JPWO2017104357A1 - Electrode for plasma CVD film forming apparatus, electrode manufacturing method, plasma CVD film forming apparatus, and functional film manufacturing method - Google Patents

Abstract

An electrode for a plasma CVD film forming apparatus excellent in productivity by suppressing arc discharge and a decrease in film forming speed, a method for manufacturing the electrode, a plasma CVD film forming apparatus including the electrode, and the plasma CVD process Provided is a method for producing a functional film using a membrane device. The plasma CVD film-forming apparatus (31) is characterized by having dielectric layers (37) and (38) on the surface containing alumina and titania in a mass ratio of alumina / titania = 80/20 to 40/60. Electrodes (39) and (40). Moreover, it is the manufacturing method of the said electrode by a plasma spraying method. Moreover, it is a plasma CVD film-forming apparatus (31) provided with the said electrode. Moreover, it is a manufacturing method of the functional film which forms a functional film (3) on a base film (2) using the said plasma CVD film-forming apparatus.

Description

  The present invention relates to an electrode used in a plasma CVD film forming apparatus, a method for manufacturing the electrode, a plasma CVD film forming apparatus including the electrode, and a method for manufacturing a functional film using the plasma CVD film forming apparatus.

In recent years, various functional films in which a thin film layer is formed on a flexible resin substrate such as a plastic film or a sheet have been proposed because of the advantages of being light and difficult to break.
For example, a gas barrier film in which a metal or metal oxide film is formed on a base film is a packaging material for articles that require blocking of water vapor, oxygen, etc., in particular, to prevent alteration of food, industrial goods, pharmaceuticals, etc. It is widely used as a packaging material. Gas barrier films are also used as substrates for organic electronic devices such as liquid crystal display elements, photoelectric conversion elements (solar cells), organic electroluminescence elements (organic EL elements), and the like.

  Such a functional film is manufactured by forming a functional film on a base film in a roll-to-roll manner while continuously conveying a long base film in order to improve productivity. The In the case of a gas barrier film, there is a plasma CVD method as a typical film forming method of the gas barrier film.

  In the case where a film is formed on a base film by a plasma CVD method by a roll-to-roll method, a method of continuously forming a film on the electrode using a roll-shaped electrode is known. At this time, in order to increase the film formation speed and productivity, the power supplied between the electrodes is increased. However, when the power is increased, unintentional irregular arc discharge (abnormal discharge) occurs between the electrodes, causing a problem that the film forming apparatus stops or a film defect of the gas barrier film occurs.

  In order to suppress such irregular abnormal discharge between the electrodes, for example, the outer peripheral surface of a roll-shaped electrode (metal can) is covered with an insulating layer mainly composed of alumina, and film formation is performed by a plasma CVD method. A film forming method and a film forming apparatus are disclosed (see Patent Document 1).

Japanese Patent Laid-Open No. 11-6071

  However, in the method of covering the electrode with an insulating layer mainly composed of alumina, the effective power input into the plasma space is greatly reduced, the film quality (gas barrier property and optical characteristics) fluctuates, and the film formation speed is increased. Has been found to cause problems such as lowering.

  The present invention has been made in view of the above situation. That is, an object of the present invention is to suppress an arc discharge, suppress a decrease in film formation rate, and have excellent productivity for an electrode for a plasma CVD film forming apparatus, a method for manufacturing the electrode, and a plasma CVD including the electrode It is providing the manufacturing method of a functional film using a film-forming apparatus and the said plasma CVD film-forming apparatus.

  The present inventors have examined the cause of the above-mentioned problem in order to solve the above-mentioned problems. When the input power is increased in order to increase the productivity of a functional film (for example, a gas barrier film), arc discharge is likely to occur between the electrodes. When arc discharge occurs during film formation, defects occur in the gas barrier film, and the gas barrier property is remarkably lowered.

  In the prior art, alumina, which is a low dielectric constant material (10 or less), is generally used as a coating material for electrodes. However, when alumina is used as the electrode covering material, the voltage drop in the alumina layer during discharge increases, so that not only the discharge starting voltage increases but also the electrode surface temperature increases compared to when there is no covering. It becomes easy. When the temperature of the electrode surface is increased during film formation, the film density, film growth, and thermal deformation of the base film are greatly affected, and the film quality is deteriorated.

