JP2013234365A - Method for producing gas barrier film - Google Patents

Abstract

The present invention provides a method for producing 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 a substrate.
In a method for producing a gas barrier film having a step of forming an inorganic layer formed by physical vapor deposition on at least one surface of a substrate that is continuously conveyed, the inorganic layer is generated from a vapor deposition source. Are arranged at predetermined intervals of the gas pipe extending 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 so that the steam is sandwiched therebetween. It is formed by reacting oxygen gas having substantially the same linear velocity supplied from a plurality of gas supply ports in the vicinity of the base material, and between the base material on the transport roll and the plurality of gas supply ports. Is a method for producing a gas barrier film, characterized in that the distance is 1 to 200 mm.
[Selection] Figure 1

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 of forming a gas barrier film by the PVD method, aluminum oxide, 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 an 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.

  On the other hand, as a method of forming a gas barrier thin film by a CVD method, for example, a method of forming a chemical vapor deposition film on a substrate by a plasma CVD method using hexamethyldisiloxane (HMDSO) is known ( Patent documents 3 to 5). In each of these conventional methods, a plasma gas is generated by introducing an inert gas for plasma generation into a vacuum chamber equipped with an electrode for plasma generation, and a source gas obtained by vaporizing HMDSO or the like in the plasma generation space. And, if necessary, a reactive gas such as oxygen gas is introduced to form a film.

  In these methods, since the source gas and the reaction gas diffuse in the plasma generation space, when forming a thin film on a continuously running substrate, a gas concentration distribution is generated in the vicinity of the substrate. There is a problem that the gas barrier property in the surface of the formed film tends to vary. In the method, the reaction product of the source gas and the reaction gas is formed on the substrate, and at the same time, the reaction product may adhere to the plasma generating electrode and contaminate the electrode. is there. If the plasma discharge becomes unstable due to this, there is a problem that the film cannot be formed for a long time or the gas barrier property of the film obtained by causing plasma damage to the substrate is lowered.

JP 2008-138290 A JP-A-5-339704 JP 2011-144438 A JP 2007-522343 A JP 2008-274385 A

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. .

In any of the methods described in the above-mentioned patent documents, since the source gas is introduced into the plasma generation space, when the film is formed by the CVD method on the continuously running base material, There arises a problem that the gas barrier property in the surface tends to vary and the plasma generating electrode is easily contaminated.
In Patent Document 3, it is described that a plurality of gas introduction pipes for introducing the processing gas may be arranged in order to distribute the processing gas evenly between the electrodes. Are arranged in the running direction of the substrate, and no mention is made of improving the uniformity of the film in the width direction of the substrate.

  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 is as follows.
[1] In the method for producing a gas barrier film having a step of forming an inorganic layer formed by physical vapor deposition on at least one surface of a substrate that is continuously conveyed, the inorganic layer is generated from a vapor deposition source. The steam and the gas pipes extending in the width direction of the transport roll are arranged at predetermined intervals on the upstream side and the downstream side in the transport direction of the base material on the transport roll so that the steam is sandwiched therebetween. It is formed by reacting oxygen gas having substantially the same linear velocity supplied from a plurality of gas supply ports in the vicinity of the base material, and between the base material on the transport roll and the plurality of gas supply ports. A method for producing a gas barrier film, wherein the distance is from 1 to 200 mm.

[2] In the method for producing a gas barrier film having a step of forming an inorganic layer by chemical vapor deposition on at least one surface of a substrate that is continuously conveyed, the inorganic layer is the substrate on a conveying roll. The source gas having substantially the same linear velocity supplied from a plurality of gas supply ports arranged at a predetermined interval of the gas pipe extending in the width direction of the transport roll on each of the upstream side and the downstream side in the transport direction of It is formed by being activated by plasma in the vicinity of the base material, reacting and forming a film on the base material, and the distance between the base material on the transport roll and the plurality of gas supply ports is 1 to 200 mm. A method for producing a gas barrier film, which is characterized in that it exists.

  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 for foods and pharmaceuticals, a packaging material for electronic devices, a member for electronic paper, a member for solar cell, and a member for organic EL (electroluminescence).

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 composition schematic diagram showing an example of gas piping used for the present 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 an example of the chemical vapor deposition apparatus used for this invention. It is a cross-sectional schematic diagram perpendicular | vertical to the conveyance direction of a base material which shows the structure of an example of the chemical vapor deposition apparatus used for this invention.

The manufacturing method of the 1st gas barrier film of this invention is a manufacturing method of the gas barrier film which has the process of forming an inorganic layer by the physical vapor deposition method on the at least one surface of the base material conveyed continuously.
Moreover, the manufacturing method of the 2nd gas barrier film of this invention is a manufacturing method of the gas barrier film which has the process of forming an inorganic layer by the chemical vapor deposition method on the at least one surface of the base material conveyed continuously. is there.
Hereinafter, each will be described in detail.

[1. First gas barrier film production method]
<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, and the vacuum chamber 10 is partitioned by a partition wall 13 into a film conveyance unit 11 located above the conveyance roll 21 and a vapor deposition unit 12 located below the conveyance roll 21. In the film transport unit 11, the substrate 1 is continuously transported by being unwound from the upstream roll 22, hung on the transport roll 21, and wound on the downstream roll 23.
In FIG. 2, illustration of the partition wall 13 and the shielding plate 6 described later is omitted.

The inorganic layer causes the vapor 4 generated from the vapor deposition source 3 to react with oxygen gas supplied from a plurality of gas supply ports 5 provided in the gas pipe 51 in the vicinity of the substrate 1 on the transport roll 21. It is formed by.
The vapor deposition source 3 is arrange | positioned non-contactingly under the base material 1 on the conveyance roll 21, as FIG. 1 shows. Although there is no restriction | limiting in particular in the distance of the base material 1 and the vapor deposition source 3, It is preferable that it is 10-500 mm, and it is more preferable that it is 30-400 mm. Further, from the viewpoint of making the gas barrier property and transparency in the substrate width direction uniform, it is preferable that a plurality of vapor deposition sources 3 are arranged in the width direction of the transport roll 21 as shown in FIG.
The diameter of the vapor deposition source 3, the number of the vapor deposition sources 3, and the like can be appropriately determined according to the width direction length of the substrate 1 and the distance between the substrate 1 and the vapor deposition source 3. From the viewpoint of forming a uniform film, when a plurality of vapor deposition sources 3 are arranged, it is preferable to arrange them at equal intervals.
Examples of the vapor deposition source 3 include a crucible filled with an inorganic substance constituting an inorganic layer and a boat type using a wire feed. The vapor 4 can be generated by heating the crucible by a resistance heating method or the like. . The inorganic substance will be described later.

