JP2013234364A - Method for producing gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a gas barrier film excellent in uniformity of gas barrier property and of transparency, especially in the width direction of a substrate.SOLUTION: A method for producing a gas barrier film includes a step of forming an inorganic layer by a physical vapor deposition method. In the method for producing the gas barrier film, the inorganic layer is formed by reacting a vapor generated by the vaporization of a vapor deposition material with a reaction gas near the substrate on the conveyor roller, the reaction gas is fed from a plurality of gas feed ports arranged in the width direction of the conveyor roller on each of the upstream and downstream sides in the direction of conveyance of the substrate on the conveyor roller, the shortest distance between the substrate on the conveyor roller and the plurality of the gas feed ports is 10 mm to 500 mm, the circumferences of the plurality of the gas feed ports on the upstream and downstream sides are shielded with shield plates 6a and 6b so as to avoid contact with the vapor, and the vapor is fed onto the substrate from the opening formed by the shield plates 6a and 6b.

Description

  The present invention relates to a method for producing a gas barrier film, and more particularly to a method for producing a gas barrier film having an inorganic layer formed by physical vapor deposition and having excellent gas barrier properties and transparency.

The gas barrier film is mainly used as a packaging material for foods and pharmaceuticals to prevent the influence of oxygen and water vapor, which can change the quality of the contents, and is formed on liquid crystal display panels and EL display panels. In order to avoid the deterioration of performance due to contact of oxygen and water vapor with the element being used, it is used as a packaging material for electronic devices and the like. In recent years, a gas barrier film may be used for reasons such as imparting flexibility and impact resistance to a portion where glass or the like has been conventionally used.
In general, such a gas barrier film uses a plastic film as a base material and forms a gas barrier thin film on one side or both sides thereof. The gas barrier film is formed by various methods such as chemical vapor deposition (CVD) and physical vapor deposition (PVD).

As a method for forming a gas barrier film by the PVD method, aluminum, silicon, silicon oxide, or the like is used as a deposition material, and this is reacted with oxygen gas on a substrate such as a plastic film, whereby the deposition material is formed on the substrate. A method of forming a gas barrier film made of the above oxide is known. In the above method, the balance between gas barrier properties and transparency of the obtained film varies depending on the degree of oxidation (hereinafter referred to as “primary oxidation”) from evaporation of the vapor deposition material to film formation. The degree of primary oxidation is controlled by the evaporation amount of the vapor deposition material, the introduction amount of oxygen gas, and the partial pressure. For example, if the amount of oxygen gas introduced is small relative to the evaporation amount of the vapor deposition material, the degree of primary oxidation will be low, and the formed film will be a dense film, and the gas barrier property will improve, but the transparency will tend to decrease. . On the other hand, when the amount of introduced oxygen gas is large, the degree of primary oxidation is increased and the transparency is improved, but the formed film becomes a rough film and the gas barrier property is lowered.
Thus, various studies have been made on a method of forming a gas barrier film having high gas barrier properties and high transparency by the PVD method. For example, in Patent Document 1, an aluminum oxide vapor deposition film is provided on a plastic film using a PVD method, and immediately after the vapor deposition film is formed, oxygen gas is supplied inline to the aluminum oxide vapor deposition film surface. A method for producing an aluminum oxide vapor-deposited film having a high barrier property and high transparency, characterized in that it is supplied and a treatment surface with the oxygen gas is provided. Further, in Patent Document 2, in a method in which a polymer resin film base material is continuously conveyed and an aluminum oxide film is continuously formed on the base material, aluminum between the base material and the deposition preventing plate does not fly. A method for producing a transparent gas barrier film in which oxygen is introduced into the space is described.

JP 2008-138290 A JP-A-5-339704

However, according to FIG. 3 disclosed in Patent Document 1, the oxygen ejection port 19 through which oxygen gas is ejected when an aluminum oxide vapor deposition film is formed is provided only at one position on the back surface of the apparatus. Since it is considered that oxygen gas diffuses easily into the system, it is necessary to introduce a large amount of oxygen gas. Furthermore, it is expected that the gas barrier property and transparency within the same plane of the obtained deposited film will vary.
Patent Document 2 aims to stably produce a film having particularly high transparency and excellent gas barrier properties. According to the drawings disclosed in Patent Document 2, the introduction position of oxygen gas is based on the position. Since there is only one place in the width direction of the material, there is a problem that concentration distribution of oxygen gas occurs in the width direction of the base material, and variations in gas barrier properties and transparency occur in the width direction of the obtained gas barrier film. .

  The problem to be solved by the present invention is to solve the above-mentioned problems of the prior art, and has high gas barrier properties and transparency, in particular, uniformity of gas barrier properties and transparency in the width direction of the substrate. The object is to provide a method for producing an excellent gas barrier film.

The present invention
[1] In the method for producing a gas barrier film having a step of forming an inorganic layer by physical vapor deposition on at least one surface of a substrate that is continuously conveyed by a conveying roll, the inorganic layer is made of a vapor deposition material. The reaction gas is formed in the vicinity of the base material on the transport roll, and the reaction gas is formed on the upstream side and the downstream side in the transport direction of the base material on the transport roll. Respectively supplied from a plurality of gas supply ports arranged in the width direction of the transport roll, the shortest distance between the base material on the transport roll and the plurality of gas supply ports is 10 mm or more and 500 mm or less, and upstream The plurality of gas supply ports on the side are shielded by an upstream shielding plate so as not to contact the steam, and the plurality of downstream gas supply ports are shielded by a downstream shielding plate so as not to contact the steam. Shielded Cage, the steam is characterized in that it is supplied on the substrate from the shield plate and the opening formed by the downstream and the upstream side of the shielding plate, a method of manufacturing a gas barrier film,
About.

  According to the present invention, it is possible to provide a gas barrier film having high gas barrier properties and transparency, and particularly excellent gas barrier properties and transparency uniformity in the width direction of the substrate. Such a gas barrier film is useful as a packaging material such as food and pharmaceuticals, a packaging material such as an electronic device, a solar cell member, an electronic paper member, and an organic EL (electroluminescence) member.

It is a cross-sectional schematic diagram parallel to the conveyance direction of a base material which shows the structure of an example of the physical vapor deposition apparatus used for this invention. It is a cross-sectional schematic diagram parallel to the width direction of a base material which shows the structure of an example of the physical vapor deposition apparatus used for this invention. It is a plane schematic diagram which shows the structure of an example of the gas supply port used for this invention. It is the elements on larger scale of the cross-sectional schematic diagram parallel to the conveyance direction of a base material which shows the structure of an example of the physical vapor deposition apparatus used for this invention. It is a cross-sectional schematic diagram parallel to the conveyance direction of a base material which shows the structure of the physical vapor deposition apparatus of the comparative example 2.

  Hereinafter, the present invention will be described in more detail. The present invention relates to a method for producing a gas barrier film having a step of forming an inorganic layer by physical vapor deposition on at least one surface of a substrate that is continuously conveyed.

<Physical vapor deposition system>
FIG.1 and FIG.2 is a schematic diagram which shows a structure of an example of the physical vapor deposition apparatus 100 used for this invention. The physical vapor deposition apparatus 100 includes a vacuum chamber 10, which includes a transport roll 21, an upstream roll 22, a downstream roll 23, a vapor deposition material 3, a plurality of upstream gas supply ports 5 a, and a plurality of downstream streams. Gas supply port 5b, upstream shielding plate 6a and downstream shielding plate 6b. The vacuum chamber 10 is divided into a base material transfer chamber 11 and a vapor deposition chamber 12 by partition walls 13a and 13b.

