JP6569685B2 - Film forming apparatus and gas barrier film manufacturing method - Google Patents

Description

  The present invention relates to a film forming apparatus and a gas barrier film manufacturing method. More specifically, the present invention relates to a film forming apparatus by plasma CVD suitable for manufacturing a film having excellent gas barrier performance, and a method for manufacturing a gas barrier film using the film forming apparatus.

  Conventionally, a film having a gas barrier performance (hereinafter also referred to as a gas barrier film) in which a thin film of a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on a plastic substrate or a film surface is a material such as water vapor or oxygen. It is widely used for packaging of articles that need to block various gases, packaging for preventing deterioration of foods, industrial products, pharmaceuticals, and the like. In addition to packaging applications, it is used in liquid crystal display elements, solar cells, organic electroluminescence (hereinafter abbreviated as organic EL) elements, and the like. In particular, liquid crystal display elements, organic EL elements, and the like are required to have high gas barrier properties (gas barrier properties) because internal penetration of water vapor or air causes deterioration in quality.

The demand for such a high gas barrier property such as water vapor and air has become increasingly severe in recent years, and various attempts have been made for that purpose.
For example, Patent Document 1 describes a film forming apparatus that generates plasma between metal electrodes and forms a gas barrier layer (film) on a film on the electrodes. In a film having a gas barrier layer manufactured by using the film forming apparatus, the minute protrusions existing on the film and the surface contamination of the metal roller are triggered to cause electric field concentration, dielectric breakdown, and arc discharge. . As a result, the gas barrier layer is broken, and minute defects are generated, causing the performance of the gas barrier layer to deteriorate.

  Patent Document 2 describes a plasma enhanced chemical vapor deposition (PECVD) film forming apparatus in which an insulating layer is coated on a roller electrode. By using the film forming apparatus, an insulating substrate and Similarly, it is described that a film can be formed on a conductive substrate. Therefore, when the film forming apparatus was used for forming a film having a gas barrier layer, a film having sufficient gas barrier performance could not be formed.

JP 2012-82466 A International Publication No. 2014/0888302

  The present invention has been made in view of the above-described problems and situations, and a solution to the problem is a film forming apparatus capable of producing a gas barrier film excellent in gas barrier performance, and a gas barrier for producing the gas barrier film. It is to provide a method for producing a film.

In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, etc., coats the electrode roller with a dielectric having a relative dielectric constant within a predetermined range, and circulates in the electrode roller. It was found that by setting the relative dielectric constant within a predetermined range, a gas barrier film having excellent gas barrier performance can be produced, and the present invention has been achieved.
The above-mentioned problem according to the present invention is solved by the following means.

1. A film forming apparatus for forming a film on a substrate by a plasma CVD method,
A first electrode roller provided with magnetic field forming means;
A second electrode roller disposed opposite the first electrode roller and provided with magnetic field forming means;
A controller that adjusts the relative permittivity of the surfaces of the first electrode roller and the second electrode roller,
The first electrode roller and the second electrode roller have a dielectric on the surface that contacts the substrate and a heat medium circulating inside,
The frequency of plasma discharge generated between the first electrode roller and the second electrode roller is in the range of 50 to 100 kHz,
The dielectric constant of the dielectric of the first electrode roller and the second electrode roller is in the range of 13-20, and
The film forming apparatus, wherein a relative dielectric constant of the heat medium of the first electrode roller and the second electrode roller is in a range of 40 to 70.

  2. The film forming apparatus according to claim 1, wherein the dielectric constant of the dielectric of the first electrode roller and the second electrode roller is in the range of 15-18.

3. A first electrode roller provided with a magnetic field forming means; a second electrode roller arranged opposite to the first electrode roller; and provided with a magnetic field forming means; surfaces of the first electrode roller and the second electrode roller; A gas barrier film manufacturing method for forming a film on a substrate by a plasma CVD method using a film forming apparatus including a control unit for adjusting a relative dielectric constant,
The film forming apparatus comprises a dielectric and a heat medium circulating in the surface on the surface of the first electrode roller and the second electrode roller in contact with the base material,
The frequency of plasma discharge generated between the first electrode roller and the second electrode roller is in the range of 50 to 100 kHz,
The dielectric constant of the dielectric is in the range of 13-20, and
A method for producing a gas barrier film, comprising forming a gas barrier film under a condition in which a relative dielectric constant of the heat medium is in a range of 40 to 70.

  By the means of the present invention, it is possible to provide a film forming apparatus capable of producing a gas barrier film excellent in gas barrier performance and a method for producing a gas barrier film for producing the gas barrier film.

The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
In the film forming apparatus of the present invention for forming a gas barrier film using a plasma CVD method, the frequency of plasma discharge generated between the first electrode roller and the second electrode roller is in the range of 50 to 100 kHz. The dielectric constant of the dielectric material on the surfaces of the electrode roller and the second electrode roller is controlled to 13 to 20, and the relative dielectric constant of the heat medium circulating inside the first electrode roller and the second electrode roller is controlled to 40 to 70. Therefore, it is assumed that the input electric power can be efficiently converted into plasma energy, the defects of the minute gas barrier film can be reduced, and a gas barrier film having excellent gas barrier performance can be obtained. ing.

Schematic of a film forming apparatus which is an example of the present invention

The film forming apparatus of the present invention is a film forming apparatus for forming a film on a substrate by a plasma CVD method, and is disposed opposite to the first electrode roller having a magnetic field forming means and the first electrode roller. A second electrode roller provided with magnetic field forming means, and a controller for adjusting a relative dielectric constant of the surfaces of the first electrode roller and the second electrode roller, and the first electrode roller and the second electrode roller. The electrode roller has a dielectric and a heat medium circulating in the surface in contact with the substrate, and the frequency of plasma discharge generated between the first electrode roller and the second electrode roller is 50 to 100 kHz. The dielectric constant of the dielectric of the first electrode roller and the second electrode roller is in the range of 13 to 20, and the first electrode roller and the second electrode roller The dielectric constant of the heat medium having, characterized in that it is in the range of 40 to 70.
This feature is a technical feature common to the claimed invention.

  As an embodiment of the present invention, it is preferable that the dielectric constant of the dielectric of the first electrode roller and the second electrode roller is in the range of 15 to 18 from the viewpoint of the effect of the present invention. .

