JP2020059875A - Film deposition apparatus and film deposition method - Google Patents

Abstract

To improve adhesion of a vapor-deposited film to a substrate.SOLUTION: A film deposition apparatus deposits a vapor-deposition film containing aluminum on a surface of a substrate. The film deposition apparatus includes a plasma pre-processing mechanism which has an electrode part on which voltage is applied between the film deposition apparatus and a pre-processing roller for transferring the substrate wounded and generates plasma between the pre-processing roller and the electrode part, and a vapor deposition mechanism which has a film deposition roller positioned in a downstream side of the plasma pre-processing mechanism in a substrate transfer direction, and an evaporation mechanism evaporating a vapor deposition material containing aluminum such that the vapor deposition material reaches a surface of the substrate wounded on the film deposition roller and a plasma supply mechanism which supplies plasma between the surface of the substrate and the evaporation mechanism, and a film deposition mechanism which deposits a vapor deposition film on the surface of the substrate wound on the film deposition roller, the plasma supply mechanism having a hollow cathode.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a film forming apparatus and a film forming method for forming a vapor deposition film on a substrate.

Conventionally, a laminated film provided with a film formed on a substrate of a long film or sheet such as plastic has been used in various applications. For example, a barrier laminated film in which a barrier layer made of a thin film of aluminum oxide or the like is provided on a plastic film to have a function of a barrier against oxygen and water vapor has been developed.
As a means for forming a film on the surface of a base material such as plastic, a method based on a vapor deposition method such as a vacuum vapor deposition method is known. Further, a film forming apparatus for forming a film on the surface of a base material using these means is known.

  Further, for example, as disclosed in Patent Document 1, when an aluminum oxide film is formed on the surface of a film by an evaporation method using an evaporation source of aluminum, oxygen gas and aluminum are efficiently reacted. For that purpose, it is known to supply plasma to the space between the evaporation source and the substrate.

  Further, for example, as disclosed in Patent Document 1, when a film of aluminum oxide is formed on the surface of the film by a vapor deposition method, the film is subjected to a surface treatment using plasma or the like, and an aluminum oxide film It is known to form a film.

JP, 2017-177343, A

  An object of the present invention is to provide a film forming apparatus having a barrier property and capable of forming a vapor-deposited film that is difficult to be peeled off from a base material on the base material.

  The present invention is a film forming apparatus for forming a vapor deposition film containing aluminum on a surface of a base material, wherein a voltage is applied between a pretreatment roller that conveys the wound base material and the pretreatment roller. A plasma pretreatment mechanism that has an applied electrode portion and generates plasma between the pretreatment roller and the electrode portion, and a downstream side of the plasma pretreatment mechanism in the transport direction of the substrate. Of the film-forming roller located at, the evaporation mechanism that evaporates the evaporation material containing aluminum so as to reach the surface of the base material wound around the film-forming roller, and the surface of the base material and the evaporation mechanism. And a plasma supply mechanism for supplying plasma between, and a film formation mechanism for forming the vapor deposition film on the surface of the base material wound around the film formation roller, wherein the plasma supply mechanism is , Holoca Having over de, a film formation apparatus.

In the film forming apparatus according to the present invention, the plasma pretreatment mechanism, even by generating plasma density 100W · sec / m ² or more 8000W · sec / m ² or less of the plasma between the electrode portion and the pretreatment roller Good.

  In the film forming apparatus according to the present invention, the plasma pretreatment mechanism may further include a magnetic field forming unit that forms a magnetic field between the pretreatment roller and the electrode unit.

  In the film forming apparatus according to the present invention, the electrode section has a gas ejection section for ejecting gas, an AC voltage is applied between the electrode section and the pretreatment roller, and the plasma pretreatment mechanism supplies a plasma source gas. Further comprising a plasma source gas supply unit, the plasma source gas supply unit supplies the plasma source gas between at least the pretreatment roller and the electrode unit, the plasma pretreatment mechanism, the electrode unit Plasma may be generated between the pretreatment roller and the electrode portion based on the AC voltage applied between the pretreatment roller and the pretreatment roller.

  In the film forming apparatus according to the present invention, the plasma raw material gas may include at least one gas selected from the group consisting of oxygen, nitrogen, carbon dioxide gas, ethylene and argon.

  In the film forming apparatus according to the present invention, the electrode unit may be applied with an alternating voltage of 250 V or more and 1000 V or less with the pretreatment roller.

  In the film forming apparatus according to the present invention, the electrode unit has a first surface facing the pretreatment roller and a second surface located on the opposite side of the first surface, and between the pretreatment roller and the pretreatment roller. An AC voltage is applied, the magnetic field forming unit is provided on the second surface side of the electrode unit, and the plasma pretreatment mechanism applies the AC voltage between the electrode unit and the pretreatment roller. The plasma may be generated based on

  In the film forming apparatus according to the present invention, the electrode portion may be applied with an alternating voltage having a frequency of 20 kHz or more and 500 kHz or less with the pretreatment roller.

  In the film forming apparatus according to the present invention, the plasma pretreatment mechanism includes two or more electrode parts and two or more magnetic field forming parts, and the two or more electrode parts are in a conveyance direction of the base material. The two or more magnetic field forming sections may be provided on the second surface side of each of the two or more electrode sections.

  In the film forming apparatus according to the present invention, the electrode unit may be applied with an alternating voltage of 250 V or more and 1000 V or less with the pretreatment roller.

  In the film forming apparatus according to the present invention, the film forming apparatus further includes an AC power supply that is electrically connected to the pretreatment roller and the electrode unit and is capable of applying an AC voltage, The pretreatment mechanism may generate plasma by applying an AC voltage between the pretreatment roller and the electrode portion using the AC power supply.

  In the film forming apparatus according to the present invention, the plasma pretreatment mechanism is arranged in a plasma pretreatment chamber, the film formation mechanism is separated from the plasma pretreatment chamber, and the plasma pretreatment chamber in a transfer direction of the substrate. It may be arranged in the film forming chamber located on the downstream side.

  The present invention is a film forming method for forming a vapor deposition film containing aluminum on the surface of a base material using a film forming apparatus, wherein the film forming apparatus conveys the wound base material. A plasma pretreatment mechanism having an electrode part, a film forming roller located on the downstream side of the plasma pretreatment mechanism in the transport direction of the substrate, and an evaporation mechanism for evaporating a vapor deposition material containing aluminum. A film forming mechanism having, and applying a voltage between the pretreatment roller and the electrode portion, while generating a plasma between the pretreatment roller and the electrode portion, the generated plasma A plasma pretreatment step of performing a pretreatment on the surface of the base material using, and using the evaporation mechanism while generating plasma between the surface of the base material and the evaporation mechanism using the hollow cathode. , Said An evaporation material including aluminum is evaporated so as to reach the surface of the substrate wound around the rollers, comprising a film forming step of forming a deposited film containing aluminum, and a film formation method.

  In the film forming method according to the present invention, the plasma pretreatment mechanism of the film forming apparatus may further include a magnetic field forming unit that forms a magnetic field between the pretreatment roller and the electrode unit.

  In the film forming method according to the present invention, arc discharge may be generated using the hollow cathode in the film forming step.

  According to the present invention, the barrier property of the vapor deposition film can be improved.

It is sectional drawing which shows an example of the laminated film provided with the film | membrane. It is a figure which shows an example of the film-forming apparatus which concerns on embodiment of this invention. It is sectional drawing which shows an example of the plasma pretreatment mechanism of a film-forming apparatus. It is sectional drawing which shows an example of the film-forming mechanism of a film-forming apparatus. It is a figure which shows the modification of the film-forming apparatus. It is a figure which shows the modification of the film-forming apparatus. It is a figure which shows the modification of the film-forming apparatus. It is a figure which shows the modification of the film-forming apparatus. It is a figure which shows the evaluation result of Example 1 and Comparative Examples 1-4.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in the drawings attached to the present specification, for convenience of illustration and understanding, the scale and the vertical and horizontal dimension ratios are appropriately changed from those of the actual product and exaggerated.

  1 to 4 are diagrams for explaining an embodiment of the present invention. In the following embodiments and modifications thereof, a film forming apparatus for forming a laminated film by forming an evaporated film on the surface of a plastic substrate will be described as an example.

  1a, 1b, and 1c are cross-sectional views showing an example of a laminated film produced using the film forming apparatus according to the present embodiment. A laminated film produced by using the film forming apparatus according to the present embodiment is, for example, the laminated film A shown in FIG. 1, the base material 1 and the vapor deposition film 2 located on one surface of the base material 1. And The laminated film may further include a barrier coating layer 3 on the vapor-deposited film 2 of the laminated film A, like the laminated film B shown in FIG. 1b. The laminated film, like the laminated film C shown in FIG. 1c, further comprises the adhesive layer 4, the second base material 5, the adhesive layer 6, and the sealant layer on the barrier coating layer 3 of the laminated film B. 7 may be provided in this order.