The substrate transport chamber 11 includes a transport roll 21, an upstream roll 22, and a downstream roll 23. In the base material transport chamber 11, the base material 1 is continuously transported by being unwound from the upstream roll 22, transported by the transport roll 21, and wound on the downstream roll 23.
In FIG. 2, illustration of a part of the base material transfer chamber 11 and illustration of a shielding plate 6a described later are omitted.

The vapor deposition chamber 12 includes a vapor deposition material 3, a plurality of upstream gas supply ports 5a, a plurality of downstream gas supply ports 5b, an upstream shielding plate 6a, and a downstream shielding plate 6b. Moreover, a part of conveyance roll 21 exists in the vapor deposition chamber 12, and an inorganic layer is formed on the base material 1 on it.
The vapor deposition material 3 is arrange | positioned by the non-contact under the base material 1 on the conveyance roll 21, as FIG. 1 shows. The shortest distance between the substrate 1 and the vapor deposition material 3 is not particularly limited, but is preferably in a range where the shortest distance is 100 mm or more and 1000 mm or less, and more preferably in a range of 200 mm or more and 600 mm or less. . Further, from the viewpoint of making the gas barrier property and transparency in the width direction of the base material uniform, it is preferable that a plurality of vapor deposition materials 3 are arranged in the width direction of the transport roll 21 as shown in FIG.
The outer diameter of the vapor deposition material 3, the number of the vapor deposition materials 3, and the like can be appropriately determined according to the length in the width direction of the substrate 1 and the distance between the substrate 1 and the vapor deposition material 3. From the viewpoint of forming a uniform film, when a plurality of vapor deposition materials 3 are arranged, it is preferable to arrange them at equal intervals.
The vapor deposition material 3 includes an inorganic substance for forming an inorganic layer, and the inorganic substance is filled in a boat-type container using a crucible or a wire feed. Steam 4 can be generated by heating this by a resistance heating method or the like. The inorganic substance will be described later.

The plurality of gas supply ports 5a on the upstream side and the plurality of gas supply ports 5b on the downstream side both have a reaction gas that reacts with the vapor 4 formed by vaporizing the vapor deposition material 3 in the vicinity of the base material 1 on the transport roll 21. To supply.
The shape of the gas supply ports 5a and 5b is not particularly limited, but may be a nozzle injection port or a through-hole penetrating the side surfaces of the gas pipes 51a and 51b. FIG. 3 is a schematic plan view showing an example of the configuration of a plurality of gas supply ports 5a. In FIG. 3, the gas supply port 5a is a through-hole penetrating the side surface of the gas pipe 51a. The gas pipe 51a has a long and substantially cylindrical shape. By introducing gas from one end, both ends, or near the center of the gas pipe 51a, the gas pipe 51a is provided near the base material 1 on the transport roll 21 from a plurality of gas supply ports 5a. Gas can be supplied. The gas supply port 5b has the same configuration as the gas supply port 5a.
The inner diameters of the gas supply ports 5a and 5b are preferably in the range of 0.1 mm or more and 5.0 mm or less from the viewpoint of increasing the gas supply rate and improving the productivity, and are 0.2 mm or more and 3.0 mm or less. The range is more preferable, and the range of 0.5 mm to 2.0 mm is even more preferable.
When the gas supply ports 5a and 5b are nozzle injection ports, the length of the nozzle is arbitrary, but from the viewpoint of increasing the gas supply rate and improving productivity, it is preferably 5 mm or more and 200 mm or less. More preferably, it is 10 mm or more and 100 mm or less.

From the viewpoint of efficiently supplying the gas to the vicinity of the base material 1 on the transport roll 21, the lengths of the gas pipes 51 a and 51 b are preferably equal to or longer than the length in the width direction of the base material 1.
The inner diameters of the gas pipes 51a and 51b are preferably in the range of 1 mm to 100 mm, and more preferably in the range of 5 mm to 50 mm. There is no restriction | limiting in particular as a material of gas piping 51a and 51b, Copper and stainless steel are mentioned, Stainless steel is preferable from the point which is hard to corrode.

The plurality of gas supply ports 5a formed in the gas pipe 51a are arranged at predetermined intervals in the longitudinal direction of the gas pipe 51a (the axial direction of the gas pipe 51a), and the plurality of gas supply ports formed in the gas pipe 51b. 5b are also arranged at predetermined intervals in the longitudinal direction of the gas pipe 51b (the axial direction of the gas pipe 51b). A plurality of gas supply ports 5 a and 5 b are arranged in the vapor deposition chamber 12 so as to be aligned in the width direction of the transport roll 21 on the upstream side and the downstream side in the transport direction of the substrate 1 on the transport roll 21. The
Here, the “predetermined interval” can be appropriately selected depending on the length in the width direction of the substrate 1, etc., but from the viewpoint of efficiently supplying the gas near the substrate 1 on the transport roll 21, The plurality of gas supply ports 5a are arranged one by one near both ends in the width direction of the substrate 1, and preferably between 1 mm and 500 mm between the two gas supply ports 5a formed near both ends, More preferably, they are arranged at equal intervals in the range of 2 mm to 250 mm. The same applies to the plurality of gas supply ports 5b.
From the viewpoint of efficiently supplying the gas near the base material 1 on the transport roll 21, the gas supply ports 5a and 5b are arranged so that the reactive gas is supplied in the direction of the transport roll 21 as shown in FIG. It is preferable. FIG. 4 is a partially enlarged view of FIG.

The shortest distance between the base material 1 on the transport roll 21 and the plurality of gas supply ports 5a on the upstream side efficiently supplies the reaction gas to the vicinity of the base material 1, and the width direction of the base material of the obtained gas barrier film From the viewpoint of making the gas barrier property and the transparency uniform in 10 mm or more and 500 mm or less, and preferably 30 mm or more and 400 mm or less. The same applies to the shortest distance between the base material 1 on the transport roll 21 and the plurality of downstream gas supply ports 5b.
Here, the shortest distance between the base material 1 on the transport roll 21 and the plurality of upstream gas supply ports 5a is located on the most upstream side of the base material 1 on the transport roll 21 on the vapor deposition chamber 12 side. The distance between the base material to be used and a plurality of gas supply ports 5a on the upstream side (or the tip of the nozzle if the gas supply port 5a is a nozzle), and the base material 1 on the transport roll 21 and a plurality of gases on the downstream side The shortest distance to the supply port 5b is a base material located on the most downstream side of the base material 1 on the transport roll 21 on the vapor deposition chamber 12 side and a plurality of downstream gas supply ports 5b (gas supply ports 5b). When the nozzle is a nozzle, it is the distance to the tip of the nozzle.

