JP2021000817A - Gas barrier laminate and method for producing the same - Google Patents

Abstract

To provide a transparent gas barrier laminate using a resin base material, that has a good water vapor barrier property, and to provide a method for producing the same.SOLUTION: The gas barrier laminate comprises a resin base material and a silicon and Group 6 element-containing transparent oxide film layer formed on one or both sides of the resin base material. The water vapor permeability at measuring condition of 40°C and 90% R.H. is 0.01 g/(m2 day) or less. The method for producing a gas barrier laminate includes a step of film-forming a transparent oxide film layer by using a magnetron sputtering apparatus capable of periodically applying voltage to an electrode.SELECTED DRAWING: Figure 1

Description

The present invention relates to a gas barrier laminate using a resin base material and a method for producing the same.

A gas barrier laminate is a laminate that has the property of impermeable to oxygen and water vapor (gas barrier property), and blocks various gases such as precision electronic parts, electronic components, and packaging for foods and pharmaceuticals. Widely used in various fields of need.

The required gas barrier properties vary depending on the application, but in general, a sealing film for a display such as organic electroluminescence (EL) or electronic paper has a high water vapor barrier property of 0.01 g / (m ² · day) or less. It is said to be necessary, and in recent years there has been an increasing demand for an even higher level of water vapor barrier properties. In addition, these films are required to be transparent.

In recent years, in the fields of organic EL and electronic paper, there is a tendency that resin is used as a base material instead of glass for reasons such as flexibility, damage prevention, and weight reduction. However, since the resin base material has a low gas barrier property against oxygen gas and water vapor, deterioration of these elements, electronic members, and the like becomes a problem.

Therefore, various materials have been developed in order to realize high gas barrier properties and transparency by using a resin base material, but in recent years, metal oxide films such as silicon oxide and aluminum oxide, and oxynitride of various metals have been developed. Many gas barrier laminates in which a material film is provided on a resin substrate on a nanoscale have been proposed.

In addition, as a method for producing a gas barrier laminate, since it is easy to increase the area and develop it into a roll-to-roll method, physical formation such as an induction heating method, a resistance heating method, an electron beam vapor deposition method, and a sputtering method is performed. Membrane methods are being studied.

In order to realize higher gas barrier properties, it is necessary to form a dense gas barrier layer made of an inorganic compound, and a dense inorganic compound film can generally be easily produced by a sputtering method. ..

Further, in order to realize higher transparency, it is required that there is little reflection at the interface between the resin base material and the inorganic compound film and 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 base material.

For example, Patent Document 1 below describes a transparent resin substrate (gas barrier laminate) having high transparency and high water vapor barrier performance. The gas barrier laminate contains tin oxide and silicon (Si) as an additive element at a ratio of 46 atomic% or more and 63 atomic% or less with respect to the total of Si and Sn, and is an amorphous film. A transparent oxide film having 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 DC (DC) pulse sputtering method.

However, it is stated that the water vapor permeability of the gas barrier laminate is less than 0.01 g / (m ² · day) measured by the Mocon method according to the JIS standard K7129 method, and it is certainly high in water vapor. Although it has a gas barrier property, in order to meet the higher level of water vapor barrier property that has been demanded in recent years, further improvement is required.

Japanese Patent No. 4788463

Therefore, an object of the present invention is to provide a transparent gas barrier laminate using a resin base material having good water vapor barrier properties and a method for producing the same.

One aspect of the present invention for solving the above problems is a transparent oxide containing a resin base material and silicon (Si) and a Group 6 element (referred to as A) formed on one or both sides of the resin base material. A film layer is provided, and the measurement conditions are 40 ° C. and 90% R.I. H. It is a gas barrier laminated body having a water vapor transmittance of 0.01 g / (m ² · day) or less.

In the gas barrier laminate according to the present invention, the Group 6 element (A) of the transparent oxide film layer may be molybdenum (Mo) or tungsten (W).

In the gas barrier laminate according to the present invention, the Group 6 element (A) of the transparent oxide film layer may contain both molybdenum (Mo) and tungsten (W).

In the gas barrier laminate according to the present invention, measurement conditions were 40 ° C. and 0% R. H. Helium permeability ^{1200cc / (m 2 · day ·} atm) may be less in the.

Further, in the gas barrier laminate according to the present invention, the measurement conditions were 40 ° C. and 0% R.M. H. Neon transmittance ^{2.0cc / (m 2 · day ·} atm) may be less in the.

Further, in the gas barrier laminate according to the present invention, the ratio of the number of atoms of silicon (Si) in the transparent oxide film layer to the total number of atoms of silicon (Si) and the group 6 element (A) (Si /). (Si + A)) is 0.10 or more and 0.98 or less, and the ratio (O / (Si + A)) of the number of atoms of oxygen (O) to the total number of atoms of silicon (Si) and group 6 element (A). )) May be 0.80 or more and 3.00 or less.

Further, in the gas barrier laminate according to the present invention, the refractive index n of the transparent oxide film layer is 1.45 or more and 2.00 or less, and the optical film thickness is represented by the product of the film thickness d and the refractive index n. The nd may be 7 nm or more and 1000 nm or less.

Further, in the gas barrier laminate according to the present invention, the light absorption rate of the transparent oxide film layer at a wavelength of 400 nm may be 10% or less.

Further, in the gas barrier laminate according to the present invention, the arithmetic average roughness of the surface of the transparent oxide film layer may be 5.0 nm or less.

Further, in the gas barrier laminate according to the present invention, the transparent oxide film layer is Mg, Al, Ca, Sc, Ti, V, Zn, Ga, Ge, Sr, Y, Zr, Nb, In, Sn, Ba, At least one element selected from Hf and Ta may be further contained.

Further, in the gas barrier laminate according to the present invention, the transparent oxide film layer may further contain nitrogen (N).

Further, the gas barrier laminate according to the present invention further has an undercoat layer between the resin base material and the transparent oxide film layer, and the undercoat layer is a thermosetting resin, a thermoplastic resin, and an ultraviolet curable. It may be formed from at least one or more of a resin and an electron beam curable resin.