  The base material 1 is not particularly limited. When a plastic substrate is used as the substrate 1, a known plastic film or sheet can be used. For example, polyethylene-based resins such as polyethylene terephthalate, polyester derived from biomass, polybutylene terephthalate and polyethylene naphthalate, polyamide-based resins such as polyamide resin 6, polyamide resin 66, polyamide resin 610, polyamide resin 612, polyamide resin 11 and polyamide resin 12. A film made of a resin, a polyolefin resin such as a polymer of α-olefin such as polyethylene or polypropylene, or the like can be used.

  The thickness of the plastic film as the plastic substrate as described above is not particularly limited, and can be pretreated or film-formed when the vapor deposition film 2 is formed by the film-forming device described later. However, the range of 6 μm or more and 100 μm or less is preferable from the viewpoint of flexibility and shape retention. When the thickness of the plastic film is within the above range, it is easy to bend and does not break during transportation, and it is easy to handle in a film forming apparatus used for manufacturing a laminated film having the vapor deposition film 2 with improved adhesion. .

  Next, the vapor deposition film 2 will be described. The vapor deposition film 2 contains aluminum. Aluminum exists in the vapor deposition film 2 in a state of, for example, aluminum oxide (Al2O3) or aluminum hydroxide (Al2O4H). The deposited film 2 further includes a metal oxide such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, or zirconium oxide, or a metal thereof. It may contain a nitride or a carbide.

  The laminated film having the above structure is, for example, a laminated film in which the vapor deposition film 2 containing aluminum oxide or the like is provided on the surface of the base material 1 which is a plastic film. More specifically, it is a laminated film in which a vapor deposition film 2 containing aluminum oxide having a thickness of 5 nm to 50 nm is provided on the surface of a substrate 1 containing polyethylene terephthalate having a thickness of 12 μm. The laminated film having the above structure has excellent barrier properties because the vapor deposition film 2 has barrier properties against oxygen and water vapor. Therefore, it can be suitably used as a packaging material for electronic devices such as electronic paper, foods, pharmaceuticals, and pet foods.

  Next, the film forming apparatus 10 suitably used for manufacturing a laminated film having the vapor deposition film 2 with improved barrier properties will be described. As shown in FIG. 2, the film forming apparatus 10 includes a base material transport mechanism 11A for transporting the base material 1, a plasma pretreatment mechanism 11B for performing plasma pretreatment on the surface of the base material 1, and a vapor deposition film 2. A film forming mechanism 11C for forming a film. In the example shown in FIG. 2, the film forming apparatus 10 further includes a decompression chamber 12. The decompression chamber 12 has a decompression mechanism such as a vacuum pump described later that adjusts the atmosphere of at least part of the space inside the decompression chamber 12 to atmospheric pressure or less.

  In the example shown in FIG. 2, the decompression chamber 12 includes a substrate transport chamber 12A in which the substrate transport mechanism 11A is located, a plasma pretreatment chamber 12B in which the plasma pretreatment mechanism 11B is located, and a film deposition mechanism 11C. The membrane chamber 12C is included. The decompression chamber 12 is preferably configured to prevent the atmospheres inside each chamber from mixing with each other. For example, as shown in FIG. 2, the decompression chamber 12 includes a substrate transfer chamber 12A and a plasma pretreatment chamber 12B, a plasma pretreatment chamber 12B and a film formation chamber 12C, and a substrate transfer chamber 12A and a film formation. It may have partition walls 35a to 35c which are located between the chambers 12C and separate the chambers.

  The substrate transfer chamber 12A, the plasma pretreatment chamber 12B and the film forming chamber 12C will be described. The plasma pretreatment chamber 12B and the film forming chamber 12C are provided in contact with the base material transfer chamber 12A, and each has a portion connected to the base material transfer chamber 12A. Thereby, the base material 1 can be transferred between the base material transfer chamber 12A and the plasma pretreatment chamber 12B and between the base material transfer chamber 12A and the film forming chamber 12C without being exposed to the atmosphere. For example, between the base material transfer chamber 12A and the plasma pretreatment chamber 12B, the base material 1 can be transferred via the opening provided in the partition wall 35a. The same structure is provided between the base material transfer chamber 12A and the film formation chamber 12C, and the base material 1 can be transferred between the base material transfer chamber 12A and the film formation chamber 12C.

  The function of the decompression mechanism of the decompression chamber 12 will be described. The decompression mechanism of the decompression chamber 12 is configured so that the atmosphere in at least the plasma pretreatment mechanism 11B or the film formation mechanism 11C of the film formation apparatus 10 can be decompressed to atmospheric pressure or lower. The decompression mechanism may be configured to decompress each of the substrate transfer chamber 12A, the plasma pretreatment chamber 12B, and the film formation chamber 12C, which are partitioned by the partition walls 35a to 35c, to atmospheric pressure or lower.

  The structure of the decompression mechanism of the decompression chamber 12 will be described. The decompression chamber 12 may have, for example, a vacuum pump connected to the plasma pretreatment chamber 12B. By adjusting the vacuum pump, it is possible to appropriately control the pressure in the plasma pretreatment chamber 12B when the plasma pretreatment described below is performed. Further, it is possible to suppress the plasma supplied into the plasma pretreatment chamber 12B from diffusing into another chamber by the method described later. The decompression mechanism of the decompression chamber 12 may have a vacuum pump connected to the film forming chamber 12C, as well as a vacuum pump connected to the plasma pretreatment chamber 12B. As the vacuum pump, a dry pump, a turbo molecular pump, a cryopump, a rotary pump, a diffusion pump or the like can be used.

The base material transfer mechanism 11A for the base material 1 of the film forming apparatus 10 according to the present embodiment will be described together with the transfer path for the base material 1.
The base material transfer mechanism 11A is a mechanism for transferring the base material 1, which is arranged in the base material transfer chamber 12A. In the example shown in FIG. 2, the base material transport mechanism 11A includes an unwinding roller 13 to which a roll-shaped raw material of the base material 1 is attached, a winding roller 15 that winds up the base material 1, and guide rolls 14a to 14d. Have. The base material 1 sent out from the base material transport mechanism 11A is then provided with a pretreatment roller 20 described later, which is arranged in the plasma pretreatment chamber 12B, and a film formation roller 25 described below, which is arranged in the film formation chamber 12C. And are transported by.

  Although not shown, the base material transport mechanism 11A may further include a tension pickup roller. Since the base material transport mechanism 11A has the tension pickup roller, the base material 1 can be transported while adjusting the tension applied to the base material 1.

(Plasma pretreatment mechanism)
The plasma pretreatment mechanism 11B will be described. The plasma pretreatment mechanism 11B is a mechanism for performing plasma pretreatment on the surface of the base material 1. The plasma pretreatment mechanism 11B shown in FIG. 2 includes a pretreatment roller 20 disposed in the plasma pretreatment chamber 12B, an electrode unit 21, and a magnetic field forming unit that forms a magnetic field between the pretreatment roller 20 and the electrode unit 21. 23 and a plasma raw material gas supply unit 22 for supplying a plasma raw material gas.

  The pretreatment roller 20 will be described. FIG. 3 is an enlarged view of the portion surrounded by the alternate long and short dash line indicated by reference numeral III in FIG. 2. Note that, in FIG. 3, the description of the power supply wiring 31 that connects the power source 32 illustrated in FIG. 2 and the electrode portion 21 described later is omitted. The pretreatment roller 20 has a rotation axis X. The pretreatment roller 20 is provided so that at least the rotation axis X is located in the plasma pretreatment chamber 12B partitioned by the partition walls 35a and 35b. The substrate 1 having a dimension in the direction of the rotation axis X is wound around the pretreatment roller 20. In the following description, the dimension of the base material 1 in the direction of the rotation axis X is also referred to as the width of the base material 1. The direction of the rotation axis X is also referred to as the width direction of the base material 1.

  As shown in FIG. 2, the pretreatment roller 20 may be provided so that a part thereof is exposed to the side of the base material transport chamber 12A. In the example shown in FIG. 2, the plasma pretreatment chamber 12B and the substrate transfer chamber 12A are connected through an opening provided in the partition wall 35a, and a part of the pretreatment roller 20 is passed through the opening. Is exposed on the side of the base material transfer chamber 12A. There is a gap between the partition wall 35a between the substrate transfer chamber 12A and the plasma pretreatment chamber 12B and the pretreatment roller 20, and the substrate transfer chamber 12A to the plasma pretreatment chamber 12B passes through the gap. Then, the base material 1 can be transported. Although not shown, the pretreatment roller 20 may be provided so as to be located entirely inside the plasma pretreatment chamber 12B.

