JP2013072100A - Vacuum film-forming device, gas barrier laminate, and method of producing the same - Google Patents

Abstract

A vacuum that provides transparency and high barrier properties while ensuring a high film formation rate, and can minimize damage to the film due to bumping or splashing generated from the vapor deposition material. A film forming apparatus and a method for producing a gas barrier laminate are provided.
A vacuum film-forming apparatus 30 is a vacuum film-forming apparatus that forms a thin film on one surface of a substrate by an evaporation method, and an electron beam gun 20 that is an evaporation means for evaporating an evaporation material, and is evaporated. A hollow cathode gun 18 using hollow cathode discharge, which is a plasma generating means for generating plasma for activating the vapor deposition material, and a foreign matter guard 24, which is a foreign matter catching means installed between the vapor deposition material and the substrate. It comprises.
[Selection] Figure 1

Description

  The present invention relates to a vacuum film forming apparatus for forming a thin film on a substrate. The present invention also relates to a method for manufacturing a laminate having oxygen and water vapor barrier properties using this vacuum film forming apparatus.

  As a packaging material for food, for example, a pouch material for retort food, a laminated packaging material in which a plastic film as a base material, an aluminum foil as an oxygen and water vapor barrier layer, and a thermoplastic resin film for heat sealing are sequentially laminated. Conventionally, what is printed on the entire surface of the bag to enhance the decoration effect has been widely used. In recent years, with the widespread use of microwave ovens in the home, the market for food packaging materials using packaging films made of flexible plastic films with barrier properties that can be distributed at room temperature and that can be applied to microwave ovens for each packaging material has expanded. doing.

  As a material that satisfies the above characteristics, there is a packaging film in which a flexible plastic film is used as a base material, a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is vapor-deposited on this surface, and another film is laminated on the vapor-deposited surface. Proposed. This packaging film is also used as a protective material for packaging materials such as pharmaceuticals, electronic members, and optical members, taking advantage of its excellent disposal property and the ability to confirm the contents from the outside.

  Examples of a method for forming a ceramic layer such as an aluminum oxide layer or a silicon oxide layer include vapor deposition methods such as an induction heating method, a resistance heating method, and an electron beam heating method. While these vapor deposition methods can form a gas barrier film at a high film formation rate, it is also a difficult technique to obtain a dense and high gas barrier film.

  Therefore, a vapor deposition method using a pressure gradient type plasma gun as a material evaporation method has been devised as a technique for obtaining a denser film than a normal vapor deposition method (for example, Patent Document 1). In this method, plasma emitted from the plasma gun is guided to the material by converging using a magnetic field, etc., and the material is heated and evaporated. At the same time, the atoms and molecules being evaporated pass through the plasma emitted from the plasma gun. A dense film can be obtained by being activated and incident on the substrate with higher kinetic energy than that during evaporation. In addition, as a technique for improving the transparency of a gas barrier film and imparting higher barrier properties, high-density plasma by hollow cathode discharge is applied during film formation by vapor deposition such as induction heating, resistance heating, or electron beam heating. A technique to be used has been devised (for example, Patent Document 2).

JP 2005-34831 A JP 2011-21214 A

  However, when the gas barrier layer is formed by an evaporation method such as an induction heating method, a resistance heating method, or an electron beam heating method, there is a problem that the film is damaged due to bumping or splashing from the evaporation material during the film formation. When the film is damaged due to such troubles, there is a problem that the gas barrier property is deteriorated, the appearance is deteriorated, and foreign matter is mixed, so that the value as a product is remarkably impaired or the product cannot be commercialized.

  Moreover, when the method described in Patent Document 1 is used, the film formation rate is slower than the resistance heating method, the induction heating method, and the electron beam heating method, and the productivity as a flexible packaging material or industrial material is improved. Lack. Further, when the technique described in Patent Document 2 is used, the transparency and gas barrier properties may be improved, but there is a problem that bumping and splashing are more easily caused.

  In view of the above problems, the present invention secures a high film formation rate by vapor deposition such as induction heating, resistance heating, and electron beam heating, and improves the transparency of the gas barrier laminate. Vacuum deposition apparatus and gas barrier laminate capable of minimizing damage to the film due to bumping, splash, etc. generated from the vapor deposition material when using plasma as a method for imparting barrier properties It aims at providing the manufacturing method of.