Further, in the gas barrier laminate according to the present invention, the undercoat layer is a layer composed 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. May be an acrylic polyol resin.

Further, the gas barrier laminate according to the present invention further has an overcoat layer on the outside of the transparent oxide film layer, and the overcoat layer is a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and an electron beam curing. It may be formed from at least one or more of the sex resins.

Further, the gas barrier laminate according to the present invention is formed by containing at least one selected from the group consisting of a water-soluble polymer having a hydroxy group, an alkoxysilane and a hydrolyzate thereof, in an overcoat layer. You may.

Another aspect of the present invention is the above-mentioned method for producing a gas barrier laminate, in which a transparent oxide film layer is formed by using a magnetron sputtering apparatus capable of periodically applying a voltage to an electrode. It is a method for producing a gas barrier laminate including a step.

Further, in the method for producing a gas barrier laminate according to the present invention, a voltage can be periodically applied by a magnetron sputtering apparatus in a step of forming a transparent oxide film layer, and a voltage is applied during off-time of voltage application. A pulse voltage having a positive or negative positive or negative value may be applied.

Further, another aspect of the present invention is the above-mentioned method for manufacturing a gas barrier laminate, in which two electrodes are located in parallel, and voltages can be applied to each electrode alternately positive and negative, and each of the two electrodes can be applied alternately. Is a method for producing a gas-barrier laminate, which comprises a step of forming a transparent oxide film layer by alternately using a magnetron sputtering apparatus that acts as a cathode and an anode.

Another aspect of the present invention is the method for producing a gas barrier laminate described above, wherein a transparent oxide film layer is formed by using a magnetron sputtering apparatus provided with a cylindrical electrode having a rotating mechanism. It is a method of manufacturing a gas-barrier laminate including the step of performing.

Further, in the method for producing a gas barrier laminate according to the present invention, the film forming pressure when forming a transparent oxide layer may be set in the range of 0.05 Pa or more and 5.00 Pa or less.

According to the present invention, it is possible to provide a transparent gas barrier laminate using a resin base material having good water vapor barrier properties and a method for producing the same.

It is sectional drawing of the gas barrier laminated body which concerns on 1st Embodiment of this invention. It is sectional drawing of the gas barrier laminated body which concerns on 2nd Embodiment of this invention. It is sectional drawing of the gas barrier laminated body which concerns on 3rd Embodiment of this invention.

<First Embodiment>
The 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 the present embodiment comprises a resin base material 11 and a transparent oxide film layer 13 formed on one side of the resin base material 11. Actually, the transparent oxide film layer 13 may be laminated on both sides of the resin base material 11. Here, in the following description, the transparent oxide film layer formed (laminated) on the resin base material 11 and the transparent oxide film layer 13 have the same meaning.

(Resin base material)
The material of the resin base material 11 is not particularly limited, and known materials can be used. For example, polyolefin-based (polyethylene, polypropylene, etc.), polyester-based (polyethylene terephthalate, polyethylene naphthalate, etc.), polyimide-based, polyamide-based (nylon-6, nylon-66, etc.), polystyrene, ethylene vinyl alcohol, polyvinyl chloride, polyimide, Examples thereof include polyvinyl alcohol, polyvinyl carbonate, polyether sulfone, acrylic, cellulose type (triacetyl cellulose, diacetyl cellulose, etc.), but are not particularly limited. In practice, it is desirable to make an appropriate selection according to the application and required physical characteristics, and for packaging that protects contents that are extremely water-sensitive, such as electronic members and optical members, polyethylene naphthalate, polyimides, polyether sulfone, etc. Although it is desirable to use the resin base material 11 which itself has a high gas barrier property, the present invention is not limited to these examples.

The thickness of the resin base material 11 is not limited, but it is easy to use about 12 μm to 300 μm depending on the application. The resin base material 11 having a thickness within this range is preferable because it is flexible and can be wound into a roll.

Further, the form of the resin base material 11 may be a long material or a single-wafer material, but the long resin base material 11 can be preferably used. The length of the long resin base material 11 in the longitudinal direction is not particularly limited, but for example, a long film of 10 m or more is preferably used. The upper limit of the length is not limited, and may be, for example, about 10 km.

Further, the surface of the resin base material 11 may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, and a slip agent, if necessary. Further, in order to improve the adhesion, the surface of the resin base material 11 is subjected to physical treatment such as corona treatment, frame treatment, plasma treatment and easy adhesion treatment, and chemical treatment modification treatment such as chemical treatment with acid or alkali. May be given. The surface of the resin base material 11 contributes to the compactness in the initial growth stage of vacuum film formation, and is preferably 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), which is provided to impart gas barrier properties to the entire gas barrier laminated body. 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, elements with a size different from that of silicon (Si) form a dense film, and therefore it is thought that the effect of tungsten (W), which has a large atomic number and a large size, is large. Is 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 possible to use a sputtering method using a magnetron sputtering device in which a voltage can be periodically applied to the electrodes and a pulse different from the voltage application is applied (pulse voltage is applied) during the off-time of voltage application. preferable. Further, it is possible to use a sputtering method using a magnetron sputtering device in which two electrodes are located in parallel and voltages can be alternately applied to each electrode, and each electrode alternately serves as a cathode and an anode. preferable. Further, it is preferable to use a sputtering method using a magnetron sputtering apparatus provided with a cylindrical electrode having a rotating mechanism. Further, when the transparent oxide layer is formed by these sputtering methods, it is preferable to set the film forming pressure in the range of 0.05 Pa or more and 5.00 Pa or less.