  Although not shown, the pretreatment roller 20 may have a temperature adjusting mechanism for adjusting the temperature of the surface of the pretreatment roller 20. For example, the pretreatment roller 20 may have a temperature adjustment mechanism including a pipe for circulating a temperature adjustment medium such as a refrigerant or a heat medium inside the pretreatment roller 20. The temperature adjusting mechanism adjusts the temperature of the surface of the pretreatment roller 20 to a target temperature within a range of, for example, −20 ° C. or higher and 100 ° C. or lower.

  Since the pretreatment roller 20 has the temperature adjusting mechanism, it is possible to prevent the base material 1 from shrinking or being damaged by heat during plasma pretreatment.

  The pretreatment roller 20 is formed of a material containing at least one of stainless steel, iron, copper, and chromium. The surface of the pretreatment roller 20 may be subjected to a hard chrome hard coat treatment or the like to prevent scratches. These materials are easy to process. Further, by using the above-mentioned material as the material of the pretreatment roller 20, the thermal conductivity of the pretreatment roller 20 itself becomes high, so that the temperature of the pretreatment roller 20 can be easily controlled.

  The electrode part 21 will be described. The electrode portion 21 according to the present embodiment faces the pretreatment roller 20. A voltage is applied to the electrode portion 21 between the electrode portion 21 and the pretreatment roller 20. For example, as shown in FIG. 2, when the film forming apparatus 10 includes a power supply 32, the electrode portion 21 is connected to the power supply wiring 31, and the power supply wiring 31 is connected to the power supply 32. In this case, the electrode section 21 is applied with a voltage between the electrode section 21 and the pretreatment roller 20 by using the power source 32.

  Although not shown, the electrode portion 21 according to the present embodiment has a gas ejection portion that ejects gas and an electrode to which a voltage is applied between the pretreatment roller 20. The ejection unit according to the present embodiment ejects gas so as to apply gas pressure to at least a part of the surface of the electrode. This can prevent the voltage between the electrode and the pretreatment roller 20 from becoming unstable due to the adhesion of foreign matter. The gas ejected by the ejection unit is, for example, argon gas. The foreign matter is, for example, dust on the base material 1.

  The material of the electrodes is at least electrically conductive so that a voltage can be applied between it and the pretreatment roller 20. It is preferable that the material used for the electrode is excellent in plasma resistance, has heat resistance, has high cooling efficiency with cooling water (high thermal conductivity), is a nonmagnetic material, and has excellent workability. As a material for the electrodes, for example, aluminum, copper or stainless steel is preferably used.

  The plasma source gas supply unit 22 will be described. The plasma raw material gas supply unit 22 is configured to supply the plasma raw material gas at least between the pretreatment roller 20 and the electrode unit 21. The position of the plasma raw material gas supply unit 22 according to the present embodiment is not particularly limited as long as the plasma raw material gas can be supplied at least between the pretreatment roller 20 and the electrode unit 21. In the example shown in FIG. 2, the plasma raw material gas supply unit 22 faces the pretreatment roller 20. The direction in which the plasma source gas supply unit 22 supplies the plasma source gas is not particularly limited as long as the plasma source gas can be supplied at least between the pretreatment roller 20 and the electrode unit 21. In the example shown in FIG. 2, the plasma raw material gas supply unit 22 supplies the plasma raw material gas toward the base material 1 wound around the pretreatment roller 20.

  The film forming apparatus 10 may include a raw material volatilization supply device 18 that is provided outside the decompression chamber 12 and supplies the plasma raw material gas. In this case, the plasma source gas supply unit 22 is connected to the source volatilization supply device 18.

  The number of plasma source gas supply units 22 is preferably 2 or more. The two or more plasma source gas supply units 22 are preferably arranged in the conveyance direction of the base material 1. In the example shown in FIG. 2 and FIG. 3, an example in which three plasma source gas supply units 22 are arranged side by side in the transport direction of the substrate 1 is shown. Further, although not shown, the plasma raw material gas supply unit 22 may have a plurality of gas supply ports arranged in the width direction of the base material 1. In this case, the plasma raw material gas supply unit 22 supplies the plasma raw material gas from each of the plurality of gas supply ports.

  As the plasma raw material gas supplied by the plasma raw material gas supply unit 22, for example, an inert gas such as argon, an active gas such as oxygen, nitrogen, carbon dioxide, ethylene or a mixed gas of these gases is supplied. As the plasma raw material gas, even if one of the inert gases is used alone, or one of the active gases is used alone, two or more kinds of the inert gas or the gas contained in the active gas are used. You may use the mixed gas of. As the plasma source gas, it is preferable to use a mixed gas of an inert gas such as argon and an active gas.

  In the film forming apparatus 10 according to the present embodiment, the plasma raw material gas supply unit 22 is used to supply the plasma raw material gas between the pretreatment roller 20 and the electrode unit 21, while the pretreatment roller 20 and the electrode unit 21 are being supplied. As shown in FIGS. 2 and 3, the plasma P can be generated between the pretreatment roller 20 and the electrode portion 21 by applying a voltage between and.

  The magnetic field forming unit 23 will be described. The magnetic field forming unit 23 is configured to form a magnetic field between the pretreatment roller 20 and the electrode unit 21.

  The shape and number of the magnetic field forming unit 23 is such that a magnetic field can be formed between the pretreatment roller 20 and the electrode unit 21, and the electrode unit 21 is used between the pretreatment roller 20 and the magnetic field forming unit 23. There is no particular limitation as long as plasma can be supplied. FIGS. 2 and 3 show an example in which the plasma pretreatment mechanism 11B has a plurality of magnetic field forming units 23, and the plurality of magnetic field forming units 23 are arranged in the transport direction with a gap therebetween. In the example shown in FIGS. 2 and 3, the four magnetic field forming units 23 are arranged in the carrying direction, but four or more magnetic field forming units 23 may be arranged in the carrying direction of the substrate 1. The magnetic field forming unit 23 has a first surface 23a facing the pretreatment roller 20 and a second surface 23b located on the side opposite to the first surface 23a. In this case, the plasma raw material gas supplied by the plasma raw material gas supply portion 22 is passed through the gaps between the plurality of magnetic field forming portions 23 from the second surface 23b side to the first surface 23a side, or the plasma raw material is supplied. By inserting the gas supply unit 22, plasma can be supplied between the pretreatment roller 20 and the magnetic field forming unit 23. 2 and 3 show an example in which the plasma raw material gas supplied from the plasma raw material gas supply unit 22 is passed from the second surface 23b side to the first surface 23a side through the gap.

  Although not shown, the magnetic field forming unit 23 according to the present embodiment has a plate-like shape extending in the width direction of the base material 1.

  By forming a magnetic field between the pretreatment roller 20 and the electrode portion 21, for example, the density of plasma between the pretreatment roller 20 and the electrode portion 21 can be increased.

  Examples of the type of magnet used as the magnetic field forming unit 23 include permanent magnets such as ferrite magnets and rare earth magnets such as neodymium and samarium cobalt (Samakoba). An electromagnet may be used as the magnetic field forming unit 23.

  The magnetic flux density of the magnet of the magnetic field forming unit 23 is, for example, 100 gauss or more and 10000 gauss or less. If the magnetic flux density is 100 gauss or more, a sufficiently high-density plasma can be generated by forming a sufficiently strong magnetic field between the pretreatment roller 20 and the electrode portion 21, and a good pretreatment surface can be obtained. Can be formed at high speed. On the other hand, in order to make the magnetic flux density on the surface of the substrate 1 higher than 10,000 Gauss, an expensive magnet or magnetic field generating mechanism is required.

Plasma pretreatment mechanism 11B is, for example, supplied between the pretreatment roller 20 and the electrode portion 21 of the plasma density 100W · sec / m ² or more 8000W · sec / m ² or less of the plasma.

  In the example shown in FIG. 2, the plasma pretreatment mechanism 11B is arranged in the plasma pretreatment chamber 12B which is separated from the substrate transfer chamber 12A and the film forming chamber 12C by a partition wall. By dividing the plasma pretreatment chamber 12B from other regions such as the substrate transfer chamber 12A and the film forming chamber 12C, it becomes easy to independently adjust the atmosphere of the plasma pretreatment chamber 12B. Thereby, for example, it becomes easy to control the plasma raw material gas concentration in the space where the pretreatment roller 20 and the electrode portion 21 face each other, and the productivity of the laminated film is improved.

  In the present embodiment, the voltage applied between the pretreatment roller 20 of the plasma pretreatment mechanism 11B and the electrode portion 21 is an AC voltage. By applying an AC voltage, plasma is generated between the pretreatment roller 20 and the electrode portion 21. Preferably, the application of the AC voltage forms an electric field so that the generated plasma moves toward the surface of the base material 1 and moves in a direction perpendicular to the surface of the base material 1.