  As means for solving the above-mentioned problems, the invention described in claim 1 is a vacuum film forming apparatus for forming a thin film on one surface of a base material by an evaporation method, and an evaporation means for evaporating an evaporation material; A vacuum film forming apparatus comprising: plasma generating means for generating plasma for activating evaporated vapor deposition material; and foreign matter trapping means installed between the vapor deposition material and the substrate. It is.

  The invention according to claim 2 is the vacuum film forming apparatus according to claim 1, wherein the foreign matter capturing means is in contact with the plasma.

  According to a third aspect of the present invention, in the vacuum according to the first or second aspect, the material of the foreign matter capturing means includes any one of molybdenum, tantalum, tungsten, niobium, carbon, stainless steel, and alumina. A film forming apparatus.

  According to a fourth aspect of the present invention, in any one of the first to third aspects, the evaporating means uses any one of electron beam heating, induction heating, and resistance heating. The vacuum film-forming apparatus described in 1.

  The invention according to claim 5 is characterized in that the plasma generating means uses any one of hollow cathode discharge, microwave discharge, ICP discharge, and helicon wave discharge. A vacuum film forming apparatus according to claim 1.

  The invention described in claim 6 further comprises a transport unit that transports the base material in a roll-to-roll manner. 6. The vacuum film forming apparatus according to claim 1, It is.

  The invention according to claim 7 is a method for producing a gas barrier laminate comprising a base material and a thin film formed on one surface of the base material, wherein the foreign material from the vapor deposition material evaporated by the evaporation means A foreign matter removing step of removing the vapor, a plasma activation step of activating the evaporated vapor deposition material from which the foreign matter has been removed by plasma, and a vapor deposition step of depositing the activated vapor deposition material on one surface of the substrate. This is a method for producing a gas barrier laminate.

  The invention according to claim 8 is the method for producing a gas barrier laminate according to claim 7, wherein the foreign matter removing step and the plasma activation step are performed simultaneously.

  The invention according to claim 9 is a gas barrier laminate produced by the method according to claim 7 or 8.

  According to the present invention, a high film formation rate is ensured by an evaporation method such as an induction heating method, a resistance heating method, and an electron beam heating method, and plasma is used to improve the transparency of a gas barrier laminate and to increase the barrier. In addition, the damage to the gas barrier laminate can be minimized by arcing, bumping, splash, etc. generated from the vapor deposition material.

It is the schematic diagram which showed one Embodiment of the vacuum film-forming apparatus of this invention.

  The vacuum film-forming apparatus of the present invention is a vacuum film-forming apparatus for forming a thin film on one surface of a base material by vapor deposition, and an evaporation means for evaporating the vapor-deposited material and plasma for activating the evaporated vapor-deposited material And a foreign matter trapping means installed between the vapor deposition material and the substrate. According to this vacuum film forming apparatus, damage to the gas barrier laminate can be minimized by arcing, bumping, splash, etc. generated from the vapor deposition material. FIG. 1 is a schematic view showing an embodiment of a vacuum film forming apparatus of the present invention. Hereinafter, an embodiment of the present invention will be described with reference to FIG.

  The vacuum film forming apparatus 30 shown in FIG. 1 includes a film forming chamber 10 and a take-up chamber 11, and the film base material 15 that is a base material is conveyed into the vacuum film forming apparatus 30 by roll-to-roll. Conveying means is provided. Means for transporting the film substrate 15 in a roll-to-roll manner includes an unwinding roller 12, a winding roller 13, and a main roller 14. The film substrate 15 is unwound from the unwinding roller 12 in the direction of the arrow in FIG. 1, and is wound around the winding roller 13 via the main roller 14. At this time, the vapor deposition material 16 is vapor-deposited on the surface of the film substrate 15 by the main roller 14 to form a vapor deposition film. The direction of unwinding and winding is not limited, and the unwinding roller and the winding roller may be reversed.