The plurality of gas supply ports 5 have a width of the transport roll 21 on each of the upstream side and the downstream side in the transport direction of the base material 1 on the transport roll 21 so that the vapor 4 generated from the vapor deposition source 3 is sandwiched therebetween. They are lined up at predetermined intervals in the direction. From the viewpoint of efficiently supplying oxygen gas to the vicinity of the substrate 1 on the transport roll 21, the gas supply port 5 is preferably arranged so that oxygen gas is supplied in the direction of the transport roll 21.
Although there is no restriction | limiting in particular in the shape of the gas supply port 5, A nozzle shape may be sufficient and the through-hole which penetrates the side surface of the gas piping 51 may be sufficient.

FIG. 3 is a schematic configuration diagram showing the configuration of an example of the gas pipe 51. In FIG. 3, the gas supply port 5 is a through-hole penetrating the side surface of the gas pipe 51. The gas pipe 51 is a long and substantially cylindrical shape, and is partitioned by a partition material 52 and provided with four gas supply portions 53. Three gas supply ports 5 are formed in one gas supply unit 53.
In addition, oxygen gas can be introduced from one or both ends of the gas pipe 51, and oxygen gas can also be introduced from the back surface of the gas supply port 5 as a front surface.
In addition, the arrow in FIG. 3 shows the flow direction of gas. Further, the shape of the gas pipe 51 shown in FIG. 3, the number of the gas supply parts 53, the number of the gas supply ports 5 formed by one gas supply part 53, and the like are merely examples, and the present invention is limited to the configuration of the figure. Is not to be done.

  With such a configuration, oxygen gas can be supplied from the plurality of gas supply ports 5 to the vicinity of the substrate 1 on the transport roll 21. Further, since the gas pipe 51 is provided with a plurality of gas supply portions 53, it is easy to adjust the gas supply amount (linear speed) supplied from the gas supply port 5 substantially in the width direction of the substrate. As a result, a gas barrier film having excellent gas barrier properties and transparency uniformity in the width direction of the substrate can be produced.

There is no restriction | limiting in particular as a material of the gas piping 51, Stainless steel, copper, aluminum, etc. are mentioned, Stainless steel is preferable from the point which is hard to corrode by a reactive gas.
The inner diameter of the gas pipe 51 is preferably in the range of 0.5 to 50 mm, more preferably 1 to 20 mm. The gas supply port 5 preferably has an inner diameter of 0.1 to 5.0 mm in the case of a through hole from the viewpoint of increasing the supply rate of oxygen gas and improving productivity. More preferably, it is 0.0 mm. In the case of a nozzle shape, the inner diameter is in the range of 0.1 to 5.0 mm, preferably 0.2 to 3.0 mm, and the length is 5 to 200 mm, preferably 10 to 100 mm.

The distance between the base material 1 on the transport roll 21 and the plurality of gas supply ports 5 is such that the source gas and the reactive gas are efficiently supplied in the vicinity of the base material 1, and the gas barrier property of the film in the base material width direction is increased. From a viewpoint of making it uniform, it is 1-200 mm, and it is preferable that it is 2-100 mm.
Further, from the viewpoint of suppressing the contamination of the electrode 3 by the reactant of the source gas and the reactant gas, the gas supply port 5 is near the inner side wall of the deposition chamber 12 in the source gas introduction part 14 partitioned by the shielding plate 6a. It is preferable to arrange in.
FIG. 4 is a partially enlarged view of FIG. Among the plurality of gas supply ports 5, the periphery of the plurality of gas supply ports 5a on the upstream side is such that the oxygen gas supplied from the gas supply port 5a does not come into contact with the vapor 4 at and near the supply port 5a. It is preferably shielded by a shielding plate 6a extending from the downstream side of the gas supply port 5a to the vapor deposition source 3 side. Further, the periphery of the plurality of gas supply ports 5b on the downstream side is upstream of the gas supply port 5b so that oxygen gas supplied from the gas supply port 5b does not come into contact with the supply port 5b and the vapor 4 in the vicinity thereof. Is shielded by a shielding plate 6b extending from the evaporation source 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.
There is no restriction | limiting in particular as a material of shielding board 6a and 6b, Copper, iron, aluminum, etc. are mentioned, Copper is preferable from a viewpoint of heat exchange with vapor deposition particle | grains.

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 oxygen gas concentration in the vicinity of the substrate 1 and increasing the oxygen gas concentration. It can be made uniform with respect to the conveyance direction and the width direction of the substrate 1. Accordingly, the degree of oxidation of the vapor 4 can be made constant during the reaction between the vapor 4 that reaches the substrate 1 and oxygen gas, so that the obtained gas barrier film has both high gas barrier properties and transparency. And the uniformity in the width direction of the gas barrier property and transparency can be improved.
Moreover, since oxygen gas can be supplied only to the vicinity of the base material 1, the oxygen gas can be prevented from diffusing into the vapor deposition section 12, the amount of oxygen gas supply can be reduced, and the vapor 4 reaches the base material 1. It is possible to avoid contamination of the vapor deposition section 12 by reacting with oxygen gas before the deposition.

Further, as shown in FIG. 4, the vapor 4 is supplied onto the substrate 1 from the opening 61 formed by the upstream and downstream shielding plates 6 a and 6 b, and oxygen gas and Reacts to form an inorganic layer.
The width of the opening 61 (a in FIG. 4) is appropriately selected within a range less than the width of the portion existing in the vapor deposition section 12 of the transport roll 21, but the width of the opening 61 relative to the diameter of the vapor deposition source 3 (opening section). 61 / diameter of the vapor deposition source 3) is preferably 0.5 to 2.0, and more preferably 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 vapor-deposited particles having high kinetic energy.

Further, in the physical vapor deposition apparatus 100 used in the present invention, the installation position of the exhaust port 7 for performing vacuum exhaust is set from the viewpoint of suppressing the concentration of oxygen gas supplied in the vicinity of the base material 1 and the concentration distribution. It is preferable to provide in consideration. At least one exhaust port 7 may be provided at an arbitrary position of the vapor deposition unit 12, but as shown in FIG. 2, the exhaust port 7 is below the vapor deposition source 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 oxygen gas concentration distribution arises in the base material 1 vicinity, and oxygen gas concentration can be made uniform with respect to the width direction of the base material 1, gas-barrier property with respect to the width direction of the base material 1 and A film with uniform transparency can be formed.
When a plurality of exhaust ports 7 are arranged, it is preferable to arrange them at regular intervals from the viewpoint of forming a film having uniform gas barrier properties and transparency in the width direction of the substrate 1.

<Method for producing gas barrier film>
The method for producing a gas barrier film of the present invention uses an inorganic layer (hereinafter referred to as “PVD inorganic”) formed by physical vapor deposition on at least one surface of a substrate 1 that is continuously conveyed using the physical vapor deposition apparatus 100 described above. A step of forming a layer).

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. It 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.