The value of the AC voltage applied between the pretreatment roller 20 and the electrode portion 21 is preferably 250 V or more and 1000 V or less. When the AC voltage has the above value, plasma having a sufficient plasma density can be generated between the pretreatment roller 20 and the electrode portion 21. Here, the value of the AC voltage means an effective value V _e . The effective value V _e of the AC voltage is obtained by the following formula (I) when the maximum value of the AC voltage is V _m .

  The AC voltage applied between the pretreatment roller 20 and the electrode portion 21 has a frequency of 20 kHz or more and 500 kHz or less, for example.

(Film forming mechanism)
Next, the film forming mechanism 11C will be described. In the example shown in FIG. 2, the film forming mechanism 11C includes a film forming roller 25 arranged in the film forming chamber 12C and an evaporation mechanism 24.

  The film forming roller 25 will be described. The film-forming roller 25 is a roller that winds the substrate 1 with the treated surface of the substrate 1 pretreated by the plasma pretreatment mechanism 11B facing outward and conveys the substrate 1.

  The material of the film forming roller 25 will be described. The film forming roller 25 is preferably formed of a material containing at least one of stainless steel, iron, copper and chromium. The surface of the film forming roller 25 may be subjected to a hard chrome hard coat treatment or the like to prevent scratches. These materials are easy to process. Further, by using the above-mentioned material as the material of the film forming roller 25, the thermal conductivity of the film forming roller 25 itself becomes high, so that the temperature controllability becomes excellent when the temperature is controlled. The surface average roughness Ra of the surface of the film forming roller 25 is, for example, 0.1 μm or more and 10 μm or less.

Although not shown, the film forming roller 25 may have a temperature adjusting mechanism that adjusts the temperature of the surface of the film forming roller 25.
The temperature adjusting mechanism has, for example, a circulation path for circulating a cooling medium or a heat source medium inside the film forming roller 25. The cooling medium (refrigerant) is, for example, an ethylene glycol aqueous solution, and the heat source medium (heat medium) is, for example, silicon oil. The temperature adjusting mechanism may have a heater installed at a position facing the film forming roller 25. When the film forming mechanism 11C forms a film by the vapor deposition method, the temperature adjusting mechanism preferably sets the surface temperature of the film forming roller 25 to −20 from the viewpoints of heat resistance of related mechanical parts and versatility. Adjust to a target temperature within the range of ℃ to 200 ℃.
Since the film forming roller 25 has the temperature adjusting mechanism, it is possible to suppress the temperature change of the substrate 1 due to the heat generated during the film forming.

  The evaporation mechanism 24 will be described. FIG. 4 is an enlarged view of a portion surrounded by a one-dot chain line designated by reference numeral IV in FIG. 2 and shows a specific form of the evaporation mechanism 24 which is omitted in FIG. 2 and is omitted in FIG. FIG. 6 is a diagram showing a vapor deposition material supply unit 61 for supplying a vapor deposition material. In FIG. 4, the decompression chamber 12 and the partition walls 35b and 35c are omitted. The evaporation mechanism 24 is a mechanism for evaporating a vapor deposition material containing aluminum. When the evaporated vapor deposition material adheres to the base material 1, a vapor deposition film containing aluminum is formed on the surface of the base material 1. The evaporation mechanism 24 in the present embodiment employs a resistance heating type. In the example shown in FIG. 4, the evaporation mechanism 24 has a boat 24b. In the present embodiment, the boat 24b has a power source (not shown) and a resistor (not shown) electrically connected to the power source. A plurality of boats 24b may be arranged in the width direction of the base material 1.

  As shown in FIG. 4, the film forming mechanism 11C may include an evaporation material supply unit 61 that supplies the evaporation material to the evaporation mechanism 24. In FIG. 4, the vapor deposition material supply part 61 has shown the example which continuously sends out the metal wire of aluminum.

  Although not shown, the film forming mechanism 11C has a gas supply mechanism. The gas supply mechanism is a mechanism that supplies gas between the evaporation mechanism 24 and the film formation roller 25. The gas supply mechanism supplies at least oxygen gas. The oxygen gas evaporates from the evaporating mechanism 24 and reacts with or combines with an evaporating material such as aluminum which is directed toward the substrate 1 on the film forming roller 25. As a result, a vapor deposition film containing aluminum oxide can be formed on the surface of the base material 1.

  Further, the film forming mechanism 11C includes a plasma supply mechanism 50 that supplies plasma between the surface of the base material 1 and the evaporation mechanism 24. In the example shown in FIGS. 2 and 4, the plasma supply mechanism 50 has a hollow cathode 51. In the present embodiment, the hollow cathode 51 is a cathode having a hollow portion that is partially open. The hollow cathode 51 can generate plasma in the cavity. In the example shown in FIG. 4, the hollow cathode 51 is provided so that the opening of the hollow portion of the hollow cathode 51 is located diagonally above the boat 24b. Although not shown, the plasma supply mechanism 50 according to the present embodiment has an anode facing the opening, which draws plasma from the opening of the hollow portion of the hollow cathode 51. The plasma supply mechanism 50 according to the present embodiment generates plasma in the hollow portion of the hollow cathode 51, and draws out the plasma between the surface of the base material 1 and the evaporation mechanism 24 by the opposing anode, thereby forming the base material. A strong plasma can be generated between the surface of No. 1 and the evaporation mechanism 24. The position of the facing anode is not particularly limited as long as the facing anode can draw plasma from the opening of the hollow portion of the hollow cathode 51 and supply the plasma between the surface of the substrate 1 and the evaporation mechanism 24. . In the present embodiment, a case will be described in which opposing anodes are arranged on both sides of the boat 24b in the width direction of the base material 1. In this case, the film forming mechanism 11C includes a plurality of boats 24b and a plurality of opposing anodes, and the plurality of boats 24b and the plurality of opposing anodes may be arranged alternately in the width direction of the base material 1. Good. Although not shown, the plasma supply mechanism 50 may include a raw material supply device that supplies the plasma raw material gas into at least the hollow portion of the hollow cathode 51. As the plasma raw material gas supplied by the raw material supply device, for example, the same gas that can be used as the plasma raw material gas supplied by the plasma raw material gas supply unit 22 of the plasma pretreatment mechanism 11B can be used.

  By supplying plasma between the surface of the substrate 1 and the evaporation mechanism 24 by the plasma supply mechanism 50, the aluminum and oxygen gas evaporated in the evaporation mechanism 24 are activated, and the reaction between aluminum and oxygen gas or Binding can be facilitated. Thereby, the ratio of aluminum present as aluminum oxide in the vapor deposition film 2 formed on the surface of the substrate 1 can be increased, and the characteristics of the vapor deposition film 2 can be stabilized.

  Although not shown in the drawings, the film forming apparatus 10 causes the film formation mechanism 11C to form a film in a portion of the substrate transfer chamber 12A that is located downstream of the film formation chamber 12C in the transfer direction of the substrate 1. A base material charge removing unit that performs a post-treatment for removing the charge generated on the base material 1 may be provided. The base material charge removing unit may be provided so as to remove the charge on one surface of the base material 1, or may be provided so as to remove the charge on both surfaces of the base material 1.

  The device used as the base material charge removing unit for performing the post-treatment on the base material 1 is not particularly limited, and examples thereof include a plasma discharge device, an electron beam irradiation device, an ultraviolet irradiation device, a static elimination bar, a glow discharge device, and a corona treatment device. Can be used.

  When the post-treatment is performed by forming a discharge using a plasma processing device or a glow discharge device, a discharge gas simple substance such as argon, oxygen, nitrogen, or helium, or a mixed gas thereof is supplied in the vicinity of the base material 1. However, the post-treatment can be performed using any discharge method such as alternating current (AC) plasma, direct current (DC) plasma, arc discharge, microwave, and surface wave plasma. In a reduced pressure environment, it is most preferable to perform post-treatment using a plasma discharge device.

  The base material charge removing unit is installed in a portion of the base material transfer chamber 12A, which is located on the downstream side of the film formation chamber 12C in the transfer direction of the base material 1 to remove the charge of the base material 1. The material 1 can be transported away from the film forming roller 25 at a predetermined position quickly. For this reason, it is possible to stably carry the base material, prevent damage to the base material 1 due to electrification and deterioration in quality, and improve post-processing appropriateness by improving wettability of the front and back surfaces of the base material.

(Power supply)
In the example illustrated in FIG. 2, the film forming apparatus 10 further includes a power source 32 electrically connected to the pretreatment roller 20 and the electrode portion 21. In the example shown in FIG. 2, the power supply 32 is electrically connected to the pretreatment roller 20 and the electrode portion 21 via the power supply wiring 31. The power source 32 is, for example, an AC power source. When the power supply 32 is an AC power supply, the power supply 32 can apply an AC voltage having a frequency of, for example, 20 kHz or more and 500 kHz or less between the pretreatment roller 20 and the electrode portion 21. Input power that can be applied by the power source 32 (power that can be applied per 1 m width of the electrode portion 21 in the width direction of the base material 1) is not particularly limited, but is, for example, 0.5 kW / m or more and 20 kW / m or less. is there. The pretreatment roller 20 may be electrically installed at a ground level or electrically installed at a floating level.