  Therefore, the present inventors have found that the above-mentioned problems can be solved by using a mixture of alumina and titania as the electrode covering material and setting the mixing ratio to an appropriate range. That is, the present invention has the following configuration.

1. An electrode for use in a plasma CVD film forming apparatus, comprising a dielectric layer containing alumina and titania in a mass ratio of alumina / titania = 80/20 to 40/60 on the surface.

2. 2. The electrode according to 1 above, wherein a mass ratio of the alumina and the titania is alumina / titania = 70/30 to 60/40.

3. 3. The electrode according to 1 or 2 above, wherein a nickel alloy layer is provided between the electrode surface and the dielectric layer.

4). A method for manufacturing an electrode for a plasma CVD film forming apparatus having a dielectric layer containing alumina and titania at a mass ratio of alumina / titania = 80/20 to 40/60 on the surface, the dielectric containing alumina and titania A method of manufacturing an electrode for a plasma CVD film forming apparatus, wherein a layer is formed on an electrode surface by a plasma spraying method.

5. A plasma CVD film forming apparatus comprising an electrode having a dielectric layer containing alumina and titania in a mass ratio of alumina / titania = 80/20 to 40/60 on the surface.

6). A functional film is formed on a base film using a plasma CVD film forming apparatus having an electrode having a dielectric layer on its surface containing alumina and titania in a mass ratio of alumina / titania = 80/20 to 40/60. A method for producing a functional film to be formed.

7). 7. The production of the functional film as described in 6 above, wherein the electrodes are a pair of cylindrical electrodes disposed so as to face each other, and are formed while the long base film is wound around the electrodes. Method.

  The electrode for the plasma CVD film forming apparatus of the present invention is excellent in productivity by suppressing arc discharge and suppressing a decrease in film forming speed. Moreover, the manufacturing method of the electrode for plasma CVD film-forming apparatuses of this invention can manufacture the said electrode. Moreover, the plasma CVD film-forming apparatus of this invention provided with the said electrode suppresses arc discharge, suppresses the fall of the film-forming speed | rate, and is excellent in productivity. Moreover, the manufacturing method of the functional film of this invention can manufacture a functional film with sufficient productivity.

It is a schematic diagram of the plasma CVD film-forming apparatus of this invention. It is a schematic diagram of a plasma spraying apparatus.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described below, and the embodiments can be arbitrarily changed and implemented without departing from the gist of the present invention. Is possible.

[Plasma CVD deposition system]
The plasma CVD film forming apparatus of this embodiment is a film forming apparatus that forms a functional film on a base film by a plasma CVD method. FIG. 1 is a schematic diagram of a plasma CVD film forming apparatus (hereinafter also referred to as “film forming apparatus”) of the present embodiment.

  The film forming apparatus 31 includes a feed roller 32 that feeds the base film 2, transport rollers 33, 34, 35, and 36, film forming rollers 39 and 40 that are a pair of cylindrical counter electrodes, and a film forming device. A gas supply pipe 41 for supplying a source gas, a control unit 42, a winding roller 45, and a plasma generation power source 51 for supplying power to the film forming rollers 39 and 40 are provided. The film forming rollers 39 and 40 function not only as electrodes but also as a substrate during film formation. Hereinafter, the film forming rollers 39 and 40 may be referred to as a first film forming roller 39 and a second film forming roller 40, respectively. Further, when describing the first film forming roller 39 and the second film forming roller 40 together, they are described as “film forming rollers 39 and 40”. The film forming rollers 39 and 40 have dielectric layers 37 and 38 on their surfaces, respectively.

  The film forming rollers 39 and 40, the gas supply pipe 41, and the control unit 42 are disposed in a vacuum chamber (not shown). 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.

  The pair of counter electrodes, ie, the film forming rollers 39 and 40 are insulated from each other and are connected to the control unit 42 and the plasma generating power source 51, respectively. Then, when power is supplied from the plasma generating power supply 51 to the film forming rollers 39 and 40 by the control unit 42, discharge occurs in the space between the film forming rollers 39 and 40, and the source gas is ionized to generate plasma. Occur.