The periphery of the plurality of upstream gas supply ports 5 a is shielded by the upstream shielding plate 6 a so that the gas supply ports 5 a do not contact the vapor 4. Further, the periphery of the plurality of downstream gas supply ports 5 b is shielded by a downstream shielding plate 6 b so that the gas supply ports 5 b do not contact the vapor 4.
The shielding plate 6a has a shape extending from the downstream side of the gas supply port 5a to the vapor deposition material 3 side, and the shielding plate 6b has a shape extending from the upstream side of the gas supply port 5b to the vapor deposition material 3 side. The specific shape of the shielding plates 6a and 6b is, for example, as shown in FIG. 1, having a L-shaped cross section in the conveying direction of the substrate 1, or a substantially semicircular cross section. Etc. are preferred.
The length in the longitudinal direction of the upstream shielding plate 6a is preferably equal to or longer than the length of the gas pipe 51a from the viewpoint of suppressing contamination of the plurality of gas supply ports 5a and the gas pipe 51a. The length of the shielding plate 6b in the longitudinal direction is preferably equal to or longer than the length of the gas pipe 51b from the viewpoint of suppressing contamination of the plurality of gas supply ports 5b and the gas pipe 51b.
There is no restriction | limiting in particular as a material of shielding board 6a and 6b, Copper, iron, aluminum etc. are mentioned, From the viewpoint of heat exchange with the particle | grains which consist of the vapor deposition material 3, copper is preferable.

In the present invention, the plurality of gas supply ports 5a and 5b are arranged as described above, and the shielding plates 6a and 6b are provided as described above, thereby increasing the reaction gas concentration in the vicinity of the substrate 1 and increasing the reaction gas concentration. It can be made uniform with respect to the conveyance direction and the width direction of the substrate 1. Thereby, in the reaction of the vapor | steam 4 which reached | attained the base material 1, and reaction gas, since the degree of reaction with the vapor | steam 4 can be made constant, the gas barrier film obtained has both high gas barrier property and transparency. In addition, the uniformity in the width direction of gas barrier properties and transparency can be improved.
In addition, since the reaction gas can be supplied only to the vicinity of the substrate 1, the reaction gas can be prevented from diffusing into the vapor deposition chamber 12, the amount of reaction gas supply can be reduced, and the vapor 4 reaches the substrate 1. It is possible to avoid contamination of the inside of the vapor deposition chamber 12 by reacting with the reaction gas before the deposition.

The vapor 4 obtained by vaporizing the vapor deposition material 3 is supplied onto the substrate 1 from the opening 61 formed by the upstream shielding plate 6a and the downstream shielding plate 6b, and the reaction gas is reacted on the substrate 1. It reacts with and vapor-deposits, and an inorganic layer is formed.
The width of the opening 61 (a in FIG. 4) is appropriately selected within a range that is less than the length in the transport direction of the portion existing in the vapor deposition chamber 12 of the transport roll 21, but the width of the opening 61 relative to the outer diameter of the vapor deposition material 3. The width (the width of the opening 61 / the outer diameter of the vapor deposition material 3) is preferably in the range of 0.5 to 2.0, and more preferably in the range of 0.8 to 1.2. When the width of the opening 61 is in the above range, there is an effect that an inorganic layer is formed only by the vapor 4 (vapor deposition particles) having high kinetic energy.

Moreover, the physical vapor deposition apparatus 100 used for this invention is normally provided with the exhaust port 7 from a viewpoint which suppresses that the gas supplied to base-material 1 stays and concentration distribution arises. At least one exhaust port 7 may be provided at an arbitrary location in the vapor deposition chamber 12, but as shown in FIG. 2, the exhaust port 7 is below the vapor deposition material 3 and the width direction of the transport roll 21. It is preferable to arrange a plurality of the Thereby, since it can suppress that gas concentration distribution arises in the base-material 1 vicinity and can make gas concentration uniform with respect to the width direction of the base material 1, gas-barrier property and transparency with respect to the width direction of the base material 1 can be performed. Can form a uniform film.
When a plurality of exhaust ports 7 are arranged, from the viewpoint of forming a film having a uniform gas barrier property and transparency in the width direction of the substrate 1 and from the viewpoint of exhausting the space on the inner wall side of the vapor deposition chamber 12. As shown in FIG. 2, when one exhaust port 7 is arranged at least at both ends in the width direction of the transport roll 21 and three or more exhaust ports 7 are arranged, it is preferable to arrange them at equal intervals. .
A vacuum exhaust device (not shown) such as a vacuum pump is connected to the exhaust port 7.

[Method for producing gas barrier film]
The method for producing a gas barrier film of the present invention was formed by physical vapor deposition on at least one surface of the substrate 1 continuously conveyed, preferably by vacuum vapor deposition, using the physical vapor deposition apparatus 100 described above. A step of forming an inorganic layer (hereinafter also referred to as “PVD inorganic layer”).
The inorganic layer is composed of vapor 4 formed by vaporizing the vapor deposition material 3 and reaction gas supplied from a plurality of upstream gas supply ports 5a and a plurality of downstream gas supply ports 5b on a transport roll 21. It is formed by reacting in the vicinity of the substrate 1.
Examples of the reaction gas include at least one selected from oxygen, nitrogen, ammonia, ozone, and argon, and two or more kinds may be used in combination.

In the method for producing a gas barrier film of the present invention, in order to form a dense PVD inorganic layer, it is preferably performed under reduced pressure while continuously transporting the substrate 1. The pressure for forming the PVD inorganic layer is preferably in the range of 1 × 10 ⁻⁷ to ¹ Pa, more preferably in the range of 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ Pa, from the viewpoints of vacuum exhaust capability and barrier properties. The range is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² Pa. If it is in the said range, sufficient gas barrier property will be acquired, and it will be excellent also in transparency, without generating a crack and peeling in a PVD inorganic layer.
In the case of forming a PVD inorganic layer made of an inorganic oxide, the oxygen partial pressure is preferably in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ Pa from the viewpoint of gas barrier properties and transparency. More preferably, the pressure is in the range of ^-5 to 1 × 10 ^-2 Pa.
The conveyance speed of the substrate 1 is preferably 100 m / min or more, more preferably 100 to 500 m / min, from the viewpoint of productivity and formation of a dense thin film.

The thickness of the PVD inorganic layer formed on the substrate 1 by the method of the present invention is preferably from 0.1 nm to 500 nm, more preferably from 10 nm to 500 nm, still more preferably from the viewpoint of gas barrier properties and productivity. They are 10 nm or more and 100 nm or less, More preferably, they are 10 nm or more and 50 nm or less. The thickness of the PVD inorganic layer can be measured using fluorescent X-rays, and can be specifically performed by the method described later.
Examples of the inorganic substance constituting the PVD inorganic layer include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, diamond-like carbon, and oxides, carbides, nitrides, or mixtures thereof. However, from the viewpoint of gas barrier properties, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum oxide, aluminum nitride, aluminum oxynitride, aluminum oxycarbide, diamond-like carbon, etc. are preferable. More preferably, it is at least one selected from silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbonitride, aluminum oxide, and diamond-like carbon. Among these, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbonitride, and aluminum oxide are more preferable because high gas barrier properties can be stably maintained. The PVD inorganic layer may contain one kind of the inorganic substance or two or more kinds.
Silicon oxide tends to be yellowish when the degree of oxidation is low, and tends to decrease transparency. However, by using the method of the present invention, variation in the degree of oxidation can be reduced. This is preferable in that the effect of the present invention becomes more remarkable.
The silicon oxide is preferably SiOx (x is 1.3 to 1.8) from the viewpoint of gas barrier properties and transparency. By using the method of the present invention, variation in the degree of oxidation of SiOx (that is, the value of x) can be reduced, so that an inorganic layer having both excellent gas barrier properties and transparency can be formed.