(Film forming method)
A film forming method for forming a film on the surface of the base material 1 using the film forming apparatus 10 will be described. In film formation using the film forming apparatus 10, the surface of the base material 1 is subjected to plasma pretreatment using the plasma pretreatment mechanism 11B while the base material 1 is being conveyed along the above-described conveyance path of the base material 1. A plasma pretreatment step and a film forming step of forming an evaporation film on the surface of the substrate 1 by using the film forming mechanism 11C are performed. The conveyance speed of the substrate 1 is preferably 200 m / min or more, more preferably 480 m / min or more and 1000 m / min or less.

(Plasma pretreatment process)
The plasma pretreatment process is performed, for example, by the following method. The plasma raw material gas supply unit 22 is used to supply the plasma raw material gas between the pretreatment roller 20 and the electrode unit 21 while applying the above-described AC voltage between the pretreatment roller 20 and the electrode unit 21. . When applying an AC voltage, input power control or impedance control may be performed.

  Plasma is generated at the same time as the glow discharge by the application of the AC voltage, and the plasma P is densified between the pretreatment roller 20 and the magnetic field forming unit 23. In this way, the plasma P can be supplied between the pretreatment roller 20 and the magnetic field forming unit 23. With this plasma P, plasma (ion) pretreatment can be performed on the surface of the substrate 1.

  In addition, in the present embodiment, the ejection part of the electrode part 21 supplies gas so as to apply gas pressure to at least a part of the surface of the electrode. The operation of supplying gas so as to apply gas pressure to at least a part of the surface of the electrode in the plasma pretreatment step will be described. In the plasma pretreatment step, it is possible that foreign matter adheres to the electrodes when the surface of the substrate 1 is pretreated with plasma. In the present embodiment, by supplying the gas so as to apply the gas pressure to at least a part of the surface of the electrode, it is possible to prevent foreign matter from adhering to the surface of the electrode. This can prevent the voltage between the electrode and the pretreatment roller 20 from becoming unstable due to the adhesion of foreign matter. The foreign matter is, for example, dust on the base material 1. The gas ejected by the ejection part of the electrode part 21 may be excited between the pretreatment roller 20 and the electrode part 21 to become plasma P.

  The atmospheric pressure in the plasma pretreatment chamber 12B when the AC voltage is applied between the pretreatment roller 20 and the electrode portion 21 causes the glow discharge between the pretreatment roller 20 and the electrode portion 21 due to the application of the AC voltage. It is not particularly limited as long as it can be made, but is, for example, 0.05 Pa or more and 8 Pa or less.

  The operation of the magnetic field forming unit 23 in the plasma pretreatment process will be described. The magnetic field forming unit 23 forms a magnetic field between the pretreatment roller 20 and the electrode unit 21. The magnetic field may act to trap and accelerate the electrons existing between the pretreatment roller 20 and the electrode portion 21. Therefore, in the region where the magnetic field is formed, the frequency of collision between electrons and the plasma source gas can be increased, the density of plasma can be increased, and the plasma can be localized, so that the efficiency of plasma pretreatment can be improved. it can.

(Film forming process)
In the film forming step, the film is formed on the surface of the substrate 1 by using the film forming mechanism 11C. As an example of the film forming process, a case of forming an aluminum oxide vapor deposition film by using the film forming mechanism 11C having the evaporation mechanism 24 shown in FIG. 4 will be described.

  First, a vapor deposition material containing aluminum is supplied into the boat 24 b of the evaporation mechanism 24 so as to face the film forming roller 25. A metal wire rod made of aluminum can be used as the vapor deposition material. In the example shown in FIG. 4, the vapor deposition material supply unit 61 continuously feeds the aluminum metal wire into the boat 24b to supply the vapor deposition material to the boat 24b.

  By heating, aluminum is evaporated in the boat 24b. FIG. 4 shows the evaporated aluminum vapor 63 for convenience.

  A method of supplying plasma between the surface of the substrate 1 and the evaporation mechanism 24 by the plasma supply mechanism 50 will be described. In the present embodiment, plasma is generated in the hollow portion of the hollow cathode 51 of the plasma supply mechanism 50. Next, discharge is generated between the hollow cathode 51 and the opposing anode, and the plasma in the hollow portion of the hollow cathode 51 is drawn between the surface of the base material 1 and the evaporation mechanism 24.

  In the present embodiment, the discharge generated between hollow cathode 51 and the opposing anode is arc discharge. The arc discharge means a discharge having a current value of 10 A or more, for example.

  Plasma is supplied to the aluminum vapor 63 by evaporating aluminum while supplying plasma between the surface of the base material 1 and the evaporation mechanism 24. By supplying plasma, the reaction or bonding between the aluminum vapor 63 and oxygen gas can be promoted. Thereby, the aluminum vapor 63 can be oxidized before the aluminum vapor 63 reaches the surface of the base material 1. The evaporated and oxidized aluminum adheres to the base material 1, whereby an aluminum oxide vapor deposition film can be formed on the surface of the base material 1.

  In the present embodiment, a plasma pretreatment process of supplying plasma to the surface of the base material 1 is performed before the film forming process. In the plasma pretreatment step, an AC voltage is applied between the electrode portion 21 and the pretreatment roller 20. Further, by utilizing the magnetic field forming unit 23 located on the side of the surface of the electrode portion 21 opposite to the surface facing the pretreatment roller 20, the space between the electrode portion 21 and the pretreatment roller 20. Creates a magnetic field in. Therefore, plasma can be efficiently generated in the space between the electrode portion 21 and the pretreatment roller 20, or the plasma can be vertically incident on the surface of the base material 1 wound around the pretreatment roller 20. can do. Therefore, the adhesiveness between the film formed in the film forming step and the substrate 1 can be enhanced.

  The laminated film having improved adhesion as described above is useful when used as a packaging material for producing a packaging bag for containing contents such as foods. In particular, a laminated film that maintains high adhesion even when subjected to heat treatment can be suitably used as a material for a packaging bag. The above-mentioned laminated film peels off the layers constituting the laminated film, particularly peeling off the vapor-deposited film 2 from the substrate 1 when a packaging bag made of the laminated film is subjected to retort treatment or boil treatment. Can be suppressed.

  The retort treatment is a treatment of filling the packaging bag with the contents and sealing the packaging bag, and then heating the packaging bag under pressure using steam or heated hot water. The retort treatment temperature is, for example, 120 ° C. or higher. The boil treatment is a treatment of filling the packaging bag with the contents, sealing the packaging bag, and then boiling the packaging bag under atmospheric pressure. The boil treatment temperature is, for example, 90 ° C. or higher and 100 ° C. or lower.

(Modification)
In the above-described embodiment, the example in which the magnetic field forming unit 23 of the plasma pretreatment mechanism 11B is located between the electrode unit 21 and the pretreatment roller 20 has been described. However, the present invention is not limited to this, and as in the modified example shown in FIG. 5, the magnetic field forming unit 23 is located on the side opposite to the side where the pretreatment roller 20 is located, as viewed from the electrode unit 21. Good.

  In the modification shown in FIG. 5, the electrode part 21 does not have a gas ejection part. A magnetic field forming unit 23 is provided on the side of the electrode unit 21 opposite to the side facing the pretreatment roller 20. Also by the plasma pretreatment mechanism 11B of this modification, plasma can be generated between the pretreatment roller 20 and the electrode portion 21 to pretreat the surface of the substrate 1.

  The plasma pretreatment mechanism 11B of this modification will be described in more detail with reference to FIG. FIG. 6 is an enlarged view of the portion surrounded by the alternate long and short dash line and labeled VI in FIG.

  The electrode portion 21 according to this modification will be described. In the example shown in FIGS. 5 and 6, the electrode portion 21 has a first surface 21c facing the pretreatment roller 20 and a second surface 21d located on the opposite side of the first surface 21c. In the example shown in FIGS. 5 and 6, the electrode portion 21 is a plate-shaped member, and the first surface 21c and the second surface 21d are both flat surfaces. In this modification, the electrode portion 21 generates a plasma between itself and the pretreatment roller 20 when an alternating voltage is applied between the electrode portion 21 and the pretreatment roller 20. The electrode part 21 preferably forms an electric field between itself and the pretreatment roller 20 so that the generated plasma moves toward the surface of the base material 1 and moves in a direction perpendicular to the surface of the base material 1. Form. Thereby, the base material 1 can be efficiently pretreated.