  In the film forming apparatus 31, the film forming rollers 39 and 40 are arranged so that their central axes are substantially parallel on the same plane. The long base film 2 is wound around the film forming rollers 39 and 40. While the film forming rollers 39 and 40 are rotated, the base film 2 is conveyed in a roll-to-roll manner, and a functional film is formed on the base film 2 in a space where plasma is generated between the film forming rollers 39 and 40. 3 is deposited.

  Further, it is preferable that the film forming 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 installed facing each other inside the film forming rollers 39 and 40 so as not to rotate integrally. The magnetic field generators 43 and 44 include a central magnet that extends in the same direction as the respective extending directions of the film forming rollers 39 and 40, and each of the film forming rollers 39 and 40 while surrounding the center magnet. And an annular outer magnet arranged to extend in the same direction as the extending direction of. In the magnetic field generator 43 and the magnetic field generator 44, the magnetic lines of force (magnetic field) connecting the central magnet and the external magnet form an endless tunnel.

  A source gas discharge plasma is generated in the space between the film forming rollers 39 and 40 by magnetron discharge in which the magnetic field lines intersect with the electric field formed between the film forming rollers 39 and 40. Electrons are confined in the space by the magnetic field and electric field formed in this space, so that high-density discharge plasma is formed in the space. This space is used as a film formation space for film formation by the plasma CVD method, and on the surface (film formation surface) that does not come into contact with the film formation rollers 39 and 40 of the base film 2, a film using a source gas as a forming raw material 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.

  Hereinafter, the film forming rollers 31 and 40, the control unit 42, the plasma generating power source 51, the magnetic field generating devices 43 and 44, the feed roller 32, and the transport rollers 33, 34, 35, and 36, the gas supply pipe 41 and the vacuum pump will be described in detail.

(Deposition roller)
The electrode used in the film forming apparatus 31 can generate plasma in the vacuum chamber by applying a voltage, and the shape is not particularly limited. However, as described above, a functional film can be manufactured more efficiently by using a pair of cylindrical electrodes (film-forming rollers) arranged to face each other.

  The film forming rollers 39 and 40 are a pair of cylindrical electrodes arranged so that the electrodes face each other. At the same time, the film forming rollers 39 and 40 serve as a substrate that supports the base film during film formation. The film forming rollers 39 and 40 are made of a conductive material, and their surfaces (outer peripheral surfaces) are covered with dielectric layers 37 and 38, respectively. Examples of the conductive material constituting the film forming rollers 39 and 40 include steel, titanium, and aluminum. In the following description, the film forming rollers 39 and 40 will be described together. However, the first film forming roller 39 and the second film forming roller 40 may be the same as long as the following configuration conditions are satisfied. And may be different.

  The film forming rollers 39 and 40 preferably have the same diameter from the viewpoint of forming a thin film more efficiently. Further, the diameters of the film forming rollers 39 and 40 are preferably 50 to 800 mmφ and more preferably 100 to 500 mmφ from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 50 mmφ or more, the plasma discharge space will not be reduced, and the productivity will not be reduced. Damage to the material film 2 can be reduced. On the other hand, if the film forming roller has a diameter of 800 mmφ or less, the uniformity of the plasma discharge space can be maintained, and practicality can be maintained in terms of device design.

(Dielectric layer)
The inventors of the present invention studied the formation of a dielectric layer by mixing not only alumina (aluminum oxide) but also titania (titanium oxide), which is a high dielectric constant material, as an electrode covering material. It was found that when the electrode is coated with a dielectric material mixed with alumina and titania, the voltage drop is suppressed as the impedance decreases, and the increase in the discharge start voltage is suppressed. As a result, arc discharge is suppressed, the plasma density to be generated can be maintained at a constant level, and a decrease in film formation rate can be suppressed. In addition, since the temperature rise of the electrode can be suppressed, the influence on the film quality can be suppressed.

