the overcoat layer 14, a normal coating method can be used, as with the undercoat layer 12. For example, well-known methods such as dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset, and organic deposition can be used. As a drying method, one or more heat application methods such as hot air drying, heat roll drying, high frequency irradiation, infrared irradiation, UV irradiation, and electron beam irradiation can be used in combination. In addition, a film previously coated on another resin substrate by the above-mentioned formation method may be transferred to the transparent oxide film layer 13 using a transfer method such as adhesive transfer, heat transfer, and UV transfer.

The gas barrier laminate according to the present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

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

Example 1
[Resin substrate placement process]
As the resin substrate 11, a biaxially stretched PET film having a thickness of 50 μm (manufactured by Toray Industries, Inc., product name "Lumirror T60") was used.

[Transparent oxide film layer lamination process]
A transparent oxide film layer 13 was formed on one side of the resin substrate 11 by a sputtering method (referred to as method A) using a magnetron sputtering device in which two electrodes are positioned in parallel, and a positive and negative voltage can be applied alternately to each electrode, and each electrode alternately plays the role of a cathode and an anode. The film formation conditions were a film formation pressure of 0.30 Pa, a power density of 3.3 W/ ^cm2 , and a target of an alloy target of Si and W (atomic composition ratio Si:W=90:10). An MF power source was used as a means for applying power to the two electrodes. At that time, a rectangular voltage with a frequency of 40 kHz was applied to the two electrodes positioned in parallel. Argon gas and oxygen gas were used as gases. At this time, the flow rate of oxygen gas was controlled by detecting the emission intensity of plasma and the voltage value of discharge so that the state of the target surface was in a transition state in the middle of transition from metal mode to oxide mode. A gas barrier laminate was obtained by forming a transparent oxide film layer 13 with a thickness of 100 nm.

Example 2
[Resin substrate placement process]
As in Example 1, a biaxially stretched PET film having a thickness of 50 μm (manufactured by Toray Industries, Inc., product name "Lumirror T60") was used as the resin substrate 11.

[Preparation and application process of solution for undercoat layer]
As a solution for the undercoat layer 12, a 5% methyl ethyl ketone solution was prepared by mixing an acrylic polyol (weight average molecular weight 10 x ¹⁰³ ) obtained by copolymerizing hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) as monomers as the main component and an HDI nurate type isocyanate-based curing agent in an amount of 1 equivalent relative to the amount of hydroxyl groups in the main component. The above-prepared solution was then applied onto the resin substrate 11, and an undercoat layer 12 having a thickness of 300 nm after drying was laminated.

[Transparent oxide film layer lamination process]
A gas barrier laminate was obtained by forming a transparent oxide film layer 13 having a 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.

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.

Example 4
[Resin substrate placement process]
As in Examples 1 and 2, a biaxially stretched PET film having a thickness of 50 μm (manufactured by Toray Industries, Inc., product name "Lumirror T60") was used as the resin substrate 11.

[Preparation and application process of solution for undercoat layer]
As in Example 2, an undercoat layer 12 having a thickness of 300 nm after drying was laminated on a resin substrate 11 .

[Transparent oxide film layer lamination process]
A transparent oxide film layer 13 having a 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.

[Preparation and application process of solution for overcoat layer]
A solution with a solid content of 5 mass % was prepared by mixing a hydrolysis solution of tetraethoxysilane (TEOS) and an aqueous solution of polyvinyl alcohol (PVA) so that the solid content ratio after drying would be 70:30, as a solution for the overcoat layer 14. Thereafter, the above-prepared solution was applied onto the transparent oxide film layer 13 by spin coating, and an overcoat layer 14 with a thickness of 300 nm after drying was laminated, thereby obtaining a gas barrier laminate.

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.

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.

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.

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.

<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 deposition pressure was set to 0.50 Pa.

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 deposition pressure was set to 0.8 Pa.

Example 11
The film formation conditions were the same as in Example 5, except that the film formation pressure was set to 0.15 Pa, to obtain a gas barrier laminate.

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.