  The number of electrode portions 21 according to this modification is preferably 2 or more. The two or more electrode portions 21 are preferably arranged along the transport direction of the base material 1. In the examples shown in FIGS. 5 and 6, the film forming apparatus 10 has two electrode portions 21. Moreover, the number of the electrode parts 21 is 12 or less, for example.

  The effect of arranging two or more electrode portions 21 along the transport direction of the base material 1 will be described. As described above, the plasma is generated between the electrode portion 21 and the pretreatment roller 20. The region where plasma is generated expands as the dimension of the electrode portion 21 in the transport direction increases. On the other hand, when the electrode portion 21 is a flat plate-shaped member, the larger the dimension of the electrode portion 21 in the transport direction is, the first surface 21c of the electrode portion 21 in the transport direction, which is the surface facing the pretreatment roller 20. The distance from the end of the pretreatment roller 20 to the pretreatment roller 20 becomes large, and the treatment capacity by plasma decreases.

  In the film forming apparatus 10 according to this modification, two or more electrode portions 21 are arranged side by side in the transport direction of the base material 1. Therefore, even when the dimension of the electrode portion 21 in the transport direction of the base material 1 is small, plasma can be generated over a wide range in the transport direction. Further, by reducing the size of the electrode portion 21, the distance from the end of the first surface 21c of the electrode portion 21 to the pretreatment roller 20 in the transport direction can be reduced, and plasma is uniformly generated in the transport direction. Can be made.

  As shown in FIGS. 5 and 6, the electrode portion 21 according to the present modification has a first end portion 21e and a second end portion 21f located on the first surface 21c of the electrode portion 21. The first end 21e is an end on the upstream side in the transport direction of the substrate 1, and the second end 21f is an end on the downstream side in the transport direction of the substrate 1. As described above, by reducing the dimension of the electrode portion 21 in the transport direction of the base material 1, the distance from the first end portion 21e and the second end portion 21f of the electrode portion 21 in the transport direction to the pretreatment roller 20 is reduced. Can be made smaller. The dimension of the electrode portion 21 in the transport direction of the base material 1 corresponds to the angle θ shown in FIG. The angle θ is an angle formed by a straight line passing through the first end 21e and the rotation axis X and a straight line passing through the second end 21f and the rotation axis X. The angle θ is preferably 20 ° or more and 90 ° or less, more preferably 60 ° or less, and further preferably 45 ° or less. When the angle θ is in the above range, when the first surface 21c of the electrode portion 21 is a flat surface, plasma can be uniformly generated in the transport direction between the electrode portion 21 and the pretreatment roller 20. it can.

  The material of the electrode portion 21 according to this modification is not particularly limited as long as it has conductivity. Specifically, aluminum, copper, and stainless steel are preferably used as the material of the electrode portion 21.

  The thickness L3 of the electrode portion 21 when viewed in a direction perpendicular to the first surface 21c of the electrode portion 21 according to the present modification is not particularly limited, but is 15 mm or less, for example. When the thickness of the electrode portion 21 is the above value, a magnetic field can be effectively formed between the pretreatment roller 20 and the electrode portion 21 by the magnetic field forming portion 23 according to the present modification described later. The thickness L3 of the electrode portion 21 is, for example, 3 mm or more.

  The magnetic field forming unit 23 according to this modification will be described. As shown in FIGS. 5 and 6, the magnetic field forming unit 23 is provided on the side of the electrode unit 21 opposite to the side facing the pretreatment roller 20. The magnetic field forming unit 23 according to this modification is a member that forms a magnetic field between the pretreatment roller 20 and the electrode unit 21. The magnetic field between the pretreatment roller 20 and the electrode portion 21 contributes to generation of higher density plasma when the plasma is generated using the plasma pretreatment mechanism 11B, for example. The magnetic field forming unit 23 illustrated in FIGS. 5 and 6 includes a first magnet 231 and a second magnet 232 provided on the second surface 21d of the electrode unit 21.

  The number of the magnetic field forming units 23 according to this modification is preferably 2 or more. When the plasma pretreatment mechanism 11B has two or more electrode portions 21 and two or more magnetic field forming portions 23, each of the two or more magnetic field forming portions 23 corresponds to each of the two or more electrode portions 21. It is preferably provided on the side opposite to the side facing the pretreatment roller 20. In the example illustrated in FIGS. 5 and 6, each of the two magnetic field forming units 23 is provided on each of the second surfaces 21 d of the two electrode units 21.

The structures of the first magnet 231 and the second magnet 232 in the direction normal to the second surface 21d of the electrode portion 21 will be described. As shown in FIGS. 5 and 6, the first magnet 231 and the second magnet 232 have an N pole and an S pole, respectively. The symbol N shown in FIGS. 5 and 6 indicates the north pole of the first magnet 231 or the second magnet 232. The symbol S shown in FIGS. 5 and 6 indicates the S pole of the first magnet 231 or the second magnet 232.
One of the N pole and the S pole of the first magnet 231 is located closer to the base material 1 than the other. The other of the N pole and the S pole of the second magnet 232 is located closer to the base material 1 than the one is. In the example shown in FIGS. 5 and 6, the N pole of the first magnet 231 is located closer to the base material 1 side than the S pole of the first magnet 231, and the S pole of the second magnet 232 is the second magnet. It is located closer to the substrate 1 than the N pole. Although not shown, the south pole of the first magnet 231 is located closer to the base material 1 side than the north pole of the first magnet 231, and the north pole of the second magnet 232 is closer to the base than the south pole of the second magnet 232. It may be located on the material 1 side.

  Next, the structure of the first magnet 231 and the second magnet 232 in the surface direction of the second surface 21d of the electrode portion 21 will be described. FIG. 7 is a plan view of the electrode part 21 and the magnetic field forming part 23 shown in FIG. 5 as viewed from the magnetic field forming part 23 side. FIG. 8 is a sectional view showing a section taken along line VIII-VIII in FIG. 7. Further, in FIG. 7, the direction D1 is the direction in which the rotation axis X of the pretreatment roller 20 extends.

As shown in FIGS. 7 and 8, the first magnet 231 has a first axial portion 231c. As shown in FIG. 7, the first axial portion 231c extends along the direction D1, that is, along the rotation axis X of the pretreatment roller 20.
The 1st magnet 231 provided in one electrode part 21 may have one 1st axial part 231c, and may have two or more 1st axial parts 231c. In the example shown in FIG. 7, the first magnet 231 provided in one electrode portion 21 has one first axial portion 231c.

  Further, as shown in FIGS. 7 and 8, the second magnet 232 has a second axial portion 232c. As shown in FIG. 7, the second axial portion 232c also extends along the direction D1, that is, the rotation axis X, similarly to the first axial portion 231c.

  Since the first magnet 231 and the second magnet 232 each include a portion extending along the rotation axis X, the uniformity of the magnetic field strength formed around the base material 1 in the width direction of the base material 1 is enhanced. be able to. Thereby, the uniformity of the distribution density of the plasma formed around the base material 1 in the width direction of the base material 1 can be improved.

  The second magnet 232 provided on one electrode part 21 may have one second axial portion 232c or may have two or more second axial portions 232c. In the example shown in FIGS. 7 and 8, the second magnet 232 provided in one electrode portion 21 has two second axial portions 232c. The two second axial portions 232c may be positioned so as to sandwich the first axial portion 231c in the direction D2 orthogonal to the rotation axis X in the surface direction of the second surface 21d of the electrode portion 21.

The dimension L4 of the first axial direction portion 231c and the dimension L5 of the second axial direction portion 232c in the transport direction of the base material 1 shown in FIG. 8 are not particularly limited.
Further, the ratio between the dimension L4 of the first axial direction portion 231c and the dimension L5 of the second axial direction portion 232c in the transport direction of the base material 1 is not particularly limited. The dimension L4 of the first axial portion 231c may be equal to the dimension L5 of the second axial portion 232c, and the dimension L4 of the first axial portion 231c may be larger than the dimension L5 of the second axial portion 232c. .

  The distance L6 between the first axial portion 231c and the second axial portion 232c in the direction D2 is such that the magnetic field generated by the first axial portion 231c and the second axial portion 232c is between the pretreatment roller 20 and the electrode portion 21. Are set to be formed.

  The second magnet 232 may surround the first magnet 231 when the magnetic field forming unit 23 is viewed along the normal direction of the second surface 21d of the electrode unit 21. For example, as shown in FIG. 7, the second magnet 232 has two second axial portions 232c and two connecting portions 232d provided so as to connect the two second axial portions 232c. Good.

