JP2011195850A - Film-forming method and gas barrier film - Google Patents

Abstract

A film forming method for forming a gas barrier film having high gas barrier performance, and a gas barrier film formed by using these film forming methods are provided.
A film forming method forms an inorganic film on a surface of a substrate in a chamber having a predetermined degree of vacuum while a long substrate is wound around a predetermined region on the surface of the drum and transported in a predetermined transport direction. A film forming unit for forming an inorganic film on the surface of the substrate in the chamber, and a vapor deposition unit for depositing a metal having a function of adsorbing moisture on a material other than the substrate. Thus, vapor deposition by the vapor deposition section is performed before forming the inorganic film on the surface of the substrate and at least at one timing during the formation of the inorganic film.
[Selection] Figure 1

Description

  The present invention relates to a gas barrier film used for a liquid crystal display, a plasma display, an organic EL display, and the like, and a film forming method used for manufacturing the gas barrier film, and in particular, for forming a gas barrier film having high gas barrier performance. The present invention relates to a film forming method and a gas barrier film formed by using these film forming methods.

Packaging used for packaging parts, parts, food, clothing, electronic parts, etc. that require moisture resistance in various devices such as optical devices, display devices such as liquid crystal displays and organic EL displays, semiconductor devices, thin film solar cells, etc. As a material, a gas barrier film obtained by forming a film (hereinafter also referred to as a gas barrier film) that exhibits gas barrier properties on a plastic film (substrate film) such as a polyethylene terephthalate (PET) film is used.
As a gas barrier film formed on such a gas barrier film, films made of various inorganic substances (inorganic compounds) such as silicon nitride, silicon oxide (SiOx), and aluminum oxide are known. As for a silicon oxide film (SiOx film), it is known that gas barrier performance such as oxygen permeability and water vapor permeability changes when the degree of oxidation is different.

For example, Patent Document 1 discloses that a gas and moisture barrier film is manufactured by forming a SiOx layer as a gas barrier film on one or both surfaces of a polymer film by a high-frequency magnetron sputtering method. In addition, x shows an oxidation degree and in patent document 1, this x is 1.0-1.8. In the gas and moisture barrier film of Patent Document 1, the oxygen permeability is 2 cm ³ / m ² / day or less, and the water vapor permeability is 1 g / m ² / day or less.

Japanese Patent No. 3192249

  When manufacturing a gas barrier film using a roll-to-roll method, a silicon oxide film is used as a gas barrier film, and a long substrate is formed by various film forming methods while being transported in the chamber. There is a problem that the degree of oxidation of the formed silicon oxide (SiOx film) cannot always be controlled by the gas component remaining in the substrate. As described above, it is known that the gas barrier performance is improved by changing the oxidation degree as described above. Patent Document 1 discloses a gas and moisture barrier film in which the oxidation degree of the SiOx layer is adjusted. However, a gas barrier film having a predetermined performance cannot be obtained.

  An object of the present invention is to provide a film formation method for forming a gas barrier film having high gas barrier performance, and a gas barrier film formed by using these film formation methods, which solves the problems based on the conventional technology. There is.

  In order to achieve the above object, the first aspect of the present invention is to wrap a long substrate around a predetermined area on the surface of the drum and transport it in a predetermined transport direction in a chamber having a predetermined degree of vacuum. A film forming method for forming an inorganic film on a surface of the substrate, wherein a film forming unit for forming the inorganic film on the surface of the substrate in the chamber and a metal having a function of adsorbing moisture other than the substrate A vapor deposition unit for vapor deposition is provided, and the vapor deposition by the vapor deposition unit is performed at least at one timing during the formation of the inorganic film before the inorganic film is formed on the surface of the substrate by the film formation unit. It is an object of the present invention to provide a film forming method characterized in that it is performed.

In this case, before the inorganic film is formed on the surface of the substrate by the film forming unit, a step of forming an organic film on the surface of the substrate is provided, and the inorganic film is formed on the organic film. preferable.
The inorganic film is preferably formed by a vacuum deposition method or a CVD method.
Moreover, it is preferable that the pressure in the chamber before the formation of the inorganic film is 1 × 10 ⁻³ Pa or less and the water pressure is 6 × 10 ⁻⁴ Pa or less. This moisture pressure (6 × 10 ⁻⁴ Pa) corresponds to 60% or less of the total pressure in the chamber.
Moreover, it is preferable that the pressure in the chamber during the formation of the inorganic film is 1 × 10 ⁻² Pa or less and the water pressure is 3 × 10 ⁻³ Pa or less. This moisture pressure (3 × 10 ⁻³ Pa) corresponds to 30% or less of the total pressure in the chamber.
The inorganic film is preferably formed using silicon oxide.
The metal to be deposited is preferably titanium or aluminum.

A second aspect of the present invention includes a substrate and an inorganic film formed as a gas barrier film on the surface of the substrate, and the gas barrier film is manufactured using the film forming method according to the first aspect of the present invention. The present invention provides a gas barrier film characterized by being made.
In this case, an organic film is preferably formed between the surface of the substrate and the gas barrier film.

According to the present invention, before forming the inorganic film on the surface of the substrate and at least one timing during the formation of the inorganic film, the vapor deposition unit deposits the metal having a function of adsorbing moisture on the substrate other than the substrate. As a result, the amount of moisture in the chamber can be reduced. Thereby, the oxidation degree of the inorganic film to be formed can be controlled, and an inorganic film having excellent gas barrier performance can be obtained. Therefore, a gas barrier film having excellent gas barrier performance can be obtained.
Further, according to the present invention, since the amount of moisture in the chamber can be reduced by vapor deposition before forming the inorganic film on the surface of the substrate, the vacuum exhaust until the inside of the chamber is set to a predetermined degree of vacuum. The time can be shortened, and the cost for forming the inorganic film can be reduced.

It is typical sectional drawing which shows an example of the film-forming apparatus used for the film-forming method which concerns on embodiment of this invention. It is a schematic diagram which shows the organic film film-forming apparatus used for the film-forming method concerning embodiment of this invention. (A) is typical sectional drawing which shows an example of the gas barrier film obtained by the film-forming method which concerns on embodiment of this invention, (b) is the gas barrier obtained by the film-forming apparatus which concerns on embodiment of this invention. It is typical sectional drawing which shows an example of a film.

Hereinafter, a film forming method and a gas barrier film of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
FIG. 1 is a schematic cross-sectional view showing an example of a film forming apparatus used in a film forming method according to an embodiment of the present invention.

  A film forming apparatus 10 shown in FIG. 1 is a roll-to-roll type film forming apparatus, and is supplied through a predetermined path from a supply chamber 12 through a film forming chamber 14 to a winding chamber 16. For example, a gas barrier function is continuously applied to a surface Zf (see FIG. 3A) of a long substrate Z (refer to FIG. 3A) while being conveyed through the long substrate Z from the chamber 12 to the winding chamber 16. An inorganic film 102 is formed as a gas barrier film having the gas barrier film 100 (see FIG. 3A). This inorganic film 102 is, for example, a SiOx film made of silicon oxide.