Moreover, as a manufacturing method of the gas barrier film which manufactures the gas barrier film of this invention, it arrange | positioned facing the said 1st electrode roller and the 1st electrode roller provided with the magnetic field formation means, and was equipped with the magnetic field formation means. A film forming apparatus including a second electrode roller and a control unit that adjusts the relative permittivity of the surfaces of the first electrode roller and the second electrode roller is used to form a film on a substrate by a plasma CVD method. A method for producing a gas barrier film, wherein the film forming apparatus includes a dielectric and a heat medium circulating inside on a surface of the first electrode roller and the second electrode roller that are in contact with the base material, The frequency of the plasma discharge generated between the electrode roller and the second electrode roller is in the range of 50 to 100 kHz, and the relative dielectric constant of the dielectric is in the range of 13 to 20, One, the dielectric constant of the heat medium, under conditions in the range of 40 to 70, characterized by forming a gas barrier film.
Thereby, the gas barrier film which has the outstanding gas barrier performance can be obtained.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "to" is used in the meaning which includes the numerical value described before and behind as a lower limit and an upper limit.
First, an example of a preferred embodiment of a film forming apparatus of the present invention will be described with reference to the drawings.

[Configuration of deposition system]
A film forming apparatus 31 (hereinafter also referred to as a plasma CVD film forming apparatus) shown in FIG. 1 includes a delivery roller 32, transport rollers 33, 34, 35, and 36, and electrode rollers 39 and 40 (hereinafter referred to as a first electrode roller). 39 and the second electrode roller 40. When describing the first electrode roller and the second electrode roller together, they are described as “both electrode rollers”), a gas supply pipe 41, and a control unit 42. And magnetic field generators 43 and 44 installed inside both electrode rollers 39 and 40, a winding roller 45, and a plasma generating power source.

The first electrode roller 39 includes a dielectric 37A on the surface of the electrode roller, and is adjusted to a relative dielectric constant within a predetermined range by the control unit 42. Similarly, the second electrode roller 40 includes a dielectric 37B, and is adjusted to a relative dielectric constant within a predetermined range by the control unit.
Furthermore, the first electrode roller 39 and the second electrode roller 40 are provided with heat media 38A and 38B inside the respective electrode rollers, and the relative permittivity is adjusted by the control unit 42. As shown in FIG. 1, the heat medium that each electrode roller has is not limited to the case where it is disposed at the center of the electrode roller. For example, the heat medium may also be disposed inside the magnetic field generators 43 and 44. Good.

  Further, in such an apparatus, at least both the electrode rollers 39 and 40, the gas supply pipe 41, the control unit 42, and the magnetic field generators 43 and 44 are arranged in a vacuum chamber (not shown). Furthermore, in the film forming apparatus 31 for forming a film by such a plasma CVD method, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump. It has become.

In addition, it is also preferable to appropriately provide a deposition preventing member in the vacuum chamber.
There are no particular restrictions on the installation location, but there are places where there are relatively many types of film formation (for example, in the vicinity of the plasma space, in the vicinity of the gas supply unit, in the vicinity of the vacuum exhaust mechanism, etc.) It is preferable to install in.
Further, it is preferable that the adhesion preventing member is removable, and it is desirable to replace it appropriately with a new or cleaned adhesion preventing member. The timing of replacement of the adhesion-preventing member is not particularly limited.

The material of the adhesion-preventing member is not particularly limited, but metal (for example, stainless steel, iron, aluminum, titanium, etc.), ceramic (for example, alumina), glass, resin (for example, polyimide, Teflon (registered trademark), polyethylene Terephthalate, polyethylene naphthalate, olefin resin, acrylic resin, polyamide, etc.) can be used.
Moreover, the new or cleaned adhesion preventing member to be replaced may be wiped with a highly volatile solvent such as ethanol or heated before or after being attached in the chamber. The heating temperature is not particularly limited, but is preferably equal to or higher than the maximum temperature that rises during film formation.

In the film forming apparatus 31, each electrode roller is connected to the control unit 42 so that the pair of electrode rollers (the first electrode roller 39 and the second electrode roller 40) can function as a pair of counter electrodes. Has been.
Therefore, in the film forming apparatus 31, it is possible to discharge to the space between the first electrode roller 39 and the second electrode roller 40 by supplying electric power to the power source for plasma generation by the control unit 42, Thereby, plasma can be generated in the space between the first electrode roller 39 and the second electrode roller 40.

Further, in the film forming apparatus 31, the pair of electrode rollers (electrode rollers 39 and 40) are arranged so that their central axes are substantially parallel on the same plane, that is, they extend in parallel and face each other. ing. Thus, by arranging a pair of electrode rollers (electrode rollers 39 and 40), the film formation rate can be doubled and a film having the same structure can be formed. Both rollers are formed of a conductive material and convey the substrate 2 while rotating. The first electrode roller 39 and the second electrode roller 40 are insulated from each other and connected to a common control unit 42.
Further, both the electrode rollers 39 and 40 have magnetic field generators 43 and 44 stored therein. The magnetic field generators 43 and 44 are members that form a magnetic field in the space, and are stored so that the electrode rollers 39 and 40 do not rotate as a unit.

  The magnetic field generators 43 and 44 include a central magnet extending in the same direction as the extending direction of the electrode rollers 39 and 40, and the extending direction of the electrode rollers 39 and 40 while surrounding the center magnet. And an annular external magnet arranged extending in the direction. In the magnetic field generator 43, the magnetic lines of force (magnetic field) connecting the central magnet and the external magnet form an endless tunnel. Similarly, in the magnetic field generator 44, the magnetic lines connecting the central magnet and the external magnet form an endless tunnel.

  A discharge plasma of the film forming gas is generated by a magnetron discharge in which the lines of magnetic force and the electric field formed between the first electrode roller 39 and the second electrode roller 40 intersect. That is, this space is used as a film formation space for performing film formation by the plasma CVD method, and film formation is performed on the surface (film formation surface) that does not contact the first electrode roller 39 and the second electrode roller 40 in the substrate 2. A film using a gas as a forming material is formed.

  According to such a film forming apparatus 31, it is possible to form the gas barrier layer 3 on the surface of the base material 2 by plasma CVD, and it is formed on the surface of the base material 2 on the first electrode roller 39. While depositing the film component, the film deposition component can also be deposited on the surface of the substrate 2 also on the second electrode roller 40.

In the film forming apparatus 31 as described above, film formation is performed on the substrate 2 as follows. First, the inside of the vacuum chamber is set to a reduced pressure environment, and a voltage is applied to both electrode rollers 39 and 40 to generate an electric field in the space. Electrons are emitted from both electrode rollers 39 and 40 into the vacuum chamber.
At this time, since the magnetic field generators 43 and 44 form the above-described endless tunnel-like magnetic field, by introducing the film forming gas, the magnetic field and the electrons emitted into the space are introduced into the tunnel. A donut-shaped film-forming gas discharge plasma is formed. Since this discharge plasma can be generated at a low pressure in the vicinity of several Pa, the temperature in the vacuum chamber can be in the vicinity of room temperature.