  In the present embodiment, the dielectric layers 37 and 38 that are electrode covering materials contain alumina and titania in a mass ratio of alumina / titania = 80/20 to 40/60. Here, assuming that the total mass of alumina and titania is 100, a numerical value is defined as a relative mass ratio between the two. When the content ratio of alumina and titania is in the above range, the arc discharge is suppressed, the decrease in the film forming rate is suppressed, and the productivity is excellent. The mass ratio of alumina and titania is preferably alumina / titania = 70/30 to 60/40. The composition of the dielectric layers 37 and 38 is preferably about 100% by mass of alumina and titania, but may contain inevitable impurities in production in addition to alumina and titania. Moreover, you may add another component in the range which does not impair the effect of this embodiment.

  The thickness of the dielectric layers 37 and 38 is preferably 100 to 600 μm, and more preferably 200 to 400 μm, from the viewpoint of wear resistance and film stress. The thickness of the dielectric layers 37 and 38 can be measured using an eddy current film thickness meter or an ultrasonic film thickness meter.

  The dielectric layers 37 and 38 are preferably formed on the surfaces of the film forming rollers 39 and 40 with a width wider than the width with which the base film 2 is in contact. Thereby, the base film 2 can be charged efficiently without unevenness. Further, the width is preferably 10 mm or more on one side than the width in contact with the base film 2, and more preferably 30 mm or more. Further, it is preferable that the entire widths of the film forming rollers 39 and 40 are covered with the dielectric layers 37 and 38.

  The mass ratio of alumina and titania in the dielectric layers 37 and 38 can be obtained by collecting the dielectric layers 37 and 38 and analyzing them using an analysis means such as XPS.

  In order to improve the adhesion between the electrode surface and the dielectric layers (37 and 38), it is preferable to roughen the electrode surface before forming the dielectric layers (37 and 38). As a method for roughening the electrode surface, a method such as blasting can be used.

  Furthermore, it is preferable to have a nickel alloy layer between the electrode surface and the dielectric layer (37 and 38). Due to the presence of the nickel alloy layer, the adhesion between the electrode surface and the dielectric layer (37 and 38) is further improved, the peeling of the dielectric layer (37 and 38) from the electrode surface is suppressed, and the durability is improved. It is possible to improve the performance. Examples of the nickel alloy include Ni—Cr, Ni—Al, Ni—Cr—Al, and the like. The thickness of the nickel alloy layer is preferably 50 to 200 μm.

(Method of forming dielectric layer)
As a method of forming the dielectric layers 37 and 38 on the surface of the electrode, a thermal spraying method is preferable from the viewpoint of processing accuracy. The thermal spraying method is a kind of film forming technique for forming a film by melting or softening a film forming material by heating, accelerating it into fine particles and making it collide with the surface of an object. Although there are various spraying methods, the plasma spraying method is more preferable. The plasma spraying method is a method in which a powder such as metal or metal oxide is melted and sprayed onto an object using a high-temperature plasma jet having an extremely high energy density.

  FIG. 2 is a schematic diagram of the plasma spraying apparatus 10. A voltage is applied between the cathode 20 and the anode 21 to generate a DC arc. When a working gas 25 such as argon is supplied from behind, the molecules of the working gas are ionized to generate plasma. When the thermal spray powder material 24 is supplied into the plasma jet 27 with argon gas or the like, the thermal spray powder material 24 is sprayed on the surface of the object 23 to form a coating. The plasma spraying apparatus 10 has a structure in which cooling water 26 is supplied between the exterior part 22 and the interior part including the anode 21 so that the electrode part can be cooled so as not to be heated excessively.

  In the present embodiment, a dielectric powder containing alumina and titania in a mass ratio of alumina / titania = 80/20 to 40/60 is used as the thermal spray powder material 24 supplied into the plasma jet 27 in the plasma spray apparatus 10. Is supplied using argon gas or the like. By performing plasma spraying on the surfaces of the film forming rollers 39 and 40, a dielectric layer containing alumina and titania is formed on the surfaces of the film forming rollers 39 and 40. The dielectric powder containing alumina and titania may be used by mixing alumina powder and titania powder, but it is better to use a powder after mixing and melting alumina and titania. It is excellent in uniformity and is preferable. The average particle size of the dielectric powder to be sprayed is preferably 100 μm or less, and more preferably 50 μm or less.