<Base material>
The substrate 1 used in the present invention is not particularly limited as long as it is a plastic film that can be used for ordinary packaging materials, packaging materials such as electronic devices, solar cell members, electronic paper members, and organic EL members. Can be used. Specific examples of the resin constituting the plastic film include polyolefins such as homopolymers or copolymers such as ethylene, propylene, and isobutene, amorphous polyolefins such as cyclic polyolefins, polyethylene terephthalate, and polyethylene-2,6. -Polyester such as naphthalate, nylon 6, nylon 66, nylon 12, polyamide such as copolymer nylon, polyvinyl alcohol, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyether Examples include sulfone, polyether ether ketone, polycarbonate, polyarylate, fluororesin, acrylic resin, and biodegradable resin such as polylactic acid. Furthermore, polyester, polyamide, and polyolefin are preferable from the viewpoint of film strength and cost, and polyethylene terephthalate (PET) and polyethylene-2,6-naphthalate (PEN) are preferable from the viewpoint of surface smoothness, film strength, heat resistance, and the like. Particularly preferred are the polyesters.
The resin content in the plastic film is preferably 50 to 100% by mass.
The base material is a known additive, for example, an antistatic agent, a light blocking agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer such as a light stabilizer, a lubricant, a crosslinking agent, An anti-blocking agent, an antioxidant, etc. can be contained.
The plastic film as the substrate 1 is formed by using the above raw materials, but may be unstretched or stretched. Moreover, either a single layer or a multilayer may be sufficient. Such a base material 1 can be produced by a conventionally known method. For example, an unstretched film that is not substantially oriented by melting raw materials with an extruder, extruding with an annular die or T-die, and quenching. Can be manufactured. Further, by using a multilayer die, a single layer film made of one kind of resin, a multilayer film made of various kinds of resins, and the like can be produced.
A film obtained by stretching this unstretched film in a uniaxial direction or a biaxial direction by a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. Can do.
The thickness of the base material 1 is usually 5 to 500 μm, preferably 10 to 200 μm, depending on its use from the viewpoint of mechanical strength, flexibility, transparency, etc. as the base material of the gas barrier laminate film of the present invention. Including a sheet-like material selected in a range and having a large thickness. Moreover, there is no restriction | limiting in particular about the width | variety and length of a film, It can select according to a use suitably.

<Vapor deposition material>
Examples of the inorganic substance used for the vapor deposition material 3 include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, carbon, etc., or oxides, carbides, nitrides, or mixtures thereof from the viewpoint of gas barrier properties. However, from the viewpoint of gas barrier properties, silicon, silicon oxide, aluminum oxide, and carbon (for example, diamond-like carbon) are preferable.
Although the said inorganic substance may be used individually by 1 type, you may use it in combination of 2 or more type.

[Gas barrier film]
The gas barrier film obtained by the production method of the present invention may have a PVD inorganic layer formed by the above-described method on at least one surface of the substrate. The PVD inorganic layer may be a single layer formed on a substrate, or may be a laminate of a plurality of layers.
From the viewpoint of improving the gas barrier properties, it is considered that it is more effective to make a plurality of types of inorganic layers multi-layered than to increase the thickness of the single inorganic layer. That is, in the case of a single layer, cracks and the like are generated in the thin film during the film formation process, and these remain and can easily cause a gas barrier property failure. On the other hand, a plurality of types of inorganic layers are sequentially formed and multilayered. In this case, it is considered that when the inorganic layer is switched, the growth of cracks generated so far is stopped, and a new film is grown therefrom, so that cracks penetrating the entire film are hardly generated.

Therefore, a multi-layered inorganic layer is preferable as the inorganic layer, and the inorganic layer formed by PVD and the inorganic layer formed by chemical vapor deposition (hereinafter referred to as “CVD inorganic layer”). ) And the like are more preferably used.
As the inorganic layer, in particular, an inorganic layer formed by PVD (hereinafter sometimes referred to as “PVD inorganic layer (1)”), a CVD inorganic layer and an inorganic layer formed by PVD (hereinafter referred to as “PVD inorganic layer ( It is preferable that the inorganic layer formed by the PVD is formed by the method of the present invention.

  Hereinafter, the gas barrier film having the PVD inorganic layer (1), the CVD inorganic layer, and the PVD inorganic layer (2) in this order on at least one surface of the substrate will be described. In addition, about the formation method of each of a PVD inorganic layer (1) and a PVD inorganic layer (2), a composition, a film thickness, etc. in this gas barrier film, it is as above-mentioned.