On the other hand, since the temperature of electrons captured at high density in the magnetic field formed by the magnetic field generators 43 and 44 is high, discharge plasma is generated due to collision between the electrons and the deposition gas. That is, electrons are confined in the space by a magnetic field and an electric field formed in the space, so that high-density discharge plasma is formed in the space.
More specifically, a high-density (high-intensity) discharge plasma is formed in a space that overlaps with an endless tunnel-like magnetic field, and a low-density (low-density) in a space that does not overlap with an endless tunnel-like magnetic field. A strong (intensity) discharge plasma is formed. The intensity of these discharge plasmas changes continuously.

ADVANTAGE OF THE INVENTION According to this invention, the adhesion of film-forming material is reduced and the film formation apparatus provided with such an electrode roller which can be formed into a film by which the film defect was reduced by this is provided. If a gas barrier film is produced by the film forming apparatus of the present invention, a film having excellent gas barrier performance can be provided by reducing film defects.
Hereinafter, each part which comprises an apparatus is demonstrated.

[Electrode roller]
The film forming apparatus of the present invention is a film forming apparatus for forming a film on a substrate by a plasma CVD method, and is disposed opposite to the first electrode roller having a magnetic field forming means and the first electrode roller. A second electrode roller provided with magnetic field forming means, and a controller for adjusting a relative dielectric constant of the surfaces of the first electrode roller and the second electrode roller, and the first electrode roller and the second electrode roller. The electrode roller has a dielectric and a heat medium circulating in the surface in contact with the substrate, and the frequency of plasma discharge generated between the first electrode roller and the second electrode roller is 50 to 100 kHz. The dielectric constant of the dielectric of the first electrode roller and the second electrode roller is in the range of 13 to 20, and the first electrode roller and the second electrode roller The dielectric constant of the heat medium having, characterized in that it is in the range of 40 to 70.
By using such a first electrode roller and a second electrode roller exhibiting surface properties, it is possible to suppress defects generated in the gas barrier film and to be used as a film forming apparatus for obtaining a gas barrier film having excellent gas barrier performance. can do.

When the frequency of the plasma discharge generated between the first electrode roller and the second electrode roller is in the range of 50 to 100 kHz, the dielectric constant of the dielectric and the dielectric constant of the heat medium as described above are obtained. If so, the electrode rollers 39 and 40 may be made of any material.
For example, as the dielectric for coating the surface of the electrode roller, it is preferable to use alumina because it is easy to control the relative dielectric constant within the range of 13 to 20, but it is not particularly limited.

As a method for coating the dielectric, thermal spraying is preferable from the viewpoint of processing accuracy, and the processing temperature is preferably 200 ° C. or less. In addition, the sprayed surface may be sealed from the viewpoint of durability, and the sealing material is preferably selected from alkoxysilane, organosiloxane, sodium silicate, epoxy resin, phenol resin, vinyl chloride resin, More preferred are alkoxysilanes, organosiloxanes, and epoxy resins.
Similarly, the heat medium circulating inside the electrode roller is not particularly limited as long as the relative dielectric constant can be controlled within the range of 40 to 70, and for example, ethylene glycol is preferably used.
Factors controlling the relative permittivity of the dielectric and the heat medium include materials constituting the dielectric and the heat medium, the concentration of the solution circulating inside the heat medium, the temperature in the film forming apparatus, and the like. .

In addition, about the electrode roller before surface-coating a dielectric material, what is necessary is just the material generally used for an electrode roller, for example, the electrode made from titanium can be used. Furthermore, it is also preferable that at least a part of a conventional titanium electrode roller is an electrode roller coated with diamond-like carbon (hereinafter also referred to as DLC).
Diamond-like carbon is a general term for an amorphous cured film mainly composed of hydrocarbons. In the present invention, when the crystallinity of the surface of the electrode roller is evaluated by Raman spectroscopy, a cured film containing a hydrocarbon having an amorphous characteristic that can be distinguished from a crystal structure such as diamond or graphite is diamond. Like carbon. In addition to hydrocarbons, a third component element may be included.

  The DLC coating that can be preferably used in the present invention can be formed by, for example, an ionized vapor deposition method. In other words, a hydrocarbon gas such as benzene is introduced into a vacuum chamber, this gas is turned into plasma by direct current arc discharge to generate hydrocarbon ions, and these ions collide with the surface of a conventional electrode roller to thereby form an amorphous film by DLC. Can be formed. The film forming temperature of the DLC coating is preferably about 200 ° C. or less.

  For example, there are NANOCOAT-1000 and NANOCOAT-4000 (manufactured by Nanotech Co., Ltd.) as DLC film forming apparatuses, and uniform coating can be performed by an apparatus equipped with a substrate rotation mechanism. Instead of the ionized vapor deposition method, a physical vapor deposition method (PVD method) such as a high-frequency plasma CVD method, an arc ion plating method, or a sputtering method can also be used. When using the PVD method, graphite is used as a target.

In the present invention, the first and second electrode rollers are coated with the dielectrics 37A and 37B so that the relative dielectric constant falls within the range of 13 to 20, thereby suppressing abnormal plasma discharge and making the input power efficient. Since it is often used for plasma energy, it is considered that defects in a minute gas barrier film during film formation can be reduced without causing deformation of the substrate.
For example, when alumina is used as the dielectric to be coated, it is preferable to coat with a thickness in the range of 100 to 3000 μm. This is because, within this range, the stability of the plasma discharge is higher, and a uniform film can be formed.

  Note that the film thickness can be measured using a non-contact film thickness measuring apparatus using a spectral interference method. The thin film sample is irradiated with white light, and the reflection spectrum from the interface between the surface and the substrate is analyzed by a curve fitting method or FFT (Fast Fourier Transform) to measure the film thickness.

Moreover, it is preferable to use a thing with the same diameter from a viewpoint of forming both a thin film more efficiently as both the electrode rollers 39 and 40. FIG.
The diameters of both electrode rollers 39 and 40 are preferably in the range of 50 to 800 mmφ, particularly in the range of 100 to 500 mmφ, from the viewpoint of discharge conditions, chamber space, and the like.
If the diameter of the electrode roller is 50 mmφ or more, the plasma discharge space will not be reduced, so there is no deterioration in productivity, and it is possible to avoid applying the total amount of plasma discharge to the substrate 2 in a short time. 2 is preferable because it can reduce damage to 2. On the other hand, if the diameter of the electrode roller is 800 mmφ or less, it is preferable because practicality can be maintained in terms of device design including uniformity of the plasma discharge space.

  Furthermore, as will be described later, by using a gas barrier layer that satisfies the composition conditions (i), (ii), and (iii), the influence of film forming materials attached to both electrode rollers on the composition of the film is affected. Since it is easy to receive, it is preferable at the point which can reduce the defect of the obtained gas barrier layer significantly. The detailed composition of the gas barrier layer will be described in detail in the method for producing a gas barrier film.