The oxygen partial pressure when forming the PVD inorganic layer is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ Pa from the viewpoint of gas barrier properties and transparency, and 1 × 10 ⁻⁵ to 1 × 10 ^−. More preferably, it is under reduced pressure in the range of ² Pa.
Here, in this invention, the linear velocity of the oxygen gas supplied from each supply shall be substantially the same. Thereby, the gas barrier film excellent in the gas barrier property in the width direction of a base material and the uniformity of transparency can be manufactured.
As substantially the same meaning, it is preferable that the linear velocity from each supply port is in a range of ± 30% of A (A ± 0.3 A) when the average A of the linear velocity from each supply port is taken as A. More preferably, it is in the range of ± 20% of A (A ± 0.2A).
In order to make them substantially the same, in the case of FIG. 3, the partial pressure (flow rate) from the side surface side is made larger than the partial pressure (flow rate) from the back side, and the linear velocity of the gas from each gas supply unit is You may adjust so that it may be in the range.

  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.

From the viewpoint of gas barrier properties and productivity, the thickness of the PVD inorganic layer formed on the substrate 1 by the method of the present invention is preferably 0.1 to 500 nm, more preferably 10 to 500 nm, still more preferably 10 to 10 nm. It is 100 nm, more preferably 10 to 50 nm. 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. . 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. Further, from the viewpoint of gas barrier properties and transparency, SiOx (x is 1.3 to 1.8) is particularly preferable. 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>
As the substrate 1 used in the present invention, a plastic film is preferable. The raw material can be used without particular limitation as long as it is a resin that can be used for ordinary packaging materials, electronic paper, and solar cell materials. Specifically, polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene, amorphous polyolefins such as cyclic polyolefin, polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate, nylon 6, nylon 66, polyamide such as nylon 12, copolymer nylon, polyvinyl alcohol, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate, Examples include polyvinyl butyral, polyarylate, fluororesin, acrylic resin, and biodegradable resin. Among these, polyester, polyamide, polyolefin, and biodegradable resin are preferable from the viewpoint of film strength and cost, and polyethylene terephthalate (PET) and polyethylene-2 are preferable from the viewpoint of surface smoothness, film strength, heat resistance, and the like. Polyester such as 1,6-naphthalate (PEN) is particularly preferred.
In addition, the substrate 1 is a known additive such as an antistatic agent, a light blocking agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer, a lubricant, a crosslinking agent, an antiblocking agent, an oxidation agent. An inhibitor or the like can be contained.

  The plastic film as the substrate 1 is formed by using the above-mentioned raw materials, but when used as a substrate, it may be unstretched or stretched. Moreover, either a single layer or a multilayer may be sufficient. Such a substrate 1 can be produced by a conventionally known method. For example, the raw material is melted by an extruder, extruded by an annular die or a T die, and rapidly cooled to be substantially amorphous and not oriented. An unstretched film can be manufactured. The unstretched film is subjected to a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like. A film stretched in a uniaxial direction or a biaxial direction can be produced by stretching in a direction (horizontal axis) perpendicular thereto.

  The thickness of the substrate 1 is usually selected in the range of 5 to 500 μm, preferably 10 to 200 μm, depending on its use, from the viewpoint of mechanical strength, flexibility, transparency, etc. as the substrate. Includes large sheets. Moreover, there is no restriction | limiting in particular about the width | variety and length of the base material 1, According to a use, it can select suitably.

<Deposition source>
As an inorganic substance used for the vapor deposition source 3, silicon, aluminum, magnesium, zinc, tin, nickel, titanium, carbon, etc., or these from a viewpoint which can form the film | membrane which has gas barrier property by reacting with oxygen gas. Oxides, carbides, nitrides, or mixtures thereof may be mentioned. From the viewpoint of gas barrier properties, silicon oxide, aluminum oxide, and carbon (for example, a substance mainly composed of carbon such as diamond-like carbon) are preferable. In particular, silicon oxide and aluminum oxide are preferable in that high gas barrier properties can be stably maintained. 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.
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.
Further, the gas barrier film has an inorganic layer formed by a PVD method (hereinafter sometimes referred to as “PVD inorganic layer (1)”), an inorganic layer formed by a CVD method (hereinafter, referred to as “PVD method”) on at least one surface of the substrate. , And may be referred to as “CVD inorganic layer”) and an inorganic layer formed by PVD (hereinafter also referred to as “PVD inorganic layer (2)”) in this order. Is preferably formed by the method of the present invention.

  Hereinafter, the gas barrier film 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)]
In the gas barrier film of the present invention, a CVD inorganic layer is formed on the PVD inorganic layer (1). It is considered that defects such as defects generated in the PVD inorganic layer are sealed by the CVD inorganic layer, and gas barrier properties and interlayer adhesion are improved.
As the chemical vapor deposition method, the plasma CVD method is preferable because it is necessary to increase the film forming speed to achieve high productivity and to avoid thermal damage to the film substrate.

The CVD inorganic layer preferably has a carbon content measured by X-ray photoelectron spectroscopy (XPS method) of 20 at. %, More 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 0.5 at. % Or more and 10 at. %, More preferably 0.5 at. % Or more and 5 at. %, More preferably 1 at. % Or more and 5 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), For example, the method achieved by selecting the raw material in CVD, a raw material, and reaction gas (oxygen, For example, a method of adjusting by a flow rate and a ratio of nitrogen, etc., a method of adjusting by a pressure and an input power during film formation, and the like.
A specific method for measuring the carbon content by X-ray photoelectron spectroscopy (XPS method) is as described later.

  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 include titanium organic compounds such as titanium chelates such as titanium lactate, titanium acetylacetonate, titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium ethylacetoacetate and titanium triethanolaminate.

In order to ensure the sealing effect on the PVD inorganic layer, the CVD inorganic layer is preferably composed of two or more layers, more preferably 2 to 5 layers.
The thickness of the CVD inorganic layer is less than 20 nm as measured by a cross-sectional TEM method. By being in the above range, 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 preferably less than 10 nm, more preferably less than 5 nm, and still more preferably less than 3 nm.

Further, the lower limit value of the thickness of the CVD inorganic layer is preferably 0.01 nm, more preferably 0.1 nm, as a minimum film thickness for exhibiting a sealing effect on the PVD inorganic layer. Preferably, it is 0.5 nm. If the thickness is within the above range, the adhesion and gas barrier properties are good, which is preferable. Further, by setting the thickness of the CVD inorganic layer to 0.1 nm or more, the effect of sealing the open pores of the above-described lower PVD inorganic thin curtain layer is exhibited, and at the same time the surface becomes smooth, and the upper PVD inorganic layer is formed. When vapor deposition is performed, the surface diffusion of the vapor-deposited particles becomes good and the particles are deposited more densely, so that the barrier property is further improved.
From the above viewpoint, the thickness of the CVD inorganic layer is preferably 0.01 nm or more and less than 20 nm, more preferably 0.1 nm or more and less than 20 nm, more preferably 0.1 nm or more and less than 10 nm, It is still more preferably 0.1 nm or more and less than 5 nm, and even more preferably 0.1 nm or more and less than 3 nm.