The film forming apparatus 10 basically includes a supply chamber 12 for supplying a substrate Z, a film forming chamber (chamber) 14 for forming an inorganic film 102 (see FIG. 3A) on the substrate Z, and an inorganic film 102 ( The substrate Z on which the substrate Z formed on FIG. 3A, that is, the gas barrier film 100 is wound, the vacuum chamber 32, and the controller 36 are provided. The operation of each element in the film forming apparatus 10 is controlled by the control unit 36.
In the film forming apparatus 10, a slit-like opening 15 c through which the substrate Z passes is formed on a wall 15 a that partitions the supply chamber 12 and the film forming chamber 14. 16 is formed with a slit-shaped opening 15c through which the substrate Z (gas barrier film 100) on which the inorganic film 102 is formed passes.

  In the film forming apparatus 10, a vacuum exhaust unit 32 is connected to the supply chamber 12, the film forming chamber 14, and the winding chamber 16 through a pipe 34. The inside of the supply chamber 12, the film formation chamber 14, and the winding chamber 16 is brought to a predetermined degree of vacuum (pressure) by the vacuum exhaust unit 32. The pipe 34 may be provided with a valve (not shown) in the vicinity of the supply chamber 12, the film formation chamber 14, and the winding chamber 16 so that the exhaust amount of each chamber by the vacuum exhaust unit 32 can be adjusted.

The evacuation unit 32 evacuates the supply chamber 12, the film formation chamber 14, and the take-up chamber 16, and maintains a predetermined degree of vacuum (predetermined pressure). A vacuum pump such as a dry pump or a turbo molecular pump is provided. It is what you have. The supply chamber 12, the film formation chamber 14, and the winding chamber 16 are each provided with a pressure sensor (not shown) for measuring the internal pressure. Further, the film forming chamber 14 is provided with, for example, a vacuum partial pressure gauge (not shown) in order to measure the internal water pressure (H ₂ O partial pressure).
The degree of ultimate vacuum of the supply chamber 12 and the take-up chamber 16 by the evacuation unit 32 is not particularly limited, and the film formation chamber 14 is sufficient according to the film formation conditions of the inorganic film 102 as will be described later. It is sufficient to maintain a high degree of vacuum. The evacuation unit 32 is controlled by the control unit 36. Each pressure sensor and vacuum partial pressure gauge are also connected to the control unit 36, and the pressure and moisture pressure (H ₂ O partial pressure) obtained by each pressure sensor and vacuum partial pressure gauge are stored in the control unit 36. .

The supply chamber 12 is a part that supplies the substrate Z, and is provided with a rotating shaft 20 and a guide roller 21.
The rotating shaft 20 feeds the substrate Z continuously. A substrate roll 20 a in which the substrate Z is wound counterclockwise is loaded on the rotary shaft 20.
For example, a motor (not shown) is connected to the rotary shaft 20 as a drive source. Rotary shaft 20 is rotated in a direction r ₁ rewinding the substrate Z by the motor, in the present embodiment, is rotated clockwise, the substrate Z is continuously fed from the substrate roll 20a.

The guide roller 21 guides the substrate Z to the film forming chamber 14 through a predetermined transport path. The guide roller 21 is a known guide roller.
In the film forming apparatus 10 of the present embodiment, the guide roller 21 may be a driving roller or a driven roller. Further, the guide roller 21 may be a roller that acts as a tension roller that adjusts the tension when the substrate Z is transported.

In addition, it does not specifically limit as the board | substrate Z, The various elongate sheet-like board | substrate utilized for manufacture of a gas barrier film can use various.
Specifically, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, polyacrylate, polymethacrylate, polymethacrylate, polymethacrylate, etc. A plastic film (resin film) is preferably exemplified.

Although the thickness of the board | substrate Z is not specifically limited, For example, it is 10-300 micrometers. When the gas barrier film is used for an organic EL display and a liquid crystal display, it is preferable to use a substrate Z having a thickness of 10 to 150 μm from the viewpoint of mechanical strength and transparency.
Moreover, when using a gas barrier film for the back sheet | seat of a solar cell, it is preferable that the thickness of the board | substrate Z is about 300 micrometers from a viewpoint of withstand voltage property.
If the thickness of the substrate Z is less than 10 μm, the mechanical strength of the gas barrier film may be insufficient depending on the type of the substrate Z.

  In the present invention, for example, a plastic film that can also be used as the substrate Z is used as a base material, on which a protective layer, an adhesive layer, a light reflecting layer, a light shielding layer, a planarizing layer, a buffer layer, a stress, A substrate on which a layer (film) for obtaining various functions, such as a relaxation layer, is formed may be used as the substrate. As will be described later, a substrate in which the organic layer 104 is formed on the surface Zf of the substrate Z may be used as the substrate 106 (see FIG. 3B). A substrate in which a plurality of layers are formed on a base material may be used as the substrate.

  As will be described later, the winding chamber 16 is a portion of the film forming chamber 14 for winding the substrate Z on which the inorganic film 102 is formed on the surface Zf, and the winding shaft 30 and the two guide rollers 31a and 31b are provided. Is provided.

The winding shaft 30 winds the substrate Z on which the inorganic film 102 that is the gas barrier film 100 is formed in a roll shape, for example, clockwise.
For example, a motor (not shown) is connected to the winding shaft 30 as a drive source. The winding shaft 30 is rotated by this motor, and the substrate Z on which the inorganic film 102 is formed is wound.
In the winding shaft 30, the substrate Z on which the inorganic film 102 is formed is rotated by the motor in the winding direction r _{2. In} this embodiment, the substrate Z is rotated clockwise to form the inorganic film 102. Are continuously wound up, for example, clockwise to obtain the substrate roll 30a of the gas barrier film 100.

The guide rollers 31a and 31b guide the substrate Z transported from the film forming chamber 14 to the winding shaft 30 through a predetermined transport path. The guide rollers 31a and 31b are constituted by known guide rollers. As with the guide roller 21 in the supply chamber 12, the guide rollers 31a and 31b may be drive rollers or driven rollers. The guide rollers 31a and 31b may be rollers that act as tension rollers.
In the film forming apparatus 10, the feeding of the substrate Z from the substrate roll 20 a and the winding of the substrate Z on the winding shaft 36 of the winding chamber 16 are performed in synchronization, and the substrate Z is moved in the longitudinal direction along a predetermined transport path. The inorganic film 102 is formed on the substrate Z in the film formation chamber 14.