[Control unit]
The relative dielectric constants of the dielectrics 37 </ b> A and 37 </ b> B and the heat mediums 38 </ b> A and 38 </ b> B included in both electrode rollers can be controlled by the control unit 42 included in the film forming apparatus 31.
Specifically, the control unit 42 adjusts the frequency of plasma discharge generated between the first electrode roller and the second electrode roller within a range of 50 to 100 kHz, and the first electrode roller 39 and the second electrode roller. 40, adjusting the relative dielectric constant of the dielectrics 37A and 37B within the range of 13 to 20, and the relative dielectric constant of the heat mediums 38A and 38B included in the first electrode roller 39 and the second electrode roller 40, Adjust within the range of 40-70.
Further, the control unit 42 controls the entire film forming apparatus 31 and each configuration including the plasma generation power source 51 described later with respect to the on / off of the film forming apparatus 31, the adjustment of the relative dielectric constant depending on the temperature, the operation of each configuration, and the like. The known control unit 42 can be used as appropriate.

Specifically, the control unit 42 includes a CPU (Central Processing Unit) that performs overall control of the operation of the film forming apparatus 31, a program that is read and executed by the CPU, a program memory that stores fixed data, and the like. The program memory is composed of a ROM or the like, and includes a program (including temperature control) for controlling the relative permittivity and a program for controlling the operation of the film forming apparatus.
Although the temperature of the whole film-forming apparatus controlled by the control part 42, a dielectric material, and a heat medium is not specifically limited, It is preferable that it is -30 degreeC-60 degreeC from a viewpoint of this invention expression.
The CPU reads various programs such as a system program and a processing program stored in the program memory, expands them in the RAM, and executes various processes including control of relative permittivity according to the expanded programs. As these programs, known programs can be used as appropriate.

[Power supply for plasma generation]
As the plasma generating power source 51, a known power source of a plasma generating apparatus can be used as appropriate. Such a power source for generating plasma supplies power to the first electrode roller 39 and the second electrode roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge.
As such a power source for generating plasma, since it is possible to perform plasma CVD more efficiently, a power source capable of alternately reversing the polarity of the pair of electrode rollers (AC power source or the like) is used. It is preferable to do.
Moreover, since it becomes possible to implement plasma CVD more efficiently as such a power source for plasma generation, the applied power can be set to 100 W to 10 kW, and the AC frequency is in the range of 50 Hz to 500 kHz. More preferably, it can be inside.

[Magnetic field forming means]
Inside both the electrode rollers 39 and 40, magnetic field generators (magnetic field forming means) 43 and 44 fixed so as not to rotate even when the electrode rollers rotate are provided, respectively.
The magnetic field generators 43 and 44 provided on the electrode rollers 39 and 40 respectively include a magnetic field generator 43 provided on one first electrode roller 39 and a magnetic field generator 44 provided on the other second electrode roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between each other and the magnetic field generators 43 and 44 form a substantially closed magnetic circuit.
By providing such magnetic field generators 43 and 44, it is possible to promote the formation of a magnetic field in which the magnetic lines of force swell in the vicinity of the opposing surfaces of the electrode rollers 39 and 40, and the plasma is easily converged on the bulging portion. Therefore, it is excellent in that the film formation efficiency can be improved.

In addition, as the magnetic field generators 43 and 44 provided in the electrode rollers 39 and 40, respectively, known magnetic field generators can be used as appropriate.
The magnetic field generators 43 and 44 each have a racetrack-like magnetic pole that is long in the roller axis direction, and the magnetic poles are arranged so that the magnetic poles facing one magnetic field generator 43 and the other magnetic field generator 44 have the same polarity. It is preferable.
By providing such magnetic field generating devices 43 and 44, the opposing space along the length direction of the roller shaft without straddling the magnetic field generating device on the roller side where the magnetic field lines are opposed to each of the magnetic field generating devices 43 and 44. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region). Therefore, since the plasma can be converged on the magnetic field, it is excellent in that the gas barrier layer 3 can be efficiently formed using the wide base material 2 wound around the roller width direction. .

[Feeding roller and conveying roller]
As the feed roller 32 and the transport rollers 33, 34, 35, and 36 used in the film forming apparatus, known rollers can be appropriately used. Further, the take-up roller 45 is not particularly limited as long as it can take up the gas barrier film 1 in which the gas barrier layer 3 is formed on the substrate 2, and a known roller is appropriately used. Can do.

[Gas supply pipe and vacuum pump]
Further, as the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the raw material gas or the like at a predetermined speed can be appropriately used.
Further, the gas supply pipe 41 serving as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the first electrode roller 39 and the second electrode roller 40, and is a vacuum exhaust means. A certain vacuum pump (not shown) is preferably provided in the other of the opposed spaces.
As described above, by arranging the gas supply pipe 41 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film forming gas can be efficiently formed in the facing space between the first electrode roller 39 and the second electrode roller 40. Is excellent in that the film formation efficiency can be improved.

[Method for producing gas barrier film]
The film forming apparatus of the present invention shown as a preferred embodiment in FIG. 1 can be used for manufacturing any film that can be formed by a plasma CVD method. However, the film-forming apparatus by the plasma CVD method of the present invention is particularly suitable for the production of a gas barrier film.
Hereinafter, a preferable aspect is demonstrated about the manufacturing method of a gas barrier film. That is, according to this invention, the manufacturing method of the gas barrier film which has the process of forming a gas barrier layer on a base material using the film-forming apparatus of this invention is also provided.

The gas barrier film 1 preferably has a configuration in which the gas barrier layer 3 is formed on the substrate 2 by a film forming apparatus. In the present invention, “showing gas barrier properties” means the water vapor permeability (abbreviation: WVTR, temperature: 38 ° C., relative humidity) measured by a method according to JIS K 7129-2008 for a gas barrier film. RH): 90%) is 0.1 g / m ² · 24 h or less as a whole, and preferably the oxygen permeability is 0.01 ml / m ² · 24 h · atm or less.
The water vapor transmission rate can also be measured by a method described in JP 2004-333127 A. Similarly, the oxygen permeability can be measured by the method described in JIS K 7126-2006.

(Base material)
As the substrate 2, a film or sheet made of a resin or a composite material containing a resin is preferably used. Such a resin film or sheet may have translucency or may be opaque.
Examples of the resin constituting the substrate 2 include polyester resins such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polyolefin resins such as polyethylene (PE), polypropylene (PP), or cyclic polyolefin, polyamide resins, and polycarbonates. Resin, polystyrene resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, polyacrylonitrile resin, acetal resin, polyimide resin, polyether sulfide (PES) resin, etc. A combination of more than one species can also be used.
The polyester resin and the polyolefin resin are preferably selected according to necessary properties such as transparency, heat resistance, and linear expansion property, and PET, PEN, and cyclic polyolefin are more preferable.

  In addition, examples of the composite material including a resin include silicone resins such as polydimethylsiloxane and polysilsesquioxane, a glass composite substrate, and a glass epoxy substrate. Among these resins, polyester resins, polyolefin resins, glass composite substrates, and glass epoxy substrates are preferable from the viewpoint of high heat resistance and high linear expansion coefficient. Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.