  Although not shown, the plasma pretreatment mechanism 11B according to the present modification may have a plasma source gas supply unit. The plasma raw material gas supply unit supplies a gas that is a raw material of plasma into the plasma pretreatment chamber 12B. The structure of the plasma source gas supply unit is not particularly limited. For example, the plasma raw material gas supply unit is provided on the wall surface of the plasma pretreatment chamber 12B and includes a hole for ejecting a gas that is a raw material of plasma. Further, the plasma raw material gas supply unit may have a nozzle that discharges the plasma raw material gas at a position closer to the substrate 1 than the wall surface of the plasma pretreatment chamber 12B. As the plasma raw material gas supplied by the plasma raw material gas supply unit, for example, an inert gas such as argon, an active gas such as oxygen, nitrogen, carbon dioxide, ethylene, or a mixed gas of these gases is supplied. As the plasma raw material gas, even if one of the inert gases is used alone, or one of the active gases is used alone, two or more kinds of the inert gas or the gas contained in the active gas are used. You may use the mixed gas of. As the plasma source gas, it is preferable to use a mixed gas of an inert gas such as argon and an active gas.

  Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the description of the examples below as long as the gist thereof is not exceeded.

  First, a laminated film was produced using the film forming apparatus and the film forming method of Example 1 and Comparative Examples 1 to 4.

(Example 1)
As the base material 1, a plastic base material (produced by KOLON, product name “CB981”) having a thickness of 12 μm and containing polyethylene terephthalate (PET) as a material is prepared, and plasma deposition is performed using the film forming apparatus 10 of the present invention. A processing step and a film forming step were performed.

  In the film forming step, the evaporation film 24 containing aluminum was formed by the vacuum evaporation method using the evaporation mechanism 24 as shown in FIG. Specifically, after adjusting the atmospheric pressure in the film forming chamber 12C to 1 Pa, while supplying a metal wire rod of aluminum as a vapor deposition material into the boat 24b, the resistance heating type evaporation mechanism 24 is used and the inside of the boat 24b is The vapor deposition material was heated to evaporate aluminum so as to reach the surface of the base material 1, thereby forming the vapor deposition film 2 on the surface of the base material 1. By the above method, a plurality of laminated films having the base material 1 and the vapor deposition film 2 as shown in FIG. 1a were produced. The vapor deposition film 2 of the produced laminated film has a thickness of 13 nm. In the following description, the laminated film having the base material 1 and the vapor deposition film 2 as shown in FIG. 1a is also referred to as a vapor deposition film.

The specific conditions of Example 1 are as follows.
[Conditions of Plasma Pretreatment Mechanism 11B]
Form of plasma pretreatment mechanism 11B: The form shown in FIGS. 2 and 3.
The voltage applied between the pretreatment roller 20 and the electrode portion 21 is 340V.
Plasma source gas supplied by the plasma source gas supply unit 22: a mixed gas of argon (Ar) and oxygen (O ₂ ).
The plasma density between the pretreatment roller 20 and the electrode portion 21 is 144 W · sec / m ² .
Magnetic field forming unit 23: 1000 Gauss permanent magnet.
[Conditions of Film Forming Mechanism 11C]
Form of the plasma supply mechanism 50: a hollow cathode 51 shown in FIG. 4, and an anode (not shown) arranged on both sides of the base material 1 in the width direction as viewed from the boat 24b and facing the opening of the hollow portion of the hollow cathode 51. It is a form having.
How to use the plasma supply mechanism 50: Plasma source gas was supplied to the hollow portion of the hollow cathode 51, and the plasma was excited by causing discharge. This plasma was drawn between the surface of the base material 1 and the evaporation mechanism 24 by the opposing anode.

(Comparative Example 1)
Using a plasma pretreatment mechanism with a dual cathode / target structure commonly used in sputtering and plasma treatment, glow discharge pretreatment was performed by applying an AC voltage using an MF (40 kHz) power supply between the dual cathodes. Except for the above, using the same film forming apparatus as in Example 1, film formation was performed by the same method as in Example 1 to produce a plurality of vapor deposition films having the base material 1 and the vapor deposition film 2. The vapor deposition film 2 of the produced vapor deposition film has a thickness of 13 nm.

(Comparative example 2)
Except that the film forming apparatus does not have a plasma pretreatment mechanism and that the plasma pretreatment process is not performed, the film forming step is performed using the same film forming apparatus as in Example 1 and in the same manner as in Example 1. Then, a plurality of vapor deposition films having the base material 1 and the vapor deposition film 2 were produced. The thickness of the vapor deposition film 2 of the produced vapor deposition film is 10 nm.

(Comparative example 3)
A plasma pretreatment process and a film formation process similar to the case of Example 1 except that the film formation mechanism does not have a plasma supply mechanism and that the plasma supply mechanism does not supply plasma. Then, a plurality of vapor deposition films having the base material 1 and the vapor deposition film 2 were produced. The vapor deposition film 2 of the produced vapor deposition film has a thickness of 13 nm.

(Comparative example 4)
Example 1 except that the film forming apparatus does not have a plasma pretreatment mechanism and a plasma supply mechanism, does not perform a plasma pretreatment step, and does not supply plasma using the plasma supply mechanism in the film formation step. The film forming step was performed by the same method as in Example 1 using the same film forming apparatus as in Example 1 to produce a plurality of vapor deposition films having the base material 1 and the vapor deposition film 2. The vapor deposition film 2 of the produced vapor deposition film has a thickness of 13 nm.

(Evaluation of barrier property)
With respect to each of the vapor-deposited films of Example 1 and Comparative Examples 1 to 4 produced by the above method, the values of water vapor transmission rate and oxygen transmission rate were measured.

  The water vapor transmission rate was measured by using a water vapor transmission rate measuring device (manufactured by Mocon Co., product name “Permatran”) under the measurement conditions of 40 ° C. and 90% RH in accordance with JIS K 7129 B method. In addition, the oxygen transmission rate is measured by using an oxygen transmission rate measuring device (manufactured by Mocon, product name “OXTRAN”) under measurement conditions of 23 ° C. and 90% RH in accordance with JIS K 7126-2. It was measured. FIG. 9 shows the results.

(Adhesion evaluation)
Barrier properties obtained by polycondensing by a sol-gel method, containing a silicon alkoxide and a polyvinyl alcohol resin on the vapor deposition film 2 of the vapor deposition films of Example 1 and Comparative Examples 1 to 4 produced by the above method. A barrier coating layer 3 containing the composition was prepared. Here, the above-mentioned barrier coating layer 3 was prepared by the following method. First, a solution obtained by mixing 677 g of water, 117 g of isopropyl alcohol, and 16 g of 0.5N hydrochloric acid (hydrochloric acid having a concentration of 0.5 mol / L) with 285 g of tetraethoxysilane to obtain a solution (hereinafter also referred to as "solution A"). Was adjusted. Next, separately from the solution A, 70 g of polyvinyl alcohol, 1540 g of water, and 80 g of isopropyl alcohol were mixed to prepare a solution (hereinafter also referred to as “solution B”). The solution obtained by mixing the solution A and the solution B in a weight ratio of 13: 7 was used as a barrier coating agent. The obtained barrier coating agent was applied on the surface of the vapor-deposited film 2 and dried at 110 ° C. for 30 seconds to form a barrier coating layer 3 having a thickness of 0.3 μm.

Next, on the surface of the barrier coating layer 3 produced by the above method, a two-component curing type polyurethane adhesive for lamination was applied by a gravure roll coating method to a thickness of 4.0 g / m ² (dry state). Was coated to form an adhesive layer 4, and then a biaxially stretched nylon 6 film having a thickness of 15 μm as a second base material 5 was opposed to the surface of the adhesive layer 4 and was laminated by dry lamination. Next, an adhesive layer 6 for lamination is formed on the surface of the second base material 5 in the same manner as the above adhesive layer 4, and then a thickness of the sealant layer 7 is formed on the surface of the adhesive layer 6. A 70 μm unstretched polypropylene film was dry-laminated and laminated to produce a laminated film having a layer structure as shown in FIG. 1c.

  Next, a laminated film having a layer structure as shown in FIG. 1c was made to face each other so that the sealant layers face each other, and heat-sealed to form a pouch. After filling the pouch with water, retort treatment was performed at 135 ° C. for 40 minutes. The values of the normal peel strength and the wet peel strength were measured for each of the laminated films after the retort treatment.

  The normal peel strength was measured by the following method. First, among the laminated films of Example 1 and Comparative Examples 1 to 4, a laminated film having a layer structure as shown in FIG. 1c, which is a laminated film in a state after being formed into a pouch and subjected to retort treatment Each of them was cut into strips to obtain a rectangular test piece having a width of 15 mm. Next, the second base material and the barrier coating layer of the test piece were partially peeled off in the longitudinal direction of the test piece (direction orthogonal to the width direction of the test piece). The peeling of the second base material and the barrier coating layer was performed by breaking the adhesive layer between the second base material and the barrier coating layer. Further, the peeling of the second base material and the barrier coating layer was performed so that the second base material and the barrier coating layer partially maintained the bonding via the adhesive layer. Next, using a Tensilon universal material testing machine, in accordance with JIS Z6854-2, the peel strength of the adhesive interface between the second base material and the barrier coating layer was measured under conditions of a peel angle of 180 ° and a peel speed of 50 mm / min. It was measured at.