The film forming chamber 14 functions as a vacuum chamber, and is made of a material used in various vacuum chambers such as stainless steel, aluminum, or aluminum alloy. The film forming chamber 14 is a part where the inorganic film 102 is continuously formed on the surface Zf of the substrate Z by, for example, vacuum deposition while transporting the substrate Z.
Note that the film formation chamber 14 may be provided with a gas introduction means for introducing argon gas for adjusting the degree of vacuum. The gas introduction means includes or is connected to a connection means with a cylinder or the like, a gas flow rate adjustment means, or the like. As the gas introduction means, a known one used in a vacuum deposition apparatus is used.

In the film forming chamber 14, six guide rollers 24a, 24b, 25, 27, 28a, 28b, a drum 26, a film forming unit 40, and a vapor deposition unit 50 are provided.
The guide rollers 24a and 24b, the guide roller 25, the drum 26, the guide roller 27, and the guide rollers 28a and 28b are provided in this order from the upstream side to the downstream side in the transport direction D. That is, the guide rollers 24a and 24b and the guide roller 25 are provided on the upstream side with respect to the drum 26, and the guide roller 27 and the guide rollers 28a and 28b are provided on the downstream side.

The guide rollers 24a and 24b and the guide rollers 28a and 28b are arranged in parallel so as to face each other with a predetermined interval. The guide rollers 24 a and 24 b and the guide rollers 28 a and 28 b are arranged with their longitudinal directions orthogonal to the conveyance direction D of the substrate Z.
Further, the guide roller 25 and the guide roller 27 are arranged in parallel so as to face each other at a distance narrower than the distance between the guide roller 24 and the guide roller 28. The guide roller 25 and the guide roller 27 are arranged so that the longitudinal direction thereof is orthogonal to the transport direction D of the substrate Z.

The guide rollers 24 a and 24 b and the guide roller 25 are for transporting the substrate Z transported from the guide roller 21 provided in the supply chamber 12 to the drum 26. The guide rollers 24a and 24b and the guide roller 25 have, for example, a rotation axis in a direction orthogonal to the transport direction D of the substrate Z (hereinafter referred to as an axial direction) and can rotate, and the guide rollers 24a and 24b and the guide roller 25 The length of the roller 25 in the axial direction is longer than the length in the width direction orthogonal to the longitudinal direction of the substrate Z (hereinafter referred to as the width of the substrate Z).
The rotating shaft 20, the guide roller 21, the guide rollers 24a and 24b, and the guide roller 25 constitute a first transport unit of the present invention.

The guide roller 27 and the guide rollers 28 a and 28 b convey the substrate Z wound around the drum 26 to a guide roller 31 a provided in the winding chamber 16. For example, the guide roller 27 and the guide rollers 28a and 28b have a rotation shaft in the axial direction and are rotatable, and the guide roller 27 and the guide rollers 28a and 28b are longer in the axial direction than the width of the substrate Z. Also long.
The guide roller 27, the guide roller 28, the guide rollers 31a and 31b, and the take-up shaft 30 constitute the second conveying means of the present invention.
The six guide rollers 24a, 24b, 25, 27, 28a, and 28b have the same configuration as the guide roller 21 provided in the supply chamber 12 except for the above configuration, and thus detailed description thereof is omitted.

The drum 26 is provided below the space H between the guide rollers 24b and 25 and the guide rollers 27 and 28a. The drum 26 is arranged with its longitudinal direction parallel to the longitudinal direction of the four guide rollers 24b, 25, 27, 28a. The drum 26 is longer in the axial direction (longitudinal direction) than the width of the substrate Z.
The drum 26 has, for example, a cylindrical shape, and cylindrical support portions 29 are provided on both end surfaces thereof. The support portion 29 is rotatably supported by, for example, a bearing (not shown) provided on the wall surface (not shown) of the film forming chamber 14. As a result, the drum 26 rotates in the rotation direction ω around the rotation axis C.
The substrate Z is wound around the surface 26a (circumferential surface) of the drum 26, and the drum 26 rotates in the rotation direction ω, so that the substrate Z is held in a predetermined film formation position and the substrate Z is moved in the transport direction D. It is to be transported.

  In addition, about the drum 26, when the thickness of the board | substrate Z is thin, it is preferable to cool in order to prevent the board | substrate Z being cut | disconnected by the heat | fever at the time of film-forming. However, since the temperature of the drum 26 affects the film quality of the inorganic film 102, the temperature of the drum 26 is appropriately determined according to the thickness of the substrate Z, the film quality of the inorganic film 102 to be formed, and the like.

  As shown in FIG. 1, the film forming unit 40 is provided to face the lower side of the drum 26, and in a state where the substrate Z is wound around the drum 26, the drum 26 rotates and the substrate Z is conveyed. The inorganic film 102 that functions as a gas barrier film is formed on the surface Zf of the substrate Z while being transported in the direction D.

The film forming unit 40 forms the inorganic film 102 by, for example, a vacuum vapor deposition method. The film forming unit 40 includes a heating container 42, a heater 44, a temperature sensor 45, a first temperature adjusting unit 46, a pair of partition plates 48, and a shutter 49.
The partition plate 48 divides the heating container 42 in the film forming chamber 14, and the pair of partition plates 48 are arranged so as to sandwich the heating container 42.

The heating container 42 is a hollow container whose upper surface is open, and has, for example, a rectangular casing. A plurality of the heating containers 42 are provided along the axial direction (longitudinal direction) of the drum 26.
Each heating container 42 is filled with a film forming material M for forming the inorganic film 102 therein, for example, in the form of pellets. In the present embodiment, the film forming material M is, for example, SiO (silicon oxide).

  Each heating container 42 is formed of a material that does not react with the film-forming material M, has sufficient heat resistance, and has good thermal conductivity, like a general vacuum evaporation crucible. For example, it is formed of various metals or alloys or various ceramics. The material of the heating container 42 is appropriately selected according to the composition, melting point, etc. of the film forming material M.

Moreover, there is no limitation in particular in the shape of the heating container 42, The container of various shapes can be utilized.
The heating container 42 preferably has a shape such as a cylindrical shape such as a cylindrical shape or a rectangular shape that does not vary in cross section in a direction perpendicular to the vertical direction of the cylinder. By making the heating container 42 into such a cylindrical shape, the area of the evaporation surface does not change even if the film forming material to be filled evaporates and the liquid level (evaporation surface) is lowered. This is preferable in terms of stabilizing the amount, that is, the film forming rate, and stabilizing the directivity of the film forming material vapor.

  The heater 44 heats the heating container 42 to a predetermined temperature and melts the film forming material M inside the heating container 42. A heater 44 is provided so as to surround the periphery of the wall surface of the heating container 42. The heater 44 is connected to the first temperature adjustment unit 46.

  The configuration of the heater 44 is not particularly limited. Various types of heaters such as a heating wire, a resistor heater such as a conductor, and a sheath heater can be used, and are appropriately selected according to the melting point of the film forming material M and the like.