  In the gas barrier film, the thickness ratio (CVD inorganic layer thickness / PVD inorganic layer thickness) in the adjacent CVD inorganic layer and PVD inorganic layer is 0.0001 to 0.2, more preferably 0.0005. It is preferable that it is -0.1, especially 0.001-0.1. 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 produced by the Roll to Roll process. In order to continuously form the layers, it is necessary to greatly reduce the conveyance speed of the base material in accordance with the CVD inorganic 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 the expression of 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.
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.

[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 when forming a thin film by chemical vapor deposition (CVD) is preferably performed under reduced pressure to form a dense thin film, and is preferably 10 Pa or less, more preferably from the viewpoint of film formation speed and barrier properties. 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.

  As described later, the gas barrier film has a laminated structure in the order of the PVD inorganic layer (1), the CVD inorganic layer, and the PVD inorganic layer (2), so that the CVD inorganic layer itself hardly contributes directly to the gas barrier property. However, for the PVD inorganic layer, the lower layer exhibits a sealing effect and the upper layer exhibits an anchor effect. Therefore, when the PVD inorganic layer is simply formed thick, the PVD inorganic layers or the CVD inorganic layers are laminated. Compared with the case, the gas barrier property is dramatically improved.

  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 substrate of 100 m / min or more, particularly while transporting the film, preferably transporting the film. That is, after the formation of each thin film, the pressure in the vacuum chamber is returned to the vicinity of the atmospheric pressure, and the subsequent process is not performed again by evacuation, but it is preferable to continuously perform film formation 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 multilayer film of the inorganic thin film can be improved by forming the CVD inorganic layer.

(Anchor coat layer)
In this invention, in order to improve the adhesiveness of the said base material and PVD inorganic layer (1), it is preferable to provide an anchor coat layer between a base material and PVD inorganic layer (1) as needed. 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.

(Protective layer)
Moreover, it is preferable that the gas barrier film of this invention forms 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

[Configuration of gas barrier film]
As a structure of the said gas barrier film, the following aspects can be used preferably from the point of gas barrier property and adhesiveness.
In the following description, for example, the notation A / B / C indicates that layers A, B, and C are stacked in this order 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 / CVD inorganic layer / PVD inorganic layer (3) group Material / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer (4) substrate / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Protective layer (5) Base material / AC / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / Protective layer (6) Base material / AC / PVD inorganic layer / CVD inorganic layer / PVD Inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / protective layer

(7) Base material / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer (8) Base material / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer (9) Base material / PVD inorganic layer Layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer (10) substrate / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / protective layer (11) substrate / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / protective layer (12) substrate / PVD inorganic layer / CVD inorganic layer / PVD inorganic layer / CVD inorganic layer / 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 this invention, the various gas-barrier laminated | multilayer film which laminated | stacked the additional structural layer further on the said structural layer as needed can be used according to a use.
As a normal embodiment, a gas barrier laminate film in which a plastic film is provided on the inorganic layer or protective layer is used for various applications. The thickness of the plastic film is usually 5 to 500 μm, preferably 10 to 200 μm, depending on the application, from the viewpoints of mechanical strength, flexibility, transparency as a substrate of the laminated structure. . In addition, the width and length of the film are not particularly limited and can be appropriately selected according to the use, but in producing an industrial product using a barrier film, it is possible to produce a long product, From the viewpoint of productivity and cost advantage, such as being able to produce many products in a single process, it is desirable that the width and length of the film be long. The film width is preferably 0.6 m or more, more preferably 0.8 m or more, more preferably 1.0 m or more, and the film length is preferably 1000 m or more, more preferably 3000 m or more, more preferably 5000 m or more. Further, for example, by using a resin capable of heat sealing on the surface of the inorganic layer or the protective layer, heat sealing becomes possible, and it can be used as various containers. Examples of the resin that can be heat sealed include known resins such as polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, acrylic resin, and biodegradable resin.

  Another embodiment of the gas barrier laminate film is one in which a print layer is formed on the coated surface of the inorganic layer or the protective layer and a heat seal layer is further laminated thereon. As the printing ink for forming the printing layer, aqueous and solvent-based resin-containing printing inks 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 copolymer 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 a plastic film, the thing similar to the thermoplastic polymer film as a base material used for the gas barrier film of this 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.

[2. Second gas barrier film production method]
<Chemical vapor deposition equipment>
5 and 6 are schematic diagrams showing an example of the configuration of a chemical vapor deposition apparatus 200 that is preferably used in the present invention. The chemical vapor deposition apparatus 200 includes a vacuum chamber 10, which is introduced to generate a transport roll 21, an upstream roll 22, a downstream roll 23, a plasma generating electrode 3a, and plasma. It has a gas supply port 4, a plurality of gas supply ports 5, a gas pipe 51 provided on the upstream side and the downstream side, and shielding plates 6 a and 6 b. The vacuum chamber 10 is partitioned by a partition wall 13 into a film transfer chamber 11 above the transfer roll 21 and a vapor deposition chamber 12 below the transfer roll 21.

The film transport chamber 11 includes a transport roll 21, an upstream roll 22, and a downstream roll 23. The base material 1 is continuously conveyed by being unwound from the upstream roll 22, hung on the conveyance roll 21, and wound on the downstream roll 23.
In FIG. 6, illustration of a part of the film transport chamber 11 is omitted.

The vapor deposition chamber 12 includes an electrode 3a for plasma generation, a supply port 4 for an inert gas introduced to generate plasma, a gas pipe 51 provided on the upstream side and the downstream side, and shielding plates 6a and 6b. Is provided.
The vapor deposition chamber 12 is partitioned into a source gas introduction part 14 and a plasma generation part 15 by shielding plates 6a and 6b. The source gas introduction unit 14 includes gas pipes 51 on the upstream side and the downstream side. The plasma generation unit 15 includes a plasma generation electrode 3a and an inert gas supply port 4, and is “a space where an inert gas for generating plasma is introduced to generate plasma”.

Examples of the plasma generating electrode 3a provided in the plasma generating unit 15 include a parallel plate method, a dual magnetron method, and a roll electrode in which the transport roll 21 serves as a counter electrode. It is preferable to use a magnetron type electrode.
The inert gas supply port 4 is normally disposed in the vicinity of the plasma generating electrode 3a, and plasma is generated in the plasma generating unit 15 by supplying an inert gas such as argon to the vicinity of the electrode 3a.

Each of the plurality of upstream gas supply ports 5 and the plurality of downstream gas supply ports 5 provided in the source gas introduction unit 14 is a source gas for forming an inorganic layer and a reaction used as necessary. It supplies gas.
Here, it is preferable to use the gas pipe 51 shown in FIG. 3, and the plurality of gas supply ports 5 may be nozzle-shaped or may be through holes penetrating the side surface of the gas pipe 51. .