  The wet peel strength was measured by the same method as the method for measuring the normal peel strength except for the points described below. In the measurement of the wet peel strength, the peel strength of the adhesive interface between the vapor deposition film and the base material was measured after the vapor deposition film of the test piece and the base material were partially peeled off. Further, in the measurement of wet peel strength, when the peel strength is measured, a portion where the vapor deposition film and the base material maintain the bonding when viewed along the longitudinal direction of the test piece, and the vapor deposition film. The measurement was performed in a state where water was dropped with a dropper at the boundary between the part where the substrate and the substrate were peeled off.

  FIG. 9 shows the evaluation results of the normal state peel strength and the wet peel strength of the laminated films of Example 1 and Comparative Examples 1 to 4 together with the water vapor transmission rate and the oxygen transmission rate.

  Comparing Example 1 and Comparative Example 1, the laminated film of Example 1 was higher than the laminated film of Comparative Example 1 in both normal peel strength and wet peel strength. It is considered that this is because the pretreatment method using the plasma pretreatment mechanism of the present invention greatly improves the adhesion of the laminated film as compared with the pretreatment method of Comparative Example 1.

  In addition, the vapor deposition film of Example 1 has a lower water vapor transmission rate and a lower oxygen transmission rate than the vapor deposition film of Comparative Example 1, and the vapor deposition film of Example 1 is less than the vapor deposition film of Comparative Example 1. Also had a greater barrier.

  In order to study the cause of the improvement in the barrier property of the vapor deposited film of Example 1, a comparative study was conducted between Example 1 and Comparative Examples 2-4. Comparing Comparative Example 3 and Comparative Example 4 with each other, Comparative Example 3 showed a decrease in water vapor transmission rate of 0.2 and an oxygen transmission rate of 0.3 only. On the other hand, comparing Example 1 with Comparative Example 2, Example 1 had a decrease in water vapor permeability of 0.6 and a decrease in oxygen permeability of 0.6 compared to Comparative Example 2. Therefore, only when the pretreatment method using the plasma pretreatment mechanism of the present invention and the film formation method using the film formation mechanism having a hollow cathode are combined as in Example 1, the barrier of the vapor deposition film is limited. It was found that the effect of significantly improving the sex is obtained. Further, as in Comparative Example 3, it was found that the effect of significantly improving the barrier property of the vapor deposition film cannot be obtained only by using the pretreatment method using the plasma pretreatment mechanism of the present invention as the pretreatment method. It was As described above, the production apparatus and the production method of the present invention made it possible to provide a laminated film having excellent barrier properties as well as adhesion.

1 Base Material 2 Vapor Deposition Film 3 Barrier Coating Layer 4 Adhesive Layer 5 Second Base Material 6 Adhesive Layer 7 Sealant Layer 10 Film Forming Device P Plasma X Rotating Shaft 11A Base Material Transfer Mechanism 11B Plasma Pretreatment Mechanism 11C Film Forming Mechanism 12 Decompression chamber 12A Substrate transfer chamber 12B Plasma pretreatment chamber 12C Film forming chamber 13 Unwinding roller 14a to d guide roll 15 Winding roller 20 Pretreatment roller 21 Electrode part 22 Plasma source gas supply part 23 Magnetic field forming part 23a 1st Surface 23b Second surface 231 First magnet 231c First axial direction portion 232 Second magnet 232c Second axial direction portion 232d Connection portion 24 Evaporation mechanism 24b Boat 25 Film forming roller 31 Power supply wiring 32 Power supply 35a to 35c Partition wall 50 Plasma supply Mechanism 51 Hollow cathode 61 Deposition material supply unit 63 Aluminum vapor

Claims (15)

A film forming apparatus for forming a vapor deposition film containing aluminum on the surface of a base material,
It has a pretreatment roller that conveys the wound base material, and an electrode section to which a voltage is applied between the pretreatment roller, and a plasma is applied between the pretreatment roller and the electrode section. A plasma pretreatment mechanism to be generated,
Evaporation of a vapor deposition material containing aluminum so as to reach a film forming roller located downstream of the plasma pretreatment mechanism in the conveyance direction of the substrate and the surface of the substrate wound around the film forming roller. And a plasma supply mechanism for supplying plasma between the surface of the base material and the evaporation mechanism, and the vapor deposition film on the surface of the base material wound around the film formation roller. A film forming mechanism for forming a film,
The film forming apparatus, wherein the plasma supply mechanism has a hollow cathode. The plasma pretreatment mechanism generates plasma density 100W · sec / m ² or more 8000W · sec / m ² or less of the plasma between the pretreatment roller and the electrode portions, the film forming apparatus according to claim 1 .   The film forming apparatus according to claim 1, wherein the plasma pretreatment mechanism further includes a magnetic field forming unit that forms a magnetic field between the pretreatment roller and the electrode unit. The electrode portion has a gas ejection portion for ejecting gas, an alternating voltage is applied between the electrode portion and the pretreatment roller,
The plasma pretreatment mechanism further includes a plasma raw material gas supply unit that supplies plasma raw material gas, and the plasma raw material gas supply unit supplies the plasma raw material gas at least between the pretreatment roller and the electrode unit. Then
The plasma pretreatment mechanism generates plasma between the pretreatment roller and the electrode portion based on the AC voltage applied between the electrode portion and the pretreatment roller. The film forming apparatus according to any one of 3 above.   The film forming apparatus according to claim 4, wherein the plasma raw material gas contains at least one gas selected from the group consisting of oxygen, nitrogen, carbon dioxide, ethylene, and argon.   The film forming apparatus according to claim 4, wherein the electrode unit is applied with an alternating voltage of 250 V or more and 1000 V or less with the pretreatment roller. The electrode portion has a first surface facing the pretreatment roller and a second surface located on the opposite side of the first surface, and an AC voltage is applied between the pretreatment roller and the pretreatment roller,
The magnetic field forming unit is provided on the second surface side of the electrode unit,
The film forming apparatus according to claim 3, wherein the plasma pretreatment mechanism generates plasma based on the AC voltage applied between the electrode portion and the pretreatment roller.   The film forming apparatus according to claim 7, wherein the electrode unit is applied with an alternating voltage having a frequency of 20 kHz or more and 500 kHz or less with the pretreatment roller. The plasma pretreatment mechanism has two or more electrode portions and two or more magnetic field forming portions,
The two or more electrode parts are arranged along the transport direction of the base material,
The film forming apparatus according to claim 7, wherein each of the two or more magnetic field forming units is provided on the second surface side of each of the two or more electrode units.   The said electrode part is a film-forming apparatus as described in any one of Claim 7 thru | or 9 with which the alternating voltage of the voltage of 250V or more and 1000V or less is applied between the said pretreatment rollers. The film forming apparatus further includes an AC power source that is electrically connected to the pretreatment roller and the electrode unit and is capable of applying an AC voltage,
The plasma pretreatment mechanism uses the AC power supply to apply an AC voltage between the pretreatment roller and the electrode unit to generate plasma, and the plasma pretreatment mechanism according to claim 4. Film deposition equipment. The plasma pretreatment mechanism is disposed in the plasma pretreatment chamber,
12. The film forming mechanism is arranged in a film forming chamber which is separated from the plasma pretreatment chamber and which is located downstream of the plasma pretreatment chamber in the transport direction of the substrate. The film forming apparatus according to item 1. A film forming method for forming a vapor deposition film containing aluminum on the surface of a base material using a film forming apparatus,
The film forming apparatus is
A pretreatment roller that conveys the wound base material, and an electrode part, and a plasma pretreatment mechanism,
A film forming mechanism including a film forming roller located on the downstream side of the plasma pretreatment mechanism in the transport direction of the substrate, an evaporation mechanism for evaporating an evaporation material containing aluminum, and a plasma supply mechanism having a hollow cathode. And
While applying a voltage between the pretreatment roller and the electrode portion, plasma is generated between the pretreatment roller and the electrode portion, and pretreatment is performed on the surface of the base material using the generated plasma. A plasma pretreatment step for applying
While using the hollow cathode to generate plasma between the surface of the base material and the evaporation mechanism, the evaporation mechanism is used to reach the surface of the base material wound around the film forming roller. A film forming step of evaporating a vapor deposition material containing aluminum to form a vapor deposition film containing aluminum.   14. The film forming method according to claim 13, wherein the plasma pretreatment mechanism of the film forming apparatus further includes a magnetic field forming unit that forms a magnetic field between the pretreatment roller and the electrode unit.   15. The film forming method according to claim 13, wherein arc discharge is generated using the hollow cathode in the film forming step.