In the transparent oxide film layer 13, the ratio (Si / (Si + A)) of the number of atoms of silicon (Si) to the total number of atoms of silicon (Si) and the group 6 element (A) is 0.10 or more and 0. The ratio (O / (Si + A)) of the number of atoms of oxygen (O) to the total number of atoms of silicon (Si) and Group 6 element (A) is 0.80 or more and 3.00. It is formed as follows. Considering the refractive index and gas barrier property, the ratio (Si / (Si + A)) of the number of atoms of silicon (Si) to the total number of atoms of silicon (Si) and the group 6 element (A) is 0.20. More preferably 0.95 or less. When the Group 6 element (A) is tungsten (W), the number of atoms of silicon (Si) and that of silicon (Si) and tungsten (W) are considered in consideration of the refractive index, transparency, and gas barrier property. The ratio (Si / (Si + W)) to the total number of atoms is more preferably 0.25 or more and 0.95 or less, and further preferably 0.30 or more and 0.80 or less. When the Group 6 element (A) is molybdenum (Mo), the number of atoms of silicon (Si) and that of silicon (Si) and molybdenum (Mo) are taken into consideration in consideration of the refractive index, transparency, and gas barrier property. The ratio (Si / (Si + Mo)) to the total number of atoms is more preferably 0.50 or more and 0.85 or less. Further, it is more preferable to contain both molybdenum (Mo) and tungsten (W) as the Group 6 element (A), and considering the refractive index, transparency and gas barrier property, the number of atoms of silicon (Si) and silicon The ratio (Si / (Si + Mo + W)) to the total number of atoms of (Si), molybdenum (Mo), and tungsten (W) is more preferably 0.25 or more and 0.95 or less. As a method for determining whether or not the transparent oxide film layer 13 is within the above composition range, a conventionally known method can be used, and for example, it can be obtained by an analyzer such as XPS (X-ray photoelectron analyzer). It can be evaluated by the result.

By setting the film composition of the transparent oxide film layer 13 in 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, there is little reflection at the interface between the resin base material 11 and the transparent oxide film layer 13, and the light transmittance with visible light can be increased. The refractive index of the transparent oxide film layer 13 can be evaluated by measuring the refractive index of a film having the same composition as that of the transparent oxide film layer 13 with a refractive index meter (elypsometer).

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 transparent oxide film layer 13 cannot cover the entire resin base material 11, and sufficient gas barrier properties cannot be obtained. Further, if it exceeds 500 nm, cracks are likely to occur, and the gas barrier property may be lowered. Further, the cost increases due to an increase in the amount of material used, a long film formation time, and the like, which is not preferable from an economical 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.

Further, by setting the composition of the transparent oxide film layer 13 in the above range and the optical film thickness in the above range, the light absorption rate 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 region. When the Group 6 element (A) is tungsten (W), the ratio (Si / (Si + W)) of the number of atoms of silicon (Si) to the total number of atoms of silicon (Si) and tungsten (W) is If it is less than 0.10, light having a wavelength of 400 nm is absorbed and sufficient transparency cannot be obtained. Further, even when the optical film thickness exceeds 1000 nm, visible light may be absorbed and sufficient transparency may not be obtained. That is, the light absorption rate at a wavelength of 400 nm is preferably 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 by an ultraviolet-visible spectrophotometer.

Further, 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 having a small surface roughness has a dense structure, so that it is considered to impart gas barrier properties, but the details are unknown. Is. Further, when the transparent oxide film layer 13 has a defect such as a crack that lowers the gas barrier property, the surface roughness becomes large. Therefore, the arithmetic mean roughness of the surface of the transparent oxide film layer 13 is preferably 5.0 nm or less, 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.

Further, in the transparent oxide film layer 13, in addition to the metal elements of silicon (Si) and the group 6 element (A), Mg, Al, Ca, Sc, Ti, V, Zn, Ga, Ge, Sr, and Y , Zr, Nb, In, Sn, Ba, Hf, Ta may further contain at least one element selected from. In addition to silicon (Si) and Group 6 element (A), the transparent oxide film layer 13 contains Mg, Al, Ca, Sc, Ti, V, Zn, Ga, Ge, Sr, Y, Zr, Nb, and the like. By containing at least one element selected from In, Sn, Ba, Hf, and Ta, the gas barrier property is improved, the adhesion to the resin base material 11 is improved, the temperature and humidity durability is improved, and the refractive index is n. Adjustments can be made. Further, 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 sputtering method)
Various sputtering methods can be used as the means for forming the transparent oxide film layer 13. 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 applied periodically, the charge on the target surface is eliminated by providing the off-time for applying the voltage. Therefore, damage to the film due to arcing can be suppressed, and a high-quality film can be stably formed. Further, preferably, a sputtering method using a magnetron sputtering apparatus is used in which a voltage can be periodically applied to the electrodes and pulses different in positive and negative from the voltage application are applied during the off-time of the voltage application. According to this sputtering method, an off-time for applying a voltage is provided, and since the voltage of the off-time is positively and negatively reversed from that at the time of application, the charge on the target surface can be more easily eliminated. Therefore, damage to the film due to arcing can be further suppressed, and a high-quality film can be stably formed. Further, preferably, a sputtering method using a magnetron sputtering device in which two electrodes are located in parallel, voltages can be applied to each electrode alternately in positive and negative directions, and each electrode alternately serves as a cathode and an anode is used. Use. In this sputtering method, a material target is placed on two electrodes installed in a vacuum chamber, and a rare gas element (usually argon is used) ionized by applying a high voltage is made to collide with the target to collide with the target surface. This is a method of forming a transparent oxide film layer 13 by ejecting the atoms of the above and adhering the target element on the resin base material 11. In this sputtering method, the anode and cathode alternate between the two targets, so when one target discharges and forms a film, the other target takes on a weak reverse charge and charges the target surface. Eliminate. Therefore, damage to the film due to arcing can be suppressed, and a high-quality film can be stably formed. 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 the entire surface of the target surface becomes an erosion region by rotation, so that the utilization rate of the target is high. In addition, since the entire surface of the target surface is in a clean state and arcing can be suppressed, continuous operation for a long time is possible. Furthermore, damage to the film due to arcing can be suppressed, and a high-quality film can be stably formed. Further, two cylindrical electrodes having a rotating mechanism may be arranged in parallel, and a voltage can be applied to each electrode alternately in positive and negative directions, and each electrode alternately serves as a cathode and an anode. It may be a magnetron sputtering apparatus that fulfills. 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, a transparent oxynitride film layer may be formed by flowing nitrogen gas at the same time as the oxygen gas. Further, as the target, a target made of an alloy of Si and a Group 6 element (A) is used. The targets described above are Si and Group 6 element (A), as well as Mg, Al, Ca, Sc, Ti, V, Zn, Ga, Ge, Sr, Y, Zr, Nb, In, Sn, Ba, etc. It may further contain at least one element selected from Hf and Ta.