  The film base material 15 which is a base material is not specifically limited, A well-known thing can be used. For example, polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polystyrene, ethylene vinyl alcohol, polyvinyl chloride, polyimide, polyvinyl alcohol , Polycarbonate, polyethersulfone, acrylic, cellulose-based (triacetylcellulose, diacetylcellulose, etc.), and the like, but are not particularly limited. In practice, it is desirable to make appropriate selections depending on the application and required physical properties, and this is not an example of limitation. However, polyethylene terephthalate, polypropylene, nylon, etc. are used for packaging medical supplies, drugs, foods, etc. Easy packaging, and substrates that have high gas barrier properties such as polyethylene naphthalate, polyimides, and polyethersulfone can be used for packaging that protects extremely moisture-sensitive contents such as electronic and optical components. It is. Moreover, although the base film thickness is not limited, about 6 to 200 μm is easy to use depending on the application.

  Further, the base material on which the vapor deposition film is formed may be a sheet (flat plate) such as a substrate. When a substrate is used as the base material, the conveying means in FIG. 1 cannot be used. Therefore, for example, a means for transporting the film to the film formation chamber while holding the edge of the substrate is employed. However, in terms of improving productivity, it is more preferable to use a film base material that uses means for transporting in a roll-to-roll manner.

  In addition, the vacuum film forming apparatus of the present invention includes evaporation means for evaporating the vapor deposition material in order to deposit the vapor deposition material on one surface of the substrate. In the vacuum film-forming apparatus 30 of FIG. 1, the vapor deposition material 16 is vaporized by filling the crucible 17 with the vapor deposition material 16 and using the means heated by the electron beam gun 20 as an evaporation means.

The vapor deposition material is not particularly limited, and a known material can be used. For example, magnesium oxide (MgO), indium-tin oxide (ITO), silicon oxide compound silicon monoxide (SiO), silicon dioxide (SiO ₂ ), zinc sulfide (ZnS), zinc oxide (ZnO), tin oxide Ceramics such as (SnO) may be used, and metal materials such as aluminum (Al), silicon (Si), tin (Sn), zinc (Zn), and indium (In) may be used, and these mixed materials may be used. Also good.

  Here, when reactive vapor deposition is performed by reacting the evaporated vapor deposition material with a reactive gas, for example, oxygen, nitrogen, dinitrogen monoxide, and the like from the gas pipe 23 of the vacuum film forming apparatus 30 shown in FIG. It is also possible to flow a reactive gas such as ammonia. Thus, reactive deposition such as oxidation and nitridation can be performed when the deposition material 16 is formed on the film substrate 15.

  In the vacuum film forming apparatus 30 of FIG. 1, as the evaporation means, electron beam heating is used in which the crucible 17 is filled with the vapor deposition material 16 and heated and evaporated by the electron beam gun 20, but this is a heating method other than the electron beam gun 20. It does not matter. For example, a resistance heating method, an induction heating method using an AC voltage, or the like may be used. The resistance heating method may be a method in which a material is packed in a resistance heating crucible and heated to deposit, or a metal wire is used as a deposition material in the resistance heating boat, and the wire is fed to the resistance heating boat. There is no problem even if it is a method to do. In this case, the kind of vapor deposition material is limited to materials that can be made into wires, but it can be used as needed.

  When electron beam heating is used as a means, examples of the electron beam gun 20 include a straight electron beam gun and a deflected electron beam gun. In the present invention, it is particularly preferable to use a straight electron beam gun.

  Regardless of the method of electron generation and convergence, the definition of a straight-ahead electron beam gun is as follows: the electron beam generated from the gun is adjusted in the electron beam trajectory by preparing a magnetic field in the deposition space. This is a comparison with a deflected electron beam gun that controls the direction. The advantage of using the straight electron beam gun is that an orthogonal magnetic field for correcting the trajectory of the electron beam is not used in the film forming space in order to apply the electron beam to the vapor deposition material 16. Does not interfere with the orbital correction magnetic field. Since a deflected electron beam gun or the like actively uses a magnetic field in the film formation space in order to apply electrons to the evaporation material 16, the magnetic field generated in the space in the film formation chamber obstructs the diffusion and progression of electrons in the plasma. There is a case. For this reason, it is necessary to arrange the electron gun so that interference does not occur in the plasma, which requires a limited arrangement, and complicated and complicated installation. In the case of using a straight electron beam gun, it is necessary to set a certain angle and position in advance so that the electron beam linearly strikes the vapor deposition material 16 as shown in FIG. Furthermore, examples of the electron beam gun itself include, but are not limited to, a Pierce type flat cathode electron gun and a circular cross-section converging electron gun.