[Inorganic layer formed by chemical vapor deposition (CVD)]
By laminating the PVD inorganic layer (1), the CVD inorganic layer, and the PVD inorganic layer (2) in this order, the CVD inorganic layer itself hardly contributes directly to the gas barrier property. In order to exhibit a sealing effect and an anchor effect on the upper layer, the gas barrier properties are dramatically improved compared to the case where the PVD inorganic layers are simply formed thick and the PVD inorganic layers or the CVD inorganic layers are laminated. improves.
Examples of the inorganic substance constituting the CVD inorganic layer include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, diamond-like carbon, and the like, oxides, carbides, nitrides, or mixtures thereof. In view of gas barrier properties and adhesion, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum oxide, aluminum nitride, aluminum oxynitride, aluminum oxycarbide, titanium oxide, diamond-like carbon Etc. Among these, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbonitride, and aluminum oxide are more preferable because high gas barrier properties can be stably maintained. The CVD inorganic layer may contain one kind of the inorganic substance or two or more kinds.
As a raw material for forming a CVD inorganic layer made of silicon oxide or the like, for example, a silicon compound can be cited. Moreover, a titanium compound is mentioned as a raw material for CVD inorganic layer formation which consists of titanium oxide etc. If it is a compound such as a silicon compound or a titanium compound, it can be used in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent.
Examples of the silicon compound include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, die Ruaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, pro Rugyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Examples thereof include cyclotetrasiloxane, hexamethyldisiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.
Examples of the titanium compound include titanium inorganic compounds such as titanium oxide and titanium chloride, titanium alkoxides such as titanium tetrabutoxide, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate and tetramethyl titanate, Examples thereof include titanium chelates such as titanium lactate, titanium acetylacetonate, titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium ethylacetoacetate and titanium triethanolaminate.
The thickness of the CVD inorganic layer is preferably less than 20 nm as measured by a cross-sectional TEM method. By being less than 20 nm, the intermolecular force between the PVD inorganic layers acts effectively, thereby improving the adhesion. At the same time, since the production rate by the chemical vapor deposition method can be increased to the same level as that of the vacuum vapor deposition method, the production efficiency can be improved and the production equipment can be downsized and simplified, so that an inexpensive barrier film can be produced. From the above viewpoint, the thickness of the CVD inorganic layer is more preferably less than 10 nm, still more preferably less than 5 nm, and particularly preferably less than 3 nm.
Further, the lower limit of the thickness of the CVD inorganic layer is preferably 0.1 nm, more preferably 0.5 nm, as a minimum film thickness for exhibiting a sealing effect on the PVD inorganic layer. preferable. If the lower limit of the thickness is within the above range, the adhesion and gas barrier properties are good, which is preferable.
By setting the thickness of the CVD inorganic layer to 0.1 nm or more, the effect of sealing the open pores of the lower PVD inorganic layer is exhibited and the surface becomes smooth at the same time. Since the surface diffusion of the particles becomes good and the particles are deposited more densely, the barrier property is further improved.
From the above viewpoint, the thickness of the CVD inorganic layer is preferably 0.1 nm or more and less than 20 nm, more preferably 0.1 nm or more and less than 10 nm, further preferably 0.1 nm or more and less than 5 nm, It is particularly preferable that the thickness is 0.1 nm or more and less than 3 nm.
The thickness of the CVD inorganic layer can be measured by a cross-sectional TEM method using a transmission electron microscope (TEM), and specifically by the method described later.
Further, in the present invention, in the adjacent CVD inorganic layer and PVD inorganic layer, the thickness ratio (CVD inorganic layer thickness / PVD inorganic layer thickness) is 0.0001 to 0.2, more preferably 0.0005. It is preferably 0.1, particularly 0.001 to 0.1. If the CVD inorganic layer thickness is too thin compared to the PVD inorganic layer thickness, the ratio of the CVD inorganic layer to the entire inorganic layer becomes extremely small, and the characteristics of the PVD inorganic layer alone are almost unchanged, and the CVD inorganic There is a possibility that almost no effect such as sealing effect and stress relaxation by the layer can be obtained. In addition, when the CVD inorganic layer thickness is too thick compared to the PVD inorganic layer thickness, the film formation rate of the CVD method is extremely lower than that of the PVD method, and the PVD inorganic layer and the CVD inorganic layer are rolled by the Roll to Roll process. In order to form a thin film layer continuously, it is necessary to greatly reduce the conveyance speed of the base material in accordance with the CVD inorganic thin film layer having a low film formation rate, which may reduce productivity.
The surface roughness (measured by AFM) of the PVD inorganic layer is preferably about 5 nm or less, because vapor deposition particles are densely deposited, which is preferable for gas barrier properties. At this time, by setting the thickness of the CVD inorganic layer to be less than the above value, the crest portion of the vapor deposition particles is covered only very thinly while filling open vacancies in the valley portions between the vapor deposition particles (or partially). Therefore, the adhesion between the PVD inorganic layers can be further enhanced.
In order to ensure the sealing effect on the PVD inorganic layer, the CVD inorganic layer may be composed of two or more layers, and in this case, it is preferably composed of 2 to 5 layers.
Examples of the chemical vapor deposition method include plasma CVD using plasma, thermal CVD, photo CVD, MOCVD, catalytic chemical vapor deposition (Cat-CVD) in which a material gas is contact pyrolyzed using a heating catalyst. As a method for forming the CVD inorganic layer, plasma CVD is preferable because it is necessary to increase the deposition rate to achieve high productivity and to avoid thermal damage to the substrate. The formation of the CVD inorganic layer by plasma CVD is performed by evaporating the above-described raw material and introducing it into a vacuum device as a raw material gas, a direct current (DC) plasma device, a low frequency plasma device, a high frequency (RF) plasma device, a pulse wave plasma device, It can be performed by converting into plasma using a low-temperature plasma generator such as a triode plasma apparatus, a microwave plasma apparatus, a downstream plasma apparatus, a columnar plasma apparatus, and plasma assisted epitaxy. From the viewpoint of plasma stability, it is more preferable to use a radio frequency (RF) plasma apparatus.
In the present invention, the CVD inorganic layer has a carbon content measured by X-ray photoelectron spectroscopy (XPS method) of 20 at. %, Preferably 10 at. %, More preferably 5 at. %. By setting the carbon content to such a value, the surface energy of the inorganic layer is increased, and the adhesion between the inorganic layers is not hindered. Therefore, the bending resistance and peel resistance of the barrier film are improved.
The carbon content of the CVD inorganic layer is 0.5 at. % Or more, preferably 1 at. % Or more, more preferably 2 at. % Or more is more preferable. When the intermediate layer contains a small amount of carbon, the stress is efficiently relaxed, and the curl of the barrier film is reduced.
From the above points, the carbon content in the CVD inorganic layer is preferably 0.5 at. % Or more and 20 at. %, More preferably 1 at. % Or more and 10 at. %, More preferably 2 at. % Or more and 5 at. It is in the range of less than%. Here, “at.%” Indicates an atomic composition percentage (atomic%).
There is no restriction | limiting in particular as a method of achieving the carbon content measured by the said X-ray photoelectron spectroscopy (XPS method) in this invention, For example, the method achieved by selecting the raw material in CVD, a raw material, and reaction gas Examples thereof include a method of adjusting by the flow rate and ratio of (oxygen, nitrogen, etc.), a method of adjusting by the pressure during film formation and input power, and the like.
A specific method for measuring the carbon content by X-ray photoelectron spectroscopy (XPS method) is as described later.

[Formation conditions of CVD inorganic layer]
The formation of the CVD inorganic layer is preferably performed under a reduced pressure environment of 10 Pa or less and the substrate transport speed is 100 m / min or more.
That is, the pressure at the time of forming the inorganic layer by the chemical vapor deposition method (CVD method) is preferably performed under reduced pressure in order to form a dense thin film. More preferably, it is in the range of 1 × 10 ^{−2 to} 10 Pa, and more preferably 1 × 10 ^{−1 to 1} Pa. This CVD inorganic layer can be subjected to a crosslinking treatment by electron beam irradiation in order to improve water resistance and durability.
Moreover, it is preferable that the conveyance speed of a base material is 100 m / min or more from a viewpoint of productivity improvement, and it is more preferable that it is 200 m / min or more. Although there is no upper limit in particular regarding the said conveyance speed, 1000 m / min or less is preferable from a viewpoint of stability of film conveyance.

The CVD inorganic layer is formed by evaporating the raw material compound and introducing it into a vacuum apparatus as a raw material gas, and direct current (DC) plasma, low frequency plasma, high frequency (RF) plasma, pulse wave plasma, tripolar structure. It can be performed by converting into plasma with a low-temperature plasma generator such as plasma, microwave plasma, downstream plasma, columnar plasma, plasma assisted epitaxy or the like. From the viewpoint of plasma stability, a radio frequency (RF) plasma apparatus is more preferable.
In addition to the plasma CVD method, known methods such as a thermal CVD method, a Cat-CVD method (catalytic chemical vapor deposition), a photo CVD method, and an MOCVD method can be used. Among these, the thermal CVD method and the Cat-CVD method are preferable in terms of excellent mass productivity and film forming quality.

  In the production of the gas barrier film, the PVD inorganic layer (1), the CVD inorganic layer, and the PVD inorganic layer (2) are preferably continuously formed under reduced pressure from the viewpoint of gas barrier properties and productivity. In addition, from the same viewpoint as described above, it is preferable to perform the formation of the CVD inorganic layer at a transport speed of the base material of 100 m / min or more while transporting the base material for all the formation of the inorganic layer. That is, after completion of the formation of each inorganic layer, it is preferable that the pressure in the vacuum chamber is returned to the vicinity of atmospheric pressure and the vacuum is re-evacuated to perform a post-process, and the film is continuously formed in a vacuum state. .

In the present invention, after the PVD inorganic layer (1) is formed, the CVD inorganic layer and the PVD inorganic layer (2) are formed. The formation of the CVD inorganic layer and the PVD inorganic layer is further repeated once or more. You may go. That is, in the present invention, from the viewpoint of quality stability, one or a plurality of structural units composed of a CVD inorganic layer and a PVD inorganic layer are further formed on the PVD inorganic layer (1), the CVD inorganic layer and the PVD inorganic layer (2). Preferably, it has 1 to 3 units, more preferably 1 or 2 units.
In addition, when repeating formation of each said inorganic layer, it is preferable to carry out continuously under reduced pressure.
That is, in the present invention, a uniform thin film having a high gas barrier property can be obtained by the PVD inorganic layers (1) and (2). Moreover, the adhesion of each layer in the multilayered inorganic thin film can be improved by the CVD inorganic layer.