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 device in which a voltage can be applied periodically to the electrode and a pulse having a different positive and negative polarity from the voltage application is applied during the off time of the voltage application was used, and 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 source was used as a means for applying power to the electrode. At that time, a pulse voltage with a frequency of 10 kHz (on time: 95%, off time: 5%, negative voltage is applied during the on time and positive voltage is applied during the off time) was applied to the electrode. As film formation conditions, the film formation pressure was 0.35 Pa and the power density was 3.3 W/cm ^2. As gases, argon gas and oxygen gas were used, and the flow rate of the oxygen gas was adjusted so that an oxide film was obtained.

<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.

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.

<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.

<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 deposition pressure was set to 0.50 Pa.

<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 device in which two cylindrical electrodes having a rotating mechanism are provided in parallel, and a voltage can be applied alternately between positive and negative, with each electrode alternately serving as a cathode and an anode, was used, and 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, an MF power source was used as a means for applying power to the two electrodes. At this time, a rectangular voltage with a frequency of 40 kHz was applied to the two electrodes positioned in parallel. As gases, argon gas and oxygen gas were used. At this time, the flow rate of 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 transition from the metal mode to the oxide mode. As film formation conditions, the film formation pressure was 0.30 Pa, and the power density was 3.3 W/cm ² .

<Example 19>
A gas barrier laminate was obtained under the same film formation conditions 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.

<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.

<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.

<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.

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

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

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

<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.

<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.

<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.

<Evaluation and Method>
[Measurement of film composition of transparent oxide film layer of gas barrier laminate]
The film composition of the gas barrier laminates produced in Examples 1 to 19 and Comparative Examples 1 to 5 was measured using X-ray photoelectron spectroscopy (JPS-9010MX manufactured by JEOL Ltd.). In this case, composition analysis was repeated four or more times in the depth direction of the vapor-deposited film using Ar ions, and the average was calculated to calculate Si/(Si+A) and O/(Si+A). In addition, when tungsten (W) was included as the Group 6 element (A), the composition of the outermost surface was analyzed because it was affected by reduction by Ar ions.

[Measurement of refractive index of transparent oxide film layer of gas barrier laminate]
The refractive index of the gas barrier laminates produced in Examples 1 to 19 and Comparative Examples 1 to 5 was measured using an ellipsometer (VUV-VASE) manufactured by J.A. Woollam Corporation.

[Measurement of light absorptance of transparent oxide film layer of gas barrier laminate]
The light absorptance of each of the gas barrier laminates produced in Examples 1 to 19 and Comparative Examples 1 to 5 was measured using an ultraviolet-visible spectrophotometer (UV-2450) manufactured by Shimadzu Corporation.

[Surface Roughness of Transparent Oxide Film Layer of Gas Barrier Laminate]
The arithmetic mean roughness of the surface of each of the gas barrier laminates produced in Examples 1 to 19 and Comparative Examples 1 to 5 was measured using a scanning probe microscope (AFM5400L) manufactured by Hitachi High-Tech Science Co., Ltd. In this case, the arithmetic mean roughness was analyzed from an image obtained by observing an area of 1 μm square per visual field.

[Measurement of gas barrier properties of gas barrier laminate]
For the gas barrier laminates produced in Examples 1 to 23 and Comparative Examples 1 to 5, the water vapor transmission rate (g/m2·day) was measured in an environment of 40°C and 90% RH (temperature 40°C, relative humidity 90%) using a water vapor transmission rate meter (AQUATRAN-Model II) manufactured by MOCON Corporation in the United ^States using a method conforming to JIS-K7129. The helium transmission rate (cc/( ^m2 ·day·atm)) and neon transmission rate (cc/( ^m2 ·day·atm)) were measured using a pressure sensor type gas measurement device (Deltaperm DP-2MST) manufactured by Technolox Corporation using a differential pressure method conforming to JIS K 7126A method at 40°C and 0% RH.

[Measurement result]
The measurement results are shown in the following Tables 1 to 3. 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.

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

In Examples 13 to 17, sputtering method B was used, but similar to Example 2, which used sputtering method A, good results were obtained in terms of water vapor permeability, helium permeability, and neon permeability.

In Examples 18 and 19, sputtering method C was used, but similar to Example 2, which used sputtering method A, good results were obtained in terms of water vapor permeability, helium permeability, and neon permeability.