  In FIG. 1, an electron beam heating method using a straight electron beam gun is easier to handle as the evaporation means than a deflected electron beam gun. On the other hand, even if a straight-ahead electron beam gun is used, if the plasma itself generates a magnetic field, it is affected by this magnetic field, so it is necessary to make detailed arrangements regarding the installation position and irradiation conditions of the straight-ahead electron beam gun. Further, when a magnetic field such as a converging magnetic field is provided on the hollow cathode gun 18 and the external electrode 25, the electron beam method may cause interference regardless of whether it is deflection or straight travel. The resistance heating method becomes easier to handle.

  In addition, the vacuum film forming apparatus of the present invention includes plasma generating means for generating plasma for activating the evaporated deposition material in order to deposit the deposition material on one surface of the substrate. The vacuum film forming apparatus 30 of FIG. 1 includes a hollow cathode gun 18 using a hollow cathode discharge as plasma generating means for activating the evaporated vapor deposition material 16 with plasma 27. The evaporated vapor deposition material 16 is incident on the film substrate 15 held by the main roller 14 as vapor deposition particles 26. At this time, the vapor deposition particles 26 are activated by passing through the plasma 27 before the vapor deposition particles 26 are incident on the film substrate 15.

  The plasma for activating the deposited particles is preferably high-density plasma, and any one of hollow cathode discharge, microwave discharge, ICP discharge, and helicon wave discharge is preferably used. Here, the hollow cathode discharge generally refers to a plasma that is generated by repetition of ionization as electrons accelerated by the sheath voltage move in the hollow cathode in the cylindrical shape. . The microwave discharge generally refers to plasma generated by applying a microwave to a plasma generating tube inserted in a waveguide that transmits the microwave. ICP discharge generally refers to plasma generated from an induction current generated by a high-frequency magnetic field in an induction coil through which a high-frequency current flows. The helicon wave plasma generally refers to a plasma generated by a helicon wave generated by applying a high frequency electric field to an antenna and a magnetic field. The vapor deposition particles can form a dense film when the vapor deposition particles themselves are turned into plasma and activated by the above discharge. Among these discharges, a hollow cathode discharge is more preferable in that a higher density plasma for activating the deposited particles can be generated.

  In the case of the vacuum film forming apparatus 30 using the hollow cathode discharge of FIG. 1, the hollow cathode gun 18 is installed in the vacuum film forming apparatus 30, and the hollow cathode 28 is installed inside the hollow cathode gun 18 as a cathode. ing. Furthermore, an internal electrode 19 positioned inside the hollow cathode gun 18 or an external electrode 25 positioned outside the hollow cathode gun 18 is installed as an anode. The hollow cathode gun 18 is connected to DC power sources 21 and 22 for hollow cathode discharge for generating hollow cathode discharge. For discharge in the hollow cathode gun 18, the anode may be either the internal electrode 19 or the external electrode 25, or both may be used at the same time, and may be used appropriately depending on the application.

  In the hollow cathode discharge, electrons accelerated by the sheath voltage in the cylindrical hollow cathode 28 move in the radial direction in the hollow cathode 28 and decelerate by the sheath voltage of the hollow cathode 28. The decelerated electrons are accelerated by the sheath voltage again, and move in the hollow cathode 28 in the radial direction, whereby the impact ionization is repeated, and indicates high density plasma generated. In the method of introducing the inert gas X from the hollow cathode 28, a pressure difference is generated between the vacuum film formation chamber 10 and the hollow cathode 28, and the high-density plasma generated at the hollow cathode 28 is formed. It becomes possible to actively pull out to the chamber 10 side. Here, examples of the inert gas X include noble gases such as helium and argon, nitrogen, and a mixed gas thereof.