(Anchor coat layer)
The gas barrier film produced by the method of the present invention can be provided with an anchor coat layer on the base material in order to improve the adhesion between the base material and the inorganic layer formed on the base material, if necessary. preferable. The main components constituting the anchor coat layer include polyester resins, urethane resins, acrylic resins, nitrocellulose resins, silicone resins, polyvinyl alcohol resins, ethylene vinyl alcohol resins, vinyl ester resins, isocyanate groups. -Containing resins, carbodiimide resins, alkoxyl group-containing resins, epoxy resins, oxazoline group-containing resins, styrene resins, polyparaxylylene resins, etc., and these may be used alone or in combination of two or more. Also good.
From the group consisting of polyester resin, urethane resin, acrylic resin, nitrocellulose resin, silicone resin and isocyanate group-containing resin, from the viewpoint of gas barrier properties and adhesion when used as a gas barrier film as the resin. It is preferable to use at least one selected resin. Among these, at least one resin selected from the group consisting of polyester resins, urethane resins, acrylic resins, and isocyanate group-containing resins is more preferable, and polyester resins and acrylic resins are more preferable.
The molecular weight of the polymer constituting the resin is preferably a number average molecular weight of 3,000 to 50,000, more preferably 4,000 to 40,000, even more preferably from the viewpoint of gas barrier properties and adhesion. 5,000 to 30,000.

Moreover, it is preferable to mix | blend and harden | cure a hardening | curing agent to an anchor coat layer. Examples of the curing agent include isocyanate compounds.
Examples of the isocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, and aromatic polyisocyanates such as xylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene diisocyanate, tolidine diisocyanate, and naphthalene diisocyanate. Etc. From the viewpoint of gas barrier properties and adhesion, a polyisocyanate having two or more isocyanate groups is preferable, and a polyisocyanate having three or more isocyanate groups is more preferable.

  In addition, various known additives can be blended in the anchor coat layer. Examples of such additives include aqueous epoxy resins, alkyl titanates, antioxidants, weathering stabilizers, UV absorbers, antistatic agents, pigments, dyes, antibacterial agents, lubricants, inorganic fillers, antiblocking agents, and the like. be able to.

The thickness of the anchor coat layer provided on the substrate is usually 0.1 to 5000 nm, preferably 1 to 2000 nm, more preferably 1 to 1000 nm. If it is within the above range, the slipperiness is good, there is almost no peeling from the base material due to the internal stress of the anchor coat layer itself, and a uniform thickness can be maintained, and also in the adhesion between layers Are better.
Moreover, in order to improve the applicability | paintability and adhesiveness of the anchor coating agent to a base material, you may perform surface treatments, such as normal chemical treatment and electrical discharge treatment, before a base material's application | coating.

(Formation of protective layer)
Moreover, in the manufacturing method of the gas barrier film of this invention, it is preferable to perform the process of forming a protective layer in the uppermost layer in the side in which each said inorganic layer was formed.
Specific examples of the protective layer include polyester resins, urethane resins, acrylic resins, vinyl alcohol resins such as polyvinyl alcohol resins and ethylene vinyl alcohol resins, ethylene-unsaturated carboxylic acid copolymers, Examples of the resin layer include vinyl ester resins, nitrocellulose resins, silicone resins, epoxy resins, styrene resins, isocyanate group-containing resins, carbodiimide group-containing resins, alkoxyl group-containing resins, and oxazoline group-containing resins. Of these, from the viewpoint of improving the gas barrier property of the inorganic layer, a resin layer of a water-soluble resin is preferable, and examples of the water-soluble resin include polyvinyl alcohol resin, ethylene vinyl alcohol resin, and ethylene-unsaturated carboxylic acid copolymer. At least one selected from coalescence is preferred. Resin used for the said protective layer may be used individually by 1 type, and may be used in combination of 2 or more type.
The protective layer contains one or more inorganic particles selected from particulate inorganic fillers and layered inorganic fillers such as silica sol, alumina sol and other inorganic oxide sols in order to improve gas barrier properties, abrasion resistance, and slipperiness. can do.
The thickness of the protective layer is preferably 0.05 to 10 μm, more preferably 0.1 to 3 μm, from the viewpoints of printability and processability. A known coating method is appropriately adopted as the formation method. For example, any method such as a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, a bar coater, or a coating method using a spray can be used. Moreover, after forming an inorganic layer, a structural unit layer, etc. in a base material, you may immerse in a coating liquid and may form a protective layer. After coating, a uniform protective layer is formed by evaporating the solvent using a known drying method such as hot air drying at a temperature of about 80 to 200 ° C., heat roll drying, or infrared drying. The

As the gas barrier film produced by the method of the present invention, from the viewpoints of gas barrier properties and adhesion between each layer, the following layer configuration embodiments (1) to (8) are preferable embodiments. In the following, for example, the notation of A / B / C indicates that layers are stacked in the order of A, B, and C from the bottom (or from the top).
(1) Base material / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer (2) Base material / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD inorganic layer / CVD inorganic layer / PVD Inorganic layer (3) Base material / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer ( 4) Substrate / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD Inorganic layer / CVD inorganic layer / PVD inorganic layer (5) substrate / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / protective layer (6) substrate / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic Layer / AC / PVD inorganic layer / VD inorganic layer / PVD inorganic layer / protective layer (7) substrate / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / protective layer (8) substrate / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / protective layer In the above embodiment, AC represents an anchor coat layer.

In the present invention, after the anchor coat layer is formed, the inorganic layer is formed, or the protective layer is formed, heat treatment is performed from the viewpoint of gas barrier properties, adhesion, stabilization of the constituent layers, and the like. Is preferred. Furthermore, it is preferable to perform the heat treatment after forming all the layers constituting the gas barrier film.
The conditions for the heat treatment vary depending on the types of components constituting the constituent layers of the gas barrier film, the thickness of the layers, and the like, but the method is not particularly limited as long as the necessary temperature and time can be maintained. For example, a method of storing in an oven or temperature-controlled room set to the required temperature, a method of blowing hot air, a method of heating with an infrared heater, a method of irradiating light with a lamp, or heating directly by contact with a hot roll or hot plate A method for imparting a microwave, a method for irradiating with a microwave, and the like can be used. Moreover, even if it heat-processes, after cutting a film into the magnitude | size which is easy to handle, it may heat-process with a film roll. Furthermore, as long as necessary time and temperature can be obtained, a heating device can be incorporated in a part of a film production apparatus such as a coater or a slitter, and heating can be performed in the production process.
The temperature of the heat treatment is not particularly limited as long as it is a temperature not higher than the heat resistance temperature of the base material, plastic film, etc. used, but it is 60 ° C. or higher because the treatment time required for the effect of heat treatment can be set appropriately. It is preferable that the temperature is 70 ° C. or higher. The upper limit of the heat treatment temperature is usually 200 ° C. or less, preferably 160 ° C. or less, from the viewpoint of preventing the gas barrier property from being lowered due to thermal decomposition of the components constituting the gas barrier film. The treatment time depends on the heat treatment temperature, and is preferably shorter as the treatment temperature is higher. For example, when the heat treatment temperature is 60 ° C., the treatment time is about 3 days to 6 months, when it is 80 ° C., the treatment time is about 3 hours to 10 days, and when it is 120 ° C., the treatment time is about 1 hour to 1 day. In the case of 150 ° C., the treatment time is about 3 to 60 minutes, but these are merely guidelines and can be appropriately adjusted depending on the type of components constituting the gas barrier film, the thickness of the constituent layers, and the like.