  From the viewpoint of efficiently supplying the raw material gas and the reactive gas to the vicinity of the base material 1 on the transport roll 21, the length of the gas pipe 51 is preferably equal to or longer than the length in the width direction of the base material 1.

The plurality of gas supply ports 5 formed in the gas pipe 51 are arranged at predetermined intervals in the width direction of the transport roll 21 on the upstream side of the transport roll 21 in the transport direction of the base material 1 on the transport roll 21. . In addition, the plurality of gas supply ports 5 formed in the other gas pipe 51 are provided in the width direction of the transport roll 21 on the downstream side of the transport roll 21 in the transport direction of the base material 1 on the transport roll 21. They are lined up at intervals.
Here, the “predetermined interval” can be appropriately selected according to the length of the substrate 1 in the width direction.
From the viewpoint of efficiently supplying the source gas and the reactive gas to the vicinity of the base material 1 on the transport roll 21 and preventing contamination in the deposition chamber by the reactants of the source gas and the reactive gas, the plurality of gas supply ports 5 are gas It is preferable to arrange the injection port so as to be directed to the transport roll 21 and to be horizontal.

The distance between the base material 1 on the transport roll 21 and the plurality of gas supply ports 5 is such that the source gas and the reactive gas are efficiently supplied in the vicinity of the base material 1, and the gas barrier property of the film in the base material width direction is increased. From the viewpoint of uniformity, it is in the range of 1 to 200 mm, preferably 2 to 100 mm.
Further, from the viewpoint of suppressing the contamination of the electrode 3a by the reactant of the source gas and the reactant gas, the gas supply port 5 is near the side wall inside the vapor deposition chamber 12 in the source gas introduction part 14 partitioned by the shielding plate 6a. It is preferable to arrange in.

The gas supply port 5 on the upstream side is at least a plasma generation unit 15 so as not to contact a space (that is, the plasma generation unit 15) in which an inert gas for generating plasma is introduced and plasma is generated in the vapor deposition chamber 12. The side is shielded by the shielding plate 6a. As the shape of the shielding plates 6a and 6b, for example, as shown in FIG. 5, a shape extending horizontally from the inner side wall of the vapor deposition chamber 12 toward the center is preferable. The shielding plates 6a and 6b may be in contact with the inner diameter of the vacuum chamber 10 or may be separated as appropriate.
There is no restriction | limiting in particular as a material of shielding board 6a and 6b, Stainless steel, aluminum, etc. are mentioned, Aluminum is preferable from a viewpoint of plasma stability.
The inner diameter of the gas pipe 51 is preferably in the range of 0.5 to 50 mm, more preferably 1 to 20 mm. The gas supply port 5 preferably has an inner diameter of 0.1 to 5.0 mm in the case of a through hole from the viewpoint of increasing the supply rate of oxygen gas and improving productivity. More preferably, it is 0.0 mm. In the case of a nozzle shape, the inner diameter is in the range of 0.1 to 5.0 mm, preferably 0.2 to 3.0 mm, and the length is 5 to 200 mm, preferably 10 to 100 mm.

In the present invention, by arranging the plurality of gas supply ports 5 as described above and further providing the shielding plates 6a and 6b as described above, the concentration of the source gas and the reaction gas in the vicinity of the substrate 1 is increased, and the gas concentration Can be made uniform with respect to the conveying direction and the width direction of the substrate 1. Thereby, the uniformity in the width direction of the gas barrier property of the obtained film is improved.
Further, by providing a shielding plate so that the source gas and the reaction gas do not enter the plasma generation space, it is possible to suppress contamination of the electrode 3a with the reactant of the source gas and the reaction gas. As a result, plasma discharge is stabilized, film formation can be performed for a long time, plasma damage to the substrate 1 can be suppressed, and a gas barrier film having high gas barrier properties can be produced.

Further, as shown in FIG. 5, the plasma generated in the vicinity of the electrode 3a is supplied to the vicinity of the substrate 1 from the opening 61 formed by the shielding plates 6a and 6b on the upstream side and the downstream side. The source gas and the reaction gas activated by plasma in the vicinity of the substrate 1 are formed on the substrate 1 to form an inorganic layer.
The width of the opening 61 is appropriately selected within a range that is less than the width of the portion existing in the vapor deposition chamber 12 of the transport roll 21, but the width of the opening 61 with respect to the width of the electrode 3 a is 0.05 to 1.0 is preferable, and 0.1 to 0.8 is more preferable. When the width of the opening 61 is within the above range, the plasma density of the opening 61 is increased, the reactivity of the source gas and the reaction gas is improved, and a film such as an inorganic film or an organic layer that is uniform in the width direction is formed on the substrate 1. There is an effect that it can be formed on top.

Further, the chemical vapor deposition apparatus 200 suitably used in the present invention is usually provided with an exhaust port 7. At least one exhaust port 7 may be provided at an arbitrary location in the vapor deposition chamber 12, but as shown in FIG. 6, it is preferable to arrange a plurality of exhaust ports 7 in the width direction of the transport roll 21. More preferably, an opening adjustment valve for the exhaust port is provided at the exhaust port. Thereby, since the gas concentration distribution and the degree of vacuum in the width direction can be made uniform, a film having a uniform gas barrier property with respect to the width direction of the substrate 1 can be formed. In the case where a plurality of exhaust ports 7 are arranged in the vapor deposition chamber, as shown in FIG. 6, at least in the width direction of the transport roll 21 from the viewpoint of forming a film having a uniform gas barrier property with respect to the width direction of the substrate 1. It is preferable to arrange one exhaust port 7 at each end of each. When 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. From the viewpoint of increasing the degree of vacuum in the vapor deposition chamber 12 and stabilizing the plasma discharge, a known vacuum exhaust device can be used, but a turbo molecular pump capable of powerful exhaust is preferably used.

  When forming the above-mentioned CVD inorganic layer, devices for generating plasma include direct current (DC) plasma, low frequency plasma, high frequency (RF) plasma, pulse wave plasma, tripolar structure plasma, microwave plasma, downstream plasma, Examples thereof include low temperature plasma generators such as columnar plasma and plasma assisted epitaxy. From the viewpoint of plasma stability, a radio frequency (RF) plasma apparatus is more preferable.

<Method for producing gas barrier film>
The method for producing a gas barrier film of the present invention preferably uses the above-described chemical vapor deposition apparatus 200 to form an inorganic layer (hereinafter referred to as “the chemical vapor deposition method”) on at least one surface of the substrate 1 that is continuously conveyed. A step of forming a CVD inorganic layer).