The thickness of the base material 2 is appropriately set in consideration of stability and the like when the base material 2 is manufactured. However, since the transport of the base material 2 is easy even in a vacuum, the thickness is in the range of 5 to 250 μm. It is preferable to be within.
Furthermore, in the formation of the gas barrier film employed in the present embodiment, since the discharge is performed through the base material 2, the thickness of the base material 2 is more preferably in the range of 50 to 200 μm, and the range of 50 to 150 μm. It is particularly preferred that
The substrate 2 may be subjected to a surface activation treatment for cleaning the surface from the viewpoint of adhesion to the gas barrier film to be formed. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

(Gas barrier layer)
The gas barrier layer is a layer that exhibits the gas barrier performance of the gas barrier film, and preferably satisfies the following relationship.
(I) The distance (L) from the gas barrier layer surface in the layer thickness direction of the gas barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (silicon atomic ratio) A silicon distribution curve showing the relationship, an oxygen distribution curve showing the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of oxygen), and the L and silicon atoms, In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of oxygen atoms and carbon atoms (the atomic ratio of carbon), a region of 90% or more (upper limit: 100%) of the thickness of the gas barrier layer In this order, (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in this order (atomic ratio is O>Si> C).
(Ii) The carbon distribution curve has at least two extreme values.
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter also simply referred to as “C _max −C _min difference”) is 3 at% or more.

First, the gas barrier layer comprises (i) a distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer, and a ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms. The silicon distribution curve showing the relationship with (atom ratio of silicon), the oxygen distribution curve showing the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (oxygen atomic ratio) And 90% or more of the thickness of the gas barrier layer in a carbon distribution curve showing a relationship between the L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio) ( (Upper limit: 100%) in the order of (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) (atomic ratio is O>Si> C).
When the above condition (i) is satisfied, the resulting gas barrier film has better gas barrier properties and flexibility.

Here, in the carbon distribution curve, the relationship between (atomic ratio of oxygen), (atomic ratio of silicon) and (atomic ratio of carbon) is at least 90% or more (upper limit: 100%) of the thickness of the gas barrier layer. ) And more preferably at least 93% or more (upper limit: 100%).
The term “at least 90% or more of the thickness of the gas barrier layer” does not need to be continuous in the gas barrier layer, and only needs to satisfy the above-described relationship at a portion of 90% or more.

In the gas barrier layer, (ii) the carbon distribution curve has at least two extreme values.
The gas barrier layer preferably has at least three extreme values in the carbon distribution curve, more preferably at least four extreme values, but may have five or more extreme values. When the extreme value of the carbon distribution curve is at least two, the gas barrier property when the obtained gas barrier film is bent is more excellent.
The upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 or less, more preferably 25 or less, for example. Since the number of extreme values is also caused by the thickness of the gas barrier layer, it cannot be specified unconditionally.

Here, in the case of having at least three extreme values, from the surface of the gas barrier layer in the thickness direction of the gas barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value. The absolute value of the difference in distance (L) (hereinafter also simply referred to as “distance between extreme values”) is preferably 200 nm or less, more preferably 100 nm or less, and 75 nm or less. It is particularly preferred.
With such a distance between extreme values, there are portions with a high carbon atom ratio (maximum value) in the gas barrier layer at an appropriate period, so that the gas barrier layer is provided with an appropriate flexibility, and the gas barrier Generation of cracks when the film is bent can be more effectively suppressed / prevented.
In this specification, “extreme value” means a maximum value or a minimum value of an atomic ratio of an element to a distance (L) from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer.

In the present specification, the “maximum value” means that the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from increasing to decreasing when the distance from the surface of the gas barrier layer is changed. And the atomic ratio of the element at a position where the distance from the point in the layer thickness direction of the gas barrier layer to the surface of the gas barrier layer is further changed within the range of 4 to 20 nm from the value of the atomic ratio of the element at that point. This is the point at which the value decreases by 3 at% or more. That is, when changing in the range of 4-20 nm, the value of the atomic ratio of an element should just decrease by 3 at% or more in either range.
Similarly, in this specification, “minimum value” means that the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from decrease to increase when the distance from the surface of the gas barrier layer is changed. The value of the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer from the point is further changed by 4 to 20 nm than the value of the atomic ratio of the element at that point Is a point that increases by 3 at% or more.

  That is, when changing within the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range. Here, in the case of having at least three extreme values, the lower limit of the distance between extreme values is particularly high because the smaller the distance between extreme values, the higher the effect of suppressing / preventing crack generation during bending of the gas barrier film. Although not limited, in consideration of the flexibility of the gas barrier layer, the effect of suppressing / preventing cracks, thermal expansion, and the like, the thickness is preferably 10 nm or more, and more preferably 30 nm or more.

Furthermore, the gas barrier layer preferably has (iii) the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.
When the absolute value is 3 at% or more, the gas barrier property is more excellent when the obtained gas barrier film is bent. The C _max -C _min difference is preferably 5 at% or more, more preferably 7 at% or more, and particularly preferably 10 at% or more.
By setting the C _max −C _min difference, the gas barrier property can be further improved. In the present specification, the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values. Here, the upper limit of the C _max -C _min difference is not particularly limited, but it is preferably 50 at% or less and 40 at% or less in consideration of the effect of suppressing / preventing crack generation at the time of bending of the gas barrier film. It is more preferable that

In the present invention, the oxygen distribution curve of the gas barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and more preferably has at least three extreme values. When the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved.
The upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the thickness of the gas barrier layer, and it cannot be defined unconditionally.

In the case of having at least three extreme values, the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer at one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value. The absolute value of the difference is preferably 200 nm or less, and more preferably 100 nm or less.
With such a difference in distance between extreme values, the occurrence of cracks when the gas barrier film is bent can be more effectively suppressed / prevented. Here, in the case of having at least three extreme values, the lower limit of the distance between the extreme values is not particularly limited, but considering the effect of suppressing / preventing crack generation at the time of bending of the gas barrier film, the thermal expansion property, etc. The thickness is preferably 10 nm or more, and more preferably 30 nm or more.

In addition, in the present invention, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the gas barrier layer (hereinafter also simply referred to as “O _max −O _min difference”) is 3 at. % Or more, more preferably 6 at% or more, and further preferably 7 at% or more. When the absolute value is 3 at% or more, the gas barrier property when the obtained gas barrier film is bent is further improved. Here, the upper limit of the O _max -O _min difference is not particularly limited, but it is preferably 50 at% or less, and 40 at% or less in consideration of the effect of suppressing / preventing crack generation during bending of the gas barrier film. It is more preferable that

In the present invention, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of the gas barrier layer (hereinafter also simply referred to as “Si _max −Si _min difference”) is 10 at% or less. Preferably, it is 7 at% or less, more preferably 3 at% or less. When the absolute value is 10 at% or less, the gas barrier properties of the obtained gas barrier film are further improved.
The lower _limit of Si max _{-Si min} difference _has a high effect of improving the crack generation suppression / prevention during bending of Si max _{-Si min} difference gas barrier film The smaller is not particularly limited, gas barrier properties, etc. Is considered to be 1 at% or more, and more preferably 2 at% or more.