  As manufacturing conditions for the dielectric layers 37 and 38 containing alumina and titania by plasma spraying, known conditions can be appropriately selected and used.

  The dielectric layers 37 and 38 formed by the plasma spraying method may be porous and form fine pores therein. Therefore, in order to improve the strength and durability of the dielectric layers 37 and 38, it is preferable to perform a sealing process for closing the fine holes. The sealing treatment is performed by a method in which after the dielectric layers 37 and 38 are formed, a sealing agent is applied to the surfaces of the dielectric layers 37 and 38 and cured. The sealing agent is preferably selected from alkoxysilane, organosiloxane, sodium silicate, epoxy resin, phenol resin, vinyl chloride resin, etc., more preferably alkoxysilane, organosiloxane, and epoxy resin. After performing the sealing treatment, the surfaces of the dielectric layers 37 and 38 are further polished to improve the denseness and electrical insulation of the dielectric layers 37 and 38.

(Control part)
The controller 42 can control the entire film forming apparatus 31 and each configuration including the plasma generating power source 51. The control unit 42 includes a central processing unit (CPU) 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.

(Power source for plasma generation)
As the plasma generating power source 51, a known power source of a plasma generating apparatus can be used as appropriate. The plasma generating power supply 51 supplies power to the film forming rollers 39 and 40 connected thereto, and makes it possible to use them as a counter electrode for discharging. As the plasma generation power source 51, since it is possible to perform plasma CVD more efficiently, an AC power source capable of alternately reversing the polarity of the pair of film forming rollers 39 and 40 can be used. preferable. As such a plasma generation power source 51, it is preferable to set the applied power to 100 W to 10 kW and the AC frequency to 50 Hz to 500 kHz because plasma CVD can be performed more efficiently.

(Magnetic field generator)
It is preferable that magnetic field generators 43 and 44 are provided inside the film forming rollers 39 and 40, respectively. Since the film forming rollers 39 and 40 have the magnetic field generators 43 and 44 inside, a magnetic field is applied, and as described above, a space of discharge plasma in which electrons are confined by the magnetic field and the electric field is formed. Effective film formation is possible. The magnetic field generation devices 43 and 44 are fixed inside the film formation rollers 39 and 40 so that the magnetic field generation devices 43 and 44 do not rotate even when the film formation rollers 39 and 40 rotate.

  As the magnetic field generators 43 and 44, 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 formed near the roller surface facing the (discharge region). Then, since the plasma can be focused on the magnetic field, the functional layer 3 can be efficiently formed on the wide base film 2 wound along 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 31, known rollers can be appropriately used. Further, the winding roller 45 is not particularly limited as long as it can wind the functional film 1 in which the functional film 3 is formed on the base film 2, and a known roller is appropriately used. be able to.

(Gas supply pipe and vacuum pump)
As the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the raw material gas at a predetermined speed can be appropriately used. In addition, the gas supply pipe 41 that is a gas supply unit is preferably provided in one of the opposing spaces (discharge regions) between the first film formation roller 39 and the second film formation roller 40, and is a vacuum that is a vacuum exhaust unit. A pump (not shown) is preferably provided on the other side of the facing space. 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 raw material is efficiently provided in the facing space between the first film formation roller 39 and the second film formation roller 40. Gas can be supplied, and film formation efficiency can be improved.

(Base film)
As the base film 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 base film 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, Examples include polycarbonate resin, polystyrene resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, polyacrylonitrile resin, polyacetal resin, polyimide resin, polyether sulfide (PES), and the like. Two or more kinds may be used in combination.

  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.

  The thickness of the base film 2 is appropriately set in consideration of stability and the like when the base film 2 is manufactured, but in order to facilitate the transport of the base film 2 even in vacuum, It is preferable to be in the range of 250 μm. Furthermore, in the formation of the gas barrier film employed in this embodiment, since the discharge is performed through the base film 2, the thickness of the base film 2 is more preferably in the range of 50 to 200 μm, and is preferably 50 to 150 μm. It is particularly preferable that it is within the range.