  The first temperature adjusting unit 46 applies a voltage, current, power, or the like applied to each heater 44 according to the temperature at which the heating container 42 is heated, that is, the set temperature that is sufficient to evaporate the film forming material M. It is for adjusting. The first temperature adjustment unit 46 is connected to the control unit 36.

  The temperature sensor 45 is provided, for example, at the top of each heating container 42 and is constituted by a thermocouple. Each temperature sensor 45 is connected to the control unit 36 although not shown. Depending on the set temperature and the temperature measured by the temperature sensor 45 by the control unit 36, for example, each heater 44 from the first temperature adjustment unit 46 so that the temperature in the heating container 42 becomes the set temperature by feedback control. The voltage, current or power supplied to the is controlled.

The film forming unit 40 is provided with a shutter 49 that blocks the vapor of the film forming material M from the opening of the heating container 42. The shutter 49 is composed of a plate-like member that blocks the vapor of the film forming material M from the opening of the heating container 42 and has a size that covers the entire opening of the heating container 42. The shutter 49 is connected to a rotation support shaft (not shown), and a motor (not shown) is connected to the rotation support shaft. By this motor, the shutter 49 is rotated via the rotation support shaft, the upper part of the opening of the heating container 42 is opened, and the vapor of the film forming material M reaches the surface Zf of the substrate Z.
The motor is also connected to the control unit 36, and the control unit 36 controls the rotation thereof, that is, the blocking of the vapor of the film forming material M from the opening of the heating container 42 by the shutter 49.

The vapor deposition part 50 vapor-deposits the metal m which has a function which adsorb | sucks moisture on things other than the board | substrate Z by a vacuum vapor deposition method. In this embodiment, the vapor deposition part 50 vapor-deposits the metal m which has the function to adsorb | suck a water | moisture content to the mask 59, for example. The metal m having a function of adsorbing moisture is, for example, Al or Ti.
The vapor deposition unit 50 includes a heating container 52, a heater 54, a temperature sensor 55, a second temperature adjustment unit 56, a pair of partition plates 58, and a mask 59. It is the same composition as. However, the vapor deposition unit 50 is different from the film forming unit 40 in that at least one heating container 52 is sufficient.
The partition plate 58 partitions the heating container 52 in the film forming chamber 14, and the pair of partition plates 58 are arranged so as to sandwich the heating container 52.

  Since the heating container 52, the heater 54, and the temperature sensor 55 of the vapor deposition unit 50 have the same configuration as the heating container 42, the heater 44, and the temperature sensor 45 of the film forming unit 40, detailed descriptions thereof are omitted. In the vapor deposition section 50, the heating container 52 is filled with, for example, Al or Ti as a metal m having a function of adsorbing moisture in the form of pellets. The heater 54 is connected to the second temperature adjustment unit 56. The heater 54 is also appropriately selected according to the melting point of the metal m, like the heater 44 of the film forming unit 40.

The second temperature adjustment unit 56 adjusts the voltage, current, power, or the like applied to the heater 54 according to the temperature at which the heating container 52 is heated, that is, the set temperature that is sufficient to evaporate the metal m. Is for. The second temperature adjustment unit 56 is also connected to the control unit 36, and the temperature sensor 55 is also connected to the control unit 36 although not shown.
According to the set temperature and the temperature measured by the temperature sensor 55 by the control unit 36, the heater 54 is supplied from the second temperature adjustment unit 56 so that the temperature in the heating container 52 becomes the set temperature by feedback control, for example. The voltage, current or power supplied to the is controlled.

The vapor deposition section 50 is provided with a mask 59 above the opening of the heating container 52. Al or Ti is deposited on the mask 59. The moisture in the film forming chamber 14 is adsorbed by the Al or Ti vapor, and the water pressure in the film forming chamber 14 can be set to 6 × 10 ⁻⁴ Pa or less, for example. The moisture pressure in the film forming chamber 14 is preferably 6 × 10 ⁻⁴ Pa or less before the inorganic film 102 is formed, for example. This moisture pressure (6 × 10 ⁻⁴ Pa) corresponds to 60% or less of the total pressure in the film forming chamber 14.
In addition, the moisture pressure in the film forming chamber 14 is preferably 3 × 10 ⁻³ Pa or less during the formation of the inorganic film 102, for example. This moisture pressure (3 × 10 ⁻³ Pa) corresponds to 30% or less of the total pressure in the film forming chamber 14.

By adjusting the moisture pressure in this manner, when the SiOx film is formed as the inorganic film 102 by the vacuum vapor deposition method using SiO in the film forming unit 40, the degree of oxidation can be reduced. Therefore, it is possible to obtain the inorganic film 102 having a low water vapor permeability, oxygen permeability, etc., that is, excellent gas barrier performance. Moreover, since Al or Ti for adsorbing moisture is deposited on the mask 59 other than the substrate Z, the vapor of Al or Ti does not scatter in the film forming chamber 14 and adheres to the substrate Z as a foreign substance. There is nothing.
The vapor deposition performed by the vapor deposition section 50 is not limited to the mask 59, and the vapor deposition position is not particularly limited as long as it does not adversely affect the formation of the inorganic film 102 at a place other than the surface Zf of the substrate Z. It is not something.

In the present embodiment, the vapor deposition section 50 is provided in the region α on the upstream side of the drum 26 in the film formation chamber 14. However, the present invention is not limited to this. 26 may be provided in the region β on the downstream side. When vapor deposition is performed before film formation, it is preferably provided in the upstream region α where the substrate Z is transported. When vapor deposition is performed during film formation after the start of film formation, the substrate Z after film formation is provided. Is preferably provided in the downstream region β where the toner is conveyed.
Further, the film chamber 14 may be disposed in both the upstream region α and the downstream region β of the drum 26. In this case, both of them may be vapor-deposited at the same time. The film in the upstream region α is vapor-deposited before the film formation, and the film in the downstream region β is vapor-deposited after the film formation is started. You may switch things.
Further, the number of heating containers 52 of the vapor deposition section 50 is not particularly limited, and is appropriately determined according to the volume of the film forming chamber 14, the thickness and type of the substrate, the thickness and type of the organic film, and the moisture pressure. Is to be selected.

Further, the heating method using the heater is used to heat the heating container 42 of the film forming unit 40. If the inorganic film 102 can be formed by evaporating the film forming material M (for example, SiO), the heating method is particularly It is not limited. As a heating method, a resistance heating method in which a current is applied to the film forming material M to generate heat, an electromagnetic induction heating method, an electron beam beam heating method, a laser heating method, or the like can be used.
Also, in the evaporation unit 50, if the metal m having a function of adsorbing moisture, for example, Al or Ti, can be evaporated, the heating method is limited to the heating method by the heater as in the film forming unit 40. There is nothing, and the various heating methods described above similar to those of the film forming unit 40 can be used.