In the present invention, the total amount of carbon and oxygen atoms with respect to the thickness direction of the gas barrier layer is preferably substantially constant. Thereby, a gas barrier layer exhibits moderate flexibility, and the crack generation at the time of bending of a gas barrier film can be suppressed and prevented more effectively.
More specifically, the distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer and the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms In the oxygen-carbon distribution curve showing a relationship with (atomic ratio of oxygen and carbon), the absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the oxygen-carbon distribution curve (hereinafter simply referred to as “OC”). _"max- OC _min difference") is preferably less than 5 at%, more preferably less than 4 at%, and even more preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property of the obtained gas barrier film is further improved. _The lower limit of the OC max _{-OC min difference,} since preferably as OC max _{-OC min} difference is small, but is 0 atomic%, it is sufficient if more than 0.1 at%.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon distribution curve use both X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon. Thus, it can be created by so-called XPS depth profile measurement in which the surface composition analysis is sequentially performed while the inside of the sample is exposed.
A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).

In the element distribution curve with the horizontal axis as the etching time, the etching time is generally correlated with the distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the thickness direction. Therefore, as the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”, the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement The distance from can be adopted.
Moreover, a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve can be created under the following measurement conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 μm × 400 μm oval

The thickness (dry layer thickness) of the gas barrier layer is not particularly limited as long as the above (i) to (iii) are satisfied. The thickness of the gas barrier layer is preferably 20 to 3000 nm, more preferably 50 to 2500 nm, and particularly preferably 100 to 1000 nm. With such a thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending.
In addition, when a gas barrier layer is comprised from 2 or more layers, it is preferable that each gas barrier layer has thickness as mentioned above. In addition, the thickness of the entire gas barrier layer when the gas barrier layer is composed of two or more layers is not particularly limited, but the thickness of the entire gas barrier layer (dry layer thickness) is preferably about 1000 to 2000 nm. . With such a thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending.

In the present invention, from the viewpoint of forming a gas barrier layer having a uniform and excellent gas barrier property over the entire film surface, the gas barrier layer is substantially in the film surface direction (direction parallel to the surface of the gas barrier layer). Are preferably uniform.
Here, the gas barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve, and the carbon distribution curve at any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement. When the oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the maximum value of the atomic ratio of carbon in each carbon distribution curve And the absolute value of the difference between the minimum values is the same as each other or within 5 at%.

Furthermore, in the present invention, it is preferable that the carbon distribution curve is substantially continuous. Here, “substantially continuous carbon distribution curve” means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. Between the distance (x, unit: nm) from the surface of the gas barrier layer in the thickness direction of at least one of the gas barrier layers to be formed and the atomic ratio of carbon (C, unit: at%) Means satisfying the condition represented by the following formula 1.
Formula 1:
(DC / dx) ≦ 0.5
In the gas barrier film according to the present invention, the gas barrier layer satisfying all the conditions (i) to (iii) may include only one layer or two or more layers. Furthermore, when two or more such gas barrier layers are provided, the materials of the plurality of gas barrier layers may be the same or different.

In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atomic ratio, the oxygen atomic ratio, and the carbon atomic ratio are in the region where 90% or more of the thickness of the gas barrier layer is (i). In the gas barrier layer, the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably 20 to 45 at%, More preferably, it is ˜40 at%.
The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably 45 to 75 at%, more preferably 50 to 70 at%. .
Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably 0 to 25 at%, more preferably 1 to 20 at%. .

(Gas barrier layer manufacturing method)
The gas barrier layer described above is formed by using the film forming apparatus 31 shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the electrode roller, and the film (base The gas barrier layer according to the present invention can be manufactured by appropriately adjusting the conveyance speed of the material.
That is, using the film forming apparatus 31 shown in FIG. 1, discharge is generated between a pair of electrode rollers (both electrode rollers 39 and 40) while supplying a film forming gas (raw material gas or the like) into the vacuum chamber. Thus, the film forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer 3 is formed on the surface of the substrate 2 on the first electrode roller 39 and on the surface of the substrate 2 on the second electrode roller 40. Is formed by plasma CVD. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller shafts of both electrode rollers 39 and 40, and the plasma is converged on the magnetic field.

For this reason, when the base material 2 passes A point of the 1st electrode roller 39 in FIG. 1, and B point of the 2nd electrode roller 40, the maximum value of a carbon distribution curve is formed in a gas barrier layer. On the other hand, when the base material 2 passes the points C1 and C2 of the first electrode roller 39 and the points C3 and C4 of the second electrode roller 40 in FIG. 1, the carbon distribution curve is minimized in the gas barrier layer. A value is formed.
For this reason, five extreme values are usually generated for two electrode rollers. Further, the distance between extreme values of the gas barrier layer (distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value (L) (The absolute value of the difference) can be adjusted by the rotational speed of the electrode rollers 39 and 40 (the conveying speed of the substrate).
In such film formation, the substrate 2 is conveyed by the delivery roller 32, the first electrode roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. A gas barrier layer is formed thereon.

Further, when generating plasma in the plasma CVD method, it is preferable to generate plasma discharge in the space between the plurality of electrode rollers, and a pair of electrode rollers is used, and the base material is used for each of the pair of electrode rollers. More preferably, a plasma is generated by discharging between the pair of electrode rollers.
In this way, by using a pair of electrode rollers, disposing a base material on the pair of electrode rollers and discharging between the pair of electrode rollers, a group present on one electrode roller at the time of film formation While forming the surface portion of the material, the surface portion of the base material existing on the other electrode roller can be simultaneously formed, and the thin film can be produced efficiently.
Furthermore, the film formation rate can be doubled compared to the plasma CVD method without using a normal roller, and a film having almost the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled, and the efficiency It is possible to form a layer that satisfies all the conditions (i) to (iii).

Moreover, when discharging between a pair of electrode rollers in this way, it is preferable to reverse the polarities of the pair of electrode rollers alternately.
Further, the film forming gas used in such a plasma CVD method preferably includes an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation.
In the gas barrier film of the present invention, the gas barrier layer is preferably a layer formed by a continuous film forming process.

Moreover, it is preferable that the gas barrier film which concerns on this invention forms the said gas barrier layer on the surface of the said base material by a roll to roll system from a viewpoint of productivity.
Further, an apparatus that can be used when producing a gas barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of electrode rollers and a control unit, and the pair of electrode rollers. For example, in the case of using the film forming apparatus by the plasma CVD method shown in FIG. 1, a roll-to-roller using the plasma CVD method is used. It is also possible to manufacture by a roll method.