  Furthermore, in the gas barrier film produced by the method of the present invention, an additional layer may be laminated on the above-described configuration as required, for example, a plastic film is provided on the inorganic layer or the protective layer. Thus, a gas barrier laminated film used for various applications is obtained. The thickness of the plastic film is usually selected in the range of 5 to 500 μm, preferably 10 to 200 μm, depending on the application, from the viewpoints of mechanical strength, flexibility, transparency and the like. Moreover, there is no restriction | limiting in particular in the width | variety and length of this film, According to a use, it can select suitably. For example, by laminating a plastic film capable of heat sealing on the surface of the inorganic layer or the protective layer, it becomes a gas barrier laminated film capable of heat sealing and can be used as various containers. Examples of heat-sealable plastic films include films made of known resins such as polyethylene resins, polypropylene resins, ethylene-vinyl acetate copolymers, ionomer resins, acrylic resins, and polylactic acid. Can be mentioned.

  As another embodiment, a printing layer is formed on the inorganic layer or protective layer of the gas barrier film, and a heat seal layer is further laminated thereon. As the printing ink for forming the printing layer, a printing ink containing a water-soluble and solvent-soluble resin can be used. Here, examples of the resin used in the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate resins, and mixtures thereof. Furthermore, for printing inks, antistatic agents, light shielding agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, antifoaming agents, crosslinking agents, antiblocking agents, antioxidants, etc. These known additives may be added.

Although it does not specifically limit as a printing method for providing a printing layer, Well-known printing methods, such as an offset printing method, a gravure printing method, and a screen printing method, can be used. For drying the solvent after printing, a known drying method such as hot air drying, hot roll drying, or infrared drying can be used.
It is also possible to laminate at least one paper or plastic film between the printing layer and the heat seal layer. As the plastic film, the same resin as that used for the base material of the gas barrier film of the present invention can be used. Among these, paper, polyester resin, polyamide resin, or biodegradable resin is preferable from the viewpoint of obtaining sufficient rigidity and strength of the laminate.

  The gas barrier film produced by the method of the present invention can be used for packaging articles that require shielding of various gases such as water vapor and oxygen, such as packaging materials such as foods and pharmaceuticals, solar cells, organic EL, electronic paper, etc. This material can be suitably used as a packaging material for electronic devices.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following examples. In addition, the evaluation method of the film in the following examples is as follows.
<Film thickness of PVD inorganic layer>
Measurement of the film thickness of the inorganic layer was performed using fluorescent X-rays. This method uses the phenomenon of emitting fluorescent X-rays peculiar to atoms when they are irradiated with X-rays, and knowing the number (amount) of atoms by measuring the intensity of emitted fluorescent X-rays. Can do. Specifically, a thin film having two known thicknesses is formed on the film, the specific fluorescent X-ray intensity emitted for each is measured, and a calibration curve is created from this information. Similarly, the fluorescent X-ray intensity was measured for the measurement sample, and the film thickness was measured from the calibration curve.
<Film thickness of CVD inorganic layer>
A sample was prepared by an epoxy resin-embedded ultrathin section method, and measured with a cross-sectional TEM apparatus (JEM-1200EXII) manufactured by JEOL Ltd. under an acceleration voltage of 120 KV.
As for the thickness of the CVD inorganic layer of 10 nm or less, since it is difficult to obtain an accurate value even in the measurement by the cross-sectional TEM method, a relatively thick CVD inorganic layer of 20 nm or more formed under the same film forming conditions is used. The film forming rate per unit traveling speed was calculated by measuring by the cross-sectional TEM method, and the thickness when the film was formed at the traveling speed described in the examples was calculated.
<Carbon content of CVD inorganic layer>
Using an XPS analyzer K-Alpha manufactured by Thermo Fisher Scientific Co., Ltd., the binding energy was measured by XPS (X-ray photoelectron spectroscopy), and from the peak area corresponding to Si2P, C1S, N1S, O1S, etc. The elemental composition (at.%) Was calculated by conversion. The carbon content of the CVD inorganic layer was evaluated by reading the value of the CVD inorganic layer portion of the XPS chart.

<Yellowness (Transparency)>
The gas barrier film was divided into 6 equal parts in the width direction of the substrate to obtain 6 gas barrier films of 200 mm × 100 mm square. Next, for each gas barrier film, a yellowness meter (SD6000 manufactured by Nippon Denshoku Industries Co., Ltd.) was used to determine the yellowness by a transmission method. The average value of the obtained six yellownesses was defined as yellowness, and the difference between the maximum value and the minimum value was defined as the yellowness width direction difference.

<Water vapor transmission rate (WvTR)>
The gas barrier film was divided into 6 equal parts in the width direction of the substrate to obtain 6 gas barrier films of 200 mm × 100 mm square. Next, each gas barrier film was folded in half in the width direction so that the inorganic layer surface was on the outside, and six 100 mm × 100 mm bags with four sides sealed were prepared. Each bag is put in a constant humidity device at a temperature of 40 ° C. and a relative humidity of 90% RH, and the mass is measured from the 14th day when the water vapor transmission rate is stabilized to the 30th day at intervals of 72 hours or more. The water vapor transmission rate (g / m ² / day) was calculated from the slope of the regression line with the bag weight.
The average value of the obtained six water vapor transmission rates (g / m ² / day) was the water vapor transmission rate (g / m ² / day), and the difference between the maximum value and the minimum value was the water vapor transmission rate width difference (g / M ² / day).

Example 1
As a base material, a biaxially stretched polyethylene naphthalate film having a width of 1.2 m and a thickness of 12 μm (“Q51C12” manufactured by Teijin DuPont) was used, and an isocyanate compound (“Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.) was used on the corona-treated surface. ) And saturated polyester (“Byron 300” manufactured by Toyobo Co., Ltd., number average molecular weight 23000) were mixed at a 1: 1 mass ratio and dried to form an anchor coat layer having a thickness of 100 nm.
Next, using a physical vapor deposition apparatus having the configuration shown in FIG. 1, SiO is evaporated by a heating method under a vacuum of 8 × 10 ⁻³ Pa, and a 22 nm thick SiOx physical vapor deposition film is formed on the anchor coat layer. Formed. At this time, a gas pipe 51a having a length of 1100 mm, an inner diameter of 40 mm, and 100 through holes (gas supply ports 5a) having an inner diameter of 1 mm on the side surface at equal intervals is provided on the upstream side in the transport direction of the base material. The shortest distance from the gas supply port 5a was 70 mm. Further, a gas pipe 51b having a length of 1100 mm, an inner diameter of 40 mm, and 100 through holes (gas supply ports 5b) having an inner diameter of 1 mm on the side surface at equal intervals is provided downstream of the base material 1 and the gas pipe 51b. The shortest distance from the gas supply port 5b was 70 mm. Film formation was performed while oxygen gas partial pressure was introduced from one direction of the gas pipes 51a and 51b at 4 × 10 ⁻³ Pa to obtain a gas barrier film having an inorganic layer on one side of the substrate.
The ratio between the width of the opening 61 formed by the shielding plates 6a and 6b and the outer diameter of the vapor deposition material 3 was 3: 2. Seven crucibles filled with SiO as the vapor deposition material 3 are arranged at equal intervals in the width direction of the transport roll, and the physical vapor deposition apparatus has an exhaust port on the lower side of the vapor deposition material at two locations in the width direction of the transport roll. Arranged.
Next, a urethane adhesive (AD900 manufactured by Toyo Morton Co., Ltd.) and CAT-RT85 were blended at a ratio of 10: 1.5 on the surface of an unstretched polypropylene film (P1146 manufactured by Toyobo Co., Ltd.) having a thickness of 60 μm. Are coated and dried to form an adhesive layer having a thickness of about 3 μm, and the SiOx thin film (PVD inorganic layer) surface side of the gas barrier film is laminated on the adhesive layer to obtain a gas barrier laminated film. It was.
Said evaluation was performed about the obtained gas-barrier film and gas-barrier laminated | multilayer film. The results are shown in Table 1.