Next, the operation of the film forming apparatus 10 of this embodiment will be described.
In the film forming apparatus 10, for example, the substrate Z is transported to the film forming chamber 14 through the guide roller 21 from the substrate roll 20 wound counterclockwise. In the film forming chamber 14, the film is conveyed to the winding chamber 16 through the guide rollers 24 a and 24 b, the guide roller 25, the drum 26, the guide roller 27, and the guide rollers 28 a and 28 b. In the winding chamber 16, the substrate Z is wound around the winding shaft 30 through the guide rollers 31 a and 31 b. Thus, after passing the substrate Z through this transfer path, the inside of the supply chamber 12, the film formation chamber 14, and the winding chamber 16 is brought to a predetermined degree of vacuum by the vacuum exhaust unit 32.

Thereafter, while the temperature of the heating container 52 is monitored by the temperature sensor 55 by the control unit 36, the heating container 52 is heated to a predetermined temperature while adjusting the voltage, current, and the like applied from the second temperature adjusting unit 56 to the heater 54. Then, in the vapor deposition section 50, Al or Ti is melted and evaporated to deposit Al or Ti on the mask 59. At this time, Al or Ti vapor is deposited on the mask 59 while adsorbing moisture in the film forming chamber 14. Thereby, the water pressure in the film formation chamber 14 can be lowered to 6 × 10 ⁻⁴ Pa or less, for example.
In the film formation chamber 14, for example, before the formation of the inorganic film 102, the moisture pressure in the film formation chamber 14 is preferably 6 × 10 ⁻⁴ Pa or less. At this time, the pressure in the film forming chamber 14 is preferably 1 × 10 ⁻³ Pa or less.
After the pressure in the film forming chamber 14 and the water pressure reach the above-described pressures, the controller 36 stops the heating of the heater 54 by the second temperature adjusting unit 56, and the deposition unit 50 deposits Al or Ti. Stop.

  Next, while the temperature of the heating container 42 is monitored by the temperature sensor 45 by the control unit 36, the heating container 42 is brought to a predetermined temperature while adjusting the voltage, current, etc. applied to the heater 44 from the first temperature adjustment unit 46. Heating is performed, and in the film forming unit 40, SiO as the film forming material M is melted and evaporated.

  Next, the control unit 36 rotates the shutter 49 to open the opening of the heating container 42, and the SiO vapor reaches the surface Zf of the substrate Z. In such a state, the substrate Z is wound at a predetermined transport speed while holding the substrate Z at a position where the vapor of SiO reaches the drum 26, and SiO is deposited on the surface Zf of the substrate Z. Thereby, a SiOx film is formed as the inorganic film 102.

  By the vapor deposition by the vapor deposition section 50, the moisture pressure in the film forming chamber 14 is reduced, and SiO can be deposited in an atmosphere with a low moisture pressure. Since SiO is deposited in such an atmosphere, the oxidation of SiO is suppressed, and the SiOx film formed as the inorganic film 102 has an oxidation degree as small as, for example, 1.0 to 1.4. Become. Thereby, the inorganic film | membrane 102 excellent in gas barrier performance is obtained. As a result, the gas barrier film 100 having high gas barrier performance can be obtained.

  Then, the rotating shaft 20 is sequentially rotated clockwise by a motor, and the substrate Z is continuously fed out. The drum 26 is held at a position where the SiO vapor reaches the drum 26, and the drum 26 is moved at a predetermined speed. The inorganic film 102 is continuously formed on the surface Zf of the substrate Z so as to have a predetermined film thickness by rotating the film. Then, the substrate Z on which a predetermined film is formed on the surface Zf is wound around the winding shaft 30 via the guide rollers 28a and 28b and the guide rollers 31a and 31b, so that the gas barrier film 100 is obtained.

  In the present embodiment, an SiOx film having a low degree of oxidation is provided by providing the vapor deposition unit 50 and performing vapor deposition in the vapor deposition unit 50 before film formation by the film formation unit 40 to reduce the water pressure in the film formation chamber 14. The gas barrier film 100 with excellent gas barrier performance can be obtained.

In the present embodiment, vapor deposition by the vapor deposition unit 50 is not limited to before the inorganic film 102 is formed. For example, vapor deposition by the vapor deposition unit 50 may be performed after the start of film formation of the inorganic film 102, and further, vapor deposition by the vapor deposition unit 50 may be performed after the film formation of the inorganic film 102 is started before the film formation of the inorganic film 102. You may go.
When vapor deposition is performed in the vapor deposition section 50 after the start of film formation of the inorganic film 102, that is, when vapor deposition is performed in the vapor deposition section 50 during formation of the inorganic film 102, the moisture pressure in the film formation chamber 14 is set to 3 × 10 ^−. It is preferable that the pressure in the film forming chamber 14 is ³ Pa or less and 1 × 10 ⁻² Pa or less. At this time, the control unit 36 appropriately heats the heater 54 by the second temperature adjusting unit 56 so that the pressure and moisture pressure are within the ranges described above, and causes the vapor deposition unit 50 to appropriately deposit Al or Ti. In such a state, the inorganic film 102 is formed as described above.
Note that when vapor deposition is performed in the vapor deposition section 50 during the formation of the inorganic film 102, the pressure and moisture pressure in the film formation chamber 14 before the film formation of the inorganic film 102 are not particularly limited.

Furthermore, vapor deposition is performed in the vapor deposition section 50 before the inorganic film 102 is formed and also during the formation of the inorganic film 102, and the moisture pressure in the film formation chamber 14 is 6 × 10 ⁻⁴ Pa or less before the inorganic film 102 is formed. As described above, the pressure is 1 × 10 ⁻³ Pa or less, the moisture pressure in the film formation chamber 14 is 3 × 10 ⁻³ Pa or less, and the pressure is 1 × 10 ⁻² Pa or less during the formation of the inorganic film 102. Alternatively, the inorganic film 102 may be formed.

  Even in the case of vapor deposition by the vapor deposition unit 50 during film formation after the start of film formation of the inorganic film 102 and vapor deposition by the vapor deposition unit 50 after the film formation of the inorganic film 102 is started before film formation of the inorganic film 102, As described above, since the moisture pressure around the deposited SiO can be reduced, the SiOx film formed as the inorganic film 102 has an oxidation degree as small as x = 1.0 to 1.4.