Comparing Examples 13 to 17, which correspond to the second embodiment and use sputtering method B, with Comparative Example 5, Examples 13 to 17, which contain Si and W as metal elements in the target and transparent oxide film layer 13, showed better results in terms of water vapor permeability, helium permeability, and neon permeability than Comparative Example 5, which contains Si and Sn.

Example 12 corresponds to the second embodiment, uses sputtering method A, and contains three types of metal elements, Si, Mo, and W, in the target and transparent oxide film layer 13. As with Examples 2 and 3, which contain only Si and Mo, and Examples 5 to 11, which contain only Si and W, good water vapor permeability, helium permeability, and neon permeability results were obtained.

Examples 4 and 5, which correspond to the third embodiment, have an overcoat layer laminated therein, but similar to Example 2, which corresponds to the second embodiment in which no overcoat layer is laminated, good results were obtained in terms of water vapor permeability, helium permeability, and neon permeability.

In Examples 20 to 22, targets containing metal elements other than Si and Group 6 elements were used as the metal elements of the target, but good results were obtained for water vapor permeability, helium permeability, and neon permeability, similar to Example 1, in which a target containing only Si and Group 6 elements as the metal elements of the target was used.

In Example 23, nitrogen gas was used simultaneously with oxygen gas as the reactive gas in the sputtering process, but good results were obtained for water vapor permeability, helium permeability, and neon permeability, similar to Example 1, in which only oxygen gas was used as the reactive gas in the sputtering process.

Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above embodiments, and even if the changes are made within the scope of the gist of the present invention, they are still included in the present invention.

The gas barrier laminate of the present invention is expected to be particularly suitable for use in fields such as electronic device-related materials, where high gas barrier properties are required.

11: Resin substrate 12: Undercoat layer 13: Transparent oxide film layer 14: Overcoat layer

Claims (13)

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 0.80 or less;
or a gas barrier laminate containing both tungsten (W) and molybdenum (Mo) and having an atomic ratio Si/(Si+A) of 0.50 or less (excluding those in which the transparent oxide film layer contains 0.1 to 10 mass % Mo). 2. The gas barrier laminate according to claim 1, which has a helium permeability of 1200 cc/( ^m2 ·day·atm) or less under measurement conditions of 40° C. and 0% R.H. 3. The gas barrier laminate according to claim 1 or 2, which has a neon permeability of 2.0 cc/( ^m2 ·day·atm) or less under measurement conditions of 40° C. and 0% R.H. The gas barrier laminate according to any one of claims 1 to 3, wherein the ratio (Si/(Si+A)) of the number of silicon (Si) atoms in the transparent oxide film layer to the total number of atoms of silicon (Si) and the Group 6 element (A) is 0.10 or more and 0.80 or less, and the ratio (O/(Si+A)) of the number of oxygen (O) atoms to the total number of atoms of silicon (Si) and the Group 6 element (A) is 0.80 or more and 3.00 or less. The gas barrier laminate according to any one of claims 1 to 4, wherein the refractive index n of the transparent oxide film layer is 1.45 or more and 2.00 or less, and the optical thickness nd, which is expressed as the product of the thickness d and the refractive index n, is 7 nm or more and 1000 nm or less. The gas barrier laminate according to any one of claims 1 to 5, 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. The gas barrier laminate according to any one of claims 1 to 6, wherein the transparent oxide film layer further contains nitrogen (N). The gas barrier laminate according to any one of claims 1 to 7, wherein the transparent oxide film layer has a light absorption rate of 10% or less at a wavelength of 400 nm. The gas barrier laminate according to any one of claims 1 to 8, wherein the arithmetic mean roughness of the surface of the transparent oxide film layer is 5.0 nm or less. The gas barrier laminate according to any one of claims 1 to 9, 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. 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 contains a polyisocyanate, and the acrylic resin is an acrylic polyol resin. The gas barrier laminate according to any one of claims 1 to 11, further comprising an overcoat layer on the outside 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. The gas barrier laminate according to claim 12, wherein the overcoat layer is formed by containing a water-soluble polymer having a hydroxyl group and at least one selected from the group consisting of alkoxysilanes and their hydrolysates.

Images