Even when a magnetron sputtering device that can periodically apply a voltage to the electrodes is used, the two electrodes are located in parallel, and the voltage can be applied to each electrode alternately positive and negative, and each electrode alternately cathodes. The power supply that applies voltage to the electrodes is not particularly specified, regardless of whether a magnetron sputtering device that acts as an anode is used or a magnetron sputtering device that has a cylindrical cathode having a rotating mechanism is used. It may be AC (AC) or DC, but it is desirable to use a DC pulse power supply. This is because it is more effective to make the applied voltage waveform a pulse wave to alleviate the charge-up at the anode during the off-time of voltage application. The frequency of the DC pulse power supply is not particularly limited and can be set as appropriate. Preferably, it is 1 kHz or more and 100 kHz or less, and more preferably 10 kHz or more and 50 kHz or less.

Even when a magnetron sputtering device that can periodically apply a voltage to the electrodes is used, the two electrodes are located in parallel, and the positive and negative voltages can be applied to each electrode alternately, and each electrode alternately cathodes. , Even when a magnetron sputtering device that acts as an anode is used, or when a magnetron sputtering device having a cylindrical cathode having a rotating mechanism is used, film formation when forming a transparent oxide layer is performed. The pressure is preferably set in the range of 0.05 Pa or more and 5.00 Pa or less. By forming a film within the range of this film forming pressure, a film having few surface defects can be obtained.

The gas barrier laminate according to the present embodiment is configured by laminating the above-mentioned transparent oxide film layer 13 on the resin base material 11. As a result, the measurement conditions were 40 ° C. and 90% R. H. The water vapor permeability in the above can be 0.01 g / (m ² · day) or less. Further, by forming the transparent oxide film layer 13 into a dense film, the measurement conditions were 40 ° C. and 0% R.D. H. The helium transmittance in is 1200 cc / (m ² · day · atm) or less. Further, the measurement conditions were 40 ° C. and 0% R. H. Neon transmittance can be ^{2.0cc / (m 2 · day ·} atm) or less in. Further, by using the sputtering method using the magnetron sputtering apparatus described above, it is possible to suppress film defects due to arcing and to produce a gas barrier laminate having a dense transparent oxide film layer 13. Therefore, according to the present embodiment, it is possible to realize a gas barrier laminate having good gas barrier properties and a method for producing the same.

<Second Embodiment>
The second embodiment of the present invention will be described below.
The gas barrier laminate according to the present embodiment has an undercoat layer between the resin base material 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. 12 is further provided. Further, the undercoat layer 12 and the transparent oxide film layer 13 may be sequentially laminated on both surfaces of the resin base material 11.

The undercoat layer 12 enhances the adhesion between the resin base material 11 and the transparent oxide film layer 13 on the resin base material 11, prevents the transparent oxide film layer 13 from peeling off, and further scratches, scratches, etc. Provided to protect against mechanical trauma. The material of the undercoat layer 12 is not particularly limited, but a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, an electron beam curable resin and the like can be used.

Examples of the thermosetting resin forming the undercoat layer 12 include a thermosetting urethane resin composed of an acrylic polyol resin and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin. Be done. Among them, the resin base material 11 and the transparent oxide film layer are formed by using a composite of an acrylic polyol resin containing a hydroxy group and an isocyanate compound having at least two NCO groups in the molecule. Adhesion with 13 can be improved.

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 another monomer. It has a hydroxy group at the end and a side chain, and reacts with the NCO group of an isocyanate compound. The (meth) acrylic acid derivative monomer has a hydroxy group at the terminal and the side chain. Examples of the (meth) acrylic acid derivative monomer include hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like.

The above other monomers can be copolymerized with a (meth) acrylic acid derivative monomer having a hydroxy group at the terminal and a side chain. Examples of the above-mentioned other monomers include (meth) acrylic acid 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. Derivative monomer, (meth) acrylic acid, etc. having a carboxy group in the side chain (meth) acrylic acid derivative monomer, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. having an aromatic ring or cyclic structure in the side chain (meth) ) Acrylic acid derivative monomer and the like can be considered. Other than the (meth) acrylic acid derivative monomer, styrene monomer, cyclohexylmaleimide monomer, phenylmaleimide monomer and the like can be considered. The other monomers mentioned above may themselves have hydroxy groups at the ends and side chains.

The acrylic polyol resin is particularly 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 is formed by using a composite of an acrylic polyol resin obtained by polymerizing a monomer having a carboxy group and an isocyanate compound. Can be obtained.

The acrylic polyol resin containing a hydroxy group that can be used in the undercoat layer 12 is not particularly limited, but it is desirable that the hydroxy group value is 50 mgKOH / g or more and 250 mgKOH / g or less. Here, the hydroxy group value (mgKOH / g) is an index of the amount of hydroxy groups in the acrylic polyol resin, and mg of potassium hydroxide required for acetylating the hydroxy groups in 1 g of the acrylic polyol resin. Show the number. The weight average molecular weight of the acrylic polyol resin is not particularly limited, but specifically, it is preferably 3000 or more and 200,000 or less. In particular, it is preferably 5000 or more and 100,000 or less. Further, it is more preferably 5000 or more and 40,000 or less.

The isocyanate-based 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), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), and bisisocyanate. An aliphatic isocyanate such as methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI) and the like can be considered. In addition, polymers or derivatives of these monomeric isocyanates can also be used. For example, there are a trimer nurate type, an adduct type reacted with 1,1,1-trimethylolpropane and the like, a biuret type reacted with biuret and the like.