  When the internal electrode 19 is used as an anode, for example, the plasma generated from the hollow cathode gun 18 using argon gas as the inert gas X diffuses into the film formation space because it is bipolarly diffused. In this case, activation of the vapor deposition particles 26 is promoted including diffusion of a relatively high density plasma into the film formation chamber 10 and ionization. The ionized vapor deposition particles 26 and argon ions are The material 15 enters the material 15 with acceleration of the electric field of the plasma sheath.

  Moreover, since the discharge becomes unstable when the internal electrode 19 is contaminated by the vapor deposition material 16, there may be a structure such as providing a cover and a protection plate so that the internal electrode 19 is hardly contaminated.

  On the other hand, the external electrode 25, like the internal electrode 19, is an anode for the hollow cathode 28 and may be positioned outside the hollow cathode gun 18. For example, as shown in FIG. 1, it can be installed at a position facing the hollow cathode gun 18, but is not particularly limited.

  When the external electrode 25 is used as an anode, a high-density plasma is generated in the vapor deposition space like the plasma 27 in FIG. The vapor deposition particles 26 immediately after evaporation pass through the high-density plasma generated between the hollow cathode gun 18 and the external electrode 25, so that activation is violently promoted, and the vapor deposition particles 26 are radicalized, In addition to that, the vaporized particles and argon ions ionized by ionization are incident on the film substrate 15 after accelerating the electric field of the plasma sheath. Therefore, the external electrode 25 is preferably installed at a position where the region where the plasma 27 is generated and the region where the vapor deposition particles 26 exist overlap.

  When the vapor deposition material 16 is an insulating material, the external electrode 25 is contaminated by the vapor deposition material 16 during vapor deposition, and electrons do not flow when the contamination progresses excessively. To do. For this reason, when the vapor deposition material 16 is an insulating material, there may be contrivances such as arranging an adhesion preventing plate or the like so as not to contaminate.

  A plurality of hollow cathode guns 18 may be installed in the film forming apparatus depending on the size of the film base 15 in the width direction. When the external electrode 25 is used as the anode, the external electrode 25 is installed at a position facing the hollow cathode gun 18, but a plurality of external electrodes 25 may be installed according to the number of the hollow cathode guns 18.

  As for the discharge conditions of the plasma 27, the higher the current value, from several A to several hundreds A per hollow cathode, the higher the plasma density is preferable. However, when the flow rate of the gas introduced into the hollow cathode gun 18 is large, or when the flow rate of the gas introduced through the gas pipe 23 is large, depending on the exhaust capacity of the pump that exhausts the deposition chamber 10, The vapor pressure of the vapor deposition material 16 is such that the atmospheric pressure increases, the mean free path of the vapor deposition particles 26 is shortened, the vapor deposition particles 26 lose kinetic energy, and the film density and adhesion of the film to be deposited decrease. It occurs depending on the type. For this reason, the discharge condition of the hollow cathode needs to be determined in consideration of the type of gas introduced into the hollow cathode, the type of gas introduced from the gas pipe 23, the type of vapor deposition material 16, the distance between the crucible 17 and the main roller 14, and the like. There is.

  When a film is formed by a vapor deposition method, it is difficult to avoid splash or bumping from the vapor deposition material regardless of heating methods such as electron beam heating, resistance heating, and induction heating. When these troubles occur, the lump containing the vapor deposition material jumps out toward the base material, and it may cause scratches by colliding with the base material, and in some cases, it may cause serious damage such as pinholes or film breakage. . In addition, a lump containing a vapor deposition material adheres to the base material, causing foreign matter to be mixed. These are generated for various reasons, such as impurities contained in the vapor deposition material, residual gas such as water present in the vacuum, or when the surface of the vapor deposition material reacts with the reactive gas when a reactive gas is introduced. To do. In addition, by using plasma, the electrical relationship between the plasma generation means and the vapor deposition material heating means, and the charging that the plasma itself causes to the vapor deposition material and the vapor deposition, such as arcing, induce their generation. Sometimes it is done. In the vacuum film forming apparatus of the present invention, a foreign matter capturing means is installed between the vapor deposition material and the base material so that the lump containing the vapor deposition material does not reach the base material due to the generated arcing, splash or bumping. . In the vacuum film forming apparatus 30 of FIG. 1, a foreign matter guard 24, which is a foreign matter catching means, is installed between the vapor deposition material 16 packed in the crucible 17 and the film base material 15 held by the main roller 14. Here, the foreign matter is a generic name for those that cause damage to the formed film, pinholes, tears, etc., specifically, a lump containing a vapor deposition material, impurities contained in the vapor deposition material, It refers to a reactant generated by a reaction of a residual gas such as water or a reactive gas existing in a vacuum with a surface of a deposition material.