  In addition, in order to improve the adhesiveness with the gas barrier film | membrane formed, the base film 2 may give the surface activation process to the surface previously, or may provide an anchor layer. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

[Method for producing functional film]
Various functional films having the functional film 3 are formed by forming the functional film 3 on the base film 2 by plasma CVD using the film forming apparatus 31 of the present embodiment shown in FIG. 1 can be manufactured.

In the present embodiment, the functional film 1 is a film having a functional film 3 having functionality on the surface of the base film 2, and specifically, a gas barrier film, an optical film, and an antireflection film. , An infrared reflective film, a hard coat film, and the like.
Hereinafter, a gas barrier film which is a typical example of the functional film 1 will be taken up and a preferred embodiment will be described.

The gas barrier film has a configuration in which a gas barrier film is formed on the base film 2 by the film forming device 31. In the present embodiment, “having gas barrier properties” means that the gas barrier film was measured for water vapor permeability (abbreviation: WVTR, temperature: 38 ° C., relative humidity) by a method according to JIS K 7129-2008. RH): 90%) as a whole indicates less than 5 × 10 ⁻² g / (m ² · day). The water vapor transmission rate can also be measured by a method described in JP 2004-333127 A.

(Method for forming gas barrier film)
The gas barrier film is formed using the film forming apparatus 31 shown in FIG. 1, for example, the type of source gas, the power supplied from the plasma generating power supply 51, the pressure in the vacuum chamber, the diameters of the film forming rollers 39 and 40, and It can form by adjusting the conveyance speed of the base film 2 suitably.

  That is, by using the film forming apparatus 31 shown in FIG. 1 and supplying a source gas into the vacuum chamber while generating a discharge between the pair of film forming rollers 39 and 40, the source gas is decomposed by plasma. A gas barrier film is formed on the surface of the base film 2 on the first film forming roller 39 and on the surface of the base film 2 on the second film forming roller 40.

  In such film formation, the base film 2 is conveyed by the delivery roller 32, the first film formation roller 39, and the like, respectively, so that the base film 2 is formed by a roll-to-roll continuous film formation process. A gas barrier film is formed on the surface.

  Further, when plasma is generated in the plasma CVD method, a pair of film forming rollers 39 and 40 are used, and the base film 2 is disposed on each of the pair of film forming rollers 39 and 40 to form a pair of film forming films. It is more preferable in terms of production efficiency to generate plasma by discharging between the rollers 39 and 40.

(Deposition gas)
As the film forming gas supplied from the gas supply pipe 41 to the space where the pair of film forming rollers 39 and 40 are opposed, not only the source gas but also the reaction gas, the carrier gas and the discharge gas are used alone or in combination of two or more. Can be used. The source gas in the deposition gas used for forming the gas barrier film can be appropriately selected and used according to the material of the gas barrier film 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 properties such as compound handling properties and gas barrier properties of the resulting gas barrier film. 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.

  An appropriate source gas is selected from these organosilicon compound gas and organic compound gas according to the type of the gas barrier film. Further, as a source gas, monosilane may be contained in addition to the above-described organosilicon compound, and used as a silicon source for a gas barrier film to be formed.

  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.

  Although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable that it is 0.1-50 Pa. When plasma CVD is used as a low pressure plasma CVD method in order to suppress a gas phase reaction, it is usually 0.1 to 10 Pa. The power supplied to the film forming rollers 39 and 40 by the plasma generating power source 51 can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, and the like, but is 0.1 to 10 kW. It is preferable.