The isocyanate-based compound may be arbitrarily selected from the above-mentioned isocyanate-based compounds or polymers or derivatives thereof, and may be used alone or in combination of two or more.

As an example of the undercoat layer 12, it is formed by applying a solution consisting of a composite of the above acrylic polyol resin and the above isocyanate compound and a solvent onto the resin base material 11 and react-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 acrylic polyol resin and the isocyanate-based compound. Examples of the solvent include methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, dioxolane, tetrahydrofuran and the like. Actually, one kind or a combination of two or more kinds of these solvents can be used.

Examples of the thermoplastic resin forming the undercoat layer 12 include polyols having two or more hydroxy groups such as acrylic polyol, polyester polyol, polycarbonate polyol, polyether polyol, polycaprolactone polyol, and epoxy polyol, and polyacetic acid. It is appropriately selected from polyvinyl resins such as vinyl and polyvinyl chloride, polyvinylidene chloride resins, polystyrene resins, polyethylene resins, polypropylene resins, polyurethane resins and the like. Further, these may be mixed in an arbitrary ratio. The hydroxy group 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 undercoat layer 12 is not particularly limited as an organic polymer resin, but includes at least a resin having a hydroxy base value in the range of 10 or more and 100 mgKOH / g or less. Is desirable. The organic polymer resin is not particularly limited, but it is desirable to include 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 that the organic polymer resin contains at least a thermoplastic resin. When the hydroxy group 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 is weakened, and the adhesion to the transparent oxide film layer 13 is lowered. Tend. When the hydroxy group value or acid value exceeds 100 mgKOH / g, precipitates containing hydroxy groups generated by decomposition of the undercoat layer 12 in durability tests such as a moist heat resistance test are formed in the undercoat layer 12 and the transparent oxide film layer 13. Tends to hinder close contact with.

Examples of the monomer that can be used for the ultraviolet curable resin or the electron beam curable resin that forms the undercoat layer 12 include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, and N-vinylproridone. Monofunctional and polyfunctional monomers such as trimethylol propane (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, dipenta. Ellisritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate and the like can be used. Examples of the oligomer that can be used for this ultraviolet curable resin or electron beam curable resin include urethane acrylate, epoxy acrylate, and polyester acrylate.

When two or more kinds selected from a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and an electron beam curable resin are used in combination as the organic polymer resin forming the undercoat layer 12, the blending ratio thereof is particularly limited. It is not something that is done.

The undercoat layer 12 may further contain additives in addition to the organic polymer resin, if necessary. Examples of additives include antioxidants, weather resistant agents, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, silane coupling agents and the like. Can be mentioned.

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 base material 11 and the transparent oxide film layer 13 becomes insufficient. If it is thicker than 10.0 μm, the influence of internal stress becomes large, the transparent oxide film layer 13 is not laminated neatly, the development of barrier properties is insufficient, and the transparency and coating accuracy are also insufficient.

As a method for forming the undercoat layer 12, a usual 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, and organic vapor deposition method can be used. As the drying method, one or a combination of two or more methods of applying heat such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, and electron beam irradiation can be used. Further, a film previously coated on another resin base material by the above-mentioned forming method may be transferred to the resin base material 11 by using a transfer method such as adhesive material transfer, thermal transfer, or UV transfer.

<Third Embodiment>
The third embodiment of the present invention will be described below.
The gas-barrier laminate according to the present embodiment has an overcoat layer 14 further provided on the transparent oxide film layer 13 of the gas-barrier laminate of FIG. 2, like the gas-barrier laminate shown in FIG. Is. 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 of 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 two selected from a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and an electron beam curable resin. The above can be used. The ratio of the organic polymer resin to the overcoat layer 14 is not particularly limited and can be appropriately set.

Examples of the thermosetting resin forming the overcoat layer 14 include a thermosetting urethane resin composed of an acrylic polyol resin and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin. Be done. Among them, the overcoat layer 14 and the transparent oxide film layer are formed by using a composite of an acrylic polyol resin containing a hydroxy group and an isocyanate compound having at least two NCO groups in the molecule. Adhesion with 13 can be improved.

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 another monomer. It has a hydroxy group at the end and a side chain, and reacts with the NCO group of an isocyanate compound. The (meth) acrylic acid derivative monomer has a hydroxy group at the terminal and the side chain. Examples of the (meth) acrylic acid derivative monomer include hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like.

The above other monomers can be copolymerized with a (meth) acrylic acid derivative monomer having a hydroxy group at the terminal and a side chain. Examples of the above-mentioned other monomers include (meth) acrylic acid 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. Derivative monomer, (meth) acrylic acid, etc. having a carboxy group in the side chain (meth) acrylic acid derivative monomer, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. having an aromatic ring or cyclic structure in the side chain (meth) ) Acrylic acid derivative monomer and the like can be considered. Other than the (meth) acrylic acid derivative monomer, styrene monomer, cyclohexylmaleimide monomer, phenylmaleimide monomer and the like can be considered. The other monomers mentioned above may themselves have hydroxy groups at the ends and side chains.

The acrylic polyol resin is particularly 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 is formed by using a composite of an acrylic polyol resin obtained by polymerizing a monomer having a carboxy group and an isocyanate compound. Can be obtained.

The acrylic polyol resin containing a hydroxy group in the overcoat layer 14 is not particularly limited, but it is desirable that the hydroxy group value is 50 mgKOH / g or more and 250 mgKOH / g or less. The weight average molecular weight of the acrylic polyol resin is not particularly limited, but specifically, it is preferably 3000 or more and 200,000 or less. In particular, it is preferably 5000 or more and 100,000 or less. Further, it is more preferably 5000 or more and 40,000 or less.

The isocyanate-based 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), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), and bisisocyanate. An aliphatic isocyanate such as methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI) and the like can be considered. In addition, polymers or derivatives of these monomeric isocyanates can also be used. For example, there are a trimer nurate type, an adduct type reacted with 1,1,1-trimethylolpropane and the like, a biuret type reacted with biuret and the like.