  The foreign object guard 24 may have various shapes such as a mesh shape, a slit shape, and a plate shape, and may be appropriately selected in view of the type of heating method used as the vapor deposition means, the type of the vapor deposition material 16, and the like. The foreign material guard 24 may be made of any material that can withstand the temperature rise caused by the plasma generated by the plasma generating means. For example, a high melting point metal such as molybdenum, tantalum, tungsten, niobium or a high melting point alloy, alumina, or the like. It is preferable to use a high melting point ceramic, carbon, stainless steel or the like.

  In the case of the vacuum film forming apparatus 30 using the electron beam gun 20 of FIG. 1, when the electron beam hits the foreign matter guard 24, the foreign matter guard may be melted. A guard 24 is required. The shape of the foreign object guard 24 in FIG. 1 is an example, and is not limited to this. Similarly, even in the case of the resistance heating method, if the resistance heating boat is used as the resistance heating source and the metal wire is used as the material, the foreign object guard 24 needs to have a shape that does not contact the metal wire. The foreign matter guard 24 may be appropriately determined so as to be a position where plasma heating can be obtained and the position is a passage for steam.

  Generally, the temperature at the time of film formation of the foreign matter guard 24 is sufficiently lower than that of the crucible 17, so that the vapor deposition material 16 evaporated from the crucible 17 is directly formed on the foreign matter guard 24. Alternatively, the vapor deposition particles staying in the vapor deposition space are re-formed. For this reason, when the mesh-shaped or slit-shaped foreign material guard 24 is used, clogging occurs due to the evaporated vapor deposition material 16, and the film formation speed changes, or the film is formed from the foreign material guard 24. The film may peel off and the particles may fall into the crucible 17 and cause problems such as further splashing and bumping.

  On the other hand, in the vacuum film forming apparatus 30 of FIG. 1, since the plasma 27 for activating the evaporated vapor deposition material 16 is generated during film formation, the high density generated from the hollow cathode gun 18 toward the external electrode 25 is generated. The foreign matter guard 24 is directly heated by the plasma, and the temperature of the foreign matter guard 24 is sufficiently higher than when the plasma is not used or when the plasma is not used. Contamination of the guard 24 can be prevented. For this reason, if the vacuum film-forming apparatus of the present invention is used, not only does the foreign matter catching means block splash and bumping generated from the vapor deposition material, and it does not cause a quality defect, but the foreign matter catching means itself has a further splash or It is possible to form a film without inducing bumping, without causing splash or arcing by itself, and without causing a decrease in film formation speed.

  The foreign matter catching means may be installed between the vapor deposition material and the base material so that a lump containing the vapor deposition material does not reach the base material, but the foreign matter catching means itself may induce further splash or bumping. Alternatively, in order to prevent the occurrence of splash or arcing by itself, it is preferably installed in the vicinity of the plasma, and more preferably, the foreign matter capturing means is in contact with the plasma.

  Further, the foreign matter catching means may be installed as an anode for the hollow cathode 28 in order to prevent the foreign matter catching means itself from inducing further splash or bumping, or causing the splash or arcing itself. . Further, the foreign substance capturing means may be provided at one place as in the vacuum film forming apparatus 30 of FIG. 1 or may be provided at a plurality of places. For example, a plurality of vapor deposition materials and base materials may be provided in the width direction, or a plurality of devices may be installed in accordance with the number of hollow cathode guns in the case of a vacuum film forming apparatus using hollow cathode discharge.

  In addition to the foreign matter guard 24 installed in the vacuum film forming apparatus 30 of FIG. 1, the foreign matter catching means can catch foreign matter and has any form as long as the evaporated deposition material is efficiently deposited on the substrate. For example, the thing along the curved surface of the main roller 14 may be sufficient.