  The CVD inorganic layer is formed by supplying an inert gas such as argon from the inert gas supply port 4 provided in the vicinity of the electrode 3a of the chemical vapor deposition apparatus 200 described above, and applying it to the electrode 3a under reduced pressure to generate plasma. Plasma is generated in the part 15. In addition, source gas and reaction gas used as needed are introduced from both ends of the gas pipe 51 and the back of the gas supply port 5, and these are supplied from the plurality of gas supply ports 5 by the source gas introduction unit 14 in the vapor deposition chamber 12. These gases are supplied to the vicinity of the substrate 1 to form a CVD inorganic layer on the substrate 1 that is continuously conveyed.

The formation of the CVD inorganic layer is preferably performed under a reduced pressure environment of 1 Pa or less and the transport speed of the substrate 1 is 100 m / min or more.
That is, the pressure when forming a thin film by chemical vapor deposition (CVD) is preferably performed under reduced pressure in order to form a dense thin film, and is preferably 1 Pa or less, more preferably from the viewpoint of film formation speed and barrier properties. 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 the base material 1 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 about the said conveyance speed, 1000 m / min or less is preferable from a viewpoint of stability of base material conveyance.

As an inorganic substance which comprises a CVD inorganic layer, the thing similar to the manufacturing method of a 1st gas barrier film can be applied.
From the viewpoint of the uniformity of the inorganic layer, the flow rate of the source gas supplied when forming the CVD inorganic layer is preferably a partial pressure of 1 × 10 ^{−2 to} 10 Pa, and a partial pressure of 1 × 10 ^{−1 to 1} Pa. It is more preferable that
Here, in this invention, the linear velocity of the oxygen gas supplied from each supply shall be substantially the same. Thereby, the gas barrier film excellent in the gas barrier property in the width direction of a base material and the uniformity of transparency can be manufactured.

As substantially the same meaning, it is preferable that the linear velocity from each supply port is in a range of ± 30% of A (A ± 0.3 A) when the average A of the linear velocity from each supply port is taken as A. More preferably, it is in the range of ± 20% of A (A ± 0.2A).
In order to make them substantially the same, in the case of FIG. 3, the partial pressure (flow rate) from the side surface side is made larger than the partial pressure (flow rate) from the back side, and the linear velocity of the gas from each gas supply unit is You may adjust so that it may be in the range.

In addition to the raw material gas, a reactive gas such as nitrogen or oxygen may be used as necessary for forming the CVD inorganic layer. By using these reaction gases, a thin film having a desired degree of oxidation and / or nitridation can be formed.
The reaction gas is usually mixed with the source gas and supplied from the gas supply port b to the source gas introduction unit 14 in the vapor deposition chamber 12.

The thickness of the CVD inorganic layer formed as described above is preferably less than 20 nm as measured by a cross-sectional TEM method. By being in the above range, the production rate by chemical vapor deposition can be increased to the same level as that of physical vapor deposition, so that production efficiency is improved and manufacturing equipment can be downsized and simplified. can do. From the above viewpoint, the thickness of the CVD inorganic layer is preferably less than 10 nm, more preferably less than 5 nm, and still more preferably less than 3 nm.
Further, the lower limit value of the thickness of the CVD inorganic layer is preferably 0.01 nm, more preferably 0.1 nm, and still more preferably 0.5 nm. When the thickness is within the above range, adhesion, gas barrier properties and the like are improved. From the above viewpoint, the thickness of the CVD inorganic layer is preferably 0.01 nm or more and less than 20 nm, more preferably 0.1 nm or more and less than 20 nm, more preferably 0.1 nm or more and less than 10 nm, It is still more preferably 0.1 nm or more and less than 5 nm, and even more preferably 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.

<Base material>
As a base material used for this invention, the thing similar to the manufacturing method of a 1st gas-barrier film is applicable.

[Gas barrier film]
The gas barrier film obtained by the production method of the present invention only needs to have the CVD inorganic layer formed by the aforementioned 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.
The gas barrier film has an inorganic layer formed by PVD (hereinafter sometimes referred to as “PVD inorganic layer (1)”), an inorganic layer formed by CVD (hereinafter referred to as “hereinafter referred to as“ PVD inorganic layer (1) ”)” on at least one surface of the substrate. And an inorganic layer formed by PVD (hereinafter also referred to as “PVD inorganic layer (2)”) in this order. It is preferably formed by the method of the present invention.

Hereinafter, the gas barrier film will be described.
[Inorganic layer formed by physical vapor deposition (PVD)]
The gas barrier film preferably produced by the method of the present invention has a PVD inorganic layer (1), a CVD inorganic layer, and a PVD inorganic layer (2) in this order on at least one surface of the substrate. Examples of the inorganic substance constituting each of the PVD inorganic layers provided on the upper and lower layers of the CVD inorganic layer include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, diamond-like carbon, and oxides, carbides, and nitrides thereof. From the viewpoint of gas barrier properties, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum oxide, aluminum nitride, aluminum oxynitride, oxycarbonized are preferable. Aluminum, 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 PVD inorganic layer may contain one kind of the inorganic substance or two or more kinds.

For the formation of each of the PVD inorganic layers (1) and (2) on the substrate, it is preferable to use physical vapor deposition in that a uniform thin film having high gas barrier properties can be obtained.
The thickness of each of the PVD inorganic layers (1) and (2) has a lower limit of generally 0.1 nm, preferably 0.5 nm, more preferably 1 nm, particularly preferably 10 nm, and the upper limit is generally It is 500 nm, preferably 100 nm, more preferably 50 nm. The thickness of the PVD inorganic layer is preferably 0.1 or more and 500 nm or less, more preferably 10 nm or more and 500 nm or less, further preferably 10 nm or more and 100 nm or less, and particularly preferably 10 nm or more from the viewpoint of gas barrier properties and film productivity. 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.
Each of the PVD inorganic layers (1) and (2) is formed under reduced pressure in order to form a dense thin film, preferably while conveying the film. The pressure for forming each of the PVD inorganic layers (1) and (2) is preferably 1 × 10 ^{−7 to} 1 Pa, more preferably 1 × 10 ⁻⁶ to 1 ×, from the viewpoints of vacuum exhaust capability and barrier properties. The range is 10 ⁻¹ Pa, more 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 is excellent also in transparency, without generating a crack and peeling in a PVD inorganic layer.

[Inorganic layer formed by chemical vapor deposition (CVD)]
In the gas barrier film preferably produced by the method of the present invention, a CVD inorganic layer is formed on the PVD inorganic layer (1) by the method. It is considered that defects such as defects generated in the PVD inorganic layer are sealed by the CVD inorganic layer, and gas barrier properties and interlayer adhesion are improved. The method for forming the CVD inorganic layer is as described above.