The isocyanate-based compound may be arbitrarily selected from the above-mentioned isocyanate-based compounds or polymers or derivatives thereof, and may be used alone or in combination of two or more.

As an example, the overcoat layer 14 is formed by applying a solution consisting of a composite of the above acrylic polyol resin and the above isocyanate compound and a solvent onto the resin base material 11 and react-curing it. To. 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 acrylic polyol resin and the isocyanate-based compound. Examples of the solvent include methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, dioxolane, tetrahydrofuran and the like. Actually, one kind or a combination of two or more kinds of these solvents can be used.

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

As the water-soluble polymer having a hydroxy group, polyvinyl alcohol, polycarboxylic acid, starch and celluloses are preferable. In particular, when polyvinyl alcohol (hereinafter referred to as PVA) is used as the coating agent of the present invention, the gas barrier property is excellent. Since PVA is a polymer containing the largest number of hydroxy groups in the monomer unit, it has a very strong hydrogen bond with the hydroxy group of the hydrolyzed organosilicon compound. The PVA referred to here is generally obtained by saponification of polyvinyl acetate, and is completely saponified in which only a few percent of acetic acid groups remain from the so-called partially saponified PVA in which several tens of percent of acetic acid groups remain. Including up to PVA. The molecular weight of PVA varies from 300 to several thousand, but there is no problem in the effect regardless of the molecular weight. However, in general, a high molecular weight PVA having a high degree of saponification and a high degree of polymerization is preferable because it has high water resistance.

Further, as the alkoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltriethoxysilane, methyltrimethoxysilane and the like can be used. Examples of the hydrolysis product of alkoxysilane include those prepared by dissolving alkoxysilane in an alcohol such as methanol, adding an aqueous solution of an acid such as hydrochloric acid to the solution, and causing a hydrolysis reaction. 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 group, so that a dense and strong network polymerization film can be formed. Therefore, the overcoat layer 14 having excellent heat resistance, water resistance, moisture resistance, bending resistance, stretch resistance, and the like can be obtained.

Further, a silane coupling agent may be added in order to improve the adhesion to the transparent oxide film layer 13. 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, and mercapto groups such as 3-mercaptopropyltrimethoxysilane. Examples thereof include those having an NCO group such as 3-isocyanatepropyltriethoxysilane, and these silane coupling agents can be used alone or in combination of two or more.

Examples of the thermoplastic resin forming the overcoat layer 14 include polyols having two or more hydroxy groups such as acrylic polyol, polyester polyol, polycarbonate polyol, polyether polyol, polycaprolactone polyol, and epoxy polyol, and polyacetic acid. It is appropriately selected from polyvinyl resins such as vinyl and polyvinyl chloride, polyvinylidene chloride resins, polystyrene resins, polyethylene resins, polypropylene resins, polyurethane resins and the like. Further, these may be mixed in an arbitrary ratio. The hydroxy group 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 as an organic polymer resin, but includes at least a resin having a hydroxy base value in the range of 10 or more and 100 mgKOH / g or less. Is desirable. The organic polymer resin is not particularly limited, but it is desirable to include 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 that the organic polymer resin contains at least a thermoplastic resin. When the hydroxy group 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 is weakened, and the adhesion to the transparent oxide film layer 13 is lowered. Tend. When the hydroxy group value or acid value exceeds 100 mgKOH / g, precipitates containing hydroxy groups generated by decomposition of the overcoat layer 14 in durability tests such as a moist heat resistance test are formed in the overcoat layer 14 and the transparent oxide film layer 13. Tends to hinder close contact with.

Examples of the monomer that can be used for the ultraviolet curable resin or the electron beam curable resin that forms the overcoat layer 14 include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, and N-vinylproridone. Monofunctional and polyfunctional monomers such as trimethylol propane (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, dipenta. Ellisritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate and the like can be used. Examples of the oligomer that can be used for this ultraviolet curable resin or electron beam curable resin include urethane acrylate, epoxy acrylate, and polyester acrylate.

When two or more kinds selected from a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and an electron beam curable resin are used in combination as the organic polymer resin forming the overcoat layer 14, the blending ratio thereof is particularly limited. It is not something that is done.

The overcoat layer 14 may further contain additives in addition to the organic polymer resin, if necessary. Examples of additives include antioxidants, weather resistant agents, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, silane coupling agents and the like. Can be mentioned.

The film thickness of the overcoat layer 14 is not particularly limited and can be set as appropriate. Preferably, it is 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 becomes insufficient, and if it is thicker than 10.0 μm, the influence of internal stress becomes large and cracks occur.

As a method for forming the overcoat layer 14, a usual coating method can be used as in the case of the undercoat layer 12. 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, and organic vapor deposition method can be used. As the drying method, one or a combination of two or more methods of applying heat such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, and electron beam irradiation can be used. Further, a film previously coated on another resin base material by the above-mentioned forming method may be transferred to the transparent oxide film layer 13 by a transfer method such as adhesive material transfer, thermal transfer, or UV transfer.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples for the gas barrier laminate according to the present invention, but the present invention is not limited to these Examples.

In Example 1, Example 20, Example 21, Example 22, Example 23, and Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4, a transparent oxide film layer was formed on one side of the resin base material 11. 13 is provided. 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 In 16, Example 17, Example 18, Example 19, 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 Examples 4 and 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, and Comparative Example 4 correspond to the gas barrier laminate shown in FIG. To do. 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. Examples 4 and 5 correspond to the gas barrier laminate shown in FIG.

<Example 1>
[Placement process of resin base material]
As the resin base material 11, a biaxially stretched PET film having a thickness of 50 μm (manufactured by Toray Industries, Inc., product name “Lumilar T60”) was used.