Example 2
In Example 1, except that the partial pressure of oxygen gas was changed to 6 × 10 ⁻³ Pa, a gas barrier film and a gas barrier laminated film were produced in the same manner as in Example 1, and the above evaluation was performed. . The results are shown in Table 1.

Example 3 (Production of gas barrier film having a multilayered inorganic layer)
After an inorganic layer (SiOx) having a thickness of 22 nm was formed on the substrate in the same manner as in Example 1, HMDSN (hexamethyldisilazane), nitrogen and Ar gas were mixed with each other without returning the pressure to atmospheric pressure. Introduced at a ratio of 1: 7: 7, plasma was generated at 50 kHz and 15 kW under a vacuum of 0.4 Pa, and a CVD inorganic layer (SiOCN (silicon oxycarbonitride) was formed on the inorganic layer surface (thickness: 1 nm). The substrate conveyance speed during the formation of the CVD inorganic layer was 250 m / min, and the carbon content of the CVD inorganic layer was 3 at.

Next, in the vacuum vapor deposition apparatus having the configuration shown in FIG. 1, an inorganic layer (SiOx) having a thickness of 22 nm was formed on the CVD inorganic layer in the same manner as in Example 1, thereby obtaining a gas barrier film. Furthermore, on the inorganic layer surface side of the obtained gas barrier film, a urethane-based adhesive (“Toyo Morton“ AD900 ”and“ CAT-RT85 ”blended at a ratio of 10: 1.5) was applied and dried, An adhesive resin layer having a thickness of about 3 μm was formed, and an unstretched polypropylene film having a thickness of 60 μm (“Pyrene Film-CTP 1146” manufactured by Toyobo Co., Ltd.) was laminated on the adhesive resin layer, and a gas barrier laminate film was formed. Obtained.
Said evaluation was performed about the obtained gas-barrier film and gas-barrier laminated | multilayer film. The results are shown in Table 1.

Comparative Example 1
In Example 1, except that oxygen gas was not introduced, a gas barrier film and a gas barrier laminated film were produced in the same manner as in Example 1, and the above evaluation was performed. The results are shown in Table 1.

Comparative Example 2
In Example 1, a gas barrier film and a gas barrier laminated film were produced in the same manner as in Example 1 except that a vacuum deposition apparatus having the configuration shown in FIG. 5 was used, and the above evaluation was performed. The results are shown in Table 1.
In FIG. 5, a gas pipe 52 is introduced into the vapor deposition chamber 12 from one side of the physical vapor deposition apparatus, and oxygen gas is supplied from the tip of the gas pipe 52. In addition, the shortest distance of the front-end | tip of gas piping 52 and a base material was 550 mm. Moreover, the shielding board was not used.

Comparative Example 3
In Example 3, a gas barrier film and a gas barrier laminated film were produced in the same manner as in Example 3 except that oxygen gas was not introduced, and the above evaluation was performed. The results are shown in Table 1.

  As shown in Table 1, according to the method of the present invention, it is possible to produce a gas barrier film having excellent gas barrier properties and transparency, and excellent gas barrier properties in the width direction of the substrate and uniformity of transparency. it can.

  According to the present invention, it is possible to provide a gas barrier film having high gas barrier properties and transparency, and particularly excellent gas barrier properties and transparency uniformity in the width direction of the substrate. Such gas barrier films are used for packaging articles that require shielding of various gases such as water vapor and oxygen, such as packaging materials such as food and pharmaceuticals, materials such as solar cells, organic EL, and electronic paper, and electronic devices. It can be suitably used as a packaging material.

DESCRIPTION OF SYMBOLS 1 Base material 10 Vacuum chamber 11 Base material conveyance chamber 12 Deposition chamber 13a, 13b Partition 21 Transport roll 22 Upstream roll 23 Downstream roll 3 Deposition material 4 Vapor 5a, 5b Gas supply port 51a, 51b Gas piping 6a, 6b Shielding plate 61 opening 7 exhaust port 100 physical vapor deposition equipment

Claims (9)

In the method for producing a gas barrier film having a step of forming an inorganic layer by physical vapor deposition on at least one surface of a substrate continuously conveyed by a conveyance roll,
The inorganic layer is formed by reacting vapor obtained by vaporizing a vapor deposition material and a reactive gas in the vicinity of the base material on the transport roll,
The reaction gas is supplied from a plurality of gas supply ports arranged in the width direction of the transport roll on each of the upstream side and the downstream side in the transport direction of the base material on the transport roll,
The shortest distance between the base material on the transport roll and the plurality of gas supply ports is 10 mm or more and 500 mm or less,
A plurality of upstream gas supply ports are shielded by an upstream shielding plate so as not to contact the steam, and a plurality of downstream gas supply ports are downstream shielding plates so as not to contact the steam. Is shielded by
The method for producing a gas barrier film, wherein the vapor is supplied onto the substrate from an opening formed by the upstream shielding plate and the downstream shielding plate.   The method for producing a gas barrier film according to claim 1, wherein a plurality of the vapor deposition sources are arranged in the width direction of the transport roll.   The manufacturing method of the gas-barrier film of Claim 1 or 2 which arrange | positions the said gas supply port so that the said reaction gas may be supplied to the said conveyance roll direction.   The manufacturing method of the gas-barrier film in any one of Claims 1-3 whose internal diameter of the said gas supply port is 0.2 mm or more and 3.0 mm or less.   Furthermore, the manufacturing method of the gas-barrier film in any one of Claims 1-4 which arrange | positions several exhaust port in the width direction of the said conveyance roll.   The inorganic substance constituting the inorganic layer is at least one selected from silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbonitride, aluminum oxide, and diamond-like carbon. Of producing a gas barrier film.   The manufacturing method of the gas-barrier film in any one of Claims 1-6 whose thickness of the said inorganic layer is 0.1 nm or more and 500 nm or less.   The method for producing a gas barrier film according to claim 1, wherein the reaction gas is at least one selected from oxygen, nitrogen, ammonia, ozone, and argon.   In a method for producing a gas barrier film having an inorganic layer formed by physical vapor deposition, an inorganic layer formed by chemical vapor deposition, and an inorganic layer formed by physical vapor deposition in this order on at least one surface of a substrate The manufacturing method of the gas-barrier film which forms the inorganic layer formed by this physical vapor deposition method by the method in any one of Claims 1-8.

Images