(Deposition gas)
As a film forming gas (such as a source gas) supplied from the gas supply pipe 41 to the facing space, a source gas, a reaction gas, a carrier gas, and a discharge gas may be used alone or in combination of two or more.
The source gas in the film-forming gas used for forming the gas barrier layer can be appropriately selected and used according to the material of the gas barrier layer to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used.
Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane.

Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting gas barrier layer.
These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene.
As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the gas barrier layer. Furthermore, it is good also as using as a silicon source of the gas barrier film | membrane which contains monosilane other than the above-mentioned organosilicon compound as source gas, and forms.

In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used.
As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used alone or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride can be used in combination.

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen can be used.

When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount.
By not excessively increasing the ratio of the reaction gas, the gas barrier layer formed is excellent in that excellent gas barrier properties and bending resistance can be obtained. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

Hereinafter, as the film forming gas, hexamethyldisiloxane (organosilicon compound, HMDSO, (CH ₃ ) ₆ Si ₂ O) as a raw material gas and oxygen (O ₂ ) as a reactive gas are used. Taking a case of producing a silicon-oxygen-based thin film as an example, a suitable ratio of the raw material gas and the reactive gas in the film forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by a plasma CVD method to produce silicon-oxygen. When a thin film of a system is produced, a reaction represented by the following reaction formula 1 occurs by the film forming gas, and silicon dioxide is generated.
Reaction formula 1:
(CH ₃ ) ₆ SiO + 12O ₂ → 6CO ₂ + 9H ₂ O + SiO ₂

  In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, a uniform silicon dioxide film is formed when oxygen is contained in the film forming gas in an amount of 12 moles or more per mole of hexamethyldisiloxane and a uniform silicon dioxide film is formed (a carbon distribution curve exists). Therefore, it becomes impossible to form a gas barrier layer that satisfies all the conditions (i) to (iii). Therefore, in the present invention, when the gas barrier layer is formed, the oxygen amount is set to the stoichiometric ratio with respect to 1 mol of hexamethyldisiloxane so that the reaction of the reaction formula 1 does not proceed completely. Preferably less than 12 moles.

In the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas Even if the (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane (flow rate), the reaction cannot actually proceed completely, and the oxygen content is reduced. It is considered that the reaction is completed only when a large excess of the stoichiometric ratio is supplied.
For example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material.

  Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer, and the conditions (i) to ( It becomes possible to form a gas barrier layer that satisfies all iii), and it is possible to exhibit excellent gas barrier properties and flex resistance in the obtained gas barrier film.

  From the viewpoint of use as a flexible substrate for devices that require transparency, such as organic EL elements and solar cells, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas The lower limit of (flow rate) is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.

  The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but the space pressure is preferably 0.1 to 50 Pa. When plasma CVD is a low pressure plasma CVD method for the purpose of suppressing a gas phase reaction, it is usually 0.1 to 10 Pa. Moreover, the electric power of the electrode drum of the plasma generator can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably 0.1 to 10 kW.

  Although the conveyance speed (line speed) of the base material 2 can be suitably adjusted according to the kind of source gas, the pressure in a vacuum chamber, etc., it is preferable that it is 0.1-100 m / min, 0.5 More preferably, it is -20 m / min. When the line speed is less than the lower limit, wrinkles due to heat tend to occur in the base material 100. On the other hand, when the line speed exceeds the upper limit, the thickness of the formed gas barrier film tends to be thin. . When transporting, the base material 2 fed out from the transport roller and formed on the first electrode roller 39 is transported to the second electrode roller 40 while the film formation surface is wound around the turn bar.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited to a following example. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented. In addition, about the gas barrier films 101-117 produced in the Example, it showed in Table 1 as the films 101-117. The relative permittivity of the dielectric provided in the first electrode roller and the second electrode roller is “relative permittivity 1”, and the relative permittivity of the heat medium circulating inside the first electrode roller and the second electrode roller is “relative permittivity”. The rate was shown as “2”.

[Production of Film 101]
(Preparation of resin base material)
A biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) was used as a resin substrate.

(Formation of anchor layer)
After applying UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation with a wire bar so that the layer thickness after drying is 4 μm on the easy adhesion surface of the resin base material, After drying at 3 ° C. for 3 minutes, curing was performed in an air atmosphere using a high-pressure mercury lamp under curing conditions of 1.0 J / cm ² to form an anchor layer.

(Formation of gas barrier layer)
200 μm of alumina is coated on the first and second electrode rollers, and then an epoxy resin solution is applied as a sealing material, dried at 200 ° C., surface-polished and finished, and a relative dielectric constant of 1 at 20 ° C. is 15. A gas barrier film was formed using a plasma CVD film forming apparatus in which an ethylene glycol aqueous solution whose concentration was adjusted so that the dielectric constant was 55 was circulated inside the film forming roller. Mount the resin substrate on the device so that the surface opposite to the surface on which the anchor layer of the resin substrate is formed is in contact with the electrode roller, and on the anchor layer according to the following film formation conditions (plasma CVD conditions) A gas barrier film was formed under the condition that the thickness was 300 nm.

<Plasma CVD conditions>
Feed rate of source gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Resin substrate transport speed: 2 m / min

[Production of Film 102]
Applying the sealing material to the alumina coated on the first and second electrode rollers and drying iteratively twice in the same manner as in the film 101 except that the relative dielectric constant 1 at 20 ° C. was adjusted to 18. A gas barrier film 102 was produced.

[Production of Film 103]
The film 101 except that the alumina purity to be coated on the first and second electrode rollers, the sealing material application to the alumina, and the drying were repeated twice in succession so that the relative dielectric constant 1 at 20 ° C. was 20. In the same manner as described above, a gas barrier film 103 was produced.

[Production of Film 104]
A gas barrier film 104 was produced in the same manner as the film 101 except that the purity of the alumina coated on the first and second electrode rollers was changed and the relative dielectric constant 1 at 20 ° C. was adjusted to 13.

[Production of Film 105]
A gas barrier film 105 was produced in the same manner as the film 101 except that the concentration of the ethylene glycol aqueous solution in the first and second electrode rollers was changed and the relative dielectric constant 2 at 20 ° C. was adjusted to 40.

[Production of Film 106]
A gas barrier film 106 was produced in the same manner as the film 101 except that the concentration of the ethylene glycol aqueous solution in the first and second electrode rollers was changed and the relative dielectric constant 2 at 20 ° C. was adjusted to 70.

[Production of Film 107]
A gas barrier film 107 was produced in the same manner as the film 101 except that the purity of the alumina coated on the first and second electrode rollers was changed and the relative dielectric constant 1 at 20 ° C. was adjusted to 12.