[Laminating process of transparent oxide film layer]
The transparent oxide film layer 13 is placed on one side of the resin base material 11, and two electrodes are located in parallel, and voltages can be applied to each electrode alternately in positive and negative directions, and the respective electrodes are alternately cathode and anode. The film was formed by a sputtering method (referred to as method A) using a magnetron sputtering apparatus that plays a role. As the film forming conditions, the film forming pressure was 0.30 Pa, the power density was 3.3 W / cm ^2, and an alloy target of Si and W (atomic composition ratio Si: W = 90:10) was used as the target. An MF power supply was used as a means for inputting power to the two electrodes. At that time, a rectangular voltage having a frequency of 40 kHz was applied to two electrodes located in parallel. As the gas, argon gas and oxygen gas were used. At this time, the flow rate of oxygen gas is controlled by detecting the emission intensity of plasma and the voltage value of discharge so that the state of the target surface becomes a transition state in which the transition from the metal mode to the oxide mode is in progress. did. A gas barrier laminate was obtained by forming a transparent oxide film layer 13 having a film thickness of 100 nm.

<Example 2>
[Placement process of resin base material]
As in Example 1, a biaxially stretched PET film having a thickness of 50 μm (manufactured by Toray Industries, Inc., product name “Lumilar T60”) was used as the resin base material 11.

[Preparation / coating process of solution for undercoat layer]
As a 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 is used as a main component, and an HDI nurate type solution is used. A 5% solution of methyl ethyl ketone was prepared by blending 1 equivalent of an isocyanate-based curing agent with respect to the amount of hydroxy groups of the main agent. Then, the above-prepared solution was applied onto the resin base material 11, and the undercoat layer 12 having a thickness of 300 nm after drying was laminated.

[Laminating process of transparent oxide film layer]
A transparent oxide film layer having 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 Mo (atomic composition ratio Si: Mo = 80: 20) was used. By forming No. 13, a gas barrier laminate was obtained.

<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>
[Placement process of resin base material]
Similar to Example 1 and Example 2, a biaxially stretched PET film having a thickness of 50 μm (manufactured by Toray Industries, Inc., product name “Lumilar T60”) was used as the resin base material 11.

[Preparation / coating process of solution for undercoat layer]
In the same manner as in Example 2, the undercoat layer 12 having a thickness of 300 nm after drying was laminated on the resin base material 11.

[Laminating process of transparent oxide film layer]
A transparent oxide film layer having a film thickness of 100 nm is applied 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) is used. 13 was formed.

[Preparation / coating process of solution for overcoat layer]
As a solution for the overcoat layer 14, a hydrolyzed solution of tetraethoxysilane (TEOS) and an aqueous solution of polyvinyl alcohol (PVA) are mixed so that the solid content ratio after drying is 70:30, and the solid content 5 A mass% solution was prepared. Then, the solution prepared above was applied onto the transparent oxide film layer 13 using a spin coat, and the overcoat layer 14 having a thickness of 300 nm after drying was laminated to obtain 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 film formation 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 film formation pressure was set to 0.8 Pa.

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

<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 using a magnetron sputtering apparatus in which a voltage can be periodically applied to the electrodes and pulses different from those applied by the voltage are applied during the off-time of the voltage application ( 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 using Method B). At this time, a DC power supply was used as a means for inputting power to the electrodes. At that time, a pulse voltage having a frequency of 10 kHz (on-time: 95%, off-time: 5%, negative voltage is applied during on-time, and positive voltage is applied during off-time) was applied to the electrodes. As the film forming conditions, the film forming pressure was 0.35 Pa and the power density was 3.3 W / cm ² . Argon gas and oxygen gas were used as the gas, and the flow rate of the oxygen gas was adjusted so that an oxide film could be 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 film formation pressure was set to 0.50 Pa.

<Example 18>
As a method for forming the transparent oxide film layer 13, two cylindrical electrodes having a rotating mechanism are provided in parallel, and a voltage can be applied to each electrode alternately in positive and negative directions, and each electrode is alternately cathode. Example 2 except that a sputtering method (referred to as method C) using a magnetron sputtering apparatus acting as an anode was used and an alloy target of Si and W (atomic composition ratio Si: W = 25: 75) was used. A gas barrier laminate was obtained in the same manner as above. At this time, an MF power supply was used as a means for inputting power to the two electrodes. At that time, a rectangular voltage having a frequency of 40 kHz was applied to two electrodes located in parallel. As the gas, argon gas and oxygen gas were used. At this time, the flow rate of oxygen gas is controlled by detecting the emission intensity of plasma and the voltage value of discharge so that the state of the target surface becomes a transition state in which the transition from the metal mode to the oxide mode is in progress. did. As the film forming conditions, the film forming pressure was 0.30 Pa and the power density was 3.3 W / cm ² .

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

<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 in the same manner as in Example 1 except that argon gas, oxygen gas, and nitrogen gas were used as the introduction gas under the sputtering conditions.

<Comparative example 1>
A gas barrier laminate was obtained in the same manner as in Example 1 except that a target formed from 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.). At that time, composition analysis was repeated 4 times or more in the depth direction of the vapor-deposited film with Ar ions, and the average was calculated to calculate Si / (Si + A) and O / (Si + A). In addition, when tungsten (W) was contained as the Group 6 element (A), it was affected by reduction by Ar ions, so the composition of the outermost surface was analyzed.

[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 by an ellipsometer (VUV-VASE) manufactured by JA Woolam Co., Ltd.

[Measurement of light absorption rate of transparent oxide film layer of gas barrier laminate]
The light absorption rate of the gas barrier laminates produced in Examples 1 to 19 and Comparative Examples 1 to 5 was measured by 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 surfaces of the gas barrier laminates prepared in Examples 1 to 19 and Comparative Examples 1 to 5 was measured by a scanning probe microscope (AFM5400L) manufactured by Hitachi High-Tech Science. At that time, the arithmetic mean roughness was analyzed from the image obtained by observing a range of 1 μm square per field of view.

[Measurement of gas barrier property of gas barrier laminate]
The gas barrier laminates produced in Examples 1 to 23 and Comparative Examples 1 to 5 were subjected to a water vapor transmittance meter (AQUATRAN-ModelII) manufactured by MOCON in the United States using a method according to JIS-K7129. , 40 ° C. 90% RH (temperature 40 ° C., relative humidity 90%), the water vapor transmittance (g / m ² · day) was measured. Helium permeability ^{(cc / (m 2 · day} · atm)) and neon transmittance ^{(cc / (m 2 · day} · atm)) 40 ℃ for using the differential pressure method pursuant to JIS K 7126A method in 0RH% , Measured with a pressure sensor type gas measuring device (Delta Palm DP-2MST) manufactured by Technolux.