In the gas barrier film, 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 in the gas barrier film 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 0.5 at. % Or more and 10 at. %, More preferably 0.5 at. % Or more and 5 at. %, More preferably 1 at. % Or more and 5 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), For example, the method achieved by selecting the raw material in CVD, a raw material, and reaction gas (oxygen, For example, a method of adjusting by a flow rate and a ratio of nitrogen, etc., a method of adjusting by a pressure and an input power during film formation, and the like.
A specific method for measuring the carbon content by X-ray photoelectron spectroscopy (XPS method) is as described later.

In order to ensure the sealing effect on the PVD inorganic layer, the CVD inorganic layer in the gas barrier film is preferably composed of two or more layers, more preferably 2 to 5 layers. .
The thickness of the CVD inorganic layer in the gas barrier film is preferably less than 20 nm as measured by a cross-sectional TEM method. By being in the above range, the intermolecular force between the PVD inorganic layers acts effectively, thereby improving the adhesion. At the same time, the production rate by the chemical vapor deposition method can be increased to the same level as that of the physical vapor deposition method, so that the production efficiency can be improved and the production equipment can be miniaturized and simplified, so that an inexpensive barrier film can be produced. From the above viewpoint, the thickness of the CVD inorganic layer is preferably less than 10 nm, more preferably less than 5 nm, and still more preferably less than 3 nm.

Further, the lower limit value of the thickness of the CVD inorganic layer in the gas barrier film is preferably 0.01 nm as a minimum film thickness for exhibiting a sealing effect on the PVD inorganic layer, preferably 0.1 nm. More preferably, it is 0.5 nm. If the thickness is within the above range, the adhesiveness, gas barrier property and the like are good and 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 0.01 nm or more and less than 20 nm, more preferably 0.1 nm or more and less than 20 nm, more preferably 0.1 nm or more and less than 10 nm, It is still more preferably 0.1 nm or more and less than 5 nm, and even more preferably 0.1 nm or more and less than 3 nm.

  In the gas barrier film, the thickness ratio (CVD inorganic layer thickness / PVD inorganic layer thickness) of the adjacent CVD inorganic layer and PVD inorganic layer is 0.0001 to 0.2, and more preferably 0.00. 0005 to 0.1, particularly 0.001 to 0.1 is preferable. 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 produced by the Roll to Roll process. In order to continuously form the layers, it is necessary to greatly reduce the conveyance speed of the base material in accordance with the CVD inorganic 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 the expression of 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.

  As described later, the gas barrier film has a laminated structure in the order of the PVD inorganic layer (1), the CVD inorganic layer, and the PVD inorganic layer (2), so that the CVD inorganic layer itself hardly contributes directly to the gas barrier property. However, for the PVD inorganic layer, the lower layer exhibits a sealing effect and the upper layer exhibits an anchor effect. Therefore, when the PVD inorganic layer is simply formed thick, PVD inorganic layers or CVD inorganic layers are laminated. Compared with the case, the gas barrier property is dramatically improved.

  In the present invention, the PVD inorganic layer (1), the CVD inorganic layer, and the PVD inorganic layer (2) are preferably formed continuously under reduced pressure from the viewpoint of gas barrier properties and productivity. Further, from the same viewpoint, in the present invention, the formation of the thin film is preferably carried out while preferably transporting the film, and in particular, the CVD inorganic layer is formed at a substrate transport speed of 100 m / min or more. Is preferred. That is, in the present invention, after the formation of each thin film, the pressure in the vacuum chamber is returned to the vicinity of the atmospheric pressure, and the subsequent process is not performed again by evacuation. Preferably it is done.

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). Further, by forming the CVD inorganic layer, the adhesion of each layer in the multilayer film of the inorganic layer can be improved.

[Anchor coat layer]
In the present invention, in order to improve the adhesion between the substrate and the PVD inorganic layer (1), an anchor coat agent is applied between the substrate and the PVD inorganic layer (1) to provide an anchor coat layer. Is preferred. As the said anchor coat layer, the thing similar to the manufacturing method of a 1st gas barrier film is applicable.

[Protective layer]
Moreover, it is preferable that the gas barrier film manufactured by the method of the present invention has a protective layer in the uppermost layer on the side on which each inorganic layer is formed. As the protective layer, the same method as that for the first gas barrier film can be applied.

[Configuration of gas barrier film]
As the gas barrier film of the present invention, the same gas barrier film production method as that of the first gas barrier film production method can be applied.

  In the present invention, it is the same as the first method for producing a gas barrier film that various gas barrier laminated films obtained by further laminating additional constituent layers as necessary on the constituent layers can be used according to applications.

  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.

<Plasma discharge stability>
Plasma discharge stability was evaluated from the number of arc discharges per second.
This is because, when an arc current is generated, the discharge is temporarily stopped when the voltage drop of the plasma electrode becomes less than half of the predetermined voltage, and the plasma discharge is stably continued in the phenomenon of restarting the discharge instantaneously. It is an indicator.
(Evaluation criteria)
○: Number of arc discharges per second or less △: Number of arc discharges 2 to 10 times per second ×: Number of arc discharges 11 times or more per second

<Yellowness (Transparency)>
The gas barrier film having a width of 1000 mm was divided into six equal parts to obtain six gas barrier films of approximately 160 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 width of 1000 mm of the gas barrier laminate film was divided into six equal parts to obtain six gas barrier laminate films of about 160 mm × 100 mm square. Next, each gas barrier laminate film was folded in half in the width direction so that the inorganic layer surface was on the outside, and six bags of about 80 mm × 100 mm with four sides sealed were produced. 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).

<Film thickness of PVD inorganic layer>
The film thickness was measured 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 transport speed is calculated by measuring by the cross-sectional TEM method, and the thickness when the film is formed at the transport speed described in the examples is the calculated value.

<Carbon content of CVD inorganic layer>
Using the XPS analyzer “K-Alpha” manufactured by Thermo Fisher Scientific Co., Ltd., the binding energy is measured by XPS (X-ray photoelectron spectroscopy), and the peak area corresponding to Si2P, C1S, N1S, O1S, etc. The elemental composition (at.%) Was calculated by converting from The carbon content of the CVD inorganic layer was evaluated by reading the value of the CVD inorganic layer portion of the XPS chart.

Example 1
As a base material, a biaxially stretched polyethylene naphthalate film having a width of 1000 mm and a thickness of 12 μm (“Q51C12” manufactured by Teijin DuPont) was used. A 100% thick anchor coat layer was formed by applying and drying a mixture of saturated polyester (“Byron 300” manufactured by Toyobo Co., Ltd., number average molecular weight 23000) in a 1: 1 mass ratio.

Next, using a physical vapor deposition apparatus having the configuration shown in FIG. 1, SiO is evaporated by a resistance heating method under a vacuum of 8 × 10 ⁻³ Pa, and a SiOx PVD inorganic layer having a thickness of 22 nm is formed on the anchor coat layer. Formed. At this time, a gas pipe 51 having a length of 1000 mm, a diameter of 40 mm, and 100 through-holes (gas supply ports) having a diameter of 1 mm on the side surface at equal intervals is transferred to each of the upstream side and the downstream side in the substrate transfer direction. The distance between the base material on the roll and the gas supply port is 70 mm, and the film is formed while introducing oxygen gas partial pressure from one direction of the gas pipe 51 at 4 × 10 ⁻³ Pa. went.