[Production of Film 108]
Except for changing the purity of the alumina coated on the first and second electrode rollers, repeating the sealing material application and drying to alumina twice in succession, and adjusting the relative dielectric constant 1 at 20 ° C. to 21. A gas barrier film 108 was produced in the same manner as the film 101.

[Production of Film 109]
By changing the alumina purity to be coated on the first and second electrode rollers, adjusting the relative dielectric constant 1 at 20 ° C. to 12, by adjusting the concentration of the aqueous propylene glycol solution in the first and second electrode rollers, A gas barrier film 109 was produced in the same manner as the film 101 except that the relative dielectric constant 2 at 20 ° C. was changed to 35.

[Production of Film 110]
A gas barrier film 110 was produced in the same manner as the film 101 except that the relative dielectric constant 2 at 20 ° C. was adjusted to 35 by adjusting the concentration of the aqueous propylene glycol solution in the first and second electrode rollers.

[Production of Film 111]
The alumina purity to be coated on the first and second electrode rollers is changed, the sealing material application to alumina and the drying are repeated twice in succession, and the relative dielectric constant 1 at 20 ° C. is adjusted to 21, A gas barrier film 111 was produced in the same manner as the film 101 except that the relative dielectric constant 2 at 20 ° C. was adjusted to 35 by adjusting the concentration of the aqueous propylene glycol solution in the first and second electrode rollers.

[Production of Film 112]
The purity of the alumina to be coated on the first and second electrode rollers is changed, the relative dielectric constant 1 at 20 ° C. is adjusted to 12, and the water is circulated in the first and second electrode rollers so that the ratio at 20 ° C. A gas barrier film 112 was produced in the same manner as the film 101 except that the dielectric constant 2 was adjusted to 80.

[Production of Film 113]
A gas barrier film 113 was produced in the same manner as the film 101 except that the water in the first and second electrode rollers was circulated and the relative dielectric constant 2 at 20 ° C. was adjusted to 80.

[Production of Film 114]
The alumina purity to be coated on the first and second electrode rollers is changed, the sealing material application to alumina and the drying are repeated twice in succession, and the relative dielectric constant 1 at 20 ° C. is adjusted to 21, A gas barrier film 114 was produced in the same manner as the film 101 except that water was circulated through the first and second electrode rollers and the relative dielectric constant 2 at 20 ° C. was adjusted to 80.

[Production of Film 115]
Coating is not carried out on the first and second electrode rollers, but the same as film 101 except that water is circulated in the first and second electrode rollers and the relative dielectric constant 2 at 20 ° C. is adjusted to 80. A gas barrier film 115 was produced.

[Production of Film 116]
Coating is not carried out on the first and second electrode rollers, but the same as the film 101 except that water is circulated in the first and second electrode rollers and the relative dielectric constant 2 at 20 ° C. is adjusted to 55. A gas barrier film 116 was produced.

[Production of Film 117]
Coating is not carried out on the first and second electrode rollers, but the same as the film 101 except that water is circulated in the first and second electrode rollers and the relative dielectric constant 2 at 20 ° C. is adjusted to 35. A gas barrier film 117 was produced.

<Water vapor permeability measurement>
The obtained gas barrier film was measured for water vapor permeability (WVTR) [g / m ² · 24 h] under conditions of 38 ° C. and relative humidity 90% using a water vapor permeability measuring device AQUATRAN manufactured by MOCON. The results are shown in Table 1. For those shown as "<2 × ^{10 -4"} indicates that water vapor permeability is less than ^{2 × 10 -4 g / m 2} · 24h.

As shown in Table 1, the films 101 to 106 in which the relative dielectric constant 1 of the surface of the electrode roller and the relative dielectric constant 2 of the internal heat medium satisfy the specified range of the present invention exhibit excellent gas barrier properties. I understood it.
In contrast, at least one of the relative dielectric constant 1 of the surface of the electrode roller and the relative dielectric constant 2 of the internal heat medium is out of the specified range of the present invention or the films 107 to 117 without the dielectric coating are It was found that the barrier property was inferior.
From the above, when the relative dielectric constant 1 of the surface of the electrode roller and the relative dielectric constant 2 of the internal heat medium satisfy the specified range of the present invention, a film surface defect of the gas barrier film occurs, and excellent gas barrier properties are obtained. It turned out that the gas barrier film which has is obtained.

  The film forming apparatus of the present invention can be used in the field of manufacturing a gas barrier film, and further requires packaging of food, industrial products, pharmaceuticals, etc. that require blocking of water vapor, oxygen, etc., and liquid crystal display elements It can be suitably used for organic electronic devices such as photoelectric conversion elements and organic EL elements.

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Base material 3 Gas barrier layer 31 Film-forming apparatus 32 Delivery rollers 33, 34, 35, 36 Transport rollers 37A, 37B Dielectric 38A, 38B Heat medium 39 First electrode roller 40 Second electrode roller 41 Gas supply Tube 42 Controllers 43, 44 Magnetic field generator 45 Winding roller 51 Power source for plasma generation

Claims (3)

A film forming apparatus for forming a film on a substrate by a plasma CVD method,
A first electrode roller provided with magnetic field forming means;
A second electrode roller disposed opposite the first electrode roller and provided with magnetic field forming means;
A controller that adjusts the relative permittivity of the surfaces of the first electrode roller and the second electrode roller,
The first electrode roller and the second electrode roller have a dielectric on the surface that contacts the substrate and a heat medium circulating inside,
The frequency of plasma discharge generated between the first electrode roller and the second electrode roller is in the range of 50 to 100 kHz,
The dielectric constant of the dielectric that the first electrode roller and the second electrode roller have is within a range of 13 to 20, and
The film forming apparatus, wherein a relative dielectric constant of the heat medium of the first electrode roller and the second electrode roller is in a range of 40 to 70.   The film forming apparatus according to claim 1, wherein a relative dielectric constant of the dielectric included in the first electrode roller and the second electrode roller is in a range of 15 to 18. A first electrode roller provided with a magnetic field forming means; a second electrode roller arranged opposite to the first electrode roller; and provided with a magnetic field forming means; surfaces of the first electrode roller and the second electrode roller; A gas barrier film manufacturing method for forming a film on a substrate by a plasma CVD method using a film forming apparatus including a control unit for adjusting a relative dielectric constant,
The film forming apparatus comprises a dielectric and a heat medium circulating in the surface on the surface of the first electrode roller and the second electrode roller in contact with the base material,
The frequency of plasma discharge generated between the first electrode roller and the second electrode roller is in the range of 50 to 100 kHz,
The dielectric constant of the dielectric is in the range of 13-20, and
A method for producing a gas barrier film, comprising forming a gas barrier film under a condition in which a relative dielectric constant of the heat medium is in a range of 40 to 70.

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