[Measurement result]
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 Examples 1 and 20 to 23. Shown.

Comparing Example 1 corresponding to the first embodiment with Comparative Examples 1 to 4, the target and the transparent oxide film layer 13 containing Si and W as metal elements are the targets of Example 1. Comparative Example 1 containing only Si as a metal element in the element and the transparent oxide film layer 13, Comparative Example 2 containing only W, Comparative Example 3 containing only 5% of Si, and Si containing Si and Mo. From Comparative Example 4, which has a content of only 10%, good results were obtained in terms of water vapor permeability, helium transmittance, and neon transmittance.

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

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

Comparing Examples 13 to 17 and Comparative Example 5 in which the sputtering method is Method B corresponding to the second embodiment, the target and the transparent oxide film layer 13 contain Si and W as metal elements. From Comparative Example 5 containing Si and Sn, better results were obtained in terms of water vapor permeability, helium transmittance, and neon transmittance.

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

Examples 4 and 5 corresponding to the third embodiment are as good as Example 2 corresponding to the second embodiment in which the overcoat layer is laminated but the overcoat layer is not laminated. Results of water vapor permeability, helium permeability and neon permeability were obtained.

In Examples 20 to 22, a target containing only Si and a metal element other than the Group 6 element was used as the target metal element, but a target containing only Si and the Group 6 element was used as the target metal element. Similar to Example 1, good water vapor permeability, helium permeability and neon permeability results were obtained.

In Example 23, nitrogen gas was used at the same time as oxygen gas as the reaction gas in the sputtering process, but as in Example 1 in which only oxygen gas was used as the reaction gas in the sputtering process, good water vapor transmission rate and helium were used. Results for transmission and neon transmission were obtained.

Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and is included in the present invention even if there are changes within a range that does not deviate from the gist of the present invention.

The gas barrier laminate according to the present invention is expected to be particularly preferably used in the field of electronic device-related members and the like when high gas barrier properties are required.

11 ... Resin base material 12 ... Undercoat layer 13 ... Transparent oxide film layer 14 ... Overcoat layer

Claims (20)

A resin base material 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 base material are provided, and the measurement conditions are 40 ° C. and 90% R. .. H. A gas barrier laminate having a water vapor permeability of 0.01 g / (m ² · day) or less. The gas barrier laminate according to claim 1, wherein the group 6 element (A) of the transparent oxide film layer is molybdenum (Mo) or tungsten (W). The gas barrier laminate according to claim 1, wherein the group 6 element (A) of the transparent oxide film layer contains both molybdenum (Mo) and tungsten (W). Measurement conditions 40 ° C, 0% R. H. The gas barrier laminate according to any one of claims 1 to 3, wherein the helium transmittance in the above is 1200 cc / (m ² · day · atm) or less. Measurement conditions 40 ° C, 0% R. H. Neon transmittance of ^{2.0cc / (m 2 · day ·} atm) or less in the gas barrier laminate according to any one of claims 1 to 3. The ratio (Si / (Si + A)) of the number of atoms of silicon (Si) 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. The ratio (O / (Si + A)) of the number of atoms of oxygen (O) to the total number of atoms of silicon (Si) and the Group 6 element (A) is 0.80 or more and 3.98 or less. The gas barrier laminate according to any one of claims 1 to 5, which is 00 or less. Claimed that the refractive index n of the transparent oxide film layer is 1.45 or more and 2.00 or less, and 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. Item 6. The gas barrier laminate according to any one of Items 1 to 6. The transparent oxide film layer is 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 7, further comprising. The gas barrier laminate according to any one of claims 1 to 8, wherein the transparent oxide film layer further contains nitrogen (N). The gas barrier laminate according to any one of claims 1 to 9, 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 10, wherein the arithmetic average roughness of the surface of the transparent oxide film layer is 5.0 nm or less. An undercoat layer is further provided between the resin base material and the transparent oxide film layer, and the undercoat layer is at least a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and an electron beam curable resin. The gas barrier laminate according to any one of claims 1 to 11, which is formed from one or more. 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 the description. An overcoat layer is further provided on the outside of the transparent oxide film layer, and the overcoat layer is 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 any one of claims 1 to 13. The 14th aspect of the present invention, wherein the overcoat layer is formed by containing at least one selected from the group consisting of a water-soluble polymer having a hydroxy group, an alkoxysilane and a hydrolyzate thereof. Gas barrier laminate. The step of forming a transparent oxide film layer by using a magnetron sputtering apparatus capable of periodically applying a voltage to an electrode, which is the method for producing a gas barrier laminate according to any one of claims 1 to 15. A method for producing a gas barrier laminate including. The gas barrier laminate according to claim 16, wherein in the step of forming the transparent oxide film layer, the magnetron sputtering apparatus applies a pulse voltage different from the voltage application during the off-time of voltage application. Production method. The method for producing a gas barrier laminate according to any one of claims 1 to 15, wherein two electrodes are located in parallel, and voltages can be alternately applied to each of the electrodes, and each of the electrodes is A method for producing a gas barrier laminate, which comprises a step of forming a transparent oxide film layer by alternately using a magnetron sputtering apparatus that plays a role of a cathode and an anode. The method for producing a gas barrier laminate according to any one of claims 1 to 15, wherein a transparent oxide film layer is formed by using a magnetron sputtering apparatus provided with a cylindrical electrode having a rotating mechanism. A method for producing a gas barrier laminate including a step. The method for producing a gas barrier laminate according to any one of claims 1 to 15, wherein the film forming pressure is set in the range of 0.05 Pa or more and 5.00 Pa or less as the film forming condition of the transparent oxide film layer. A method for producing a gas-barrier laminate, which comprises forming a film.

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