Next, a plasma CVD inorganic layer (SiOCN) having a thickness of 2 nm was formed on the SiOx PVD inorganic layer using the chemical vapor deposition apparatus 100 having the configuration shown in FIG. 5 without returning the pressure to atmospheric pressure (carbon). Content 3at.%). In addition, when forming the plasma CVD inorganic layer, HMDSN (hexamethyldisilazane) and nitrogen as a reactive gas are supplied from a plurality of gas supply ports 5 to the raw material gas introduction part 14 of the vapor deposition chamber 12 as a reactive gas, and vapor deposition is performed. Ar gas was supplied to the plasma generation unit 15 of the chamber 12 from the inert gas supply ports 4a and 4b. The molar ratio of HMDSN, nitrogen, and Ar gas was 1: 7: 7.
At this time, a gas pipe 51a having a length of 1000 mm and an inner diameter of 10 mm, in which 40 nozzles (gas supply ports 5) having an inner diameter of 1 mm are attached to the side surface at intervals of 40 mm, is parallel to the transport roll 21 on the upstream side in the transport direction of the substrate. The gas pipe 51b having the same shape as the gas pipe 51a was arranged in parallel with the transport roll 21 on the downstream side in the transport direction of the base material. The shortest distance between the base material and the tip of the nozzle of the gas supply port 5b was 30 mm, and HMDSN and nitrogen were introduced from the central portions of the gas pipes 51a and 51b.

Next, without returning the pressure to atmospheric pressure, a SiOx PVD inorganic layer having a thickness of 22 nm was formed on the plasma CVD inorganic layer in the same manner as in the formation of the first SiOx PVD inorganic layer, and gas barrier properties were obtained. A film was obtained.
The conveyance speed of the base material in forming the inorganic layer was 300 m / min.

  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 this adhesive resin layer, and a gas barrier laminate film Got. 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, a gas barrier film and a gas barrier laminated film were prepared in the same manner as in Example 1 except that the substrate conveyance speed was 200 m / min, and the above evaluation was performed. The results are shown in Table 1.

Example 3
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 the substrate conveyance speed was 100 m / min, and the above evaluation was performed. The results are shown in Table 1.

Comparative Example 1
In Example 2, except that the gas flow rate at both ends in the width direction of the gas pipe 51 in the formation of the PVD inorganic layer is ½ of the central part and the linear velocity of oxygen gas is made nonuniform. A gas barrier film and a gas barrier laminated film were prepared in the same manner and evaluated as described above. The results are shown in Table 1.

Comparative Example 2
In Example 2, except that the gas flow rate at both ends in the width direction of the gas pipe 51 is set to ½ of the central part in the formation of the plasma CVD inorganic layer, and the linear velocity of the source gas is made nonuniform. A gas barrier film and a gas barrier laminated film were prepared by the same method as in Example 1, and the above evaluation was performed. The results are shown in Table 1.

Comparative Example 3
In Example 2, in the formation of the PVD inorganic layer, the gas flow rate at both ends in the width direction of the gas pipe 51 is ½ of the central portion, the linear velocity of the oxygen gas is made nonuniform, and the formation of the plasma CVD inorganic layer A gas barrier film and a gas barrier laminate are produced in the same manner as in Example 2 except that the gas flow rate at both ends in the width direction of the gas pipe 51 is ½ of the central portion and the linear velocity of the source gas is made nonuniform. A film was prepared and evaluated as described above. The results are shown in Table 1.

  The gas barrier film obtained by the production method of the present invention is used for packaging of articles requiring shielding of various gases such as water vapor and oxygen, for example, packaging materials such as food and pharmaceuticals, solar cells, electronic paper, and organic EL (Electro It can be suitably used as a material such as luminescence) or a packaging material for electronic devices.

DESCRIPTION OF SYMBOLS 1 Base material 10 Vacuum chamber 11 Film conveyance part 12 Deposition part (deposition room)
13 Partition 14 Raw material gas introduction unit 15 Plasma generation unit 21 Transport roll 22 Upstream roll 23 Downstream roll 3 Deposition source 4 Vapor 5, 5a, 5b Gas supply port 51 Gas pipe 52 Partition material 53 Gas supply unit 6, 6a, 6b Shielding plate 61 Opening 7 Exhaust port 100 Physical vapor deposition device

Claims (8)

In the method for producing a gas barrier film having a step of forming an inorganic layer formed by physical vapor deposition on at least one surface of a substrate that is continuously conveyed,
The inorganic layer is
Vapor generated from a deposition source;
A plurality of gases arranged at predetermined intervals of gas pipes extending 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 so that the steam is sandwiched therebetween Formed by reacting oxygen gas with substantially the same linear velocity supplied from the supply port in the vicinity of the base material,
The method for producing a gas barrier film, wherein a distance between the base material on the transport roll and the plurality of gas supply ports is 1 to 200 mm. In the method for producing a gas barrier film having a step of forming an inorganic layer by chemical vapor deposition on at least one surface of a substrate that is continuously conveyed,
The inorganic layer is supplied from a plurality of gas supply ports arranged at predetermined intervals of gas pipes extending 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 source gas having substantially the same linear velocity is formed by being activated and reacted by plasma in the vicinity of the base material and forming a film on the base material,
The method for producing a gas barrier film, wherein a distance between the base material on the transport roll and the plurality of gas supply ports is 1 to 200 mm. The periphery of the plurality of gas supply ports on the upstream side is shielded by a shielding plate extending from the downstream side of the plurality of gas supply ports on the upstream side to the vapor deposition source side,
The periphery of the plurality of downstream gas supply ports is shielded by a shielding plate extending from the upstream side of the plurality of downstream gas supply ports to the vapor deposition source side. Production method.   The manufacturing method of the gas-barrier film of any one of Claims 1-3 whose internal diameter of the said gas supply port is 0.1-5.0 mm.   5. The method for producing a gas barrier film according to claim 1, further comprising an exhaust port, wherein a plurality of the exhaust ports are disposed below the vapor deposition source and in the width direction of the transport roll. .   The method for producing a gas barrier film according to any one of claims 2 to 4, further comprising an exhaust port, wherein a plurality of the exhaust ports are arranged in the width direction of the transport roll.   In the 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 the substrate, A method for producing a gas barrier film, wherein the inorganic layer formed by a vapor deposition method is formed by the method according to any one of claims 1 and 3-5.   In the method for producing a gas barrier film having, in this order, 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 on at least one surface of the substrate, A method for producing a gas barrier film, wherein the inorganic layer formed by a vapor deposition method is formed by the method according to any one of claims 2 to 4 and 6.

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