When vapor deposition is performed by the vapor deposition unit 50 during film formation after the start of film formation by the film formation unit 40, even when moisture is released from the substrate Z transported into the film formation chamber 14, or when the inorganic film 102 is formed. Even if moisture is released from the inner wall of the film forming chamber 14 by the generated heat, the moisture pressure is adsorbed by the Al or Ti vapor, so that the water pressure can be kept below a predetermined value even during film formation. For this reason, oxidation that occurs after SiO is deposited on the surface Zf of the substrate Z can be suppressed.
In particular, when vapor deposition is performed by the vapor deposition unit 50 before the inorganic film 102 is deposited and after the inorganic film 102 is deposited, the SiOx film can be formed in an atmosphere with a low moisture pressure, and the moisture pressure in the deposition chamber 14 can be increased. Since a low atmosphere can be maintained even during film formation, oxidation after SiO deposition is suppressed, and the degree of oxidation of the SiOx film can be further reduced. Thereby, the gas barrier film 100 which has still higher gas barrier performance can be obtained.
In the present embodiment, before the inorganic film 102 is formed, the moisture pressure in the film forming chamber 14 is 6 × 10 ⁻⁴ Pa or less and the pressure is 1 × 10 ⁻³ Pa or less, so that the inorganic film 102 is being formed. Then, when the water pressure in the film formation chamber 14 is 3 × 10 ⁻³ Pa or less and the pressure is 1 × 10 ⁻² Pa or less, the inorganic film 102 with better gas barrier performance can be obtained.

In addition, since the amount of moisture in the film formation chamber 14 can be reduced by vapor deposition in the vapor deposition section 50 before forming the inorganic film 102 on the surface Zf of the substrate Z, the inside of the film formation chamber 14 has a predetermined degree of vacuum. The time required for evacuation can be shortened, and the deposition cost of the inorganic film 102 can be reduced.
In the present embodiment, the moisture pressure in the film forming chamber 14 is reduced by vapor deposition in the vapor deposition section 50. However, if the moisture pressure in the film forming chamber 14 can be lowered below a predetermined value, it is not always necessary. There is no need to use the vapor deposition section 50. In this case, by taking a long time in the vacuum exhaust unit 32, the moisture pressure in the film forming chamber 14 can be reduced, for example, 6 × 10 ⁻⁴ Pa or less.

  Note that when the substrate Z is thick, the volume is large and the water content is increased, and the amount of moisture released when forming the inorganic film 102 is increased. Therefore, it is important to take measures against moisture pressure in the film formation chamber 14. In the present invention, the moisture pressure in the film formation chamber 14 is reduced as described above at least at one timing before the inorganic film 102 is formed and during the inorganic film 102 is formed. For this reason, even when the substrate Z is thick and the amount of water released is large, a SiOx film with a low degree of oxidation can be formed, and the gas barrier film 100 with excellent gas barrier performance can be obtained. When the substrate Z is thick, the gas barrier film 100 having excellent gas barrier performance can be obtained effectively by reducing the water pressure during the formation of the inorganic film 102.

Note that the thickness of the inorganic film 102 is not particularly limited, and may be set as appropriate according to required gas barrier properties, productivity, and the like. If the inorganic film 102 is too thin, the gas barrier property is low, and if it is too thick, the inorganic film is liable to break. Therefore, the thickness is preferably 10 to 300 nm, more preferably 80 to 200 nm.
By setting the film thickness of the inorganic film 102 within the above range, good gas barrier properties can be obtained, good flexibility can be obtained, good transparency can be obtained, and sufficient durability ( A favorable result can be obtained in terms of obtaining environmental resistance.

Moreover, in this embodiment, as shown to Fig.3 (a), although it was set as the structure which formed the inorganic film | membrane 102 in the surface Zf of the board | substrate Z as the gas barrier film 100, this invention is not limited to this. . For example, an organic film 104 may be formed between the substrate Z and the inorganic film 102 as in a gas barrier film 100a shown in FIG.
When forming the gas barrier film 100a shown in FIG. 3B, for example, an organic film forming apparatus 60 shown in FIG. 2 is used to form the organic film 102 on the surface Zf of the substrate Z.

  The organic film forming apparatus 60 includes a rotating shaft 62, a winding shaft 64, a coating unit 66, a drying unit 68, a curing unit 70, and guide rollers 72a and 72b. The application unit 66, the drying unit 68, and the curing unit 70 are arranged to face the conveyance path of the substrate Z between the guide rollers 72a to 72b.

The organic film forming apparatus 60 applies the substrate Z to the surface Zf of the substrate Z at atmospheric pressure while feeding the substrate Z out of the substrate roll 74 formed by winding the substrate Z into a roll and transporting the substrate Z in the longitudinal direction. In this apparatus, the organic film 104 is formed by the method, and the substrate Z on which the organic film 104 is formed is wound up again in a roll shape by the take-up shaft 64, so as to perform film formation by so-called roll-to-roll.
In addition to the members shown in the figure, the organic film forming apparatus 60 is for transporting the substrate Z along a predetermined path, such as various sensors, a pair of transport rollers, and a guide member that regulates the position in the width direction of the substrate Z. You may have the various members which the apparatus which performs the film-forming by a coating method continuously on the elongate board | substrate Z, such as various members (conveyance means).

The substrate Z sent out from the substrate roll 74 is guided by the guide roller 72 a and conveyed to the coating means 66.
The coating means 66 is prepared by dissolving (dispersing) an organic substance or the like in a solvent, a paint prepared by dissolving an organic monomer or the like, an organic monomer and a polymerization initiator or the like being dissolved in the solvent. A paint containing an organic substance that becomes the organic film 104, such as a paint, is applied to the surface Zf of the substrate Z (the film formation surface of the gas barrier laminate).
In the production method of the present invention, the coating method in the coating means 66 is not particularly limited, and examples thereof include roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, bar coating, and spin coating. Various known methods used for film formation can be used.

The drying means 68 evaporates the solvent and the like from the coating film (paint) applied to the surface Zf of the substrate Z by the coating means 66 and dries the coating film. There are no particular limitations on the means for drying the coating film, and any known drying means may be used depending on the coating film, such as drying with a heater or hot air drying.
If the coating film has sufficient viscosity or thixotropic properties and the organic film 104 can be formed only by curing by the downstream curing means 70, the drying means 68 may not be provided.

The curing means 70 cures the dried coating film to form the organic film 104. Here, when the paint contains an organic monomer as described above, the monomer is polymerized by the curing means 70 to form the organic film 104.
The curing means 70 is not particularly limited, and plasma irradiation means (plasma curing), UV (ultraviolet) irradiation means (UV curing), electron beam irradiation means (electron beam curing), light irradiation means (photocuring), heating means. A curing means corresponding to the organic material to be the organic film 104, such as (thermosetting), may be appropriately selected and used.
If the organic film 104 can be formed by sufficiently curing the coating film by only drying, the curing means 70 may not be provided. Alternatively, when drying and curing can be performed together, only one of them may be provided as a drying / curing means.