  The method for producing a gas barrier laminate of the present invention is a method for producing a gas barrier laminate comprising a base material and a thin film formed on one surface of the base material. A foreign matter removing process for removing the vapor, a plasma activation process for activating the evaporated deposition material from which the foreign substance has been removed by plasma, and a deposition process for depositing the activated deposition material on one surface of the substrate. The said manufacturing method is demonstrated with reference to FIG.

  In the foreign matter removing step, the vapor deposition material 16 packed in the crucible 17 is heated by the electron beam gun 20 which is an evaporation means. Then, from the evaporated vapor deposition material 16, a lump containing the vapor deposition material, impurities contained in the vapor deposition material, residual gas such as water existing in a vacuum, or reactive gas released from the gas pipe 23 is formed on the surface of the vapor deposition material 16. Foreign matters such as reactants generated by the reaction are removed by a foreign matter guard 24 which is a foreign matter capturing means.

  In the plasma activation process, the evaporated vapor deposition material 16 from which foreign substances have been removed passes through the plasma 27 generated between the hollow cathode gun 18 as the plasma generation means and the external electrode 25 as vapor deposition particles 26. Then, the vapor deposition particles 26 are activated.

  In the vapor deposition step, activated vapor deposition particles 26 are vapor-deposited on the surface of the film substrate 15 held by the main roller 14 to form a film.

  The order of the foreign matter removal step and the plasma activation step may be either the plasma activation step after the foreign matter removal step or the foreign matter removal step after the plasma activation step. Further, in order to prevent the foreign matter capturing means itself from inducing further splash or bumping, or causing the splash or arcing itself, the foreign matter removing step and the plasma activation step may be performed simultaneously. preferable.

  The gas barrier laminate including the film formed through each of the above steps minimizes damage due to arcing, bumping, splash, etc. generated from the vapor deposition material, thus improving the deterioration of gas barrier properties and appearance defects. be able to.

The gas barrier laminate including the film formed through each of the above steps has very few defects, a water vapor permeability of 3 g / m ² / day or less, and an oxygen permeability of 5 cc / m ² / day or less, and has a high water vapor barrier and oxygen barrier property.

  Specific examples and comparative examples of the present invention are shown below.

<Example 1>
In the vacuum film forming apparatus 30 shown in FIG. 1, a crucible 17 is filled with a block of silicon monoxide having a side of 50 mm as an evaporation material 16 and heated using an electron beam gun 20 at a film forming rate of 100 nm / sec. Vapor deposition was performed. At that time, argon gas of 200 sccm was used as the rare gas X, and a discharge current of 100 A was discharged from the hollow cathode gun 18 to the external electrode 25 to prepare a sample. At this time, a 2 mm square mesh made of Ta was exposed to the plasma as the foreign matter guard 24 and installed at the position where the silicon monoxide vapor passed, to guard against splash and bumping that occurred during film formation. At this time, a 12 μm PET film having a width of 500 mm was used as the substrate.

<Example 2>
In the vacuum film forming apparatus 30 shown in FIG. 1, 800 sccm of oxygen gas is introduced from the gas pipe 23, while the crucible 17 is filled with aluminum as the vapor deposition material 16 and heated using the electron beam gun 20 to 100 nm / sec. At this time, reactive vapor deposition was performed, and at that time, argon gas of 200 sccm was used as the rare gas X, and a discharge of 100 A was discharged from the hollow cathode gun 18 to the external electrode 25 to prepare a sample. At this time, the foreign matter guard 24 is a 2 mm square mesh made of Ta, exposed to plasma without interfering with the trajectory of the electron beam, and installed at a position where aluminum vapor passes, and splash and bumping generated during film formation. Guarded. At this time, a 12 μm PET film having a width of 500 mm was used as the substrate.

<Comparative Example 1>
In the vacuum film forming apparatus 30 shown in FIG. 1, a crucible 17 is filled with a block of silicon monoxide having a side of 50 mm as an evaporation material 16 and heated using an electron beam gun 20 at a film forming rate of 100 nm / sec. Vapor deposition was performed and a sample was produced without using plasma generating means. At this time, a 12 μm PET film having a width of 500 mm was used as the substrate.