  Although the conveyance speed of the base film 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, 0.5-20 m / min. More preferably, it is min. If the transport speed is less than the lower limit, the base film 2 tends to be wrinkled due to heat. On the other hand, if the transport speed exceeds the upper limit, the thickness of the formed gas barrier film tends to be thin. . When the base film 2 is transported, the base film 2 fed from the transport roller and formed on the first film forming roller 39 has the second film forming roller 40 while the film forming surface is wound around the turn bar. To be transported. Thereafter, the base film 2 is formed again on the second film forming roller 40 and wound up by the winding roller 45.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Gas barrier film No. Production of 1 to 9]
(Preparation of film forming roller)
First, alumina-titania was mixed at a mass ratio shown in Table 1 to prepare melt-pulverized thermal spray particles. Using the plasma spraying apparatus shown in FIG. 2, the surface (outer peripheral surface) of two SUS rollers (diameter 200 mmφ) is coated with the obtained spray particles containing alumina-titania to a thickness of 300 μm, A dielectric layer was formed. The spraying conditions in the plasma spraying method were as follows.
Thermal spraying method: atmospheric pressure plasma spraying method Current value: 600A
Argon gas flow rate: 70 l / min
Hydrogen gas flow rate: 10 l / min
Thermal spray distance: 100mm
Thermally sprayed particle size: 30 μm

  After plasma spraying, an epoxy resin solution was applied as a sealing agent to the formed dielectric layer and dried at 200 ° C. for sealing treatment. Thereafter, the surface was buffed to form a film forming roller.

(Preparation of base film)
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 the base film.

(Formation of anchor layer)
A UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied to the easily adhesive surface of the base film with a wire bar so that the layer thickness after drying was 4 μm. Thereafter, after drying at 80 ° C. for 3 minutes as a drying condition, curing was performed under an irradiation condition of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere to form an anchor layer.

(Gas barrier film formation)
The plasma CVD film forming apparatus shown in FIG. 1 provided with two film forming rollers on which the dielectric layer is formed as a first film forming roller and a second film forming roller was used.
The base film is mounted on a plasma CVD film forming apparatus so that the surface opposite to the surface on which the anchor layer of the base film is formed is in contact with the film forming roller, and the following film forming conditions (plasma CVD conditions) Thus, a gas barrier film was formed on the anchor layer 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: 3.0Pa
Applied power from the power source for plasma generation: 1.5 kW
Frequency of power source for plasma generation: 120 kHz
Substrate film transport speed: 2 m / min

[Evaluation method]
The obtained gas barrier film No. About 1-9, the generation frequency of arc discharge, the film-forming speed | rate, and gas barrier property were evaluated in accordance with the following evaluation methods.

(Occurrence frequency of arc discharge)
The traveling wave from the power source for plasma generation of the high frequency power applied from the high frequency power source to the film forming apparatus and the reflected wave thereof are recorded, and the number of occurrences is measured by using the reflected wave generated after the start of film formation as an arc discharge. The occurrence frequency X (arks / min) of the hit arc was evaluated.

The occurrence frequency of arc discharge was evaluated in the following five stages. Three or more were judged to be acceptable.
1: 5 <X
2: 1 <X ≦ 5
3: 0.1 <X ≦ 1
4: 0 <X ≦ 0.1
5: X = 0

(Deposition rate)
The film formation rate was evaluated under the following conditions.
The film thickness of the formed gas barrier layer was measured using a transmission electron microscope (TEM: JEM-2000FX, JEM-2000FX), and the coating film thickness per unit time was determined.
The reduction rate x (%) of the film formation rate was measured in comparison with an electrode having no dielectric layer on the surface.

The film formation rate was evaluated in the following five stages. Three or more were judged to be acceptable.
1:20 <x
2: 15 <x ≦ 20
3: 10 <x ≦ 15
4: 5 <x ≦ 10
5: x ≦ 5

(Gas barrier properties)
The gas barrier property was evaluated by measuring the water vapor transmission rate by the following measuring method using the following apparatus.
(Equipment etc.)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Raw material: Metal that reacts with moisture and corrodes: Calcium (granular)
Water vapor impermeable metal: Aluminum (3-5mmφ, granular)

(Preparation of water vapor barrier property evaluation cell)
Using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400), on one side of each gas barrier film, mask the portions other than the portion (12mm x 12mm 9 locations) where metal calcium is to be deposited. Was evaporated. Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited from another metal vapor deposition source on the entire surface of one side of the gas barrier film, and the portion where the metal calcium vapor was vapor-deposited was sealed. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

The obtained sample with both surfaces sealed is stored at 60 ° C. and 90% RH under high temperature and high humidity for 1000 hours, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The water content obtained was calculated and the water vapor transmission rate (WVTR) obtained was evaluated according to the following criteria.
In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample obtained by depositing metallic calcium on a quartz glass plate having a thickness of 0.2 mm was used instead of the gas barrier film as a comparative sample. The cell was similarly stored under high temperature and high humidity of 60 ° C. and 90% RH, and it was confirmed that corrosion of metallic calcium did not occur even after 1000 hours.