In the organic film forming apparatus 60, the substrate roll 74 is loaded on the rotating shaft 62. When the substrate roll 74 is loaded on the rotary shaft 62, the substrate Z is pulled out of the rotary shaft 62, guided by the guide rolls 72a and 72b, and wound around the winding shaft 64 through a predetermined transport path.
When preparation for processing by the coating unit 66, the drying unit 68, and the curing unit 70 is completed, the conveyance of the substrate Z is started. The coating means 66 applies the coating material for forming the organic film 104 while the substrate Z is conveyed in the longitudinal direction by synchronizing the feeding of the substrate Z from the substrate roll 74 and the winding of the substrate Z on the winding shaft 64. Then, the drying unit 68 dries the paint, and the curing unit 70 cures to form the organic film 104 on the surface Zf of the substrate Z.

  In the present invention, the method for forming the organic film 104 is not limited to a coating method, and a layer (film) made of an organic substance under atmospheric pressure, such as a transfer method for transferring the organic film 104 formed into a sheet shape. Any film forming method can be used as long as it can form a film. However, the coating method is preferable in consideration of the film formation rate (deposition rate), the embedding property of unevenness on the substrate surface, and the like.

  In the present invention, the organic film 104 is not limited to a single layer formed at atmospheric pressure, and the organic film 104 may have a multi-layer structure. In the case of a multi-layer structure, each layer may be a layer made of the same compound or a layer made of different compounds.

In the present invention, the material for forming the organic film 104 is not particularly limited, and various organic substances that can be formed at atmospheric pressure (film formation) such as a coating method can be used.
Examples include TMPTA (trimethylolpropane triacrylate), epoxy resin, acrylic resin, methacrylic resin, polyester, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, poly Examples include ether imide, cellulose acylate, polyurethane, polyether ketone, polycarbonate, fluorene ring-modified polycarbonate, alicyclic ring-modified polycarbonate, and fluorene ring-modified polyester.

Next, a method for manufacturing the gas barrier film 100a having the organic film 104 will be described. In this case, first, for example, using the organic layer forming apparatus 60, the organic film 104 is formed on the surface Zf of the substrate Z, and the substrate roll 76 on which the substrate 106 on which the organic film 104 is formed is wound is obtained. The substrate roll 76 is set on the rotating shaft 20 of the film forming apparatus 10 described above.
Then, the substrate 106 is transported from the substrate roll 76 to the film forming chamber 14 via the guide roller 21, and the guide rollers 24 a and 24 b, the guide roller 25, the drum 26, the guide roller 27, and the guide rollers 28 a and 28 b in the film forming chamber 14. Then, the substrate 106 is transferred to the winding chamber 16. In the winding chamber 16, the substrate 106 is wound on the winding shaft 30 through the guide rollers 31 a and 31 b. In this way, after passing the substrate 106 through this transport path, the inorganic film 102 is formed on the surface 106a of the substrate 106 as described above, and the gas barrier film 100a shown in FIG. 3B is obtained. The method for forming the inorganic film 102 is the same as the method for forming the inorganic film 102 on the surface Zf of the substrate Z described above except that it is formed on the surface 106a of the substrate 106. Omitted.

Even when the inorganic film 102 is formed on the surface 106a of the substrate 106, Al or Ti is vapor-deposited on the mask 59 by the vapor deposition unit 50 before the inorganic film 102 is formed, and the moisture pressure is set to 6 × 10 ⁻⁴ Pa, for example. At this time, the pressure in the film forming chamber 14 is set to 1 × 10 ⁻³ Pa or less. After the degree of vacuum and the water pressure are equal to or lower than predetermined values, the vapor deposition by the vapor deposition unit 50 is stopped, and the formation of the SiOx film by the film forming unit 40 is started. Even when the substrate 106 on which the organic film 104 is formed is used, a SiOx film having a low degree of oxidation can be formed as the inorganic film 102 because SiO vapor adheres to the surface 106a of the substrate 106 in an atmosphere having a low moisture pressure. .

  In the present embodiment, the organic film 104 is provided as a base layer of the inorganic film 102 (gas barrier film), so that the unevenness existing on the surface Zf of the substrate Z is buried and the film formation surface of the inorganic film 102 is flattened. can do. Thereby, the characteristic as a gas barrier film of the inorganic film 102 can fully be expressed. In addition, since the SiOx film having a low degree of oxidation can be formed as the inorganic film 102, the characteristics as a gas barrier film can be further improved. For this reason, by providing the organic film 104, it is possible to obtain a gas barrier film 100 a having higher gas barrier performance than the gas barrier film 100.

  In the case of forming the gas barrier film 100a, as in the case of forming the gas barrier film 100, the deposition unit 50 performs deposition during the deposition after the start of the deposition of the inorganic film 102, thereby forming the deposition chamber 14. Since moisture is contained in the organic film 104 of the substrate 106 transferred into the substrate 106 and the moisture is released into the film formation chamber 14, it proceeds after the SiO adheres to the surface 106 a of the substrate 106. Oxidation can be suppressed. Thereby, a SiOx film having a lower degree of oxidation can be formed. Furthermore, by performing vapor deposition by the vapor deposition section 50 before and during the formation of the inorganic film 102, an atmosphere having a low moisture pressure in the film formation chamber 14 can be maintained even during film formation. Further, a low SiOx film can be formed.

  In the present embodiment, the method for forming the organic film 104 is not limited to the method using the organic film forming apparatus 60 described above, and various forming methods can be used. As a method for forming the organic film 104, flash vapor deposition is preferably used because of its high cleanliness and high surface smoothness. Also in this flash vapor deposition, the material for forming the organic film 104 that can be used in the organic film forming apparatus 60 can be used.

  In the case where the organic film 104 is formed by flash vapor deposition, the organic film 104 is formed in a vacuum. Further, as described above, the inorganic film 102 is also formed in a vacuum. Processing can be performed in a vacuum until film formation is completed. Therefore, after the second organic layer 14 is formed, the inorganic film 102 is formed in a state where the adhesion of dust and foreign matters is suitably prevented and the clean surface, which is one of the features of flash vapor deposition, is maintained. can do. That is, it is possible to prevent the gas barrier property from being lowered due to the presence of dust or foreign matter on the film formation surface of the inorganic film 102.

In the present embodiment, the organic film forming apparatus 60 that forms the organic film 104 by coating and the film forming apparatus 10 that performs film formation in a vacuum are separate apparatuses, but the present invention is not limited thereto. Will not be done. The gas barrier film 100a may be manufactured by forming the organic film 104 and the inorganic film 102 with the same roll-to-roll film forming apparatus.
In this case, for example, in the film forming apparatus 10 shown in FIG. 1, an organic layer film forming chamber having the same configuration as the organic film forming apparatus 60 shown in FIG. 2 is provided between the supply chamber 12 and the film forming chamber 14. Good. In this case, it is necessary to adjust the deposition rate of the organic film 104 in accordance with the deposition rate of the inorganic film 102.
On the other hand, when the film forming apparatus 10 shown in FIG. 1 and the organic film forming apparatus 60 shown in FIG. 2 are configured separately, the organic in the organic film forming apparatus 60 is matched with the film forming speed of the inorganic film 102 in the film forming apparatus 10. It is not necessary to adjust the film formation rate of the film 104, and the operating conditions of the manufacturing equipment and the degree of freedom of equipment configuration can be increased.