<Comparative example 2>
In the vacuum film forming apparatus 30 shown in FIG. 1, 800 sccm of oxygen gas is introduced from the gas pipe 23, while the crucible 17 is filled with aluminum as the vapor deposition material 16 and heated using the electron beam gun 20 to 100 nm / sec. Reactive vapor deposition was carried out at a film forming rate, and a sample was produced without using plasma generating means. At this time, a 12 μm PET film having a width of 500 mm was used as the substrate.

  About the produced sample, the number of the pinhole defects which arose due to splash and bumping was investigated.

(Pinhole defect evaluation method)
About the produced sample 1000m, the number of pinhole defects and foreign material defects was counted and converted as the number of defects per square meter.

  About the produced sample, water vapor permeability and oxygen permeability were measured with the following method.

(Evaluation method of water vapor permeability and oxygen permeability)
The water vapor permeability was measured by the MOCON method. The measuring instrument used was measured by MOCON PERMATRAN 3/33 at 40 ° C. and 90% Rh, and the oxygen permeability was measured by MOCON OX-TRAN 2/20 at 23 ° C. and 0% Rh.

  Table 1 shows the number of defects, water vapor permeability, and oxygen permeability of the samples produced in Examples 1 and 2 and Comparative Examples 1 and 2.

  From the results in Table 1, when the vacuum film forming apparatus of the present invention was used, a gas barrier film having very few defects and high water vapor barrier property and oxygen barrier property was obtained at high speed film formation of 100 nm / sec. .

  The vacuum film-forming apparatus of the present invention is a device for producing a gas barrier laminate and a method for producing the gas barrier laminate, and the produced oxygen and water vapor barrier laminate is a packaging material for foods, pharmaceuticals, etc., and an electronic member It is also used for protective materials such as optical members.

DESCRIPTION OF SYMBOLS 10 ... Film-forming chamber 11 ... Winding chamber 12 ... Unwinding roller 13 ... Winding roller 14 ... Main roller 15 ... Film base material 16 ... Deposition material 17 ... · Crucible 18 ··· Hollow cathode gun 19 ··· Internal electrode 20 ··· Electron beam gun 21 ··· DC power source 22 for hollow cathode discharge ··· DC power source 23 for hollow cathode discharge ··· Gas pipe 24 ··· Foreign object guard 25 ... external electrode 26 ... deposited particles 27 ... plasma 28 ... hollow cathode 30 ... vacuum film forming apparatus X ... inert gas

Claims (9)

A vacuum film forming apparatus for forming a thin film on one surface of a substrate by vapor deposition,
An evaporation means for evaporating the vapor deposition material;
Plasma generating means for generating plasma for activating the evaporated deposition material;
A vacuum film-forming apparatus comprising a foreign matter capturing means installed between the vapor deposition material and the base material.   The vacuum film forming apparatus according to claim 1, wherein the foreign matter capturing means is in contact with the plasma.   3. The vacuum film forming apparatus according to claim 1, wherein a material of the foreign matter capturing means includes any one of molybdenum, tantalum, tungsten, niobium, carbon, stainless steel, and alumina.   4. The vacuum film forming apparatus according to claim 1, wherein the evaporation unit uses any one of electron beam heating, induction heating, and resistance heating. 5.   5. The vacuum film forming apparatus according to claim 1, wherein the plasma generating unit uses any one of a hollow cathode discharge, a microwave discharge, an ICP discharge, and a helicon wave discharge. 6.   The vacuum film forming apparatus according to any one of claims 1 to 5, further comprising a conveying unit that conveys the base material in a roll-to-roll manner. A method for producing a gas barrier laminate comprising a substrate and a thin film formed on one surface of the substrate,
A foreign matter removal step of removing foreign matter from the vapor deposition material evaporated by the evaporation means;
A plasma activation process for activating the evaporated deposition material from which foreign substances have been removed with plasma;
And a vapor deposition step of depositing an activated vapor deposition material on one surface of the base material.   The method for producing a gas barrier laminate according to claim 7, wherein the foreign matter removing step and the plasma activation step are performed simultaneously.   A gas barrier laminate produced by the method according to claim 7 or 8.