The gas barrier property of the gas barrier film was evaluated in the following five stages. Three or more were judged to be acceptable.
1: 5 × 10 ⁻¹ g / (m ² · day) or more 2: 5 × 10 ⁻² g / (m ² · day) or more, less than 5 × 10 ⁻¹ g / (m ² · day) 3: 5 × 10 ⁻³ g / (m ² · day) or more, less than 5 × 10 ⁻² g / (m ² · day) 4: 1 × 10 ⁻⁴ g / (m ² · day) or more, 5 × 10 ⁻³ Less than g / (m ² · day) 5: 1 × 10 ⁻⁴ Less than g / (m ² · day)

  The evaluation results are shown in Table 1.

  Gas barrier film No. 3-7, the mass ratio of alumina and titania in the dielectric layer is in the range of alumina / titania = 80/20 to 40/60, the frequency of arc discharge, the deposition rate, and the gas barrier properties of the gas barrier film In any of these performances, it had excellent performance.

  Gas barrier film No. 1 is that the dielectric layer is made only of alumina, and the frequency of occurrence of arc discharge is low and good, but the loss of electrical energy input from the electrode to the plasma space is large, so the deposition rate is greatly reduced. And it was inferior to productivity and the gas barrier property of a gas barrier film. Gas barrier film No. No. 2 has a small titania ratio in the dielectric layer, and the occurrence frequency of arc discharge is low and good, but the film formation rate is low and the productivity is poor. Further, the gas barrier property of the gas barrier film was relatively low. Gas barrier film No. No. 8 has a high titania ratio in the dielectric layer, and although the film formation rate is high, the insulation of the dielectric layer is lowered, the occurrence frequency of arc discharge is increased, and the gas barrier property of the gas barrier film is increased. It was low. Gas barrier film No. No. 9 does not have a dielectric layer, and although the film formation rate is high, the occurrence frequency of arc discharge is high, and therefore the gas barrier property of the gas barrier film is inferior.

DESCRIPTION OF SYMBOLS 1 Functional film 2 Base film 3 Functional film 31 Film-forming apparatus 32 Delivery rollers 33, 34, 35, 36 Transport rollers 37, 38 Dielectric layer 39 First film-forming roller 40 Second film-forming roller 41 Gas supply pipe 42 Control units 43 and 44 Magnetic field generator 45 Winding roller 51 Power source for plasma generation

Claims (7)

An electrode used in a plasma CVD film forming apparatus,
An electrode having a dielectric layer containing alumina and titania in a mass ratio of alumina / titania = 80/20 to 40/60 on the surface.   The electrode according to claim 1, wherein a mass ratio of the alumina to the titania is alumina / titania = 70/30 to 60/40.   The electrode according to claim 1, further comprising a nickel alloy layer between the electrode surface and the dielectric layer. A method for producing an electrode for a plasma CVD film forming apparatus having a dielectric layer on the surface containing alumina and titania in a mass ratio of alumina / titania = 80/20 to 40/60,
A dielectric CVD layer containing alumina and titania is formed on an electrode surface by plasma spraying.   A plasma CVD film forming apparatus comprising an electrode having a dielectric layer containing alumina and titania in a mass ratio of alumina / titania = 80/20 to 40/60 on the surface.   A functional film is formed on a base film using a plasma CVD film forming apparatus having an electrode having a dielectric layer on its surface containing alumina and titania in a mass ratio of alumina / titania = 80/20 to 40/60. A method for producing a functional film to be formed.   The functional film according to claim 6, wherein the electrode is a pair of cylindrical electrodes disposed so as to face each other, and is formed while the long base film is wound around the electrodes. Production method.

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