In the present embodiment, the film forming unit 40 is formed by a vacuum vapor deposition method, but is not limited thereto. For example, a SiOx film having a predetermined oxidation degree is formed as the inorganic film 102. If possible, the CVD method may be used.
Examples of the CVD method include CCP (Capacitively Coupled Plasma) -CVD, ICP (Inductively Coupled Plasma) -CVD, microwave CVD, ECR (Electron Cyclotron Resonance) -CVD, and atmospheric pressure barrier discharge CVD. Various plasma CVD methods such as can be used.
By forming the inorganic film 102 using the plasma CVD method, a higher gas barrier property can be obtained, and further, cracking due to the structure inside the film can be suitably prevented, and flexibility can be improved. Can be manufactured with high productivity.

  The present invention is basically as described above. As mentioned above, although the film-forming method and gas barrier film of this invention were demonstrated in detail, this invention is not limited to the said embodiment, In the range which does not deviate from the main point of this invention, you may make a various improvement or change. Of course.

Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.
In this example, a SiOx film having a thickness of 100 nm is formed as an inorganic film directly on a substrate or on an organic film formed on the substrate by a vacuum deposition method under the deposition conditions shown in Table 1 below. And the gas barrier film of Experimental Examples 1-6 of the structure shown in following Table 1 was produced.

In the film formation conditions shown in Table 1 below, when the column of the vapor deposition portion is “Ti vapor deposition”, this indicates that Ti was vapor deposited on the mask at a film deposition rate of 0.5 nm / second for 30 minutes. A column of “Not used” in the column of the vapor deposition section indicates that Ti was not vapor deposited on the mask.
Moreover, the column of the timing of a vapor deposition part shows the timing which vapor-deposited Ti. For those not using the vapor deposition section, the column of the vapor deposition timing is “−”.
The ultimate vacuum and ultimate H ₂ O partial pressure in the film formation condition column shown in Table 1 below show values before the SiOx film is formed if the timing column of the vapor deposition part is “before SiOx film formation”, If “SiOx film is being formed”, the value during the formation of the SiOx film is indicated.

  As the substrate, a polyethylene terephthalate film (PET film, manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine A4300) having a thickness of 100 μm was used. Further, a TMPTA film having a thickness of 1 μm was formed as the organic film.

About the gas barrier film of each Experimental example 1-6, gas barrier performance was evaluated.
WVTR (water vapor transmission rate) was used as an index of gas barrier performance. This WVTR (water vapor transmission rate) was measured using a water vapor transmission rate measuring apparatus AQUATRAN (registered trademark) manufactured by MOCON under the measurement conditions of a temperature of 40 ° C. and a relative humidity of 90%. The results are shown in Table 1 below.

As shown in Table 1, Experimental Examples 1 and 2 in which the vapor deposition section was operated during the formation of the inorganic film (SiOx film) had a small value of WVTR (water vapor permeability) and excellent gas barrier performance. Further, in Experimental Examples 1 and 2, Experimental Example 1 with lower ultimate vacuum and ultimate H ₂ O partial pressure had better gas barrier performance than Experimental Example 2.
In Experimental Example 3, the vapor deposition part was operated before the formation of the inorganic film, and the ultimate vacuum and the ultimate H ₂ O partial pressure were the same as in Experimental Example 2. Experimental Example 3 was excellent in gas barrier performance. However, Experimental Example 3 has a lower gas barrier performance than Experimental Example 2 in which the vapor deposition section was operated during the formation of the inorganic film. This is presumably because the inner wall of the chamber is heated during film formation to increase the degassing of H ₂ O. As described above, excellent gas barrier performance can be obtained when the ultimate vacuum and the ultimate H ₂ O partial pressure during the formation of the inorganic film are lower.

In Experimental Example 4, the vapor deposition section was operated before the formation of the inorganic film, and there was no organic film. Experimental Example 4 was superior in gas barrier performance to Experimental Example 5 in which the structure was the same and an inorganic film was formed without operating the vapor deposition section.
Experimental Example 6 has the same configuration as Experimental Examples 1 to 3, but an inorganic film is formed without operating the vapor deposition section. In Experimental Example 6, the value of WVTR was 10 times or more compared with Experimental Examples 1 to 3, and an excellent gas barrier performance could not be obtained.

DESCRIPTION OF SYMBOLS 10 Film-forming apparatus 12 Supply chamber 14 Film-forming chamber 16 Wind-up chamber 20 Substrate roll 21, 24a, 24b, 25, 27, 28a, 28b, 31a, 31b Guide roller 26 Drum 30 Wind-up roll 32 Vacuum exhaust part 36 Control part DESCRIPTION OF SYMBOLS 40 Film-forming part 42,52 Heating container 44,54 Heater 46 1st temperature control part 50 Vapor deposition part 56 2nd temperature control part 59 Mask 60 Organic film formation apparatus D Conveyance direction omega Rotation direction Z Substrate

Claims (9)

A film forming method for forming an inorganic film on a surface of a substrate in a chamber having a predetermined degree of vacuum while winding a long substrate around a predetermined region of the surface of the drum and transporting the substrate in a predetermined transport direction,
A film forming unit for forming an inorganic film on the surface of the substrate in the chamber, and a vapor deposition unit for depositing a metal having a function of adsorbing moisture on a material other than the substrate are provided.
A film forming method comprising performing vapor deposition by the vapor deposition section before forming the inorganic film on the surface of the substrate by the film forming section and at least one timing during the formation of the inorganic film.   2. The method according to claim 1, further comprising a step of forming an organic film on the surface of the substrate before forming the inorganic film on the surface of the substrate by the film forming unit, and the inorganic film is formed on the organic film. The film forming method.   The film formation method according to claim 1, wherein the inorganic film is formed by a vacuum deposition method or a CVD method. 4. The composition according to claim 1, wherein the pressure in the chamber before the formation of the inorganic film is 1 × 10 ⁻³ Pa or less and the water pressure is 6 × 10 ⁻⁴ Pa or less. Membrane method. 5. The composition according to claim 1, wherein the pressure in the chamber during the formation of the inorganic film is 1 × 10 ⁻² Pa or less and the water pressure is 3 × 10 ⁻³ Pa or less. Membrane method.   The film formation method according to claim 1, wherein the inorganic film is formed using silicon oxide.   The film forming method according to claim 1, wherein the metal to be deposited is titanium or aluminum. A substrate and an inorganic film formed as a gas barrier film on the surface of the substrate;
The gas barrier film produced by using the film forming method according to claim 1, wherein the gas barrier film is a gas barrier film.   The gas barrier film according to claim 8, wherein an organic film is formed between the surface of the substrate and the gas barrier film.